Compositions and Uses of Programmable Particles

Abstract

Stimulus-responsive hollow yolk-shell particles (HYSP) comprise: a) at least one orientation-controllable polyphasic yolk containing at least two colorants and at least one stimulus-responsive element, and b) at least one layer of shell encapsulating the orientation-controllable polyphasic yolk. At least a part of the shell contains a material transparent to at least a part of the visible electromagnetic spectrum from about 380 nm to about 800 nm. The orientation-controllable polyphasic yolk is configured to move within the shell in response to an applied force.

Description

Technical Field

[0001] The present disclosure relates, in part, to compositions comprising orientation-controllable polymorphic particles responsive to a magnetic field, methods of firing the same, and uses thereof.

[0002] Cross-reference to Related Applications This application claims the benefit and priority of U.S. Provisional Application No. 63 / 349,796, filed on June 7, 2022, the content of which is hereby incorporated by reference in its entirety.

Background Art

[0003] Stimuli-responsive nanoparticles and microparticles that can actively respond to external stimuli (e.g., heat, light, mechanical stress, electric field) have revolutionized various practical applications of such particles. For example, functionalized chromogenic stimuli-responsive particles that reversibly undergo color switching under an external field have attracted great attention in the development of rewritable paper.

[0004] Among stimuli-responsive particles, yolk-shell particles have attracted great attention due to their attractive structure and tunable physical and chemical properties. Yolk-shell particles (YSP) are a subclass of hybrid materials that contain a movable core (yolk) within a hollow cavity surrounded by an outer shell (s). Due to the applicability and functionality of both the yolk and the hollow shell, YSPs are promising for various notable applications. The configuration of the yolk incorporated in the YSP can be changed under an external field without any spatial change. This feature makes YSPs a promising material for switching optical properties without reconfiguration or volume transition.

[0005] There is still a need for hollow YSPs (HYSPs) that can operate without auxiliary devices in many environments, including a wide temperature range indoors and outdoors, withstand high transitions between states, maintain the directionality of state changes, and can be designed to accommodate various transitions and effects, and exhibit reversible and reusable optical signal properties.

Summary of the Invention

[0006] Accordingly, the present disclosure provides, in part, at least one orientation-controllable polyphasic yoke comprising at least two colorants and at least one stimulus-responsive element, and at least one shell layer encapsulating the orientation-controllable polyphasic yoke (at least a part of the shell comprises a material that is transparent to at least a part of the visible electromagnetic spectrum from about 380 nm to about 800 nm); the orientation-controllable polyphasic yoke is configured to move within the shell in response to an applied force, a composition comprising stimulus-responsive yoke-shell particles (HYSP). In embodiments, the applied force is a magnetic field.

[0007] In an embodiment, the HYSP includes dimensions of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 50 μm.

[0008] In an embodiment, the HYSP includes a space between at least one orientation-controllable polyphase yoke and at least one layer of a shell: about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, or about or at least about 20 μm.

[0009] In an embodiment, the HYSP includes one or more shapes, geometric shapes, and / or morphologies among spherical, elliptical, spindle-shaped, rod-shaped, cubic, star-shaped, cylindrical, plate-shaped, tetrahedral, and dodecahedral.

[0010] In an embodiment, at least one orientation-controllable polyphase yoke includes a material including one or more of metal, metal oxide, silica, organic polymer, inorganic polymer, biopolymer, synthetic polymer, and combinations thereof.

[0011] In an embodiment, one or more synthetic polymers include plastic, thermoresponsive polymer, latex, hydrocarbon, crude oil derivative, and / or petroleum derivative. In an embodiment, one or more thermoresponsive polymers include poloxamer, styrene-butadiene block copolymer, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and / or combinations thereof.

[0012] In an embodiment, one or more synthetic polymers include poly(tert-butyl acrylate)-poly(3-(triethoxysilyl)propyl methacrylate) (PtBA-PTPM), polystyrene latex polymer, carboxylated latex polymer, aminated latex polymer, colored polystyrene polymer (dye injection and / or pigment injection), colored polystyrene-based carboxylated latex polymer (dye injection and / or pigment injection), fluorescent polystyrene-based polymer, fluorescent polystyrene-based carboxylated latex polymer, fluorescent aminated polystyrene-based polymer, surfactant-free polystyrene, carboxylated surfactant-free polymer, polymethyl methacrylate (PMMA) latex polymer, and / or divinylbenzene (DVB)-crosslinked polystyrene latex polymer.

[0013] In embodiments, the one or more biological polymers include nucleic acids (DNA, RNA), amino acids (peptides, proteins), polysaccharides, and / or lipids. In embodiments, the one or more biological polymers include strand nucleic acids arranged in one or more patterns and / or configurations, with the one or more strand nucleic acids being disposed on and / or within at least one polymorphic yoke.

[0014] In an embodiment, at least one orientation-controllable polyphase yoke includes dimensions of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 50 μm.

[0015] In embodiments, at least one orientation-controllable polyphase yoke includes dimensions that are smaller than the HYSP. In embodiments, at least one orientation-controllable polyphase yoke is smaller than the HYSP by about or at least about 1 nm, about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 15 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 30 μm, or about or at least about 40 μm.

[0016] In an embodiment, at least one orientation-controllable polyphase yoke includes one or more of a spherical, elliptical, spindle-shaped, rod-shaped, cubic, star-shaped, cylindrical, plate-shaped, regular-shaped, irregular-shaped, triangular, trapezoidal, octagonal, tetrahedral, and dodecahedral structure, shape, geometric shape, and / or form.

[0017] In an embodiment, at least one orientation-controllable polyphase yoke includes Janus particles. In an embodiment, at least one orientation-controllable polyphase yoke includes one or more magnetic particles contained within polymer beads.

[0018] In an embodiment, at least one orientation-controllable polyphase yoke is coated with a protective coating. In an embodiment, the protective coating includes chemical functionalization, lubricants, surface treatment, coatings, abrasives, and / or combinations thereof. In an embodiment, the protective coating includes a polymeric material, inorganic oxides, carbon materials, polytetrafluoroethylene (PTFE), hydroxylated self-assembled monolayers, vitreous enamels, ceria (cerium oxide), ceramics, anodized metals, silica, and / or combinations thereof.

[0019] In an embodiment, at least one orientation-controllable polyphase yoke includes a shape, geometric shape, and / or form that conforms to the congruent shape, geometric shape, or form of the inner surface of at least one shell layer. In an embodiment, the shape, geometric shape, or form of at least one orientation-controllable polyphase yoke includes pins that fit within congruent grooves of at least one shell layer.

[0020] In an embodiment, the yoke is suspended in a fluid medium, semi-solid medium, non-Newtonian fluid or medium, and / or combinations thereof.

[0021] In an embodiment, at least one orientation-controllable polyphase yoke is configured to rotate about its own axis when exposed to a magnetic field. In an embodiment, at least one orientation-controllable polyphase yoke is suspended within at least one shell layer and configured to move freely in response to a magnetic field.

[0022] In an embodiment, at least one orientation-controllable polyphase yoke includes solid nanoparticles. In an embodiment, at least one orientation-controllable polyphase yoke includes a fluid, a ferrofluid, a semi-solid, and / or a non-Newtonian fluid.

[0023] In an embodiment, at least one stimulus-responsive element includes a magnetic material. In an embodiment, the magnetic material is ferromagnetic, ferrimagnetic, antiferromagnetic, diamagnetic, paramagnetic, superparamagnetic, and / or antiferromagnetic. In an embodiment, the magnetic material is an organic, carbon-based, and / or biomolecular system including one or more of tetracyanoethylene (TCNE) salts, [Fe(C5Me5)2]+[TCNE]·-, Li[TCNE], [MnIITPP][TCNE]·(TPP = tetraphenylporphyrin), [FeII(TCNE)(NCMe)2][FeIIICl4], MnII(TCNE)I(OH2), MnII(TCNE)[C4(CN)8]1 / 2, Fe(TCNE)[C4(CN)8]1 / 2, MnII(TCNE)3 / 2(I3)1 / 2, VII[TCNE]x(x≒2), C7H5ClN3Se4, magnetic organic polymers, and / or polymer-bonded magnets. In an embodiment, the magnetic material includes iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), manganese (Mn), chromium (Cr), samarium (Sm), their alloys or oxides; alloys, intermetallic compounds, and / or oxides of Fe, Co, Ni, Zn, Mn, Sm; oxides of iron, Fe2O3, FeO, and / or Fe3O4; Co, Ni, Zn, and / or Mn:FexOy, and / or ferrite materials and / or doped materials of magnetite.

[0024] In an embodiment, the magnetic material includes magnetic particles and / or beads. In an embodiment, the magnetic particles and / or beads have dimensions of about or at least about 5 nm, about or at least about 10 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 5 μm, about or at least about 10 μm, about or at least about 50 μm, or include dimensions in the range of about or at least about 5 nm to about or at least about 50 nm, about or at least about 5 nm to about or at least about 100 nm, about or at least about 5 nm to about or at least about 500 nm, about or at least about 5 nm to about or at least about 1,000 nm, about or at least about 5 nm to about or at least about 2,000 nm, about or at least about 5 nm to about or at least about 5,000 nm, about or at least about 10 nm to about or at least about 5,000 nm, about or at least about 100 nm to about or at least about 5,000 nm, about or at least about 1,000 nm to about or at least about 5,000 nm.

[0025] In an embodiment, the magnetic material is configured to generate a magnetic field of about or at least about 200 gauss, about or at least about 500 gauss, about or at least about 800 gauss, about or at least about 1,000 gauss, about or at least about 2,500 gauss, about or at least about 12,500 gauss, about or at least about 15,000 gauss, about or at least about 20,000 gauss, or about or at least about 25,000 gauss, or a magnetic field in the range of about or at least about 200 gauss to about or at least about 25,000 gauss. In an embodiment, at least one stimulus-responsive element includes a magnetic material configured to be magnetized and / or generate a magnetic field.

[0026] In an embodiment, the HYSP includes two colorants, three colorants, four colorants, five colorants, six colorants, seven colorants, colorants, colorants, or ten or more colorants. In an embodiment, at least two colorants include colors within the visible electromagnetic spectrum that include attenuation, absorption, emission, reflection, scattering, and / or interference at wavelengths of about or at least about 350 nm to about or at least about 800 nm. In an embodiment, the colors include one or more of white, black, red, orange, yellow, green, blue, indigo, violet, and variations in hue, shade, and intensity therebetween.

[0027] In an embodiment, at least two colorants include dyes, pigments, stains, phosphors, metal salts, and / or chromophores.

[0028] In an embodiment, at least two colorants include one or more dyes. In an embodiment, the dye is an organic dye or an inorganic dye. In an embodiment, the dyes include one or more of rhodamine B, congo red, crystal violet, methylene blue, acridine orange, nile red, malachite green, eosin Y, cresol red, fluorescein, and indigo.

[0029] In an embodiment, two or more colorants include pigments. In an embodiment, the pigment includes a water-soluble pigment. In an embodiment, the water-soluble pigment is one or more of anthocyanin, anthraquinone, carotenoid, violacein, melanin, phycocyanin, prodiginine, asperversin, benzoquinone, anthraquinone, and their derivatives.

[0030] In the embodiment, the pigment includes one or more of titanium white (PW6), zinc white (PW4), carbon black (PBk7), Mars black (PBk11), iron oxide red (PR101), cadmium red (PR108), alizarin crimson (PR83), cadmium orange (PO20), cadmium yellow (PY35), lemon yellow (PY3), chrome green oxide (PG17), phthalocyanine green (PG7), ultramarine blue (PB29), cobalt blue (PB28), cerulean blue (PB35), Prussian blue (PB27), burnt sienna (PBr7), raw umber (PBr7), rose sienna (PBr7), and yellow ochre (PY43).

[0031] In the embodiment, the pigment is an organic pigment. In the embodiment, the pigment is an inorganic pigment.

[0032] In the embodiment, the organic pigment or the inorganic pigment includes a white pigment. In the embodiment, the white pigment is one or more of lead white (2PbCO3·Pb(OH)2), kaolin, silica (SiO2), titanium dioxide (TiO2 / rutile and anatase), zinc oxide (ZnO), zinc sulfide (ZnS), and / or lithopone (ZnS+BaSO4).

[0033] In the embodiment, the organic pigment or the inorganic pigment includes a black pigment. In the embodiment, the black pigment is one or more of coal (charcoal), groutite (α-MnOOH), manganate (γ-MnOOH),hausmannite (Mn3O4), carbon black, iron oxide black (Fe3O4), and / or spinel black (CuCr2O4).

[0034] In the embodiment, the organic pigment or the inorganic pigment includes a coloring pigment.

[0035] In an embodiment, the coloring pigment includes a yellow pigment. In the embodiment, the yellow pigment is yellow ocher (α-FeOOH), orpiment (As2S3), lead yellow earth (PbO), lead-tin yellow (Pb2SnO4, PbSn2SiO7), Naples yellow (Pb(SbO3)2), zinc yellow (Zn2CrO4), Indian yellow (C 19 H 16 O 10 ), iron oxide yellow (α-FeOOH), chromium titanium yellow ((Ti,Cr,Sb)O2), nickel titanium yellow ((Ti,Ni,Sb)O2), chrome yellow (PbCrO4), cadmium yellow (CdS), bismuth yellow (BiVO4), or one or more thereof.

[0036] In an embodiment, the coloring pigment includes a red pigment. In the embodiment, the red pigment is red ocher (α-Fe2O3), terra di siena (α-Fe2O3), vermilion (HgS), red lead (Pb3O4), alizarin madder varnish, alizarin red (C 14 H8O4), iron oxide red (α-Fe2O3), molybdate red (Pb(Cr,S,Mo)O4), cadmium red (Cd(S,Se)), or one or more thereof.

[0037] In an embodiment, the coloring pigment includes a green pigment. In the embodiment, the green pigment is green earth (Fe silicate), Schweinfurt green (C4H6As6Cu4O 16 ), chromium oxide green (Cr2O3), chromium oxide hydrate green (CrOOH), cobalt green (Co2TiO4), or one or more thereof.

[0038] In an embodiment, the coloring pigment includes a blue pigment. In the embodiment, the blue pigment is lazurite (lapis lazuli), Egyptian blue (CaCuSi4O 10 ), azurite (2CuCO3·Cu(OH)2), malachite (CuCO3·Cu(OH)2), cobalt blue (CoAl2O4), ultramarine blue (Na6Al6Si6O 24 (NaSn)), Prussian blue (K[Fe III Fe IIIt contains one or more of (CN)6·xH2O).

[0039] In an embodiment, the coloring pigment contains a brown pigment. In an embodiment, the brown pigment contains one or more of burnt umber (Fe2O3·xMnO2), brown ocher (α-Fe2O3 + Mn oxide), limonite (a mixture of various Fe oxides).

[0040] In an embodiment, the pigment is an oxide or oxyhydroxide pigment (TiO2, ZnO, α-Fe2O3, α-FeOOH, γ-Fe2O3, Fe3O4, Cr2O3, CrOOH, PbO, PB3O4, Mn3O4, -MnOOH, Sb2O3), a complex oxide pigment (CoAl2O4, CuCr2O4, Co2TiO4, (Ti,Ni,Sb)O2, (Ti,Cr,Sb)O2), a carbonate hydroxide pigment (2PbCO3·Pb(OH)2, 2CuCO3·Cu(OH)2, CuCO3·Cu(OH)2), a sulfide / selenide pigment (ZnS, CdS, Cd(S,Se), CdSe, γ-Ce2S3, HgS, As2S3), a chromate / molybdate pigment (PbCrO4, Pb(Cr,S)O4, Pb(Cr,S,Mo)O4, ZnCrO4, BaCrO4, SrCrO4), a vanadate pigment (BiVO4, 4BiVO4·3Bi2MoO6), a stannate pigment (Pb2SnO4, PbSn2SiO7, Co2SnO4, CoSnO3), a phosphate pigment (Co3(PO4)2), an antimonate pigment (Pb(SbO3)2), an arsenate pigment (Cu(AsO3)2), an ultramarine pigment (Na6Al6Si6O 24 (NaSn)), a hexacyanoferrate / hexacyanoferrate pigment (K[FeIIIFeII(CN)6]·xH2O (x = 14 - 16)), an oxonitride pigment (CaTaO2N, LaTaON2), an elemental pigment (C, Al, Cu, Cu / Zn, Au), a spinel-based pigment, and / or a rutile-based metal pigment, or one or more thereof.

[0041] In an embodiment, the inorganic pigment is one or more of a transparent effect pigment, a goniochromatic pigment, a nacreous luster pigment, a metallic pigment, an interference pigment, a metallic effect pigment, a fluorescent pigment, a luminescent pigment, a phosphorescent pigment, a magnetic pigment, and a corrosion-inhibiting pigment.

[0042] In an embodiment, the metallic pigment includes one or more of aluminum, bronze, and copper metallic pigments.

[0043] In an embodiment, the nacreous luster pigment includes one or more of mica, titanium dioxide, and bismuth oxychloride.

[0044] In an embodiment, the fluorescent pigment includes one or more fluorescent dyes and pigments containing a fluorescent mineral.

[0045] In an embodiment, the phosphorescent pigment includes zinc sulfide and / or strontium aluminate.

[0046] In an embodiment, the interference pigment includes titanium dioxide-coated mica and / or aluminum oxide-coated mica.

[0047] In an embodiment, two or more colorants include anisotropic particles.

[0048] In an embodiment, the anisotropic particles include one or more metal nanoparticles, which optionally include one or more nanorods of gold (Au), silver (Ag), and aluminum (Al).

[0049] In an embodiment, one or more colorants include a plasmonic material. In an embodiment, the plasmonic material includes a pigment, particles, foil, and / or a film. In an embodiment, the film includes a polymer film loaded with noble metal nanoparticles.

[0050] In an embodiment, the goniochromatic pigment includes aluminum coated with magnesium fluoride embedded in chromium.

[0051] In embodiments, at least one shell layer includes a single uniform thickness and / or various thicknesses. In embodiments, at least one shell layer is about or at least about 1 nm, about or at least about 5 nm, about or at least about 10 nm, about or at least about 15 nm, about or at least about 20 nm, about or at least about 25 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 200 nm, about or at least about 300 nm, about or at least about 400 nm, about or at least about 500 nm, about or at least about 600 nm, about or at least about 700 nm, about or at least about 800 nm, about or at least about 900 nm, about or at least about 1 μm, about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 10 μm, about or at least about 15 μm, about or at least about 20 μm, about or at least about 25 μm, about or at least about 30 μm, about or at least about 35 μm, about or at least about 40 μm thick.

[0052] In embodiments, at least one shell layer includes at least an opaque portion. In embodiments, the opaque portion optionally optically absorbs, deflects, blocks, and / or scatters light within the visible electromagnetic wave range of about 380 nm to about 800 nm. In embodiments, the opaque portion is about or at least about 1 nm, about or at least about 5 nm, about or at least about 10 nm, about or at least about 25 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 250 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 2.5 μm, about or at least about 5 μm, or about or at least about 10 μm thick.

[0053] In an embodiment, at least one shell layer comprises a material including one or more of glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), nylon, thermoresponsive polymer, and combinations thereof.

[0054] In an embodiment, at least one shell layer is composed of one or more of polysaccharide, lipid, amino acid, DNA, RNA, plastic, thermoresponsive polymer, hydrocarbon, crude oil, or petroleum derivative, and combinations thereof, and / or is disposed thereon.

[0055] In an embodiment, at least one shell layer includes one or more depressions, grooves, and spaces disposed on an inner surface for fixing at least one orientation-controllable polyphase yoke.

[0056] In an embodiment, at least one shell layer includes one or more materials for reducing friction between the inner surface and at least one orientation-controllable polyphase yoke.

[0057] In an embodiment, HYSP is disposed on a surface and / or a substrate. In an embodiment, the surface and / or the substrate is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue or skin.

[0058] In an embodiment, the surface and / or the substrate is planar or non-planar. In an embodiment, the surface and / or the substrate includes at least a convex portion, a concave portion, or a portion having no distinct shape. In an embodiment, the surface and / or the substrate is on the inner surface of the object, the outer surface of the object, or both, and the object is a non-HYSP object.

[0059] In an embodiment, the surface and / or the substrate includes depressions and / or recesses. In an embodiment, the depressions and / or recesses are arranged in an array. In an embodiment, the HYSP is disposed in and / or on the depressions and / or recesses. In an embodiment, the surface and / or the substrate includes pillars, posts, and / or stoppers. In an embodiment, the HYSP is disposed in and / or on the pillars, posts, and / or stoppers. In an embodiment, the surface and / or the substrate includes one or more grooves. In an embodiment, the HYSP is disposed in and / or on the one or more grooves.

[0060] In an embodiment, the surface and / or the substrate changes color in response to the presence of a magnetic field.

[0061] In an embodiment, the HYSP is incorporated into the substrate, material, and / or surface of a fluid, suspension, ink, liquid film, and / or adhesive. In an embodiment, the substrate, material, and / or surface of the fluid, suspension, ink, liquid film, and / or adhesive is suitable for application to an object.

[0062] In an embodiment, the HYSP is incorporated into the substrate, material, and / or surface of a foil, film, thin plastic, and / or paper. In an embodiment, the substrate, material, and / or surface of the foil, film, thin plastic, and / or paper is suitable for being fixed to or embedded in an object.

[0063] In an embodiment, the HYSP is incorporated into the substrate, material, and / or surface of a fiber, yarn, thread, and / or twisted yarn. In an embodiment, the substrate, material, and / or surface of the fiber, yarn, thread, and / or twisted yarn is suitable for being woven into a clothing item, fabric, and / or waterproof sheet.

[0064] In an embodiment, the HYSP is disposed between a first substrate and a second substrate. In an embodiment, at least one of the first substrate and the second substrate includes a material that is transparent to at least a portion of the visible electromagnetic (EM) spectrum. In an embodiment, the material includes glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), and / or nylon. In an embodiment, the material includes a thickness of about or at least about 50 nm, about or at least about 100 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 10 μm, about or at least about 100 μm, about or at least about 1 mm, about or at least about 5 mm, or about or at least about 10 mm.

[0065] In an embodiment, the HYSP includes at least a first surface having a shape complementary to the shape of the second surface of the HYSP. In an embodiment, the HYSP is disposed on and / or embedded in a surface and / or substrate that has been treated with one or more of a lubricant, an adhesive, a surface treatment agent, a coating agent, and / or an abrasive.

[0066] In one aspect, in an embodiment, a method for manufacturing hollow yoke-shell particles (HYSP) is described herein, the method comprising: i) preparing at least one orientation-controllable polyphasic yoke (the at least one orientation-controllable polyphasic yoke comprising at least two colorants and at least one stimulus-responsive element); ii) forming a dissolution layer disposed on the at least one orientation-controllable polyphasic yoke; iii) forming at least one shell layer encapsulating the orientation-controllable polyphasic yoke (the at least one shell layer comprising pores); iv) repositioning the dissolution layer through the pores of the at least one shell layer to form a cavity between the at least one orientation-controllable polyphasic yoke and the at least one shell layer; and v) curing the at least one shell layer to form a non-porous shell (the orientation-controllable polyphasic yoke being configured to move within the shell in response to an external energy). In an embodiment, the external energy is a magnetic field.

[0067] In an embodiment, the method further comprises applying a coating to the at least one orientation-controllable polyphasic yoke before forming the dissolution layer. In an embodiment, the coating comprises one or more of a protective coating, chemical functionalization, a lubricant, a surface treatment, and / or an abrasive.

[0068] In an embodiment, the method further comprises forming one or more additional shells encapsulating the at least one shell layer.

[0069] In an embodiment, the method further comprises disposing one or more materials within the cavity formed by the removal.

[0070] In an embodiment, the one or more materials comprise a thermoresponsive polymer and / or a fluid medium.

[0071] In an embodiment, the at least one shell layer comprises at least a portion of a shell comprising a material that is transparent to at least a portion of the visible electromagnetic spectrum from about 380 nm to about 800 nm.

[0072] In embodiments, one or more of i) preparing at least one orientation-controllable polyphase yoke, ii) forming a dissolution layer, and iii) forming at least one shell layer include the assembly, adhesion, and / or fixation of two or more components; injection molding and / or micro-injection molding; self-assembly, adsorption, coacervation, and / or mixing; polymerization, extrusion, and / or manipulation of polymers; additive manufacturing, CNC machining (computer numerical control machining), urethane casting, microcontact printing, dip-pen lithography, beam-pen lithography, photolithography, electron beam lithography, and / or 3D printing.

[0073] In embodiments, forming at least one shell layer includes performing one or more of synthesis of mesoporous materials, soft templating, calcination, and / or extraction.

[0074] In embodiments, at least one shell layer including pores includes mesoporous silica and / or a porous organic framework. In embodiments, the rearrangement of the dissolution layer includes removing, dissolving, and / or etching the dissolution layer.

[0075] In embodiments, curing at least one shell layer to form a non-porous shell includes compressing a solid mass of the shell material by heat and / or pressure.

[0076] In embodiments, preparing at least one orientation-controllable polyphase yoke includes forming the yoke by injecting a molten plastic, metal, and / or polymer-based material into a mold cavity.

[0077] In embodiments, preparing at least one orientation-controllable polyphase yoke includes a DNA origami technique. In embodiments, the DNA origami technique includes the self-assembly of at least two DNA-coated colorants and at least one DNA-coated stimulus-responsive element.

[0078] In an embodiment, one or more of i) preparing at least one orientation-controllable polyphase yoke; ii) forming a dissolution layer; and iii) forming at least one shell layer include 3D printing. In an embodiment, 3D printing includes performing one or more of fused deposition modeling (FDM), fused filament fabrication (FFF), stereolithography (SLA), selective laser sintering (SLS), binder jetting (BJ), direct energy deposition (DED), digital light processing (DLP), liquid crystal display (LCD), PolyJet, multi-jet fusion (MJF), direct metal laser sintering (DMLS), electron beam melting (EBM), laminated object manufacturing (LOM), continuous liquid interface production (CLIP), electron beam melting, and digital light processing (DLP).

[0079] In an embodiment, one or more of at least one orientation-controllable polyphase yoke, the dissolution layer, and at least one shell layer include one or more of a thermoresponsive polymer, a resin, a metal, a ceramic, a glass, quartz, a plastic, polyethylene terephthalate, a polycarbonate, polymethyl methacrylate (acrylic), polyethylene, a polyurethane, a polypropylene, a thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), an epoxy and an epoxy-based photoresist, a hydrogel, a cyclic olefin copolymer (COC), a cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ether ketone (PEEK), polyetherimide (ULTEM), nylon, and combinations thereof.

[0080] In an embodiment, the one or more thermoresponsive polymers and resins include one or more of poloxamer, styrene-butadiene block copolymer, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and combinations thereof.

[0081] In an embodiment, preparing at least one orientation-controllable polyphase yoke includes Janus particles. In an embodiment, the Janus particles include poly(tert-butyl acrylate)-poly(3-(triethoxysilyl)propyl methacrylate) (PtBA-PTPM), polystyrene latex polymer, carboxylated latex polymer, aminated latex polymer, colored polystyrene polymer (dye injection and / or pigment injection), colored polystyrene-based carboxylated latex polymer (dye injection and / or pigment injection), fluorescent polystyrene-based polymer, fluorescent polystyrene-based carboxylated latex polymer, fluorescent aminated polystyrene-based polymer, surfactant-free polystyrene, carboxylated surfactant-free polymer, polymethyl methacrylate (PMMA) latex polymer, divinylbenzene (DVB)-crosslinked polystyrene latex polymer, and combinations of one or more thereof.

[0082] In an embodiment, preparing at least one orientation-controllable polyphase yoke includes coupling at least two colorants with a stimulus-responsive element composed of a material responsive to a magnetic field.

[0083] In embodiments, forming at least one shell layer includes forming at least one shell layer using one or more materials that are transparent to at least a portion of the visible electromagnetic (EM) spectrum. In embodiments, the one or more materials include glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), and / or nylon.

[0084] In embodiments, the method further includes incorporating HYSP into a substrate and / or material of a fluid, suspension, ink, liquid film, and / or adhesive. In embodiments, the substrate and / or material of the fluid, suspension, ink, liquid film, and / or adhesive is suitable for application to the surface of an object.

[0085] In embodiments, the method further includes incorporating HYSP into a substrate and / or material of a foil, film, thin plastic, and / or paper. In embodiments, the substrate and / or material of the foil, film, thin plastic, and / or paper is suitable for being fixed to or embedded in an object.

[0086] In embodiments, the method further includes incorporating HYSP into a substrate and / or material of a fiber, thread, yarn, and / or twine. In embodiments, the substrate, material, and / or surface of the fiber, thread, yarn, and / or twine is suitable for being woven into a clothing item, fabric, and / or waterproof sheet.

[0087] In an aspect, in an embodiment, a method of using hollow yoke-shell particles (HYSP) is disclosed herein. The method includes providing the HYSP as described herein; incorporating the HYSP into a substrate and / or material of a fluid, suspension, ink, liquid film, and / or adhesive; incorporating the HYSP into a substrate and / or material of a foil, film, thin plastic, and / or paper; or incorporating the HYSP into a substrate and / or material of a fiber, thread, yarn, and / or spun yarn; and applying the substrate and / or material of the fluid, suspension, ink, liquid film, and / or adhesive, the substrate and / or material of the foil, film, thin plastic, and / or paper, or the substrate and / or material of the fiber, thread, yarn, and / or spun yarn to an object and / or surface. In an embodiment, the object is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue. In an embodiment, the object and / or surface exhibits a property of changing optical characteristics in response to the application of a magnetic field.

[0088] In an aspect, in an embodiment, a method of authenticating a material is disclosed herein. The method includes providing a formulation of the HYSP as described herein (the formulation including a substrate and / or material of a fluid, suspension, ink, liquid film, and / or adhesive; a substrate and / or material of a foil, film, thin plastic, and / or paper; or a substrate and / or material of a fiber, thread, yarn, and / or spun yarn), tagging an object and / or surface with the formulation, and reading the tag. In an embodiment, the tagging is configured to be read by a sensor and / or an optical imaging device. In an embodiment, the reading includes applying a magnetic field to determine a change in the optical characteristics of the object and / or surface due to the presence of the HYSP. BRIEF DESCRIPTION OF THE DRAWINGS

[0089]

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DETAILED DESCRIPTION OF THE INVENTION

[0090] The present disclosure, in part, provides a composition of hollow yoke-shell particles (HYSP), which represents a class of hybrid materials that include a core (e.g., referred to as a “yoke” in embodiments) that can be orientationally controlled within a hollow cavity surrounded by one or more “shells”. In embodiments, the presence of a cavity within the HYSP can provide the yoke with a degree of rotational freedom while maintaining the protective effect of the shell, which is beneficial for retaining the distance-dependent properties of the yoke. In embodiments, the configuration of the yoke incorporated into the HYSP can be changed or otherwise modified under an external field without any change in space (e.g., no translational motion). This feature makes the HYSP, in embodiments, a promising material for exhibiting switchable or tunable optical properties without reconfiguration or volume transition. In embodiments, a HYSP that includes a yoke capable of changing its orientation in response to an external stimulus (e.g., a magnetic field) without disturbing the shell is referred to as a HYSP. In embodiments, the HYSP is a “magnetically colored particle”, which is a particle that exhibits various optical properties in response to a magnetic field.

[0091] In embodiments, the HYSP functions via the energy transferred thereto to assist in the movement of the HYSP, and the energy can be transferred in the form of a force. In embodiments, the energy transferred by a force that moves any object is known as work or work done, and thus work and energy are directly related. In embodiments, the terms “exogenous energy” or “applied force” as used herein refer to the energy or work applied to the HYPS or object to initiate the optical change properties as described herein.

[0092] Hollow yoke-shell particles (HYSP) This specification describes, in part, "hollow yoke-shell particles" or "HYSPs", which, in embodiments, refer to a class of hybrid materials that include at least one movable core (e.g., yoke 20, see FIGS. 1, 2A - 2B, and 3 - 6) within at least one hollow cavity surrounded by at least one outer shell layer. In embodiments, HYSPs are shown as a "yoke-shell" configuration and are sometimes described as "yoke void shell". In embodiments, if there is a "void" or empty space within the HYSP, it will not be further denoted by the notation "yoke-shell", which refers to both the yoke-shell structure and the space encapsulated therein. In embodiments, when the shell is composed of at least two layers, the nomenclature takes the form of yoke - shell 1- shell 2- shell n where n is any number of layers (such as having one or more spaces between yoke - shell 1 and shell 1- shell 2).

[0093] In embodiments, the HYSPs disclosed herein can be designed using a wide range of chemical compositions and materials, including, but not limited to, metal - polymer, metal - silica, metal - carbon, metal - metal oxide, metal - silica, DNA - silica, DNA - polymer, DNA - carbon, DNA - metal oxide, polymer - polymer, polymer - silica, silica - polymer, silica - metal oxide, silica - carbon, metal oxide - silica, silica - metal oxide, or any possible combination thereof (including the materials described herein). The HYSPs disclosed herein can, in embodiments, have at least one shell layer, and the shell and yoke of each layer can be composed of any combination of the materials described herein. In embodiments, the polymer substrate can also be selected from classes including, but not limited to, biological polymers, polysaccharides, plastics, crude oil and / or petroleum (e.g., hydrocarbon) derivatives.

[0094] In an embodiment, the size of the HYSP can be about or at least 1 nm to about or at least 50 μm. In an embodiment, the HYSP can have a dimension (e.g., radius, diameter, length, width) of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 50 μm.

[0095] In an embodiment, the distance between the yoke and the inner layer of the shell within the HYSP can be adjusted. In an embodiment, the distance between the outer portion of the yoke and the inner layer of the shell can be 1 nanometer (nm) or less. In an embodiment, the distance can range from about or at least about 1 nm to about or at least about 50 μm or more. In an embodiment, the space can be about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, or about or at least about 20 μm.

[0096] In an embodiment, the distance between the yoke and the inner layer of the shell within the HYSP has portions where the distance is uniform and / or non-uniform. In an embodiment, the distance between the yoke and the inner layer of the shell within the HYSP is, for example, from about or at least about 1 nm to about or at least about 5 nm, from about or at least about 5 nm to about or at least about 10 nm, from about or at least about 10 nm to about or at least about 20 nm, from about or at least about 20 nm to about or at least about 50 nm, from about or at least about 50 nm to about or at least about 100 nm, from about or at least about 100 nm to about or at least about 1000 nm (1 μm), from about or at least about 1 μm to about or at least about 5 μm, from about or at least about 5 μm to about or at least about 10 μm, from about or at least about 10 μm to about or at least about 20 μm, or from about or at least about 20 μm to about or at least about 50 μm.

[0097] In an embodiment, the distance between the yoke and the inner layer of the shell within the HYSP is variable and has various distances. In an embodiment, varying the distance is due to the coupling mode between the yoke and the shell to keep the yoke floating within the cavity of the shell while maintaining the degree of freedom of rotation. For example, in an embodiment, the attachment is a pin-and-groove fitting where the yoke has lumps similar to "pins", and the shell has a "groove" pattern such that the yoke remains floating within the cavity and a substantially uniform distance is maintained between the yoke and the shell in the outer surface region of the pin and the groove.

[0098] In embodiments, the HYSP can take on a variety of shapes, geometries, and / or morphologies including, but not limited to, spherical, elliptical, spindle-shaped, rod-shaped, cubic, star-shaped, cylindrical, plate-shaped, tetrahedral, dodecahedral, etc. In embodiments, the shell takes on the same shape, geometry, and / or morphology as the core (e.g., the yoke). In embodiments, the core or yoke takes on a different shape, geometry, and / or morphology than one or more shells. In embodiments, the yoke maintains at least a portion having a fit shape, geometry, and / or morphology corresponding to the shape, geometry, and / or morphology present on the surface of the shell (e.g., for attachment purposes). In embodiments, the yoke does not necessarily have to be solid particles (e.g., solid nanoparticles or microparticles), and instead can include fluids (e.g., ferromagnetic fluids), semi-solids, or non-Newtonian fluids. In such embodiments, the shape, geometry, and / or morphology of the yoke is determined by the shape, geometry, and / or morphology of the shell.

[0099] In embodiments, the average particle size of the HYSP provided herein is preferably from about 10 nm to about 50 μm. In embodiments, various techniques can be used to characterize the physicochemical properties of the HYSP, including particle size and size distribution, morphology, hydrophilicity, and other physicochemical properties. In embodiments, such techniques include, but are not limited to, scanning electron microscopy (SEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), scanning tunneling microscopy (STM), atomic force microscopy (AFM), confocal microscopy, light scattering, and other techniques used to determine the physicochemical properties of the HYSP.

[0100] In an embodiment, the HYSP, yoke, and / or shell may include one or more additional elements that provide and / or modify one or more properties. For example, in an embodiment, these additional elements may be for the purpose of improving, modifying, or otherwise imparting chemical, physical, and / or biological properties to the shell structure, yoke structure, or the HYSP as a whole. In an embodiment, one or more of the additional elements may include a lubricant (e.g., one that changes the coefficient of friction and / or the force required to move the yoke relative to the shell or the HYSP relative to the surface), a colorant (e.g., dyes, pigments, anisotropic particles, metal nanorods, plasmonic materials, etc.), and / or a material that changes geometry, shape, density, reflectivity, etc. (e.g., an additional material such as metal, ceramic, polymer, plastic, etc.).

[0101] In an embodiment, one or more of the additional elements may form a film or fiber and / or improve or facilitate the stabilization, suspension, and / or dispersion of the HYSP in an ink, suspension, liquid, or fluid medium for application to a surface. In an embodiment, the additional element may be present on at least a portion of the outside of the shell. In an embodiment, the additional element of the shell can protrude into or be introduced into the shell surface and / or the interior of the outer surface or the yoke. Alternatively, in an embodiment, these elements do not protrude into the interior of the shell and are present only, for example, on the surface of one or more shell layers and / or in the cavities of the spaces between one or more shell layers. In an embodiment, the additional element can also be present on one or more inner surfaces of the shell facing a cavity (e.g., the space between layers or the space between a layer and the yoke).

[0102] In embodiments, one or more additional elements introduced on the outer surface can help prevent the resistance between the HYSP and the substrate material (such as the surface of skin, paper, cloth, metal, clay board, ceramic, plastic, polymer, metal, glass, etc.), or the resistance between the yoke (core) and the shell when the yoke (core) rotates, for example, when an external stimulus (such as a magnetic field) is applied. In embodiments, the additional elements are designed to make the surface of the HYSP adhesive, so that the HYSP can adhere or bond more strongly to the substrate. In such cases, in embodiments, the HYSP can adhere to or be embedded in the surface, and the yoke (core) can move freely within the shell of the HYSP in response to an external stimulus (such as a magnetic field), which will impart this property to the surface.

[0103] In embodiments, for example, one or more additional elements that can improve the chemical, physical, and / or biological properties of the shell are applied to the inner surface of the shell so that the yoke can be more easily oriented when exposed to an applied force or energy, to overcome the frictional force within the cavity of the HYSP. In embodiments, the additional elements impart low-friction behavior to the inner surface within the cavity to facilitate the rotation of the yoke. In embodiments, the lack or change in the amount of such additional elements can finely adjust the friction, and thereby finely adjust the strength of the magnetic field required to move the yoke. In such embodiments, by changing the coefficient of friction of each shell-yoke combination, a HYSP with a variable response to an applied force or energy (such as a magnetic field) can be fabricated.

[0104] Orientation-controllable polyphase yoke In part, an orientation-controllable polyphase particle core (i.e., a "yoke") is described herein, which can respond to an external stimulus (e.g., a magnetic field) in embodiments. In embodiments, the core (e.g., yoke 20 referring to FIGS. 1, 2A-2B, and 3-6) has at least one degree of freedom (e.g., a rotational degree of freedom). In embodiments, the response of the yoke after applying an external stimulus (e.g., a magnetic field) is to change (e.g., rotate) the orientation of the yoke within the interstitial space between the core and the shell, independent of the movement of the HYSP in space. In non-limiting embodiments, this is represented in FIGS. 2A and 2B, as well as FIG. 3.

[0105] In embodiments, the "yoke" refers to a movable (orientation-controllable) core within the cavity of the HYSP (independent of the presence of one or more shells). In embodiments, the yoke can rotate about one or more of its own axes during and / or after exposure to an external stimulus (e.g., a magnetic field). In embodiments, the yoke can be composed of a combination of different materials as described herein. For example, in embodiments, the yoke can be a combination of materials (e.g., but not limited to, nucleic acids, biologics, colorants (e.g., dyes, pigments, anisotropic particles, metal nanorods, plasmonic materials, etc.), inorganic particles, metals, ceramics, polymers, and / or plastics).

[0106] In embodiments, the yoke within the cavity of the HYSP is encapsulated by at least one shell layer. In embodiments, the HYSP incorporates at least one yoke (core) particle. In embodiments, only one yoke is encapsulated within the cavity of a single HYSP. In embodiments, multiple yokes are encapsulated within the cavity of a single HYSP.

[0107] In embodiments, the yoke can be formed of any kind of material (including, but not limited to, metals, metal oxides, silica, organic and / or inorganic polymers, lipids, DNA, RNA, and combinations thereof). In embodiments, the polymer substrate can be selected from polymer classes (including, but not limited to, biological polymers, polysaccharides, plastics, thermoresponsive polymers, crude oil or petroleum (e.g., hydrocarbon) derivatives, and / or polymers compatible with additive manufacturing techniques (e.g., 3D printing)). In embodiments, the yoke includes and / or is a fluid (e.g., a ferromagnetic fluid), a semi-solid material, and / or a non-Newtonian fluid or material.

[0108] In embodiments, the yoke is suspended within a fluid medium, a semi-solid medium, a non-Newtonian fluid or medium, and / or combinations thereof within one or more shell layers. In such embodiments, the yoke can freely change direction within the shell while maintaining a uniform distance from the fluid medium (e.g., a ferromagnetic fluid), the semi-solid material, and / or the non-Newtonian fluid or medium. In embodiments, the yoke is suspended within a fluid medium to control the friction between the yoke and the shell.

[0109] In embodiments, the particle size of the yoke can be about or at least about 1 nm to about or at least about 50 μm. In embodiments, the yoke can have a size or dimension (e.g., radius, diameter, length, width) of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 50 μm.

[0110] In an embodiment, the yoke particles in the HYSP can have a range of sizes or dimensions (e.g., radius, diameter, length, width) including, for example, from about or at least about 1 nm to about or at least about 5 nm, from about or at least about 5 nm to about or at least about 10 nm, from about or at least about 10 nm to about or at least about 20 nm, from about or at least about 20 nm to about or at least about 50 nm, from about or at least about 50 nm to about or at least about 100 nm, from about or at least about 100 nm to about or at least about 1000 nm (1 μm), from about or at least about 1 μm to about or at least about 5 μm, from about or at least about 5 μm to about or at least about 10 μm, from about or at least about 10 μm to about or at least about 20 μm, or from about or at least about 20 μm to about or at least about 50 μm.

[0111] In an embodiment, the average particle size of the yoke provided herein is from about 10 nm to about 10 μm.

[0112] In an embodiment, the yoke is smaller in size than the HYSP. In an embodiment, the yoke is smaller in size or dimension by about or at least about 1 nm, about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 15 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 30 μm, or about or at least about 40 μm than the HYSP.

[0113] In embodiments, the yoke can take on a variety of structures, shapes, geometric shapes, and / or morphologies, including but not limited to spherical, elliptical, spindle-shaped, rod-shaped, cubic, star-shaped, cylindrical, plate-shaped, regular shapes (e.g., regular polygons), irregular shapes (e.g., combinations of two or more different shapes), triangular, trapezoidal, octagonal, tetrahedral, dodecahedral, etc. In embodiments, the yoke takes on the same shape, geometric shape, and / or morphology as the entire HYSP and / or the shell. In embodiments, the yoke takes on a shape, geometric shape, and / or morphology that is different from one or more shells and / or the entire HYSP. In embodiments, the yoke is a substantially solid nanoparticle. In embodiments, the yoke contains and / or is a fluid (e.g., a ferromagnetic fluid), semi-solid, or non-Newtonian fluid that conforms to the shape of the cavity and / or shell contained therein.

[0114] In embodiments, the yoke (i.e., the core) particles of the HYSP have a surface that can be modified and / or functionalized. In embodiments, the surface can be functionalized using chemical techniques known to those skilled in the art to enable the assembly of other elements on the surface of the yoke particles. For example, in embodiments, materials (e.g., biological and / or synthetic molecules) may be suitable for functionalizing the surface of the yoke particles.

[0115] As used herein in connection with the yoke and / or the overall HYSP, "polymorphic" or "polymorphism" refers to a particle having at least two or more regions or domains (collectively referred to as "phases") on the surface of the particle (e.g., the surface of the yoke), and at least two phases are physically, structurally, and / or functionally separated from other phases of the same particle. For example, in embodiments, the yoke can have two or more surfaces, each of which has different optical properties (e.g., exhibits different colors, brightness, fluorescence, reflection, etc.), and when the yoke moves, different optical properties can be observed from any particular angle.

[0116] In an embodiment, the "structure" as used herein with respect to a yoke refers to the physical aspect of each phase, which includes, for example, but is not limited to, its depth, size, shape, topography, or texture. In an embodiment, the "function" as used herein with respect to a yoke refers to the properties of a phase as described herein (e.g., but not limited to, optical properties, chemical functionality, stimulus-responsive behavior, etc.). In an embodiment, the "function" may describe the property(ies) imparted to the product and / or surface envisioned herein from the application of HYSP.

[0117] In an embodiment, an orientation-controllable yoke is a polyphase particle having a surface with at least two homogeneous phases. In an embodiment, each homogeneous region on the surface of the yoke imparts different properties or functions. In an embodiment, referring to FIG. 2A, the polyphase yoke 20 may include at least one stimulus-responsive element 40, one or more particles imparting an optical property (e.g., property 160), and / or one or more particles imparting a second optical property (e.g., property 280).

[0118] In an embodiment, an orientation-controllable polyphase yoke is a polyphase particle having (a) at least one first colorant on a first side of the surface of the yoke, (b) at least one second colorant on a second side of the surface of the yoke, and (c) at least one type of stimulus-responsive element on the first side of the surface, on the second side of the surface, or within the yoke. In an embodiment, the first side of the surface and the second side of the surface are opposite each other across the surface of the orientation-controllable yoke. In an embodiment, the stimulus-responsive element is a stimulus-responsive particle. In an embodiment, the stimulus-responsive element imparting stimulus-responsive behavior is disposed on the first side of the surface of the yoke. In an embodiment, the stimulus-responsive element imparting stimulus-responsive behavior is disposed on the second side of the surface of the yoke. In an embodiment, the stimulus-responsive element imparting stimulus-responsive behavior is disposed on both the first side of the surface of the yoke and the second side of the surface of the yoke.

[0119] In an embodiment, the yoke includes a first colorant and a second colorant. In an embodiment, each colorant is independently selected from a dye, a pigment, a stain, a phosphor, and / or a combination thereof. In an embodiment, the first colorant and the second colorant are different. In an embodiment, the yoke includes at least two colorants, at least three colorants, at least four colorants, at least five colorants, at least six colorants, at least seven colorants, at least eight colorants, at least nine colorants, at least ten colorants.

[0120] In an embodiment, the yoke includes the properties of the colorant imparted from the materials constituting the yoke. For example, in an embodiment, since the yoke has a distinct color, it can be composed of one or more thermoresponsive polymers selected. In an embodiment, the yoke can be composed of a stimulus-responsive element that also functions as a colorant, or, for example, iron oxide particles that appear black, brown, red, orange-red, and / or orange in color. Those skilled in the art who benefit from the entire disclosure will understand the materials having the properties of the colorant that can be used to fabricate the HYSP.

[0121] In an embodiment, referring to FIG. 3, the observed color of the orientation-controllable multiphase yoke 20 can change during and / or after the application of a force or exposure to energy. Referring to FIG. 3, in an embodiment, the stimulus-responsive element 40 is magnetic particles on and / or inside the surface of the yoke. In an embodiment, the stimulus-responsive element responds to a magnetic field. For example, in an embodiment, the orientation-controllable multiphase yoke can change its optical properties by changing its orientation within the shell when a magnetic field is applied. In an embodiment, the orientation-controllable multiphase yoke can have several different colorants covering some of the surfaces of the yoke, and the observable colorants change when the direction of the applied magnetic field changes.

[0122] In an embodiment, the HYSP comprises an orientation-controllable (i.e., movable) yoke (i.e., core) which is a Janus particle having a surface comprising: 1) at least one type of colorant (e.g., dye, pigment, anisotropic particle, metal nanorod, plasmonic material, etc.) on a first side of the surface, and 2) a particle structure imparting a stimulus-responsive behavior on a second side of the surface. As used herein, in an embodiment, the Janus particle has two regions with different chemistry, polarity, functionalization, and / or other properties and substantially equal surface areas.

[0123] In an embodiment, the HYSP comprises an orientation-controllable (i.e., movable) yoke (i.e., core) which is a Janus particle having a surface comprising: 1) at least one type of colorant (e.g., dye, pigment, anisotropic particle, metal nanorod, plasmonic material, etc.) on a first side of the surface, 2) at least one second type of colorant (e.g., dye, pigment, anisotropic particle, metal nanorod, plasmonic material, etc.) on a second side of the surface, and 3) a particle structure imparting a stimulus-responsive behavior on the first side of the surface and / or on the second side of the surface. In an embodiment, the first colorant and the second colorant are of the same class or molecule but may exhibit different optical properties.

[0124] In embodiments, various techniques that focus on using polymers to generate 3D materials can be used to synthesize Janus particle yokes for HYSP. For example, in embodiments, snowman-shaped anisotropic Janus particles are described below: KANG and HONCIUC, “Influence of Geometries on the Assembly of Snowman-Shaped Janus Nanoparticles”, ACS Nano, Vol. 12, No. 4: 2018: pp. 3741-3750 (entirely incorporated herein by reference). For example, in embodiments, Janus particles can be described as typical “snowman particles”. That is, there are two parts, each part is a sphere or a hemisphere, and the Janus particle has a bottom that is larger than the top (e.g., like a “snowman-shaped” particle), but the dimensions can be changed. In embodiments, such particles can be manufactured from poly(tert-butyl acrylate)-poly(3-(triethoxysilyl)propyl methacrylate) (PtBA-PTPM).

[0125] In an embodiment, the synthesis of the snowman-shaped Janus particle-like yoke of HYSP is carried out via the formation of Janus particles. In an embodiment, a Janus particle is a type of particle characterized by having two different regions or "faces" with different physical and / or chemical properties. In an embodiment, the two faces of the Janus particle can have different surface chemistries, sizes, shapes, or polarities, which makes them useful for various applications including drug delivery, catalysis, and self-assembly. In an embodiment, "self-assembly" can include a chemical process of arrangement that occurs spontaneously by chemical forces (e.g., organization into an ordered and / or functional structure or pattern as a result of specific local interactions among their components) without substantial external direction (e.g., that which can occur by polymers, colloids, electrostatic, hydrophobic substances, hydrogen bonding, π-stacking, and shifts in the equilibrium of materials). In an embodiment, the snowman-shaped Janus particles are attractive because they are a unique class of anisotropic materials that are simple yet allow for complete control of all structural parameters. In an embodiment, each lobe within these anisotropic particles can be adjusted independently in terms of its dimensions and chemical composition. In an embodiment, the yoke and / or HYSP of the Janus particle system can be synthesized on a large scale under surfactant-free conditions.In an embodiment, the snowman-shaped Janus particles can be manufactured according to the following method: WALTHER and MULLER, “Janus Particles: Synthesis, Self-Assembly, Physical Properties, and Applications,” Chem. Rev., Vol. 113, 2013: pp. 5194-5261; VOGEL et al. “Advances in Colloidal Assembly: The Design of Structure and Hierarchy in Two and Three Dimensions,” Chem. Rev., Vol. 115, 2015: pp. 6265-6311; TANG et al., “Large Scale Synthesis of Janus Submicrometer Sized Colloids by Seeded Emulsion Polymerization,” Macromolecules, Vol. 43, 2010: pp. 5114-5120; and PHAM et al., “Synthesis of Polymeric Janus Nanoparticles and Their Application in Surfactant-Free Emulsion Polymerizations,” Polym. Chem. Vol. 6, 2015: pp. 426-435 (each of these is hereby incorporated by reference in its entirety).

[0126] In an embodiment, the yolk can be produced, at least in part, from snowman-shaped particles of a latex polymer using, for example, MAGSPHERE (micron-sized latex polymer particles) having a particle size of 15 μm in diameter. In an embodiment, the HYSP and / or the yolk can be, by way of non-limiting example, polystyrene latex polymer, carboxylated latex polymer, aminated latex polymer, colored polystyrene polymer (dye injection and / or pigment injection), carboxylated latex polymer based on colored polystyrene (dye injection and / or pigment injection), fluorescent polystyrene-based polymer, carboxylated latex polymer based on fluorescent polystyrene, fluorescent aminated polystyrene-based polymer, surfactant-free polystyrene, surfactant-free carboxylated polymer, polymethyl methacrylate (PMMA) latex polymer, divinylbenzene (DVB)-crosslinked polystyrene latex polymer.

[0127] In an embodiment, the orientation-controllable Janus yolk (core) is spherical, elliptical, spindle-shaped, cylindrical (e.g., rod-shaped), and / or anisotropic in shape. In an embodiment, the stimulus-responsive element(s) can be magnetic particles (e.g., magnetic particles 40 shown in FIGS. 2A-2B and 3, or magnetic particles 30 shown in FIGS. 4-6).

[0128] In an embodiment, the Janus yolk can be constructed using methods known in the art. For example, in an embodiment, without limitation, methods including electrohydrodynamic co-jetting, direct bulk synthesis, microfluidic synthesis, self-assembly techniques can be used to construct the Janus yolk.

[0129] In an embodiment, the core presented in the present disclosure (e.g., the yoke 20 with respect to FIGS. 1, 2A - 2B, and 3 - 6) has at least one degree of freedom, e.g., a rotational degree of freedom. In an embodiment, the response of the yoke after applying an external stimulus (e.g., a magnetic field) is to change (e.g., rotate) the orientation of the yoke within the interstitial space between the core and the shell, independent of the movement of the HYSP in space. In a non - limiting embodiment, this is illustrated in FIGS. 2A and 2B, as well as FIG. 3.

[0130] In an embodiment, the yoke is composed of a material responsive to a magnetic field having two or more different colorants disposed on its surface. As a result, when an external magnetic field is applied, the yoke is configured to change its orientation (e.g., reverse, rotate, etc.), and different portions of the surface having two or more different colorants are revealed. For example, in such an embodiment, when a magnetic field is applied, the orientation of the yoke changes, and as a result, the color of the yoke changes for an observer. In an embodiment, the color can be "reset" to its original color by reapplying the magnetic field or reversing the direction of the magnetic field.

[0131] Stimulus - responsive element The stimulus - responsive elements present in the orientation - controllable polyphase particle core (i.e., the "yoke") are described in part herein. In an embodiment, the stimulus - responsive elements impart responsiveness to an external stimulus (e.g., a magnetic field). In an embodiment, the terms "applied force", "external stimulus", "exogenous energy", and "external field" are used interchangeably. In an embodiment, the "external stimulus" as used herein refers to exposure to a HYSP (e.g., ink, fluid, suspension, film, fiber, etc.) incorporated into, e.g., any product / material's HYSP, and also refers to exposure to a force generated externally to the HYSP, product, or material in the form of an energy source. In an embodiment, the external stimulus is provided by a suitable apparatus or device. In an embodiment, the external stimulus is magnetic. In an embodiment, the energy source is configured to generate a magnetic field. In an embodiment, the external stimulus includes moving an object (e.g., a magnet or an electromagnet) near the HYSP(s) to apply a magnetic field.

[0132] In an embodiment, the stimulus-responsive element may be composed of various materials and / or particles whose binding properties or orientation and / or position in space change when a magnetic field is applied.

[0133] In an embodiment, the stimulus-responsive element(s) is / are magnetic particles and / or magnetic materials. In an embodiment, the "magnetic particles" or "magnetic materials" used herein may be composed of any suitable material known to those skilled in the art that can respond to a magnetic field. In an embodiment, the stimulus-responsive element may include magnetic particles and / or magnetic materials having various magnetic properties, including one or more of ferromagnetic, ferrimagnetic, antiferromagnetic, diamagnetic, paramagnetic, superparamagnetic, and / or antiferromagnetic.

[0134] In an embodiment, the stimulus-responsive element includes one or more particles composed of a magnetic material (e.g., by way of non-limitation, iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), manganese (Mn), chromium (Cr), samarium (Sm), etc., e.g., their chemical derivatives). In an embodiment, typical derivatives include alloys or oxides of metals (e.g., alloys, intermetallic compounds, and / or oxides of Fe, Co, Ni, Zn, Mn, Sm), or any combination thereof. In an embodiment, the oxide is an iron oxide (e.g., Fe2O3, FeO, or Fe3O4). In an embodiment, the magnetic particles are composed of a ferrite material or a doped material including, by way of non-limiting example, one or more of Co, Ni, Zn, or Mn:FexOy.

[0135] In an embodiment, the stimulus-responsive element is an organic, carbon-based, and / or biomolecular-based magnetic material (e.g., by way of non-limiting example, tetracyanoethylene (TCNE) salts, [Fe(C5Me5)2] + [TCNE]· - , Li[TCNE], [Mn II TPP][TCNE]·(TPP = tetraphenylporphyrin), [Fe II (TCNE)(NCMe)2][Fe III Cl4], MnII (TCNE)I(H₂O), Mn II (TCNE)[C₄(CN)₈] 1 / 2 、Fe(TCNE)[C₄(CN)₈] 1 / 2 、Mn II (TCNE) 3 / 2 (I₃) 1 / 2 、V II [TCNE] x (x≒2), C₇H₅ClN₃Se₄, one or more of the magnetic biopolymers), and includes one or more particles composed of.

[0136] In an embodiment, the magnetic particles include, or include magnetite. In an embodiment, magnetite is a biodegradable, biocompatible, non-toxic molecule that can be used as an imaging contrast agent (e.g., an MRI contrast agent). In an embodiment, other magnetic particles (e.g., red and / or black iron oxides (Fe₂O₃, FeO, and / or Fe₃O₄) can also be used.

[0137] It should be noted that the translation of some chemical terms may need to be further adjusted according to the specific context and professional knowledge to ensure more accurate expression.In an embodiment, the stimulus-responsive element is a transparent magnetic material. In an embodiment, the transparent magnetic material is a class of materials that exhibit both transparency to visible light and magnetic properties. In an embodiment, the transparent magnetic material of HYSP can include, for example, materials used in other applications described below (such as optoelectronics, magneto-optical devices, and transparent electronics): Loste, et al., “Transparent polymer nanocomposites: An overview on their synthesis and advanced properties,” Progress in Polymer Science (2018), doi.org / 10.1016 / j.progpolymsci.2018.10.003; Kobayashi, et al., “Optically Transparent Ferromagnetic Nanogranular Films with Tunable Transmittance,” Sci Rep, Vol. 6, No. 34227, 2016, doi.org / 10.1038 / srep34227; Babu, et al., “Indium oxide: A transparent, conducting ferromagnetic semiconductor for spintronic applications,” Journal of Magnetism and Magnetic Materials(2016), doi.org / 10.1016 / j.jmmm.2016.05.007, Chavan, et al., “A Brief Review of Transparent Conducting Oxides(TCO): The Influence of Different Deposition Techniques on the Efficiency of Solar Cells,” Nanomaterials Vol. 13, No. 1226, 2023, doi.org / 10.3390 / nano13071226; Ye, et al.,"Research and Progress of Transparent,Flexible Tin Oxide Ultraviolet Photodetector,"Crystals,2021,Vol.11,No.1479.doi.org / 10.3390 / cryst11121479;Gul S,et al.,"A Comprehensive Review of Magnetic Nanomaterials Modern Day Theranostics,"Front.Mater.Vol.6,No,179,2019,doi:10.3389 / fmats.2019.00179;Rita Policia,et al.,"Transparent Magnetoelectric Materials for Advanced Invisible Electronic Applications,"Adv.Electron.Mater.2019,1900280,doi.org / 10.1002 / aelm.201900280(each of these is hereby incorporated by reference in its entirety).

[0138] In embodiments, the transparent magnetic material includes a family of diluted magnetic semiconductors (DMSs) or oxide-based transparent magnetic materials. In embodiments, a DMS is formed by introducing low concentrations of magnetic ions (e.g., transition metal ions) into a semiconductor matrix, and magnetic properties are generated by the interaction between the magnetic ions and the host lattice. In embodiments, the oxide-based transparent magnetic material is typically composed of a transparent oxide matrix (e.g., indium tin oxide) doped with magnetic ions.

[0139] In embodiments, other types of transparent magnetic particles and materials include those based on iron oxide nanoparticles (e.g., magnetite (Fe3O4) and maghemite (γ-Fe2O3)), which can be designed to have transparent properties while retaining magnetic properties. In embodiments, the stimulus-responsive elements include ferrite nanoparticles (e.g., cobalt ferrite (CoFe2O4) or nickel ferrite (NiFe2O4)), which can be synthesized in a way to achieve transparency. In embodiments, the stimulus-responsive elements include rare earth iron garnets (e.g., yttrium iron garnet (Y3Fe5O 12 )) which can exhibit strong magneto-optical effects while maintaining a certain degree of transparency. In embodiments, further examples of transparent magnetic particles and materials include Sn-doped In2O3, FeSiB (Fe 72.5 Si 12.5 B 15 ), and Fe9Co5Al 19 F 67 . In embodiments, the transparent magnetic particles and materials can be incorporated into a polymer to form particles or beads suitable for the structures described herein.

[0140] In embodiments, the stimulus-responsive elements can include magnetite (e.g., Fe3O4), with or instead of, a number of components (e.g., metals (magnetic elements such as iron, nickel, cobalt, chromium, and / or manganese) and / or magnetic organic polymers (see, e.g.: Rajca et al., “Magnetic Ordering in an Organic Polymer,” Science, 294, 2001: pp. 1503-1505, which is incorporated herein by reference in its entirety)). In embodiments, the particles can be composed of 100% metal oxide (e.g., magnetite) or can be composite materials containing other components (e.g., polymers, polymer-bonded magnets, and / or polymers containing chromophores).

[0141] In an embodiment, the stimulus-responsive element may include magnetic beads. In an embodiment, the stimulus-responsive element may include a plurality of magnetic particles contained within polymer beads (e.g., polystyrene). In an embodiment, the stimulus-responsive element is a spherical magnetic bead or a spherical polymer-based bead containing one or more magnetic particles.

[0142] In an embodiment, the magnetic particles as the stimulus-responsive element for the yoke of HYSP may have a size range, for example, of about or at least about 5 nm in size to about or at least about 50 μm in size. In an embodiment, the magnetic particles are about or at least about 5 nm, about or at least about 10 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 5 μm, about or at least about 10 μm, about or at least about 50 μm, and include any size thereamong. In an embodiment, the average particle size of the magnetic particles may include a size range, for example, of about or at least about 5 nm to about or at least about 50 nm, about or at least about 5 nm to about or at least about 100 nm, about or at least about 5 nm to about or at least about 500 nm, about or at least about 5 nm to about or at least about 1,000 nm, about or at least about 5 nm to about or at least about 2,000 nm, about or at least about 5 nm to about or at least about 5,000 nm, about or at least about 10 nm to about or at least about 5,000 nm, about or at least about 100 nm to about or at least about 5,000 nm, about or at least about 1,000 nm to about or at least about 5,000 nm.

[0143] In an embodiment, the stimulus-responsive element includes, for example, a magnetic material (e.g., particles) that is magnetized and, for example, attachable to iron (e.g., capable of projecting its own magnetic field) and capable of generating a magnetic field outside itself naturally or by induction. In an embodiment, for example, during manufacturing and / or after use, a magnetic field can be induced in the particles, for example, by exposing the particles to a strong magnetic field (e.g., an electromagnet).

[0144] In embodiments, the generated magnetic field (e.g., magnetic flux density) is about or at least about 200 gauss to about or at least about 25,000 gauss (10,000 gauss = 1 tesla). In embodiments, the magnetic field is about at least at least about 200 gauss, about at least at least about 500 gauss, about at least at least about 800 gauss, about at least at least about 1,000 gauss, about at least at least about 2,500 gauss, about at least at least about 12,500 gauss, about at least at least about 15,000 gauss, about at least at least about 20,000 gauss, or about at least at least about 25,000 gauss. In embodiments, the magnetic particles retain the ability to project a magnetic field, i.e., they can become permanent magnets. In embodiments, the particles may lose the ability to generate a magnetic field over time and the magnetic field can be re-induced by reapplying a strong magnetic field.

[0145] The magnetic particles can be prepared using any method known to those skilled in the art. For example, in embodiments, the magnetic particles are formed by precipitation, pyrolysis, or other methods known to those skilled in the art. In embodiments, the magnetic particles can be made by mechanical milling, supercritical CO2-based precipitation of magnetite / polymer microparticles, or micelle synthesis. After manufacture, in embodiments, the particles can be sorted for size and quality, for example, by centrifugation or filtration. A number of magnetic particles are commercially available and, for example, in embodiments, are available inter alia from Ademtech (33600 Pessac, France); Bangs Laboratories, Inc. (Fishers, Indiana, USA); Pea Ridge Iron Ore Co. (Sullivan, Missouri, USA), Quantum Magnetics, Division of Clemente Associates, Inc. (Madison, Connecticut, USA). In embodiments, the magnetic particles can be sterilized using methods known in the art such as heat sterilization, chemical sterilization, or radiation sterilization.

[0146] In embodiments, the magnetic particles can be black, white, or colored, for example, by coating or synthesizing them with a chromophore or a colorant as described herein. In embodiments, to protect the particles or make them more inert, the magnetic particles can be coated with, for example, a transparent coating that is substantially visually transparent, biocompatible, non-dispersive, and / or biologically inert. In embodiments, the magnetic particles are first coated with a chromophore and then with a transparent outer coating.

[0147] In embodiments, the surface of the magnetic particles can be functionalized by any chemical technique known to those skilled in the art to enable the attachment of the magnetic particles to the surface of the yoke particles. For example, in embodiments, materials (such as biological molecules and / or synthetic molecules) are suitable for use on the surface of the magnetic particles. In non-limiting embodiments, the surface of the magnetic particles can be functionalized with biological molecules (such as DNA sequences, RNA sequences, oligomers, proteins and peptides, nucleic acid molecules (such as aptamers), or combinations thereof).

[0148] Colorant In embodiments, the HYSP(s) can change optical properties in response to an external stimulus (such as the application of a magnetic field), and the optical properties are due to the presence of one or more colorants. In embodiments, the term "colorant" refers to a chemical substance having optical properties that include absorbing, reflecting, and / or scattering the wavelength(s) of radiation in the visible spectrum (i.e., wavelengths from about 380 nm to about 800 nm). In embodiments, the term "colorant" refers to any composition of pigments, dyes, and / or non-conventional substances (such as quantum dots, phosphorescent "glow-in-the-dark" pigments, fluorescent pigments).

[0149] In an embodiment, the orientation-controllable polyphase yoke contains at least one type of colorant. In an embodiment, the orientation-controllable polyphase yoke contains at least two types of colorants. In an embodiment, the colorant adheres to the surface of the orientation-controllable yoke and can be obtained from metal salts (e.g., iron oxide and titanium dioxide) to synthetic organic dyes. In an embodiment, the colorant can be obtained from natural sources (e.g., annatto extract, melanin, beta-carotene, B-apo-8-carotenal, beet powder, canthaxanthin, caramel color, carrot oil, cochineal extract, ferrous gluconate, grape color extract, grape skin extract, paprika, riboflavin, saffron, turmeric, and vegetable juice).

[0150] In an embodiment, the colorant is a chromophore that can be detected by human vision under normal lighting conditions (e.g., the visible spectrum). In an embodiment, the chromophore can be detected when exposed to ultraviolet (UV), near-UV, infrared (IR), and / or near-IR radiation.

[0151] In an embodiment, the colorant can be functionalized by any chemical method known to those skilled in the art for attachment to the yoke particles. In an embodiment, the colorant can be attached to the surface of the orientation-controllable polyphase yoke using methods known to those skilled in the art (e.g., various covalent and / or non-covalent bond reactions). In an embodiment, the concentration of the attached colorant depends on the color and intensity of the colorant, as well as the color and texture of the substrate to which the colorant formulation (e.g., ink) is applied. In an embodiment, the specific geometric shape of the orientation-controllable polyphase yoke affects the amount of colorant required to produce the desired effect.

[0152] In an embodiment, the colorant has a color, brightness, fluorescence, reflection, etc. that can be detected by human vision. In an embodiment, the colorant is a pigment, dye, stain, phosphor, metal nanoparticle, plasmonic material, anisotropic material, and / or any combination of those categories.

[0153] In embodiments, the optical properties described herein refer to HYSP (or an object decorated with HYSP, or a material incorporating HYSP) having the ability to exhibit attenuation, absorption, luminescence, reflection, scattering, and interference properties with respect to electromagnetic radiation (e.g., light) within the visible electromagnetic spectrum having wavelengths from about 350 nm to about 800 nm. In embodiments, these properties include color, fluorescence, luminescence, and / or phosphorescence among other properties that can be observed based on the spectral properties of electromagnetic waves (light).

[0154] In embodiments, the optical property is color. In embodiments, color includes one or more of white, black, red, orange, yellow, green, blue, indigo, and / or violet, as well as variations in hue, shade, and intensity therebetween.

[0155] In embodiments, the colorant includes one or more dyes. In embodiments, the term "dye" refers to a substance that imparts color and, unlike a pigment, is used as a solution in a suitable solvent. In embodiments, dyes include rhodamine B, congo red, crystal violet, methylene blue, acridine orange, nile red, malachite green, eosin Y, cresol red, fluorescein, and / or indigo. In embodiments, the colorant is an organic dye or an inorganic dye.

[0156] In embodiments, the colorant includes a water-soluble pigment. In embodiments, the colorant is an anthocyanin. Anthocyanins are phenolic water-soluble pigments that, in embodiments, impart various colors including shades and hues of red, purple, and blue to various plant materials. In embodiments, the colorant includes pigments derived from microorganisms (e.g., bacterial or fungal pigments), which include, by way of non-limiting example, anthraquinone, carotenoid, violacein, melanin, pioscyanin, prodigiosin, aspergillin, benzoquinone, anthraquinone, and their derivatives.

[0157] In an embodiment, the colorant includes one or more pigments. In an embodiment, the term "pigment" refers to the definitions described, for example, in DIN55943:1993-11 and DIN EN971-1:1996-09 Colorant Manual (incorporated herein by reference in its entirety). In an embodiment, a pigment is a powdery or flaky material that does not dissolve in the surrounding medium, unlike a dye.

[0158] In an embodiment, HYSP incorporates a coloring pigment, which, by way of non-limiting example, includes one or more of titanium white (PW6), zinc white (PW4), carbon black (PBk7), Mars black (PBk11), iron oxide red (PR101), cadmium red (PR108), alizarin crimson (PR83), cadmium orange (PO20), cadmium yellow (PY35), lemon yellow (PY3), chrome green oxide (PG17), phthalocyanine green (PG7), ultramarine blue (PB29), cobalt blue (PB28), cerulean blue (PB35), Prussian blue (PB27), burnt sienna (PBr7), raw umber (PBr7), rose sienna (PBr7), and / or yellow ochre (PY43). The symbols in parentheses (e.g., PB29 in the case of ultramarine blue) are pigment color index numbers widely used in the art and elsewhere to classify the colors of paints.

[0159] In an embodiment, HYSP may incorporate a colorant including a pigment as described, for example, in PFAFF, “The world of inorganic pigments,” ChemTexts, Vol. 8, No. 15, 2022: 17 pages (incorporated herein by reference in its entirety). In an embodiment, the pigment is an organic pigment. In an embodiment, the pigment is an inorganic pigment.

[0160] In an embodiment, HYSP exhibits one or more colors, and one or more colors are imparted from pigments having the chemical compositions described in one or more of Table 1 and / or Table 2.

Table 1

[0161] In an embodiment, the HYSP includes an organic pigment and / or an inorganic pigment that is a white pigment. In an embodiment, the white pigment is one or more of lead white (2PbCO3·Pb(OH)2), kaolin, silica (SiO2), titanium dioxide (TiO2 / rutile and anatase), zinc oxide (ZnO), zinc sulfide (ZnS), and / or lithopone (ZnS+BaSO4).

[0162] In an embodiment, the HYSP includes an organic pigment and / or an inorganic pigment that is a black pigment. In an embodiment, the black pigment is one or more of coal (charcoal), groutite (α-MnOOH), manganate (γ-MnOOH),hausmannite (Mn3O4), carbon black, iron oxide black (Fe3O4), and / or spinel black (CuCr2O4).

[0163] In an embodiment, the HYSP includes an organic pigment and / or an inorganic pigment that is a colored pigment.

[0164] In an embodiment, the colored pigment is a yellow pigment, which, in non-limiting examples, includes one or more of yellow ocher (α-FeOOH), auripigment (As2S3), lead yellow earth (PbO), lead-tin yellow (Pb2SnO4, PbSn2SiO7), Naples yellow (Pb(SbO3)2), zinc yellow (Zn2CrO4), Indian yellow (C 19 H 16 O 10 )), iron oxide yellow (α-FeOOH), chromium titanium yellow ((Ti,Cr,Sb)O2), nickel titanium yellow ((Ti,Ni,Sb)O2), lead yellow (PbCrO4), cadmium yellow (CdS), bismuth yellow (BiVO4).

[0165] In an embodiment, the coloring pigment is a red pigment, which, in non-limiting examples, includes one or more of red ocher (α-Fe2O3), terra di Siena (α-Fe2O3), vermilion (HgS), red lead (Pb3O4), alizarin madder varnish, alizarin red (C 14 H8O4), iron oxide red (α-Fe2O3), molybdate red (Pb(Cr,S,Mo)O4), cadmium red (Cd(S,Se)).

[0166] In an embodiment, the coloring pigment is a green pigment, which, in non-limiting examples, includes one or more of green earth (Fe silicate), Schweinfurt green (C4H6As6Cu4O 16 ), chromium oxide green (Cr2O3), chromium oxide hydrate green (CrOOH), cobalt green (Co2TiO4).

[0167] In an embodiment, the coloring pigment is a blue pigment, which, in non-limiting examples, includes one or more of lazurite (lapis lazuli), Egyptian blue (CaCuSi4O 10 ), azurite (2CuCO3·Cu(OH)2), malachite (CuCO3·Cu(OH)2), cobalt blue (CoAl2O4), ultramarine blue (Na6Al6Si6O 24 (NaSn)), Prussian blue (K[Fe III Fe II (CN)6]·xH2O).

[0168] In an embodiment, the coloring pigment is a brown pigment, which, in non-limiting examples, includes one or more of burnt umber (Fe2O3·xMnO2), brown ocher (α-Fe2O3 + Mn oxide), limonite (a mixture of various Fe oxides).

[0169] In the embodiment, HYSP includes one or more of the following organic and / or inorganic pigments: oxide or oxyhydroxide pigments (TiO2, ZnO, α-Fe2O3, α-FeOOH, γ-Fe2O3, Fe3O4, Cr2O3, CrOOH, PbO, PB3O4, Mn3O4, -MnOOH, Sb2O3), composite oxide pigments (CoAl2O4, CuCr2O4, Co2TiO4, (Ti,Ni,Sb)O2, (Ti,Cr,Sb)O2), carbonate hydroxide pigments (2PbCO3·Pb(OH)2, 2CuCO3·Cu(OH)2, CuCO3·Cu(OH)2), sulfide / selenide pigments (ZnS, CdS, Cd(S,Se), CdSe, γ-Ce2S3, HgS, As2S3), chromate / molybdate pigments (PbCrO4, Pb(Cr,S)O4, Pb(Cr,S,Mo)O4, ZnCrO4, BaCrO4, SrCrO4), vanadate pigments (BiVO4, 4BiVO4·3Bi2MoO6), stannate pigments (Pb2SnO4, PbSn2SiO7, Co2SnO4, CoSnO3), phosphate pigments (Co3(PO4)2), antimonate pigments (Pb(SbO3)2), arsenate pigments (Cu(AsO3)2), ultramarine pigments (Na6Al6Si6O 24 (NaSn)), hexacyanoferrate / hexacyanoferrate pigments (K[FeIIIFeII(CN)6]·xH2O (x = 14 - 16)), oxonitride pigments (CaTaO2N, LaTaON2), elemental pigments (C, Al, Cu, Cu / Zn, Au), spinel pigments, and / or rutile metal pigments.

[0170] In the embodiment, the colorant includes organic and / or inorganic pigments that are "special effect pigments", which include, by way of non-limiting example, transparent effect pigments, goniochromatic pigments, true pearlescent pigments, metallic pigments, interference pigments, metallic effect pigments, fluorescent pigments, luminescent pigments, phosphorescent pigments, iridescent effect pigments, magnetic pigments, and / or anticorrosive pigments.

[0171] In the embodiment, the colorant includes one or more metallic pigments. In the embodiment, the metallic pigments reflect light to produce a metallic effect and a shiny finish. In the embodiment, the one or more metallic pigments include aluminum, bronze, and / or copper.

[0172] In an embodiment, the colorant includes one or more nacreous pigments. In an embodiment, the nacreous pigment produces a pearl-like iridescent effect by diffusely reflecting light. In an embodiment, the one or more nacreous pigments include mica, titanium dioxide, and / or bismuth oxychloride.

[0173] In an embodiment, the colorant includes one or more fluorescent pigments. In an embodiment, when exposed to UV light, the fluorescent pigment emits light (e.g., absorbs light), produces bright light (e.g., emits light), and provides vivid colors. In an embodiment, the one or more fluorescent pigments include pigments made from fluorescent dyes and / or fluorescent minerals.

[0174] In an embodiment, the colorant includes one or more phosphorescent pigments. In an embodiment, the phosphorescent pigment absorbs light and gradually emits light over time, creating a glowing effect. In an embodiment, the one or more phosphorescent pigments include zinc sulfide and / or strontium aluminate.

[0175] In an embodiment, the colorant includes one or more interference pigments. In an embodiment, the interference pigment produces a unique glittering effect by reflecting light in different directions depending on the viewing angle. In an embodiment, the one or more interference pigments include titanium dioxide-coated mica and / or aluminum oxide-coated mica.

[0176] In an embodiment, the colorant exhibits an optical effect observed to result from structural color. In an embodiment, structural color results from the physical structure of the material rather than from a pigment or dye. This phenomenon is also observed in nature and is the cause of the vivid colors seen in, for example, peacock feathers, butterfly wings, and many other organisms. Structural color is caused by the interference and diffraction of light waves when the light waves interact with microscopic or nanoscale structures within the material. In an embodiment, these structures can be arranged in layers, patterns, or other geometric shapes on the surface of the HYSP, affecting the way light is reflected, transmitted, or absorbed and providing a wide range of colors that can be iridescent, directional, and / or polarized.

[0177] In an embodiment, the colorant exhibits an optical property change effect by using the mechanism of color by plasmonics or a color change. In an embodiment, the plasmonic material can control and manipulate light by using artificial materials at the nanoscale and expanding it to the micron scale, millimeter scale, and even larger scales. In an embodiment, plasmonics includes the interaction between light and a metal surface, nanostructure, and / or nanoparticles. In an embodiment, plasmonics focuses on the behavior of surface plasmons, which are collective vibrations of electrons in a metal excited by light. In an embodiment, HYSP includes one or more colorants that use plasmonics involving the propagation, confinement, and manipulation of surface plasmon polaritons (SPPs). In an embodiment, an SPP is an electromagnetic wave generated from the coupling of a photon and a surface plasmon.

[0178] In an embodiment, HYSP includes one or more colorants that are anisotropic particles. In an embodiment, the anisotropic particles are one or more metal nanoparticles. In an embodiment, the one or more metal nanoparticles include one or more nanorods of gold (Au), silver (Au), and / or aluminum (Al). In an embodiment, the colorant is one or more anisotropic noble metal nanoparticles having plasmonic properties. In an embodiment, HYSP includes colorants that include anisotropic particles having shapes including, but not limited to, rod-like, star-shaped, disk-shaped, core-shell particles, hollow particles, prisms, hemispheres, cubes, and / or pyramid-shaped. In an embodiment, HYSP includes colorants that include anisotropic particles that exhibit anisotropy due to the asymmetric organization of symmetric particles, for example, in a non-limiting example, a string of two, three, four, five or more spherical particles that are very densely packed.

[0179] In an embodiment, the colorant includes anisotropic gold (Au) nanorods. For example, in an embodiment, the HYSP contains a colorant including one or more Au nanorods, whereby the optical properties change as the HYSP yoke moves within the shell. In an embodiment, the Au nanorods have a length of about 50 nm and a width of about 10 nm. In an embodiment, metal nanorods of various lengths and widths can be used. For example, in non-limiting examples, the dimensions can be about or at least about 5 nm, about or at least about 10 nm, about or at least about 15 nm, about or at least about 20 nm, about or at least about 25 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 200 nm, about or at least about 300 nm, about or at least about 400 nm, about or at least about 500 nm, or about or at least about 1000 nm or more.

[0180] In an embodiment, optically active Au nanorods (and similar nanorods that partially or fully contain Au, Ag, Al among other plasmonic metals) exhibit favorable optical properties for incorporation into the HYSP. For example, in an embodiment, the transverse mode (when the electromagnetic radiation hits the ends of the nanorods) shows a maximum attenuation at about 520 nm, while the longitudinal plasmon (when the electromagnetic radiation hits the longitudinal axis of the particle) has lower energy and peaks at about 810 nm. Thus, in an embodiment, when an observer looks at the Au nanorods (e.g., on a plane) and they are irradiated from above, using the Au nanorods, the longitudinal mode is excited and the surface appears blue. In an embodiment, when the observer observes the same surface and uses the Au nanorods when the surface of the yoke is rotated by 90°, as a result, the radiation hits the ends of the rods and the transverse mode is excited, and a burgundy red color is observed.

[0181] In an embodiment, the metal nanorod layer is incorporated into the HYSP, the yoke is stationary in a steady equilibrium state along a plane, and the major axis is parallel to the observation plane. In an embodiment, the nanorod layer (among other shapes) may be located at the bottom and on top of the yoke and / or at any other location inside and / or on the surface of the yoke. In an embodiment, the number of layers of anisotropic metal nanoparticles can be any integer layer, the metal used can be any metal exhibiting anisotropic optical properties, and the size of the nanoparticles can be any size compatible with the HYSP described herein. In an embodiment, the particles do not appear in individual layers but are continuously (or discontinuously) dispersed within the HYSP. For example, the HYSP is composed of a transparent shell substrate in which the metal nanoparticles are arranged. In an embodiment, the rods can be adsorbed, bonded, and / or fixed to a part of the outer surface of the HYSP yoke or within a part of the yoke.

[0182] In an embodiment, the colorant is a material having plasmonic properties. In an embodiment, the material is limited to the surface of the yoke of the HYSP, is a metal, and / or (depending on the shape of the metal and the properties of the surrounding medium) propagates optical properties along the surface of the metal. In an embodiment, there is a plasmonic coupling between the yoke and the surface / substrate on which the HYSP is placed, applied, injected, and / or mounted. In an embodiment, the colorant is a continuous or discontinuous thin noble metal film or a plasmonic material containing it and / or a surface incorporating or containing plasmonic particles.

[0183] For example, in an embodiment, the colorant is a polymer film loaded with noble metal nanoparticles. In an embodiment, the colorant is a plasmonic material, particle, foil, and / or film form of noble metal nanoparticles located on or near the upper part of the yoke of the HYSP. In an embodiment, the exact distance dependence of the coupling between optically active plasmonic materials depends on size and shape, and the optical coupling decreases exponentially with the distance between surfaces. For example, in an embodiment, for a HYSP with a size of about 1 μm, the coupling between the upper part of the HYSP and the surface on which it is placed is zero. However, in an embodiment, when the HYSP yoke is moved by a magnetic force, the plasmonic material can bring about sufficient proximity to be optically coupled, and the optical properties change such that an observer can recognize a change in color, reflection, brightness, or any other optical property. In an embodiment, the HYSP can be arranged such that a coloring containing a plasmonic material on or near the bottom / sides causes the plasmonic colorant to approach the plasmonic surface on which the HYSP is placed upon rotation of the yoke, and the optical properties change. In an embodiment, the degree of coupling is proportional to a change in color, reflection, brightness, or any other optical property. In an embodiment, the observed optical properties are not the sum of the independent optical properties of each material.

[0184] In an embodiment, the colorant includes one or more goniochromatic materials and / or pigments. In an embodiment, the goniochromatic material / pigment (also called gonioapparent or gonio spectral material / pigment) is a material / pigment that exhibits various colors or hues depending on the viewing angle or illumination direction. In an embodiment, this effect is due to the presence of a fine structure or surface feature that scatters and diffracts light in a way that creates various colors when viewed from different angles. In an embodiment, the color and appearance of the goniochromatic material / pigment are highly directional and change dramatically depending on a change in the viewing angle and / or a change in the incident angle of light. In an embodiment, one or more goniochromatic materials and / or pigments include aluminum coated with magnesium fluoride embedded in chromium. In an embodiment, one or more goniochromatic materials and / or pigments include silica-coated mica.

[0185] In an embodiment, the goniochromic pigment is CHROMAFLAIR (a pigment composed of thin multilayer flakes having a crystal structure that gives color-shifting properties, Viavi Solutions), which gives a color-shifting effect that varies depending on the viewing angle (e.g., as the HYSP moves). In an embodiment, the colorant is CHROMAFLAIR Green / Purple 190 (Viavi Solutions, a pigment that changes from a green face to purple (45°), then to magenta and gold). In an embodiment, the goniochromic pigment is a "color travel pigment" (e.g., XIRONA, Merck KgaA, Darmstadt, Germany), which includes specific pigments such as Nordic Sunset, Magic Mauve, Kiwi Rose, Caribbean Blue, Volcanic Fire, Golden Sky, Le Rouge, Volcanic Sparks, and Moonlight Sparks.

[0186] In an embodiment, when such a yoke is in an equilibrium state (e.g., a stationary state), a first reference color (e.g., "Color 1") is observed in a goniochromic material where fixed incident light is irradiated perpendicular to the yoke (or an array of HYSPs among other arrangements). In an embodiment, when a magnetic field is applied and the yoke changes orientation, different color(s) (e.g., "Color 2") can be observed, and a goniochrometry effect can be obtained without the observer moving. Usually, when goniochromic coloring is used (e.g., in automotive paints or cosmetics), the observer has to move to see the color change, but in an embodiment, the observer can stay at a fixed angle while the HYSP shows changing colors.

[0187] HYSP shell In an embodiment, a HYSP shell that can encapsulate an orientation-controllable polyphase yoke is described herein. In an embodiment, the HYSP can include a single continuous shell that encapsulates a yoke disposed therein. In an embodiment, the HYSP has a plurality of shells, or a plurality of layers of continuous shells. In an embodiment, the shell can be fabricated in multiple parts and then assembled into a continuous shell when the yoke is inserted. In an embodiment, the HYSP can have one or more discontinuous shells, such as a porous shell for example.

[0188] In an embodiment, the shell can have a single uniform thickness or varying thicknesses. In an embodiment, the shell material has a thickness of about or at least about 1 nm, about or at least about 5 nm, about or at least about 10 nm, about or at least about 15 nm, about or at least about 20 nm, about or at least about 25 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 200 nm, about or at least about 300 nm, about or at least about 400 nm, about or at least about 500 nm, about or at least about 600 nm, about or at least about 700 nm, about or at least about 800 nm, about or at least about 900 nm, about or at least about 1 μm, about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 10 μm, about or at least about 15 μm, about or at least about 20 μm, about or at least about 25 μm, about or at least about 30 μm, about or at least about 35 μm, about or at least about 40 μm, including sizes therebetween and ranges of those sizes.

[0189] In an embodiment, the shell(s) can have at least a portion that is transparent to the visible electromagnetic spectrum (e.g., from about 380 nm to about 800 nm) such that a colorant on the yoke can be seen through the shell(s).

[0190] In an embodiment, the shell may have at least an opaque portion. For example, in an embodiment, the shell may have an opaque first portion and a transparent second portion such that when the orientation of the yoke changes within the shell, the optical properties (e.g., color change) become partially invisible through a specific viewing angle.

[0191] In an embodiment, one or more shells or portions thereof may function as a blocking layer. In an embodiment, a "blocking layer" refers to a shell or a portion thereof that has a function of avoiding light leakage from the upper surface to the lower surface or from the side surface to the side surface, and optically absorbs, deflects, blocks, or scatters light in the visible electromagnetic range (e.g., from about 380 nm to about 800 nm). In an embodiment, the blocking layer functions like a physical "band - pass filter", allowing only specific types of wavelengths or wavelength bands and blocking or attenuating specific types of wavelengths or wavelength bands. In an embodiment, the blocking layer includes, for example, one or more opaque intermediate layers made of one or more silica sheets (e.g., mica sheets). In an embodiment, the blocking layer may have a thickness of about or at least about 1 nm, about or at least about 5 nm, about or at least about 10 nm, about or at least about 25 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 250 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 2.5 μm, about or at least about 5 μm, or about or at least about 10 μm.

[0192] In an embodiment, the shell material includes one or more of glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), and nylon. In an embodiment, the shell material includes one or more thermoresponsive polymers (e.g., thermoresponsive polymers compatible with additive manufacturing techniques such as 3D printing).

[0193] In an embodiment, the shell can be composed of any material described herein. In an embodiment, the shell material is at least partially composed of a polymer (e.g., polysaccharide, lipid, amino acid, DNA, RNA (among other biological polymers), plastic, thermoresponsive polymer, polymer of crude oil or petroleum (e.g., hydrocarbon) derivatives, and / or a polymer compatible with an additive manufacturing technique (e.g., 3D printing)).

[0194] In an embodiment, the shell can have one or more depressions, grooves, or spaces, for example, located on the inner surface of the shell, for fixing an orientation-controllable polyphase yoke therein. For example, in an embodiment, the shell and the yoke can have an arrangement of, among other mechanical couplings, particularly "flanges in grooves" or "pins in grooves", which further allows the yoke to fit inside and adhere to the shell while having a certain degree of freedom of movement. In an embodiment, such an arrangement can be made to keep the distance between the yoke and the inner side of the shell uniform and / or to reduce the friction between the yoke and the shell, with a controllable small surface area remaining in contact.

[0195] In embodiments, the shell can be functionalized with one or more materials to impart chemical, physical, and / or biological properties to the overall HYSP. Those skilled in the art who benefit from the present disclosure will understand the methods used for functionalizing the HYSP shell. In embodiments, the shell is functionalized with one or more materials that overcome the frictional forces within the cavity of the HYSP such that the yoke(s) can reorient itself upon exposure to an applied force or external energy. In embodiments, the above elements can impart an oily or low-friction behavior to the surface of the yoke within the cavity of the HYSP, facilitating the rotation of the yoke.

[0196] In embodiments, the shell can have stimulus-responsive elements and / or can be made from materials for stimulus-responsive elements. For example, in embodiments, the HYSP can have one or more shells composed of a magnetic material.

[0197] Method for preparing hollow yoke-shell particles (HYSP) In embodiments, the HYSP can be constructed using methods known to those skilled in the art. For example, methods for preparing the HYSP can include, among other methods known to those skilled in the art, hard-template methods, soft-template methods, self-template methods, and combined synthesis methods of multiple methods. The method used can vary depending on the materials, shapes, and sizes of the yoke(s) and egg layer(s). In embodiments, the method includes various self-template methods (e.g., galvanic replacement method, Kirkendall method, "ship-in-a-bottle" method, Ostwald ripening method, selective etching method).

[0198] In embodiments, the HYSP is manufactured in stages. For example, a first portion of one or more shells can be prepared, and then the yoke (which can be manufactured separately) can be placed therein, and a second portion of one or more shells can be placed thereon to encapsulate the yoke.

[0199] In an embodiment, a method for manufacturing HYSP herein includes: i) preparing at least one orientation-controllable polyphase yoke (wherein the at least one orientation-controllable polyphase yoke includes at least two colorants and at least one stimulus-responsive element); ii) forming a dissolution layer disposed on the at least one orientation-controllable polyphase yoke; iii) forming at least one shell layer enclosing the orientation-controllable polyphase yoke (wherein the at least one shell layer includes pores); iv) repositioning the dissolution layer through the pores of the at least one shell layer to form a cavity between the at least one orientation-controllable polyphase yoke and the at least one shell layer; and v) curing the at least one shell layer to form a non-porous shell. In an embodiment, the orientation-controllable polyphase yoke is configured to move inside the shell in response to an applied force or external energy (e.g., a magnetic field). In an embodiment, repositioning the dissolution layer may include removal, dissolution, and / or etching, or applying a technique for disposing the material constituting the dissolution layer in a configuration different from the original deposited location.

[0200] In an embodiment, a method for preparing a HYSP (e.g., as shown in FIG. 4) is provided herein, the HYSP comprising (a) at least one orientation-controllable polyphase yoke, and (b) at least one shell layer. Referring to FIG. 4, in an embodiment, the method comprises: i) preparing at least one orientation-controllable polyphase yoke 20 (e.g., as shown in FIG. 6); ii) optionally, applying a coating (e.g., protective coating 22) 400 (e.g., functionalization, lubricant, surface treatment, coating, abrasive, etc.); iii) forming a dissolution layer 410 (dissolution layer 24 is disposed on at least one orientation-controllable polyphase yoke 20 or any protective coating 22); iv) shell formation 420 of a shell 26 containing pores; v) etching the dissolution layer 24 to form a cavity 28 in the hollow yoke-shell particles 430; vi) curing the shell 26 to form a non-porous shell 30 440; and vii) optionally, forming one or more additional shells to form the hollow yoke-shell particles 100.

[0201] In an embodiment, a method for preparing hollow yoke-shell particles is provided, including: a) at least one orientation-controllable polyphase yoke, b) at least one shell layer, and c) a thermoresponsive polymer dispersed in the cavity of the hollow yoke-shell particles (for example, a method as shown in FIG. 5). Referring to FIG. 5, in an embodiment, the method includes: a) preparing at least one orientation-controllable polyphase yoke 20 (for example, as shown in FIG. 6), b) optionally, coating at least one orientation-controllable polyphase yoke with a protective coating 22 at 400, c) forming a dissolution layer at 410 (the dissolution layer 24 is disposed on at least one orientation-controllable polyphase yoke 20 or on any protective coating 22), d) shell formation of a shell 26 containing pores at 420, e) etching the dissolution layer 24 at 430 to form a cavity 28 in the hollow yoke-shell particles, f) adding a thermoresponsive polymer 32 at 500 (the thermoresponsive polymer 32 is capable of passing through the pores of the shell so as to be dispersed in the cavity 28 of the hollow yoke-shell particles), g) curing the shell 26 at 440 to form a non-porous shell 30, and h) optionally, forming one or more additional shells to form the hollow yoke-shell particles 100.

[0202] In an embodiment, a method for preparing hollow yoke-shell particles (for example, as shown in FIG. 8) is provided herein, the method including: A) generating a silica core; B) coating the silica core with polystyrene (PSt) to form a polystyrene layer (for example, a dissolution layer) around the silica core; C) forming a silica (SiO2) shell around the PSt layer; D) firing at a high temperature (500 °C for 4 hours) to generate a void space between the silica shell and the core; and E) etching with NH3. In an embodiment, the method may include dispersing a thermoresponsive polymer in the void space or cavity of the hollow yoke-shell particles. In an embodiment, the method includes applying one or more protective coatings (plural available) to the core, for example, instead of or in addition to the PSt layer. In an embodiment, the method may include a curing step after etching to close or seal any pores in the shell layer.

[0203] In an embodiment, the thermoresponsive polymer is selected from poloxamer, styrene-butadiene block copolymer, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and combinations thereof. Alternatively, in an embodiment, instead of the thermoresponsive polymer (e.g., as shown in FIG. 5), various other materials (e.g., materials that function as lubricants or abrasives, as well as materials used for chemical functionalization, surface treatment, etc. described herein) can be used to fill the cavity.

[0204] In an embodiment, the term "protective coating" as described herein is a chemically inert coating disposed on an orientation-controllable multiphase yoke to protect the yoke from exposure to any conditions that may interfere with the assembly of the yoke. For example, in an embodiment, the protective coating can be selected from materials including, but not limited to, polymeric materials, inorganic oxides, carbon materials, and mixtures thereof. In some embodiments, the protective coating is insoluble in organic solvents.

[0205] In an embodiment, the protective layer may include one or more of polytetrafluoroethylene (PTFE), hydroxylated self-assembled monolayers, vitreous enamel, ceria (cerium oxide), ceramics, anodized metals, and silica, and may include one or more of chemical functionalization, lubricants, surface treatments, coatings, abrasives, etc. In an embodiment, one or more functionalizations, lubricants, surface treatments, coatings, abrasives, etc. are used as a mechanism to reduce the effect of friction on the movement of the yoke within the shell. These may include, but are not limited to, in embodiments: (a) adding a lubricant between the yoke and the shell, (b) surface treatment and / or coating (e.g., TEFLON®, polytetrafluoroethylene (PTFE), hydroxylated self-assembled monolayers, vitreous enamel, etc.), (c) polishing (e.g., ceria (cerium oxide), etc.), (d) selecting a material with a low coefficient of friction (e.g., ceramics, anodized metals, silica, etc.), and / or (e) changing the dimensions and / or surface of the yoke / shell to minimize the effect of friction. In an embodiment, the yoke / shell uses a combination of factors to reduce, mitigate, or otherwise control the effect of friction on the HYSP in response to an external stimulus.

[0206] In an embodiment, the method of etching the dissolution layer includes, for example, the step of immersing the dissolution layer in a chemical substance that dissolves the dissolution layer. In an embodiment, the etching includes dry etching techniques (e.g., reactive ion etching, ion beam etching, plasma etching, or laser ablation). In an embodiment, the etching includes a wet etching process (e.g., an etching that uses an acid or a base).

[0207] In embodiments, methods that include forming a shell that includes pores include, for example, forming a mesoporous shell (e.g., having a pore size of from about 2 nm to about 50 nm). Those of ordinary skill in the art having the benefit of the present disclosure will understand some of the strategies for synthesizing mesoporous materials that can be employed, such as using organic template molecules as structure-directing agents around which the precursors are concentrated. In embodiments, so-called soft template methods can be used. In this approach, in embodiments, after mesophase formation, the organic template is removed by calcination and / or extraction. In embodiments, upon removal of the template, a regular mesopore structure is generated that allows for adjustment of the mesopore size, for example, by using different surfactants as templates. In embodiments, a variety of materials can be used for template formation, for example, cationic, amphiphilic, and anionic surfactants, chiral peptide-modified surfactants, emulsions, vitamin derivatives, ionic liquids, and biological materials can be distinguished. In embodiments, the soft template synthesis approach for generating a mesoporous matrix precursor includes the use of materials (e.g., tetraalkoxysilane, organofunctionalized alkoxysilane, metal alkoxides, and fumed silica). In embodiments, this strategy allows for precise control of mesophase formation, particle morphology, pore diameter, microporosity, and mesoporosity through modification of the synthesis conditions (e.g., addition of swelling agents and co-surfactants, presence of inorganic salts, matrix precursor / surfactant ratio, temperature changes, and many others).

[0208] In an embodiment, the method herein uses a hard template (e.g., mesoporous silica) as used in the preparation of other mesoporous materials. This approach is typically applied to the synthesis of mesoporous carbon. In an embodiment, the mesoporous template is loaded with an organic material (e.g., sucrose), and then the organic filler is carbonized in a vacuum. In an embodiment, the dissolution of the silica shell can be carried out with a sufficiently strong base (e.g., sodium hydroxide) or acid (e.g., hydrofluoric acid), as a result of which the carbon framework is exposed. Alternatively, in an embodiment, a double replication procedure can be used. In this preparation method, in an embodiment, the mesostructured silica can be used as a template for mesoporous carbon, and this hard carbon matrix can function as a replication matrix for mesoporous metal oxides.

[0209] In an embodiment, the porous shell contains mesoporous silica. In an embodiment, the porous shell contains a porous organic framework.

[0210] In an embodiment, the synthesis of a porous organic framework (POF) can be produced by the bonding of organic building units. For example, in an embodiment, the synthesized POF having mesopores within the organic framework can include, inter alia, covalent organic frameworks (COFs), crystalline triazine-based frameworks (CTFs), and porous aromatic frameworks (PAFs). In an embodiment, a COF material having mesopores can be synthesized by the condensation of diboronic acid with a hydroxylated triphenylene or tripcene derivative under mild reaction conditions. Alternatively, in an embodiment, a triazine-based polymer scaffold can be formed by the polymerization of various aromatic nitriles under severe reaction conditions (400 °C to 600 °C, molten ZnCl2). In an embodiment, a porous aromatic backbone having large pores can be synthesized by the Suzuki cross-coupling reaction of diphenyldiboric acid and tetrakis(4-bromophenyl)methane. In an embodiment, the materials described above are prepared without using a template.

[0211] In an embodiment, the curing of the porous shell can include a process (e.g., but not limited to, sintering) that compresses and forms a solid mass of material by heat or pressure without melting to the liquefaction point.

[0212] DNA origami polymorphic particles In an embodiment, a method for preparing a DNA origami orientation-controllable polymorphic yoke (e.g., as shown in FIGS. 6 and 9-11) is provided herein. In an embodiment, referring to FIG. 6, a non-limiting exemplary workflow for preparing at least one orientation-controllable polymorphic yoke 21 using the "DNA origami" process is shown. In an embodiment, the "DNA origami" described herein is a process in which chain nucleic acid molecules (e.g., single-stranded or double-stranded DNA and / or RNA, linear DNA and / or RNA, and / or circular DNA and / or RNA) are folded into various forms using one or more other nucleic acid molecules. Referring to FIG. 6, in an embodiment, the DNA molecule 600 is folded into a desired form using one or more additional DNA strands. In an embodiment, by arranging DNA-based nanostructures into extended higher-order assemblies, a desired yoke structure can be produced, and these yoke structures can optionally be coated with a protective coating 22.

[0213] In an embodiment, "DNA" refers to deoxyribonucleic acid and can refer to genomic DNA, recombinant DNA, synthetic DNA, or cDNA. In an embodiment, DNA refers to genomic DNA or cDNA. The term "DNA" is used herein to include polymeric forms of deoxyribonucleotides of any length or tertiary / quaternary structure / composition. In the embodiments where the term "DNA" is used herein, those skilled in the art will understand that the methods and devices described herein can be applied to, for example, other nucleic acids (e.g., RNA).

[0214] In embodiments, the yolk particles of the present disclosure (e.g., polymorphic movable yolk) can be constructed using DNA origami methods known to those skilled in the art. For example, DNA origami techniques (including, but not limited to, multi-stranded approaches or scaffold-based approaches) can be used. In embodiments, DNA origami-based polymorphic yolks can be formed into any shape described herein.

[0215] In embodiments, the nucleic acid origami structure is a two-dimensional or three-dimensional structure made from DNA. In embodiments, the DNA origami can have a mass on the megadalton (MDa) scale, e.g., about or at least about 1 MDa, about or at least about 5 MDa, about or at least about 10 MDa, about or at least about 50 MDa, about or at least about 100 MDa, about or at least about 500 MDa, about or at least about 1,000 MDa.

[0216] Referring to FIG. 6, in embodiments, the DNA nanostructure is made from one or more of a plurality of DNA molecules 600. In embodiments, the nucleic acid origami structure is made from a scaffold strand 610 of a nucleic acid such as DNA, which is arranged in a desired polymeric object of a custom shape. In embodiments, staple strands of DNA (e.g., unassembled origami sequences that may be shorter than the DNA scaffold strand, shown in FIG. 6) can be used to direct the folding or orientation of the DNA scaffold strand into a programmed arrangement. In embodiments, the term "origami" means that one or more strands or building blocks of a nucleic acid (e.g., DNA) can be folded or otherwise arranged into a desired structure or shape. In embodiments, the structure or shape can then be fixed into the desired structure or shape by one or more other DNA strands or building blocks (e.g., the plurality of staple strands of DNA molecule 600).

[0217] Referring to FIG. 9, in an embodiment, HYSP can be generated by assembling a DNA origami structure having one or more nucleic acid strands (e.g., single-stranded DNA) extending as "sticky ends" from the DNA origami structure. In an embodiment, these sticky ends can be complementary to one or more single-stranded nucleic acids conjugated to magnetic particles, and when these two are mixed in solution, magnetically particle-coated DNA origami will be formed. In an embodiment, the DNA origami structure can be directly conjugated to magnetic particles.

[0218] Referring to FIG. 10, in an embodiment, HYSP can be generated by designing a colorant that can adhere to DNA origami and / or magnetic particles. In an embodiment, the colorant can be assembled by conjugating a nucleic acid (e.g., single-stranded DNA) complementary to the nucleic acid within the origami structure, and when these two are combined in solution, colorant-coated DNA origami particles and / or colorant-coated magnetic particles will be formed. In an embodiment, the colorant can be directly conjugated to magnetic particles.

[0219] Referring to FIG. 10, in an embodiment, the application of the colorant to the magnetic particles and / or the DNA origami structure can be carried out stepwise such that the properties of the colorant are limited to specific regions of the overall yoke structure.

[0220] In an embodiment, the nucleic acid (e.g., single-stranded DNA) is chemically modified. In an embodiment, the chemical modification can include thiolation, phosphor, and / or cyanation of chromophores. In an embodiment, the chemical modification (e.g., metal nanoparticles, nanorods, magnetic materials, etc.) is used to generate nucleic acids that promote conjugation rather than on one or more surfaces. In an embodiment, the magnetic particles can include metal nanoparticles (e.g., silver (Ag) nanoparticles or gold (Au) nanoparticles).

[0221] Methods for fabricating DNA origami are known to those skilled in the art. In embodiments, representative methods of DNA origami can be found, for example, in the examples described below: Rothemund, “Folding DNA to Create Nanoscale Shapes and Patterns”, Nature, Vol. 440, March 2006: pp. 297 - 302; Rothemund, “Design of DNA Origami”, Proceedings of the International Conference of Computer-Aided Design (IEEE / ACM), 2005: pp. 470 - 477; U.S. Patent No. 7,842,793; Douglas et al, “Rapid prototyping of 3D DNA-origami shapes with caDNAno,” Nucleic Acids Res., Vol. 37, No. 15, 2009: pp. 5001 - 5006; Douglas et al., “Self-assembly of DNA into nanoscale three-dimensional shapes,” Nature, Vol. 459, 2009: pp. 414 - 418 (2009); Andersen et al., “Self-assembly of a nanoscale DNA box with a controllable lid,” Nature, Vol. 459, 2009: pp. 73 - 76; Dietz et al., “Folding DNA into Twisted and Curved Nanoscale Structures,” Science, Vol. 325, 2009: pp. 725 - 730; Han et al., “DNA Origami with Complex Curvatures in Three-Dimensional Space,” Science, Vol. 332, 2011: pp. 342 - 346; Liu et al., “Crystalline Two-Dimensional DNA Origami Arrays,” Angew.Chem.Int.Ed.Engl., Vol. 50, 2011: pp.264-267;Zhao et al,“Organizing DNA Origami Tiles into Larger Structures Using Preformed Scaffold Frames,”Nano Lett.,Vol.11,No.7,2011:pp.2997-3002;Woo et al.,”Programmable molecular recognition based on the geometry of DNA nanostructures,”Nat.Chem.Vol.3,2011:pp.620-627;Toning et al.,“DNA origami:a quantum leap for self-assembly of complex structures,”Chem.Soc.Rev.Vol.40,2011:pp.5636-5646;Berengut,et al.,“Design and synthesis of pleated DNA origami nanotubes with adjustable diameters,”Nucleic Acids Res.Vol.47,No,22,2019:pp.11963-75;Chen,et al.,“Nanoscale 3D spatial addressing and valence control of quantum dots using wireframe DNA origami,”Nat Comm.Vol.13,No.4935,2022;Wang,et al.,“Planar 2D wireframe DNA origami,”Sci.Adv.Vol.8,No.20,2022;Peil,et al.,“DNA Assembly of Modular Components into a Rotary Nanodevice,”ACS Nano,Vol.16,2022:pp.5284-91;and Wintersinger,et al.,“Multi-micron crisscross structures grown from DNA-origami slats,”Nat.Nanotechnol.Vol.18,2022:pp.281 - 289 (each of these is hereby incorporated by reference in its entirety).

[0222] In embodiments, the nucleic acid origami structure integrated into the orientation - controllable polyphase yoke is not composed of scaffold strands and staple strands. In embodiments, the nucleic acid origami structure can be constructed by single - stranded nucleic acid sequences that self - assemble in a tile - like manner to form a lattice of any desired shape or size. In embodiments, such single - stranded nucleic acid sequences can be newly designed and synthesized. In embodiments, such an approach includes, for example, the programmed self - organization of nucleic acid strands designed to create a wide range of structures having the desired shapes described below: Wei et al., “Complex shapes self - assembled from single - stranded DNA tiles,” Nature, Vol. 485, 2012: pp. 623 - 627 (which is hereby incorporated by reference in its entirety).

[0223] Those skilled in the art will understand that the principles of the present disclosure do not depend on a particular method of making DNA origami or a particular two - dimensional or three - dimensional nucleic acid shape. Those skilled in the art who benefit from the present disclosure in its entirety will understand that aspects of the ability of DNA origami to provide unique shapes, provide locations for hybridizing nucleic acid sequences having functional moieties or groups, or directly label or tag functional moieties or detectable moieties are useful in embodiments of the present disclosure. Those skilled in the art who benefit from the present disclosure in its entirety will understand that aspects of the ability to design DNA origami having desired hybridization sites or desired probes are useful, for example, in embodiments of the methods of the present invention for attaching coloring agents and / or stimulus - responsive elements.

[0224] In an embodiment, the scanning device can be used to visualize and distinguish nucleic acid origami structures. In an embodiment, the scanning device is an electron microscope (e.g., a transmission electron microscope (TEM), a scanning electron microscope (SEM), a scanning transmission electron microscope (STEM), an environmental scanning electron microscope (ESEM), a cryo-electron microscope (cryo-EM), and other electron microscopes known to those skilled in the art). The methods of using a transmission electron microscope and FEM are known to those skilled in the art, for example, as described below: Morel, “Visualization of Nucleic Acids,” The Spreading of Nucleic Acids, p. 35-56, CRC Press, Boca Raton (1995).

[0225] In an embodiment, referring to FIG. 6, the DNA origami is constructed to be essentially planar, the sequence “b” is nominally perpendicular to the plane and is available for binding across one plane (or face or side) of the origami structure, the sequence “a” is nominally perpendicular to the plane and is available for binding across the other side of the origami structure, and the sequence d is nominally perpendicular to the plane and is available for binding only at one end of one side of the plane. In an embodiment, referring to FIG. 6, a DNA sequence having a certain degree of complementarity with the DNA sequences (shown as a’72 and b’73) within the origami structure is attached to the coloring agent #170 and the coloring agent #290, that is, by forming the DNA-coated coloring agent #171 and the DNA-coated coloring agent #291, a DNA-coloring agent complex can be made to bind to the opposite side of the origami particle. In an embodiment, referring to FIG. 6, a third DNA sequence having a certain degree of complementarity with the DNA sequence (shown as d’32) within the origami structure is attached to a stimulus-responsive particle (e.g., magnetic particle 30), whereby the resulting DNA-coated particle 31 can be made to bind to the face of the origami structure, for example, at the end of the plane.

[0226] Referring to FIG. 6, in an embodiment, after obtaining the DNA origami shape 620, self-assembly chemistry can be used to specifically attach a stimulus-responsive element (e.g., magnetic particle 30) and a colorant (e.g., DNA-coated colorant #171, DNA-coated colorant #291) that imparts different types of properties to the surface of the DNA origami-based yoke 620. In an embodiment, these interactions include various biochemical interactions (e.g., but not limited to, ligand-receptor, DNA-DNA, antibody-antigen, etc.). In an embodiment, other techniques known to those skilled in the art (e.g., click chemistry, or -NHS coupling chemistry) can be used to attach other elements and / or colorants to the surface of the DNA origami-based yoke. In an embodiment, the assembly of the stimulus-responsive element (e.g., magnetic particle 30) and the colorant (e.g., colorant #170 and colorant #290) to the DNA origami-based yoke 620 can be directed via various non-covalent interactions (e.g., hydrogen bonding, hydrophobic forces, van der Waals forces, π-π interactions (pi-pi interactions), and / or electrostatics).

[0227] Referring to FIG. 6, in an embodiment, the DNA-coated colorant #171, the DNA-coated colorant #291, and the DNA-coated particle 31 can be obtained separately and then self-assembled on the DNA origami-based yoke 620 to obtain an exemplary orientation-controllable polymorphic yoke 21. In such an embodiment, complementary DNA sequences (e.g., a’72, b’92, and d’32) are designed to be complementary to at least a portion of the DNA sequences exposed on the surface of the DNA origami-based yoke 620, and using methods known to those skilled in the art, they can be attached to the colorant (e.g., colorant #170, colorant #290) and the stimulus-responsive element (e.g., magnetic particle 30) via covalent or non-covalent chemical action.

[0228] Additive manufacturing In an embodiment, the HYSP can be generated, prepared, and / or manufactured (or, in part, manufactured) by additional manufacturing techniques (e.g., assembly, adhesion, screwing, and / or fixing of two or more components; injection molding and / or micro-injection molding; self-assembly, adsorption, coacervation, and / or mixing; polymerization, extrusion, and / or manipulation of polymers; additive manufacturing, CNC machining (computer numerical control machining), urethane casting, micro-contact printing, dip-pen lithography, beam-pen lithography, photolithography, electron beam lithography, and / or 3D printing).

[0229] In an embodiment, the method of manufacturing the HYSP can include a number of manufacturing techniques used to generate particles in a size scale ranging from millimeters through micrometers to nanometers. In an embodiment, these methods can include, by way of non-limiting example: (i) assembly of two or more components (e.g., adhesion, screwing, fixing of an upper and a lower part; or a left and a right part), (ii) injection molding, micro-injection molding, or similar techniques including molds or castings, (iii) chemical or physical methods (including, but not limited to, self-assembly, adsorption, coacervation, and / or mixing), (iv) polymerization, extrusion, and / or manipulation of polymers, (v) additive manufacturing, also known as 3D printing, (vi) photolithography techniques, (vii) micro-contact printing, (viii) other lithography techniques (e.g., beam-pen lithography, among others), (ix) various methods.

[0230] In embodiments, one or more materials used to generate the HYSP include one or more thermoresponsive polymers, which include, for example, one or more of poloxamers, styrene-butadiene block copolymers, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and combinations thereof.

[0231] In embodiments, the generation of the HYSP includes micro-injection molding, a manufacturing process used to create small and highly precise plastic parts. In embodiments, the process includes injecting molten plastic, metal, and / or polymer-based materials into the cavities of a mold that can be designed to the exact specifications of a desired part or a portion thereof. In embodiments, the mold is then cooled and the part is removed from the mold. In embodiments, the technique typically produces parts sized on the scale of micrometers to a few millimeters. In embodiments, micro-injection molding is used for its high precision, reproducibility, and efficiency and is a suitable option for mass-producing small parts. The injection molding process is used in various industries where small and complex parts are required (e.g., medical, electronics, and automotive industries). Non-limiting examples of parts made by micro-injection molding include microgears and other small mechanical parts used in watches, cameras, and other precision devices or apparatuses, microfluidic devices used for medical and research purposes, small components for electronic devices (e.g., microconnectors, microswitches, and microlenses for cameras), small medical implants (e.g., hearing aid parts), and small automotive parts (e.g., gears, valves, and connectors used in engines and other mechanical systems). Thus, in embodiments, the method of manufacturing the HYSP and the substrate, surface, and / or material for the HYSP may use a technique for making any of the above objects.

[0232] In an embodiment, the HYSP can be manufactured by 3D printing (referred to herein as "3DP"), which is a process of creating three-dimensional objects by adding layers of molten material through a printer device compatible with various materials (e.g., plastics, polymers, ceramics, metals, etc.). In an embodiment, 3DP enables the creation of complex shapes and structures that are difficult to manufacture by conventional manufacturing methods. In an embodiment, computer-aided design (CAD) software is used to create a digital model of the object. In an embodiment, the printer reads the digital model and adds successive layers of material (plastic, metal, or biological material) until the object is completed to the specifications described in the digital model. In an embodiment, further manufacturing can be used to print a wide range of materials (e.g., plastic / polymer, metal, ceramic, composite material, and biological substances), as well as additional composite materials (e.g., paper, wood, wax, and food).

[0233] In an embodiment, 3DP has advantages compared to conventional manufacturing methods (e.g., waste reduction, shorter production times, and improved design flexibility). Currently, 3D printing methods fall into seven general categories: material extrusion, vat polymerization, powder bed fusion bonding, material jetting, binder jetting, directed energy deposition, and sheet lamination. In an embodiment, the available size of dimensions using 3DP is determined by the specific type of 3D printing technology and the performance of the printer used. Generally, the maximum dimensions available using 3DP can be several meters in length, width, and height, and the minimum dimensions available using 3DP can range from micrometers to sub-micrometers and are performed using advanced 3D printing technologies (e.g., stereolithography (SLA), digital light processing (DLP), or two-photon polymerization (2PP)) that can print with high precision and high resolution. For example, in an embodiment, a commercially available 3D printer based on two-photon polymerization (2PP) is available through UPNANO (a 3D printer manufacturer) and can generate polymer objects with dimensions ranging from centimeters to nanometers in 12 digits.

[0234] In embodiments, the HYSP and its components can be 3D printed onto a substrate surface (e.g., a glass slide) and can be released from the substrate surface via several methods. In embodiments, the 3D printed HYSP and components can be removed by mechanical separation (e.g., by scraping). For example, in scalable manufacturing embodiments, the HYSP can also be released by chemical separation (e.g., by application of a solvent), thermal separation (e.g., by heating), ultrasonic separation (e.g., by sonication), and / or vacuum release. Additional release methods are known to those skilled in the art depending on the 3D printer used, the method of 3D printing, the composition of the HYSP, and the type of substrate used.

[0235] In embodiments, the HYSP can be generated using 3D printing techniques (including but not limited to fused deposition modeling (FDM), fused filament fabrication (FFF), stereolithography (SLA), selective laser sintering (SLS), binder jetting (BJ), direct energy deposition (DED), digital light processing (DLP), liquid crystal display (LCD), polymer jetting (polyjet technology), multi-jet fusion (MJF), direct metal laser sintering (DMLS), electron beam melting (EBM), laminated object manufacturing (LOM), continuous liquid interface production (CLIP), electron beam melting, and / or digital light processing (DLP)).

[0236] Chemical manufacturing Alternatively, in embodiments, chemical techniques (e.g., coacervation) can be used to generate HYSP. In embodiments, coacervation is a process in which two or more polymers are mixed in solution and phase-separated to form two different phases. In embodiments, one phase is rich in polymer and the other phase is depleted in polymer and contains mainly solvent. In embodiments, coacervation is used to generate microspheres or microcapsules, which are small spherical particles that can be used for drug delivery, encapsulation, and other applications. In embodiments, in coacervation, the polymers undergo a process of self-organization to form complex structures through non-covalent interactions (e.g., electrostatic forces, hydrogen bonds, and van der Waals forces). The resulting microspheres or microcapsules can be tailored to have specific properties (e.g., size, shape, and composition) and are useful in various fields. In embodiments, the generation of the particles can include a combination of coacervation and the molding part of HYSP.

[0237] In embodiments, generating particles for HYSP includes chemical methods of click chemistry, which is a class of simple atom-economic reactions commonly used to couple two selected molecular entities. In embodiments, click reactions occur within a single vessel, are not water-sensitive, produce minimal by-products, and are "spring-loaded" - characterized by a high thermodynamic driving force that rapidly and irreversibly promotes the reaction to a single reaction product with high reaction specificity (in some cases, both regioselectivity and stereoselectivity) and high yield. In embodiments, generating particles for HYSP includes other well-known chemical methods for coupling two entities (particularly in the life sciences), including, by way of non-limiting example, streptavidin-biotin binding, maleimide-based reactions, and carbodiimide-based reactions.

[0238] In embodiments, various techniques that focus on using polymers to generate 3D materials can be used to synthesize HYSP. For example, in embodiments, snowman-shaped anisotropic Janus particles are described below: KANG and HONCIUC, “Influence of Geometries on the Assembly of Snowman-Shaped Janus Nanoparticles”, ACS Nano, Vol. 12, No. 4: 2018: pp. 3741-3750 (entirely incorporated herein by reference). In embodiments, such particles can be manufactured from poly(tert-butyl acrylate)-poly(3-(triethoxysilyl)propyl methacrylate) (PtBA-PTPM).

[0239] The method for manufacturing HYSP herein, in embodiments, includes incorporating HYSP into the substrates, materials, and / or surfaces of fluids, suspensions, inks, liquid films, and / or adhesives. In embodiments, the substrates, materials, and / or surfaces of fluids, suspensions, inks, liquid films, and / or adhesives are suitable for application to an object. In embodiments, incorporating HYSP into a fluid, suspension, ink, liquid film, and / or adhesive includes combining HYSP with one or more solvents. In embodiments, the solvent includes an aqueous solvent. In embodiments, the solvent includes a non-aqueous solvent. In embodiments, the solvent is an organic solvent. In embodiments, the medium includes one or more of water, ketones, alcohols, esters, nitriles, and combinations thereof.

[0240] In an embodiment, the method for manufacturing HYSP in this specification includes incorporating HYSP into a substrate, material, and / or surface of foil, film, thin plastic, and / or paper. In an embodiment, the substrate, material, and / or surface of foil, film, thin plastic, and / or paper are suitable for being fixed to or embedded in an object. In an embodiment, incorporating HYSP into foil, film, thin plastic, and / or paper includes incorporating the liquid form of HYSP and spraying a thin layer of suspended HYSP onto the surface area of foil, film, thin plastic, and / or paper.

[0241] In an embodiment, the method for manufacturing HYSP in this specification includes incorporating GRP into a substrate, material, and / or surface of fiber, thread, yarn, and / or twisted yarn. In an embodiment, the substrate, material, and / or surface of fiber, thread, yarn, and / or twisted yarn are suitable for being woven into clothing, fabric, and / or a waterproof sheet.

[0242] Composition of Hollow Yoke-Shell Particles (HYSP) In an embodiment, the HYSP of the present disclosure can be used as a colorant in various compositions (e.g., in liquid inks (e.g., solvent-based inks, aqueous inks), solid or phase change ink compositions, etc.). In an embodiment, the ink compositions presented in this specification can exist in various forms (e.g., but not limited to, liquid, curable, solid, hot melt, phase change, gel). In an embodiment, the composition includes HYSP in a suspension, fluid, and / or solvent (e.g., aqueous solvent and / or inorganic solvent). In an embodiment, the composition includes an object and / or material coated with HYSP. In an embodiment, the composition includes an object and / or material in which HYSP is embedded.

[0243] In an embodiment, the HYSP is incorporated into a substrate, material, and / or surface of a fluid, suspension, ink, liquid film, and / or adhesive. In an embodiment, the substrate, material, and / or surface of the fluid, suspension, ink, liquid film, and / or adhesive is suitable for application to an object, for example, as a paint, ink, liquid film, etc. that can be applied to the surface of the object. After drying, the HYSP can respond to a magnetic field, and the paint, ink, liquid film, etc. will change its optical properties (e.g., color) in response to the magnetic field according to the viewing angle and / or the orientation of the yoke.

[0244] In an embodiment, the composition comprises HYSP incorporated into a substrate, material, and / or surface of a fluid, suspension, ink, liquid film, and / or adhesive. In such an embodiment, the HYSP can be present at a mass per volume, for example, about or at least about 0.001 mg / mL, about or at least about 0.01 mg / mL, about or at least about 0.1 mg / mL, about or at least about 1.0 mg / mL, about or at least about 10 mg / mL, about or at least about 50 mg / mL, about or at least about 100 mg / mL, about or at least about 150 mg / mL, about or at least about 200 mg / mL, about or at least about 250 mg / mL, about or at least about 300 mg / mL, about or at least about 350 mg / mL, or about or at least about 400 mg / mL or more.

[0245] In an embodiment, the ink composition as used herein refers to a formulation of a fluid, suspension, and liquid film of HYSP that can be applied by coating or other means to a surface. Referring to FIG. 7, in an embodiment, the HYSP can be deposited and / or arranged on a surface or an object in multiple layers.

[0246] In an embodiment, the ink composition contains one or more colorants by the HYSP of the present disclosure. In an embodiment, any colorant in the ink composition (e.g., one or more pigments, dyes, a mixture of pigments and dyes, a mixture of pigments, a mixture of dyes, etc.) can be used.

[0247] In an embodiment, the colorant of the composition is HYSP or includes it. For example, the colorant is usually present in an amount of at least about 0.1 percent, such as about 0.2 percent of the weight of the ink, or at least about 0.5 percent of the weight of the ink, and usually 90 percent or less of the weight of the ink, such as 50 percent or less of the weight of the ink, or about 30 percent or less of the weight of the ink, although the amount can be outside these ranges.

[0248] In an embodiment, the disclosed particles and ink compositions may also include substances other than the HYSP of the present disclosure to improve the properties and applicability of the ink compositions on various surfaces. For example, the ink compositions of the present technology may further include beneficial compounds (including, but not limited to, viscosity modifiers, dispersants, surfactants, solvent carriers, antioxidants, viscosity controllers, additional colorants, resins, binders, or combinations thereof).

[0249] In an embodiment, the ink composition described herein is a solvent-based ink composition. In an embodiment, the solvent-based ink composition includes an ink solvent, any binder or binder resin, and one or more optional additives. In an embodiment, the ink solvent can be selected from the group consisting of water, ketones, alcohols, esters, nitriles, and combinations thereof, but is not limited thereto. In an embodiment, the ink solvent is present in an amount of about 10% to about 90%, about 20% to about 85%, about 50% to about 85%, or about 65% to about 80% based on the total weight of the ink composition.

[0250] In an embodiment, any additive is selected from the group consisting of plasticizers, surfactants, light stabilizers, defoamers, antioxidants, UV stabilizers, bactericides, conductive agents, abrasion resistance agents, and combinations thereof. In an embodiment, the additive includes one or more plasticizers for solubilizing the binder.

[0251] In an embodiment, the ink composition described herein is a polymer-based ink composition. For example, in an embodiment, the polymer-based ink composition may include a thermoplastic polymer (e.g., acrylic), a polymer that is generally curable by UV irradiation in the presence of a photoinitiator, and the like.

[0252] In an embodiment, the ink composition described herein containing the HYSP of the present disclosure can be formulated as an enamel ink composition. In an embodiment, the enamel ink may include a liquid medium (also referred to as a vehicle or carrier) for suspending inorganic pigments and oxide powders, and as a result, can be applied uniformly and homogeneously to the surface of a substrate before firing (e.g., before being placed in a kiln or heat source). In an embodiment, the liquid medium may include a solvent (e.g., alcohol), an organic oil (e.g., one or more terpenes), a polymer precursor (e.g., an acrylate precursor if the ink is cured by UV), and / or a viscosity-adjusting additive (e.g., one or more glycols, e.g., butylene glycol). In an embodiment, the liquid medium can be formulated to evaporate or be removed by other means during any drying, pre-firing, or heat treatment process.

[0253] Method of using hollow yoke-shell particles (HYSP) In an embodiment, the HYSP particles and compositions thereof of the present disclosure can be applied to an object, surface, and / or substrate (including, but not limited to, polymers, paper, fabric, metal, clay board, ceramic, window, glass, plastic, computer chip, wood, building materials, and / or human or animal tissue or skin for decorative, aesthetic, artistic, security, information storage, energy management, and / or cosmetic purposes). In an embodiment, the stimulus-responsive HYSP can be functionalized with and / or encapsulated within any element to increase the applicability of the composition and / or its use in a desired form.

[0254] In an embodiment, the surface and / or the substrate is planar or non-planar. In an embodiment, the surface and / or the substrate includes at least a convex shape, a concave shape, or a portion having no distinct shape. In an embodiment, the surface and / or the substrate is on the inner surface of the object, the outer surface of the object, or both, and the object is a non-HYSP object.

[0255] In an embodiment, the surface and / or the substrate includes depressions and / or recesses. In an embodiment, the depressions and / or recesses are arranged in an array. In an embodiment, the HYSP is disposed in and / or on the depressions and / or recesses. In an embodiment, the surface and / or the substrate includes pillars, posts, and / or stoppers. In an embodiment, the HYSP is disposed in and / or on the pillars, posts, and / or stoppers. In an embodiment, the surface and / or the substrate includes one or more grooves. In an embodiment, the HYSP is disposed in and / or on the one or more grooves.

[0256] In an embodiment, the method of the present specification using the HYSP includes providing the HYSP (wherein the formulation of the HYSP is formulated in a substrate and / or material of a fluid, a suspension, an ink, a liquid film, and / or an adhesive), and applying the substrate and / or material of the fluid, the suspension, the ink, the liquid film, and / or the adhesive to the object and / or the surface. In an embodiment, applying further includes spraying, adhering, embedding, writing, printing, and / or absorbing (such as being suitable for applying a fluid, a suspension, an ink, a liquid film, and / or an adhesive). In an embodiment, formulating may include combining the HYSP with one or more solvents or components as described herein, suspending, and / or homogenizing. In an embodiment, the object is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue. In an embodiment, the object and / or the surface exhibits a property of changing optical properties in response to the application of a magnetic field.

[0257] In embodiments, the base materials, materials, and / or surfaces of fluids, suspensions, inks, liquid films, and / or adhesives are suitable for application to an object. For example, in non-limiting embodiments, such HYSP compositions can be sprayed, written, printed, and / or blotted onto surfaces and / or base materials. In embodiments, an ink composition containing HYSP can be applied to a target base material under an external stimulus (e.g., a magnetic field) to ensure an appropriate arrangement of HYSP on the surface of the base material. For example, the appropriate orientation of HYSP can be determined by the form of the magnetic field (e.g., intensity, direction, etc.) and may depend on the properties (e.g., arrangement, physicochemical properties, etc.) of the stimulus-responsive element(s) attached to the yoke.

[0258] In embodiments, a method of using HYSP includes providing HYSP, incorporating HYSP into base materials and / or materials of foil, film, thin plastic, and / or paper, and applying the base materials and / or materials of foil, film, thin plastic, and / or paper to an object and / or surface. In embodiments, applying further includes, for example, spraying, adhering, embedding, writing, printing, and / or blotting that are suitable for applying the base materials and / or materials of foil, film, thin plastic, and / or paper. In embodiments, incorporating can include combining HYSP with one or more solvents or components as described herein and may include suspension and / or homogenization. In embodiments, the object is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue. In embodiments, the object and / or surface exhibit properties that change optical properties in response to the application of a magnetic field.

[0259] In embodiments, the substrates, materials, and / or surfaces of foil, film, thin plastic, and / or paper are suitable for being applied to, fixed to, or embedded in an object. For example, in non-limiting embodiments, such compositions of HYSP can be adhered to the surface. In non-limiting embodiments, HYSP can be sprayed onto the surface and dried to form a substrate or material of foil, film, thin plastic, and / or paper.

[0260] In embodiments, the methods of using HYSP herein include providing HYSP (wherein compounding HYSP is compounded into substrates and / or materials of fibers, yarns, threads, and / or twisted yarns) and applying substrates and / or materials of foil, fibers, yarns, threads, and / or twisted yarns to an object and / or surface. In embodiments, applying further includes, for example, weaving and / or embedding suitable for applying substrates and / or materials of fibers, yarns, threads, and / or twisted yarns. In embodiments, compounding can include combining HYSP with one or more solvents or components, weaving, and / or extruding as described herein. In embodiments, the object is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue. In embodiments, the object and / or surface exhibits properties that change optical properties in response to the application of a magnetic field.

[0261] In embodiments, substrates, materials, and / or surfaces of fibers, yarns, threads, and / or twisted yarns are suitable for being woven into clothing, fabric, and / or waterproof sheets.

[0262] In embodiments, an object can have HYSP applied thereto to impart stimulus-responsive behavior. In embodiments, the object includes consumer goods in which HYSP is incorporated, such as packages in which HYSP is incorporated, fabrics in which HYSP is woven, paper / foil products coated with HYSP (such as currency, etc.).

[0263] In an embodiment, HYSP can be used to impart a stimulus-responsive behavior to an object for displaying graphics, markings, text, and / or patterns. For example, referring to FIG. 12, in an embodiment, several types of color-shifting HYSP (e.g., four used to create the figure) can be printed on a surface in a specific pattern, and when a magnetic field is applied, the pattern may disappear, reappear, or change to display differences in graphics, text, or patterns. In an embodiment, the graphics, text, and / or patterns can incorporate any number of HYSP (e.g., 2, 3, 4, 5, 6 or more different HYSP), each having the same or different colorants.

[0264] In an embodiment, HYSP can be used to impart a stimulus-responsive behavior to an object as a security means (e.g., for banknote authentication and / or counterfeit prevention means, document authenticity markers, etc.). For example, referring to FIG. 13, in an embodiment, graphics, markings, messages, and / or patterns can be imparted to the interior and / or surface of a banknote, and when a magnetic stimulus is applied, the graphics, markings, messages, and / or patterns can change their optical properties (e.g., color). In an embodiment, it can be used as a security element or security function for banknotes and other documents. In an embodiment, the term "security element" or "security function" as used herein refers to an image or graphic element that can be used for authentication purposes. In an embodiment, the security element or security function can be an explicit and / or implicit security element. In an embodiment, the compositions described herein (e.g., ink compositions) enable the use of HYSP in the field of protecting security documents from illegal or unauthorized acts / uses such as counterfeiting. In an embodiment, HYSP can be assembled on a surface in the form of a set of types, printed, and / or imaged. In an embodiment, the object and / or surface can change its color and / or fluorescence properties after application of a magnetic field or after a change in the direction of the magnetic field.

[0265] In an embodiment, a method of tagging a material is described herein, the method comprising providing at least one HYSP or a formulation thereof as described herein, and associating the material with the at least one HYSP or formulation, thereby forming a tagged material.

[0266] In an embodiment, a method of authenticating a material and / or an object is described herein, the method comprising: a) providing a formulation of a HYSP as described herein (the formulation comprising a substrate and / or material of a fluid, suspension, ink, liquid film, and / or adhesive; a substrate and / or material of a foil, film, thin plastic, and / or paper; or a substrate and / or material of a fiber, thread, yarn, and / or spun yarn), tagging the object and / or surface with the formulation, and reading the tag. In an embodiment, the tag is configured to be read by a sensor and / or an optical imaging device. In an embodiment, reading comprises applying a magnetic field to determine a change in the optical properties of the object and / or surface due to the presence of the HYSP.

[0267] In embodiments, HYSP can be applied to a surface or object as a single "tag gant" or in combination with one or more additional tag gants. In embodiments, HYSP can be composed of non-toxic starting materials for tagging consumer objects without causing adverse effects (such as skin inflammation or dirt) to the individuals handling it. In embodiments, HYSP can be combined with an implicit tag gant to produce features with both explicit and implicit reading characteristics and a unique signature. Alternatively, in embodiments, the size of the explicit features can be reduced to a size required for authentication by a sensor or optical imaging device. In embodiments, the HYSP function includes one or more optical attributes including the use of sensor-based authentication measurements of one or more wavelengths, amplitudes, or frequencies. In embodiments, the measurements can be continuous or intermittent or can include a single acquisition. In embodiments, existing sensors used in, for example, the currency industry (such as handheld reading devices (for quality control after ink incorporation), large format sheet readers (in printers), shoe box-sized high-speed readers (for currency sorting machines), and portable pocket-sized readers (used in the field)) can read HYSP-based security features.

[0268] In embodiments, packages (such as adhesives, paper, plastics, labels, and seals); pesticides, seeds, and crops; artworks and memorabilia; computer chips; cosmetics and perfumes; compact discs (CDs), digital video discs (DVDs), and video tapes; documents, currency, and other paper products (such as labels, passports, stock certificates); inks, paints, and dyes; electronic devices; automobiles and manufacturing components; explosives; food and beverages, tobacco; fibers, clothing, footwear, designer products, and apparel labels; polymers; hazardous waste; movie props and memorabilia, sports memorabilia and apparel; manufacturing parts, petroleum, fuel, lubricants, oils; pharmaceuticals and vaccines.

[0269] In an embodiment, HYSP can be used for the use of an ink composition in the field of tissue marking of, for example, cosmetics, tattoos, and / or semi-permanent makeup. In an embodiment, HYSP is a biologically inert particle having a size of less than about 10 μm that can be disposed on or embedded within a layer of skin. For example, in an embodiment, HYSP of about 10 μm or less can be used to impart color change properties to materials used in cosmetics, tattoos, and / or semi-permanent makeup. In an embodiment, cosmetics, tattoos, and / or semi-permanent makeup change their optical properties (e.g., color) in response to exposure to a magnetic field.

[0270] In an embodiment, HYSP can be used as a camouflage. In an embodiment, the camouflage is an adaptive camouflage and / or a thermal camouflage. In an embodiment, HYSP can hide signals emitted through various ranges of electromagnetic radiation. For example, in an embodiment, HYSP can be coated and / or embedded in a fabric, sheet, or film, which can be used to filter, scatter, reduce, or otherwise block infrared signals (i.e., infrared signatures), thereby providing an adaptive and / or thermal camouflage. In an embodiment, HYSP can be used as an adaptive camouflage by changing its optical properties as a function of a magnetic field applied to a portion of the fabric, sheet, or film containing HYSP. In an embodiment, HYSP can be used as a thermal camouflage to obscure the apparent temperature difference and contrast radiation intensity of an object coated with HYSP (or a material incorporating HYSP) in relation to the environment or background of the object.

[0271] In an embodiment, the HYSP can be used for electronic memory and storage purposes. In an embodiment, the HYSPs can be arranged in an orderly manner, and optical states (e.g., two or more different optical properties) can be assigned to the HYSPs in an orderly manner for storing and / or retrieving information. For example, in an embodiment, information can be retrieved by reading the optical states of a number of HYSPs, and based on a storage mode (e.g., using each HYSP as a "bit" and reading a set of eight HYSPs in an array as one byte of information), the HYSPs can be read or decoded in another way. In an embodiment, the optical states are binary, for example, each HYSP exhibits either a first optical property or a colorant, or a second optical property or a color, depending on the orientation of the yoke. In an embodiment, the optical state changes upon application of a magnetic field.

[0272] In an embodiment, the HYSP is disposed between a first substrate and a second substrate. For example, in an embodiment, the HYSP can be used as a "sandwiched" shield between two or more substrates (e.g., glass, quartz, plexiglass, etc.) used in windows, mirrors, skylights, doors, etc. In an embodiment, the HYSP used as a shield can be arranged between two or more surfaces together with one or more HYSP layers therebetween such that when a magnetic field is applied, the visibility across two or more transparent materials becomes blurred, unclear, or blocked in another way. In an embodiment, at least one of the first substrate and the second substrate can be composed of a material that is transparent to at least a portion of the visible electromagnetic (EM) spectrum as described herein. In an embodiment, the material can have a thickness of about or at least about 50 nm, about or at least about 100 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 10 μm, about or at least about 100 μm, about or at least about 1 mm, about or at least about 5 mm, or about or at least about 10 mm.

[0273] In an embodiment, the surface and / or the substrate change color in response to the presence of a magnetic field. In an embodiment, the HYSP includes at least a first surface having a shape complementary to the shape of the second surface of the HYSP, for example, to more densely pack the HYSP disposed on the surface.

[0274] In an embodiment, the surface and / or the substrate is treated with one or more of the lubricants, surface treatment agents, adhesives, coating agents, and / or abrasives described herein. For example, the surface treatment and / or substrate treatment can be to fix the HYSP to the object.

[0275] In an embodiment, the present disclosure relates to the following embodiments.

[0276] Embodiment 1. An ink composition comprising stimulus-responsive hollow yoke-shell particles, the hollow yoke-shell particles comprising (a) at least one orientation-controllable polyphasic yoke, and (b) at least one shell layer.

[0277] Embodiment 2. The ink composition according to Embodiment 1, wherein at least one orientation-controllable polyphasic yoke can rotate about its own axis when exposed to a magnetic field.

[0278] Embodiment 3. The ink composition according to Embodiment 1, wherein the cavity of the hollow yoke-shell particles contains a thermoresponsive polymer.

[0279] Embodiment 4. The ink composition according to Embodiment 3, wherein the thermoresponsive polymer is selected from poloxamer, styrene-butadiene block copolymer, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and combinations thereof.

[0280] Embodiment 5. The ink composition according to Embodiment 3, wherein at least one orientation-controllable polyphase yoke can rotate about its own axis when exposed to a magnetic field and heat.

[0281] Embodiment 6. The ink composition according to Embodiment 1, wherein at least one orientation-controllable polyphase yoke is coated with a protective coating.

[0282] Embodiment 7. The ink composition according to Embodiment 1, wherein the protective coating is selected from the group consisting of a polymer material, an inorganic oxide, a carbon material, and mixtures thereof.

[0283] Embodiment 8. The ink composition according to Embodiment 1, wherein at least one shell layer contains silica.

[0284] Embodiment 9. The ink composition according to Embodiment 1, wherein at least one orientation-controllable polyphase yoke is a polyphase particle having a surface that includes (a) at least one first colorant on a first side of the surface, (b) at least one second colorant on a second side of the surface, and (c) at least one stimulus-responsive element on any one surface of the surface, and the first side of the surface and the second side of the surface are on opposite sides of each other.

[0285] Embodiment 10. The ink composition according to Embodiment 9, wherein the colorant is selected from a dye, a pigment, or a combination thereof.

[0286] Embodiment 11. The ink composition according to Embodiment 9, wherein at least one stimulus-responsive element is selected from a polymer, organic nanoparticles, organic microparticles, inorganic nanoparticles, inorganic microparticles, a metal, a metal salt, a lipid, DNA, or a combination thereof.

[0287] Embodiment 12. The ink composition according to Embodiment 9, wherein at least one stimulus-responsive element responds to a magnetic field.

[0288] Embodiment 13. The ink composition according to Embodiment 12, wherein the stimulus-responsive element is selected from magnetic field-responsive particles.

[0289] Embodiment 14. The ink composition according to any one of Embodiments 1 to 13, which is used for decorative, aesthetic, artistic, and security applications.

[0290] Embodiment 15. A method for preparing at least one orientation-controllable polyphase yoke according to Embodiment 1, including the DNA origami technique.

[0291] Embodiment 16. A hollow yoke-shell particle, comprising: (a) at least one orientation-controllable polyphase yoke; and (b) at least one shell layer, wherein the at least one orientation-controllable polyphase yoke is a polyphase particle having a surface including: (a) at least one first colorant on a first side of the surface; (b) at least one second colorant on a second side of the surface; and (c) at least one stimulus-responsive element on any one of the sides of the surface.

[0292] Embodiment 17. The hollow yoke-shell particle according to Embodiment 16, wherein the first side of the surface of the orientation-controllable yoke and the second side of the surface of the orientation-controllable yoke are on opposite sides of each other through the surface of the orientation-controllable yoke.

[0293] Embodiment 18. The hollow yoke-shell particle according to Embodiment 16, wherein the at least one shell layer contains silica.

[0294] Embodiment 19. The hollow yoke-shell particle according to Embodiment 16, wherein the at least one stimulus-responsive element is selected from magnetic field-responsive particles.

[0295] Embodiment 20. The hollow yoke-shell particle according to Embodiment 19, wherein the magnetic field-responsive particles are selected from ferromagnetic particles, ferrimagnetic particles, diamagnetic particles, paramagnetic particles, superparamagnetic particles, antiferromagnetic particles, or combinations thereof.

[0296] Embodiment 21. The hollow yoke-shell particles according to Embodiment 16, wherein the cavity of the hollow yoke-shell particles contains a thermoresponsive polymer.

[0297] Embodiment 22. The hollow yoke-shell particles according to Embodiment 21, wherein the thermoresponsive polymer is selected from poloxamer, styrene-butadiene block copolymer, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and combinations thereof.

[0298] Embodiment 23. The hollow yoke-shell particles according to Embodiments 16 and 21, which are used in an ink composition.

[0299] Embodiment 24. a. Preparing at least one orientation-controllable polyphase yoke; b. Optionally, coating at least one orientation-controllable polyphase yoke with a protective coating; c. Forming a dissolution layer (the dissolution layer is disposed on at least one orientation-controllable polyphase yoke or any protective coating); d. Forming a shell containing pores; e. Etching the dissolution layer to form a cavity of the hollow yoke-shell particles; f. Curing the shell to form a non-porous shell; and, e. Optionally, forming one or more shells to form the hollow yoke-shell particles of Embodiment 16. A method for adjusting the hollow yoke-shell particles according to Embodiment 16, comprising the above steps.

[0300] Embodiment 25. The method according to Embodiment 24, wherein preparing at least one orientation-controllable polyphase yoke includes a DNA origami technique.

[0301] Embodiment 26. Preparing at least one orientation-controllable polyphase yoke further includes self-assembly of at least one first colorant coated with DNA, at least one second colorant coated with DNA, and at least one stimulus-responsive element coated with DNA, according to the method described in Embodiment 25.

[0302] Embodiment 27. a. Preparing at least one orientation-controllable polyphase yoke; b. Optionally, coating at least one orientation-controllable polyphase yoke with a protective coating; c. Forming a dissolution layer (the dissolution layer is disposed on at least one orientation-controllable polyphase yoke or any protective coating); d. Forming a shell containing pores; e. Etching the dissolution layer to form a cavity of the hollow yoke-shell particle; f. Adding a thermoresponsive polymer capable of passing through pores to be dispersed within the cavity of the hollow yoke-shell particle; g. Curing the shell to form a non-porous shell; and h. Optionally, forming one or more shells to form the hollow yoke-shell particles of Embodiment 21, which is a method for preparing the hollow yoke-shell particles described in Embodiment 21.

[0303] Embodiment 28. Hollow yoke-shell particles comprising (a) at least one orientation-controllable polyphase yoke and (b) at least one shell layer.

[0304] Embodiment 29. The hollow yoke-shell particles described in Embodiment 26, wherein when at least one orientation-controllable polyphase yoke is exposed to a magnetic field, it can rotate about its own axis.

[0305] Embodiment 30. The hollow yoke-shell particles described in Embodiment 26, wherein at least one orientation-controllable polyphase yoke is formed using a technique including DNA origami.

[0306] Embodiment 31. The hollow yoke-shell particles described in Embodiment 26, wherein the cavity of the hollow yoke-shell particles contains a thermoresponsive polymer.

[0307] Embodiment 32. The hollow yoke-shell particles according to Embodiment 29, wherein at least one orientation-controllable polyphase yoke can rotate about its own axis when exposed to a magnetic field and heat.

[0308] Embodiment 33. The hollow yoke-shell particles according to Embodiment 26, wherein at least one orientation-controllable polyphase yoke is coated with a protective coating.

[0309] Embodiment 34. The hollow yoke-shell particles according to Embodiment 26, wherein the protective coating is selected from the group consisting of a polymer material, an inorganic oxide, a carbon material, and mixtures thereof.

[0310] Embodiment 35. The hollow yoke-shell particles according to Embodiment 26, wherein at least one shell layer contains silica.

[0311] Embodiment 36. The hollow yoke-shell particles according to Embodiment 26, wherein at least one orientation-controllable polyphase yoke is a polyphase particle having a surface containing (a) at least one first colorant on a first side of the surface, (b) at least one second colorant on a second side of the surface, and (c) at least one stimulus-responsive element on any one surface of the surface, and the first side of the surface and the second side of the surface are on opposite sides of each other.

[0312] Embodiment 37. The hollow yoke-shell particles according to Embodiment 34, wherein the colorant is selected from a dye, a pigment, or a combination thereof.

[0313] Embodiment 38. The hollow yoke-shell particles according to Embodiment 34, wherein at least one stimulus-responsive element is selected from a polymer, an organic nanoparticle, an organic microparticle, an inorganic nanoparticle, an inorganic microparticle, a metal, a metal salt, a lipid, DNA, or a combination thereof.

[0314] Embodiment 39. The hollow yoke-shell particles according to Embodiment 34, wherein at least one stimulus-responsive element responds to a magnetic field.

[0315] Embodiment 40. The hollow yoke-shell particles according to any one of Embodiments 26 to 37, which are used in an ink composition.

[0316] In an embodiment, the present disclosure relates to the following embodiments.

[0317] Embodiment 1001. a) At least one orientation-controllable polyphasic yoke comprising at least two colorants and at least one stimulus-responsive element; and b) at least one shell layer encapsulating the orientation-controllable polyphasic yoke (at least a part of the shell contains a material transparent to at least a part of the visible electromagnetic spectrum from about 380 nm to about 800 nm), wherein the orientation-controllable polyphasic yoke is configured to move within the shell in response to an applied force or external energy, a stimulus-responsive hollow yoke-shell particle (HYSP).

[0318] Embodiment 1002. The stimulus-responsive HYSP according to Embodiment 1001, wherein the applied force or external energy is a magnetic field.

[0319] The stimulus-responsive HYSP according to Embodiment 1001 or 1002, wherein the HYSP has a dimension of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 50 μm.

[0320] Embodiment 1004. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the HYSP includes at least one orientation-controllable polyphase yoke and a space from at least one shell layer of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, or about or at least about 20 μm.

[0321] Embodiment 1005. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the HYSP includes one or more shapes, geometric shapes, and / or morphologies among spherical, elliptical, spindle-shaped, rod-shaped, cubic, star-shaped, cylindrical, plate-shaped, tetrahedral, and dodecahedral.

[0322] Embodiment 1006. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphase yoke comprises a material including one or more of metals, metal oxides, silica, organic polymers, inorganic polymers, biopolymers, synthetic polymers, and combinations thereof.

[0323] Embodiment 1007. The stimulus-responsive HYSP according to Embodiment 1006, wherein one or more synthetic polymers include plastics, thermoresponsive polymers, latexes, hydrocarbons, crude oil derivatives, and / or petroleum derivatives.

[0324] Embodiment 1008. The stimulus-responsive HYSP according to Embodiment 1007, wherein one or more thermoresponsive polymers include poloxamers, styrene-butadiene block copolymers, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and / or combinations thereof.

[0325] Embodiment 1009. The stimulus-responsive HYSP according to Embodiment 1006, wherein one or more synthetic polymers include poly(tert-butyl acrylate)-poly(3-(triethoxysilyl)propyl methacrylate) (PtBA-PTPM), polystyrene latex polymer, carboxylated latex polymer, aminated latex polymer, colored polystyrene polymer (dye injection and / or pigment injection), colored polystyrene-based carboxylated latex polymer (dye injection and / or pigment injection), fluorescent polystyrene-based polymer, fluorescent polystyrene-based carboxylated latex polymer, fluorescent aminated polystyrene-based polymer, surfactant-free polystyrene, carboxylated surfactant-free polymer, polymethyl methacrylate (PMMA) latex polymer, and / or divinylbenzene (DVB)-crosslinked polystyrene latex polymer.

[0326] Embodiment 1010. The stimulus-responsive HYSP according to Embodiment 1006, wherein one or more biological polymers include nucleic acids (DNA, RNA), amino acids (peptides, proteins), polysaccharides, and / or lipids.

[0327] Embodiment 1011. The stimulus-responsive HYSP according to Embodiment 1006, wherein one or more biological polymers include chain nucleic acids arranged in one or more patterns and / or morphologies, and one or more chain nucleic acids are arranged on and / or inside at least one polymorphic yoke.

[0328] Embodiment 1012. A stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphase yoke includes dimensions of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 50 μm.

[0329] Embodiment 1013. A stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphase yoke includes dimensions smaller than those of the HYSP.

[0330] Embodiment 1014. At least one orientation-controllable polyphase yoke is smaller in dimension than the HYSP by about or at least about 1 nm, about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 15 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 30 μm, or about or at least about 40 μm, and includes the stimulus-responsive HYSP described in Embodiment 1013.

[0331] Embodiment 1015. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphasic yoke includes one or more structures, shapes, geometric shapes, and / or morphologies among spherical, elliptical, spindle-shaped, rod-shaped, cubic, star-shaped, cylindrical, plate-shaped, regular shape, irregular shape, triangular, trapezoidal, octagonal, tetrahedral, and dodecahedral.

[0332] Embodiment 1016. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphasic yoke includes Janus particles.

[0333] Embodiment 1017. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphasic yoke includes one or more magnetic particles contained within polymer beads.

[0334] Embodiment 1018. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphasic yoke is coated with a protective coating.

[0335] Embodiment 1019. The stimulus-responsive HYSP according to Embodiment 1018, wherein the protective coating includes chemical functionalization, lubricant, surface treatment, coating, abrasive, and / or combinations thereof.

[0336] Embodiment 1020. The stimulus-responsive HYSP according to Embodiment 1018, wherein the protective coating includes a polymer material, inorganic oxide, carbon material, polytetrafluoroethylene (PTFE), hydroxylated self-assembled monolayer, vitreous enamel, ceria (cerium oxide), ceramic, anodized metal, silica, and / or combinations thereof.

[0337] Embodiment 1021. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphasic yoke includes a shape, geometric shape, and / or morphology that conforms to the congruent shape, geometric shape, or morphology of the inner surface of at least one shell layer.

[0338] Embodiment 1022. The shape, geometry, or morphology of at least one orientation-controllable polyphase yoke includes pins that fit into the congruent grooves of at least one shell layer, the stimulus-responsive HYSP according to Embodiment 1021.

[0339] Embodiment 1023. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the yoke is floating in a fluid medium, a semi-solid medium, a non-Newtonian fluid or medium, and / or a combination thereof.

[0340] Embodiment 1024. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphase yoke is configured to rotate about its own axis when exposed to a magnetic field.

[0341] Embodiment 1025. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphase yoke is configured to move freely in response to a magnetic field while floating in at least one shell layer.

[0342] Embodiment 1026. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one orientation-controllable polyphase yoke includes solid nanoparticles.

[0343] Embodiment 1027. The stimulus-responsive HYSP according to any one of Embodiments 1001 to 1025, wherein at least one orientation-controllable polyphase yoke includes a fluid, a ferrofluid, a semi-solid, and / or a non-Newtonian fluid.

[0344] Embodiment 1028. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one stimulus-responsive element includes a magnetic material.

[0345] Embodiment 1029. The stimulus-responsive HYSP according to Embodiment 1028, wherein the magnetic material is ferromagnetic, ferrimagnetic, antiferromagnetic, diamagnetic, paramagnetic, superparamagnetic, and / or antiferromagnetic.

[0346] Embodiment 1030. The magnetic material is one or more of a tetracyanoethylene (TCNE) salt, [Fe(C5Me5)2]+[TCNE]·-, Li[TCNE], [MnIITPP][TCNE]· (TPP = tetraphenylporphyrin), [FeII(TCNE)(NCMe)2][FeIIICl4], MnII(TCNE)I(OH2), MnII(TCNE)[C4(CN)8]1 / 2, Fe(TCNE)[C4(CN)8]1 / 2, MnII(TCNE)3 / 2(I3)1 / 2, VII[TCNE]x (x≒2), C7H5ClN3Se4, a magnetic organic polymer, and / or a polymer-bonded magnet, and is an organic, carbon-based, and / or biomolecular system, the stimulus-responsive HYSP according to Embodiment 1028 or 1029.

[0347] Embodiment 1031. The magnetic material is iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), manganese (Mn), chromium (Cr), samarium (Sm), their alloys or oxides; alloys, intermetallic compounds, and / or oxides of Fe, Co, Ni, Zn, Mn, Sm; oxides of iron, Fe2O3, FeO, and / or Fe3O4; Co, Ni, Zn, and / or Mn:FexOy, and / or ferrite materials and / or doped materials of magnetite, the stimulus-responsive HYSP according to Embodiment 1028 or 1029.

[0348] Embodiment 1032. The magnetic material includes magnetic particles and / or beads, the stimulus-responsive HYSP according to any one of Embodiments 1028 to 1031.

[0349] Embodiment 1033. The magnetic particles and / or beads include dimensions of about or at least about 5 nm, about or at least about 10 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 5 μm, about or at least about 10 μm, about or at least about 50 μm, or include dimensions in the range of about or at least about 5 nm to about or at least about 50 nm, about or at least about 5 nm to about or at least about 100 nm, about or at least about 5 nm to about or at least about 500 nm, about or at least about 5 nm to about or at least about 1,000 nm, about or at least about 5 nm to about or at least about 2,000 nm, about or at least about 5 nm to about or at least about 5,000 nm, about or at least about 10 nm to about or at least about 5,000 nm, about or at least about 100 nm to about or at least about 5,000 nm, about or at least about 1,000 nm to about or at least about 5,000 nm, the stimulus-responsive HYSP according to Embodiment 1032.

[0350] Embodiment 1034. The magnetic material is configured to generate a magnetic field of about or at least about 200 gauss, about or at least about 500 gauss, about or at least about 800 gauss, about or at least about 1,000 gauss, about or at least about 2,500 gauss, about or at least about 12,500 gauss, about or at least about 15,000 gauss, about or at least about 20,000 gauss, or about or at least about 25,000 gauss, or a magnetic field having a range of about or at least about 200 gauss to about or at least about 25,000 gauss, the stimulus-responsive HYSP according to any one of Embodiments 1028 to 1033.

[0351] Embodiment 1035. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one stimulus-responsive element includes a magnetic material configured to be magnetized and / or generate a magnetic field.

[0352] Embodiment 1036. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the HYSP comprises two colorants, three colorants, four colorants, five colorants, six colorants, seven colorants, a colorant, a colorant, or ten or more colorants.

[0353] Embodiment 1037. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least two colorants include colors within the visible electromagnetic spectrum including attenuation, absorption, emission, reflection, scattering, and / or interference at wavelengths of about or at least about 350 nm to about or at least about 800 nm.

[0354] Embodiment 1038. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the color includes one or more of white, black, red, orange, yellow, green, blue, indigo, violet, and variations in hue, shade, and intensity therebetween.

[0355] Embodiment 1039. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least two colorants include dyes, pigments, stains, phosphors, metal salts, and / or chromophores.

[0356] Embodiment 1040. The stimulus-responsive HYSP according to Embodiment 1039, wherein at least two colorants include one or more dyes.

[0357] Embodiment 1041. The stimulus-responsive HYSP according to Embodiment 1040, wherein the dye is an organic dye or an inorganic dye.

[0358] Embodiment 1042. The stimulus-responsive HYSP according to Embodiment 1040, wherein the dye includes one or more of rhodamine B, congo red, crystal violet, methylene blue, acridine orange, nile red, malachite green, eosin Y, cresol red, fluorescein, and indigo.

[0359] Embodiment 1043. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein two or more colorants include a pigment.

[0360] Embodiment 1044. The stimulus-responsive HYSP according to Embodiment 1043, wherein the pigment includes a water-soluble pigment.

[0361] Embodiment 1045. The stimulus-responsive HYSP according to Embodiment 1044, wherein the water-soluble pigment is one or more of anthocyanin, anthraquinone, carotenoid, violacein, melanin, pioscyanin, prodigiosin, aspergillin, benzoquinone, anthraquinone, and derivatives thereof.

[0362] Embodiment 1046. The stimulus-responsive HYSP according to Embodiment 1043, wherein the pigment includes one or more of titanium white (PW6), zinc white (PW4), carbon black (PBk7), mars black (PBk11), iron oxide red (PR101), cadmium red (PR108), alizarin crimson (PR83), cadmium orange (PO20), cadmium yellow (PY35), lemon yellow (PY3), chrome green oxide (PG17), phthalocyanine green (PG7), ultramarine blue (PB29), cobalt blue (PB28), cerulean blue (PB35), prussian blue (PB27), burnt sienna (PBr7), raw umber (PBr7), rose sienna (PBr7), and yellow ocher (PY43).

[0363] Embodiment 1047. The stimulus-responsive HYSP according to Embodiment 1043, wherein the pigment is an organic pigment.

[0364] Embodiment 1048. The stimulus-responsive HYSP according to Embodiment 1043, wherein the pigment is an inorganic pigment.

[0365] Embodiment 1049. The stimulus-responsive HYSP according to Embodiment 1047 or 1048, wherein the organic pigment or inorganic pigment includes a white pigment.

[0366] Embodiment 1050. The stimulatory-responsive HYSP according to Embodiment 1049, wherein the white pigment is one or more of lead white (2PbCO3·Pb(OH)2), kaolin, silica (SiO2), titanium dioxide (TiO2 / rutile and anatase), zinc oxide (ZnO), zinc sulfide (ZnS), and lithopone (ZnS+BaSO4).

[0367] Embodiment 1051. The stimulatory-responsive HYSP according to Embodiment 1047 or 1048, wherein the organic pigment or inorganic pigment contains a black pigment.

[0368] Embodiment 1052. The stimulatory-responsive HYSP according to Embodiment 1051, wherein the black pigment is one or more of coal (charcoal), groutite (α-MnOOH), manganate (γ-MnOOH),hausmannite (Mn3O4), carbon black, iron oxide black (Fe3O4), and spinel black (CuCr2O4).

[0369] Embodiment 1053. The stimulatory-responsive HYSP according to Embodiment 1047 or 1048, wherein the organic pigment or inorganic pigment contains a colored pigment.

[0370] Embodiment 1054. The stimulatory-responsive HYSP according to Embodiment 1053, wherein the colored pigment contains a yellow pigment.

[0371] Embodiment 1055. The stimulatory-responsive HYSP according to Embodiment 1054, wherein the yellow pigment contains one or more of yellow ocher (α-FeOOH), gold pigment (As2S3), lead yellow earth (PbO), lead tin yellow (Pb2SnO4, PbSn2SiO7), Naples yellow (Pb(SbO3)2), zinc yellow (Zn2CrO4), Indian yellow (C19H16O10), iron oxide yellow (α-FeOOH), chromium titanium yellow ((Ti,Cr,Sb)O2), nickel titanium yellow ((Ti,Ni,Sb)O2), lead yellow (PbCrO4), cadmium yellow (CdS), and bismuth yellow (BiVO4).

[0372] Embodiment 1056. The stimulus-responsive HYSP according to Embodiment 1053, wherein the coloring pigment contains a red pigment.

[0373] Embodiment 1057. The red pigment is one or more of red ocher (α-Fe2O3), terra di Siena (α-Fe2O3), vermilion (HgS), red lead (Pb3O4), alizarin madder varnish, alizarin red (C14H8O4), iron oxide red (α-Fe2O3), molybdate red (Pb(Cr,S,Mo)O4), and cadmium red (Cd(S,Se)). The stimulus-responsive HYSP according to Embodiment 1056.

[0374] Embodiment 1058. The stimulus-responsive HYSP according to Embodiment 1053, wherein the coloring pigment contains a green pigment.

[0375] Embodiment 1059. The green pigment is one or more of green earth (Fe silicate), Schweinfurt green (C4H6As6Cu4O16), chromium oxide green (Cr2O3), chromium oxide hydrate green (CrOOH), and cobalt green (Co2TiO4). The stimulus-responsive HYSP according to Embodiment 1058.

[0376] Embodiment 1060. The stimulus-responsive HYSP according to Embodiment 1053, wherein the coloring pigment contains a blue pigment.

[0377] Embodiment 1061. The blue pigment is one or more of lazurite (lapis lazuli), Egyptian blue (CaCuSi4O10), azurite (2CuCO3·Cu(OH)2), malachite (CuCO3·Cu(OH)2), cobalt blue (CoAl2O4), cobalt blue (CoAl2O4), ultramarine blue: (Na6Al6Si6O24(NaSn)), and Prussian blue (K[FeIIIFeII(CN)6]·xH2O). The stimulus-responsive HYSP according to Embodiment 1060.

[0378] Embodiment 1062. The stimulus-responsive HYSP according to Embodiment 1053, wherein the coloring pigment contains a brown pigment.

[0379] Embodiment 1063. The stimulus-responsive HYSP according to Embodiment 1062, wherein the brown pigment contains one or more of burnt umber (Fe2O3·xMnO2), brown ocher (α-Fe2O3 + Mn oxide), and limonite (a mixture of various Fe oxides).

[0380] Embodiment 1064. The stimulus-responsive HYSP according to Embodiment 1043, wherein the pigment is one or more of oxide or oxyhydroxide pigments (TiO2, ZnO, α-Fe2O3, α-FeOOH, γ-Fe2O3, Fe3O4, Cr2O3, CrOOH, PbO, PB3O4, Mn3O4, -MnOOH, Sb2O3), composite oxide pigments (CoAl2O4, CuCr2O4, Co2TiO4, (Ti,Ni,Sb)O2, (Ti,Cr,Sb)O2), carbonate hydroxide pigments (2PbCO3·Pb(OH)2, 2CuCO3·Cu(OH)2, CuCO3·Cu(OH)2), sulfide / selenide pigments (ZnS, CdS, Cd(S,Se), CdSe, γ-Ce2S3, HgS, As2S3), chromate / molybdate pigments (PbCrO4, Pb(Cr,S)O4, Pb(Cr,S,Mo)O4, ZnCrO4, BaCrO4, SrCrO4), vanadate pigments (BiVO4, 4BiVO4·3Bi2MoO6), stannate pigments (Pb2SnO4, PbSn2SiO7, Co2SnO4, CoSnO3), phosphate pigments (Co3(PO4)2), antimonate pigments (Pb(SbO3)2), arsenate pigments (Cu(AsO3)2), ultramarine pigments (Na6Al6Si6O24(NaSn)), hexacyanoferrate / hexacyanoferrate pigments (K[FeIIIFeII(CN)6]·xH2O (x = 14 to 16)), oxonitride pigments (CaTaO2N, LaTaON2), elemental pigments (C, Al, Cu, Cu / Zn, Au), spinel pigments, and rutile metal pigments.

[0381] Embodiment 1065. The stimulus-responsive HYSP according to Embodiment 1048, wherein the inorganic pigment is one or more of transparent effect pigments, goniochromatic pigments, nacreous pigments, metallic pigments, interference pigments, metallic effect pigments, fluorescent pigments, luminescent pigments, phosphorescent pigments, magnetic pigments, and anticorrosive pigments.

[0382] Embodiment 1066. The stimulus-responsive HYSP according to Embodiment 1065, wherein the metallic pigment comprises one or more of metallic pigments of aluminum, bronze, and copper.

[0383] Embodiment 1067. The stimulus-responsive HYSP according to Embodiment 1065, wherein the pearlescent pigment comprises one or more of mica, titanium dioxide, and bismuth oxychloride.

[0384] Embodiment 1068. The stimulus-responsive HYSP according to Embodiment 1065, wherein the fluorescent pigment comprises one or more fluorescent dyes and pigments including fluorescent minerals.

[0385] Embodiment 1069. The stimulus-responsive HYSP according to Embodiment 1065, wherein the phosphorescent pigment comprises zinc sulfide and / or strontium aluminate.

[0386] Embodiment 1070. The stimulus-responsive HYSP according to Embodiment 1065, wherein the interference pigment comprises titanium dioxide-coated mica and / or aluminum oxide-coated mica.

[0387] Embodiment 1071. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein two or more colorants comprise anisotropic particles.

[0388] Embodiment 1072. The stimulus-responsive HYSP according to Embodiment 1071, wherein the anisotropic particles comprise nanoparticles of one or more metals, and optionally comprise one or more nanorods of gold (Au), silver (Au), and aluminum (Al).

[0389] Embodiment 1073. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein one or more colorants comprise a plasmonic material.

[0390] Embodiment 1074. The stimulus-responsive HYSP according to Embodiment 1073, wherein the plasmonic material comprises pigments, particles, foils, and / or films.

[0391] Embodiment 1075. The stimulus-responsive HYSP according to Embodiment 1074, wherein the film comprises a polymer film carrying noble metal nanoparticles.

[0392] Embodiment 1076. The stimulus-responsive HYSP according to Embodiment 1065, wherein the gonichromatic pigment comprises aluminum coated with magnesium fluoride embedded in chromium.

[0393] Embodiment 1077. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one shell layer comprises a single uniform thickness and / or various thicknesses.

[0394] Embodiment 1078. The stimulus-responsive HYSP according to Embodiment 1077, wherein at least one shell layer has a thickness of about or at least about 1 nm, about or at least about 5 nm, about or at least about 10 nm, about or at least about 15 nm, about or at least about 20 nm, about or at least about 25 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 200 nm, about or at least about 300 nm, about or at least about 400 nm, about or at least about 500 nm, about or at least about 600 nm, about or at least about 700 nm, about or at least about 800 nm, about or at least about 900 nm, about or at least about 1 μm, about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 10 μm, about or at least about 15 μm, about or at least about 20 μm, about or at least about 25 μm, about or at least about 30 μm, about or at least about 35 μm, about or at least about 40 μm.

[0395] Embodiment 1079. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one shell layer comprises at least an opaque portion.

[0396] Embodiment 1080. The opaque portion optionally optically absorbs, deflects, blocks, and / or scatters light within the visible electromagnetic wave range of approximately 380 nm to approximately 800 nm, of the stimulus-responsive HYSP described in Embodiment 1079.

[0397] Embodiment 1081. The opaque portion has a thickness of about or at least about 1 nm, about or at least about 5 nm, about or at least about 10 nm, about or at least about 25 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 250 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 2.5 μm, about or at least about 5 μm, or about or at least about 10 μm, of the stimulus-responsive HYSP described in Embodiment 1079 or 1080.

[0398] Embodiment 1082. At least one shell layer comprises a material including one or more of glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), nylon, thermoresponsive polymer, and combinations thereof, of the stimulus-responsive HYSP described in any one of the preceding embodiments.

[0399] Embodiment 1083. At least one shell layer is composed of one or more of polysaccharides, lipids, amino acids, DNA, RNA, plastic, thermoresponsive polymer, hydrocarbon, crude oil, or petroleum derivatives, and / or is disposed thereon, of the stimulus-responsive HYSP described in any one of the preceding embodiments.

[0400] Embodiment 1084. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one shell layer includes one or more depressions, grooves, and spaces disposed on an inner surface for fixing at least one orientation-controllable polyphase yoke.

[0401] Embodiment 1085. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein at least one shell layer includes one or more materials for reducing friction between the inner surface and at least one orientation-controllable polyphase yoke.

[0402] Embodiment 1086. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the HYSP is disposed on a surface and / or a substrate.

[0403] Embodiment 1087. The stimulus-responsive HYSP according to Embodiment 1086, wherein the surface and / or the substrate is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue or skin.

[0404] Embodiment 1088. The stimulus-responsive HYSP according to Embodiment 1086 or 1087, wherein the surface and / or the substrate is planar or non-planar.

[0405] Embodiment 1089. The stimulus-responsive HYSP according to any one of Embodiments 1086 to 1088, wherein the surface and / or the substrate includes at least a portion having a convex shape, a concave shape, or no distinct shape.

[0406] Embodiment 1090. The stimulus-responsive HYSP according to any one of Embodiments 1086 to 1089, wherein the surface and / or the substrate is on an inner surface of an object, an outer surface of the object, or both, and the object is a non-HYSP object.

[0407] Embodiment 1091. The stimulus-responsive HYSP according to any one of Embodiments 1086 to 1090, wherein the surface and / or the substrate includes depressions and / or recesses.

[0408] Embodiment 1092. The stimulus-responsive HYSP according to Embodiment 1091, wherein the depressions and / or recesses are arranged in an orderly manner.

[0409] Embodiment 1093. The stimulus-responsive HYSP according to Embodiment 1091 or 1092, wherein the HYSP is disposed in and / or on the depressions and / or recesses.

[0410] Embodiment 1094. The stimulus-responsive HYSP according to any one of Embodiments 1086 to 1093, wherein the surface and / or the substrate includes pillars, posts, and / or stoppers.

[0411] Embodiment 1095. The stimulus-responsive HYSP according to Embodiment 1094, wherein the HYSP is disposed in and / or on the pillars, posts, and / or stoppers.

[0412] Embodiment 1096. The stimulus-responsive HYSP according to any one of Embodiments 1086 to 1095, wherein the surface and / or the substrate includes one or more grooves.

[0413] Embodiment 1097. The stimulus-responsive HYSP according to Embodiment 1096, wherein the HYSP is disposed in and / or on the one or more grooves.

[0414] Embodiment 1098. The stimulus-responsive HYSP according to any one of Embodiments 1086 to 1097, wherein the surface and / or the substrate changes color in response to the presence of a magnetic field.

[0415] Embodiment 1099. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the HYSP is incorporated into the substrate, material, and / or surface of a fluid, suspension, ink, liquid film, and / or adhesive.

[0416] Embodiment 1100. The stimulus-responsive HYSP according to Embodiment 1099, wherein the substrate, material, and / or surface of the fluid, suspension, ink, liquid film, and / or adhesive is suitable for application to an object.

[0417] Embodiment 1101. The stimulus-responsive HYSP according to any one of Embodiments 1001 to 1098, wherein the HYSP is incorporated into a substrate, material, and / or surface of foil, film, thin plastic, and / or paper.

[0418] Embodiment 1102. The stimulus-responsive HYSP according to Embodiment 1101, wherein the substrate, material, and / or surface of foil, film, thin plastic, and / or paper is suitable for being attached to or embedded in an object.

[0419] Embodiment 1103. The stimulus-responsive HYSP according to any one of Embodiments 1001 to 1098, wherein the HYSP is incorporated into a substrate, material, and / or surface of fiber, thread, yarn, and / or twisted yarn.

[0420] Embodiment 1104. The stimulus-responsive HYSP according to Embodiment 1103, wherein the substrate, material, and / or surface of fiber, thread, yarn, and / or twisted yarn is suitable for being woven into clothing, fabric, and / or a waterproof sheet.

[0421] Embodiment 1105. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the HYSP is disposed between a first substrate and a second substrate.

[0422] Embodiment 1106. The stimulus-responsive HYSP according to Embodiment 1105, wherein at least one of the first substrate and the second substrate includes a material that is transparent to at least a part of the visible electromagnetic wave (EM) spectrum.

[0423] Embodiment 1107. The stimulus-responsive HYSP according to Embodiment 1106, wherein the material comprises glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), and / or nylon.

[0424] Embodiment 1108. The stimulus-responsive HYSP according to Embodiment 1106 or 1107, wherein the material comprises a thickness of about or at least about 50 nm, about or at least about 100 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 10 μm, about or at least about 100 μm, about or at least about 1 mm, about or at least about 5 mm, or about or at least about 10 mm.

[0425] Embodiment 1109. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the HYSP comprises at least a first surface having a shape complementary to the shape of the second surface of the HYSP.

[0426] Embodiment 1110. The stimulus-responsive HYSP according to any one of the preceding embodiments, wherein the HYSP is disposed on and / or embedded in a surface and / or substrate treated with one or more of a lubricant, an adhesive, a surface treatment agent, a coating agent, and / or an abrasive.

[0427] Embodiment 1111. (i) preparing at least one orientation-controllable polyphasic yoke (the at least one orientation-controllable polyphasic yoke includes at least two colorants and at least one stimulus-responsive element), (ii) forming a dissolution layer disposed on the at least one orientation-controllable polyphasic yoke, (iii) forming at least one shell layer encapsulating the orientation-controllable polyphasic yoke (the at least one shell layer includes pores), (iv) repositioning the dissolution layer through the pores of the at least one shell layer to form a cavity between the at least one orientation-controllable polyphasic yoke and the at least one shell layer, and (v) curing the at least one shell layer to form a non-porous shell (the orientation-controllable polyphasic yoke is configured to move within the shell in response to an applied force or external energy), a method for manufacturing hollow yoke-shell particles (HYSP) according to any one of Embodiments 1 to 1110.

[0428] Embodiment 1112. The method according to Embodiment 1111, wherein the applied force or external energy is a magnetic field.

[0429] Embodiment 1113. The method according to Embodiment 1111 or 1112, further comprising coating the at least one orientation-controllable polyphasic yoke before forming the dissolution layer.

[0430] Embodiment 1114. The method according to Embodiment 1113, wherein the coating includes one or more of a protective coating, chemical functionalization, a lubricant, a surface treatment, and / or an abrasive.

[0431] Embodiment 1115. The method according to any one of Embodiments 1111 to 1114, further comprising forming one or more additional shells encapsulating the at least one shell layer.

[0432] Embodiment 1116. The method according to any one of Embodiments 1111 to 1115, further comprising disposing one or more materials within the cavity formed by removal.

[0433] Embodiment 1117. The method according to any one of Embodiments 1111 to 1116, wherein one or more materials comprise a thermoresponsive polymer and / or a fluid medium.

[0434] Embodiment 1118. The method according to any one of Embodiments 1111 to 1117, wherein at least a part of the at least one shell layer comprises at least a part of a shell comprising a material transparent to at least a part of the visible electromagnetic spectrum from about 380 nm to about 800 nm.

[0435] Embodiment 1119. One or more of i) preparing at least one orientation-controllable polyphase yoke, ii) forming a dissolution layer, and iii) forming at least one shell layer is / are the assembly, adhesion, and / or fixation of two or more components; injection molding and / or micro-injection molding; self-assembly, adsorption, coacervation, and / or mixing; polymerization, extrusion, and / or manipulation of polymers; additive manufacturing, CNC machining (computer numerical control machining), urethane casting, microcontact printing, dip-pen lithography, beam-pen lithography, photolithography, electron beam lithography, and / or 3D printing. The method according to any one of Embodiments 1111 to 1118.

[0436] Embodiment 1120. The method according to any one of Embodiments 1111 to 1119, wherein forming at least one shell layer comprises performing one or more of synthesis of mesoporous materials, soft templating, calcination, and / or extraction.

[0437] Embodiment 1121. The method according to any one of Embodiments 1111 to 1120, wherein at least one shell layer comprising pores comprises mesoporous silica and / or a porous organic framework.

[0438] Embodiment 1122. The repositioning of the dissolution layer comprises removing, dissolving, and / or etching the dissolution layer. The method according to any one of Embodiments 1111 to 1121.

[0439] Embodiment 1123. The method according to any one of Embodiments 1111 to 1122, wherein forming a non-porous shell by curing at least one shell layer includes compressing a solid mass of the shell material by heat and / or pressure.

[0440] Embodiment 1124. The method according to any one of Embodiments 1111 to 1123, wherein preparing at least one orientation-controllable polyphase yoke includes forming the yoke by injecting a molten plastic, metal, and / or polymer-based material into a mold cavity.

[0441] Embodiment 1125. The method according to any one of Embodiments 1111 to 1124, wherein preparing at least one orientation-controllable polyphase yoke includes a DNA origami technique.

[0442] Embodiment 1126. The method according to Embodiment 1125, wherein the DNA origami technique includes self-assembly of at least two DNA-coated colorants and at least one DNA-coated stimulus-responsive element.

[0443] Embodiment 1127. The method according to any one of Embodiments 1111 to 1126, wherein at least one of i) preparing at least one orientation-controllable polyphase yoke; ii) forming a dissolution layer; and iii) forming at least one shell layer includes 3D printing.

[0444] Embodiment 1128. The method according to Embodiment 1127, wherein the 3D printing includes performing one or more of fused deposition modeling (FDM), fused filament fabrication (FFF), stereolithography (SLA), selective laser sintering (SLS), binder jetting (BJ), direct energy deposition (DED), digital light processing (DLP), liquid crystal display (LCD), polymer jetting (PolyJet), multi-jet fusion (MJF), direct metal laser sintering (DMLS), electron beam melting (EBM), laminated object manufacturing (LOM), continuous liquid interface production (CLIP), electron beam melting, and digital light processing (DLP).

[0445] Embodiment 1129. The method according to any one of Embodiments 1111 to 1128, wherein one or more of at least one orientable multiphase yolk, dissolution layer, and at least one eggshell layer include one or more of a thermoresponsive polymer, resin, metal, ceramic, glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), nylon, and combinations thereof.

[0446] Embodiment 1130. The method according to Embodiment 1129, wherein one or more thermoresponsive polymers and resins include one or more of poloxamer, styrene-butadiene block copolymer, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and combinations thereof.

[0447] The method according to any one of Embodiments 1111 to 1130, wherein preparing at least one orientation - controllable polyphase yoke includes forming Janus particles.

[0448] Embodiment 1132. The method according to Embodiment 1131, wherein the Janus particles include one or more of poly(tert - butyl acrylate) - poly(3 - (triethoxysilyl)propyl methacrylate) (PtBA - PTPM), polystyrene latex polymer, carboxylated latex polymer, aminated latex polymer, colored polystyrene polymer (dye injection and / or pigment injection), colored polystyrene - based carboxylated latex polymer (dye injection and / or pigment injection), fluorescent polystyrene - based polymer, fluorescent polystyrene - based carboxylated latex polymer, fluorescent aminated polystyrene - based polymer, surfactant - free polystyrene, carboxylated surfactant - free polymer, polymethyl methacrylate (PMMA) latex polymer, divinylbenzene (DVB) cross - linked polystyrene latex polymer, and combinations thereof.

[0449] The method according to any one of Embodiments 1111 to 1132, wherein preparing at least one orientation - controllable polyphase yoke includes binding at least two colorants and a stimulus - responsive element composed of a material responsive to a magnetic field.

[0450] The method according to any one of Embodiments 1111 to 1133, wherein forming at least one shell layer includes forming at least one shell layer using one or more materials transparent to at least a part of the visible electromagnetic (EM) spectrum.

[0451] Method according to embodiment 1134, wherein one or more materials comprise glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), and / or nylon.

[0452] Method according to any one of embodiments 1111 - 1135, further comprising incorporating HYSP into a substrate and / or material of a fluid, suspension, ink, liquid film, and / or adhesive.

[0453] Method according to embodiment 1136, wherein the substrate and / or material of the fluid, suspension, ink, liquid film, and / or adhesive is suitable for application to the surface of an object.

[0454] Method according to any one of embodiments 1111 - 1135, further comprising incorporating HYSP into a substrate and / or material of a foil, film, thin plastic, and / or paper.

[0455] Method according to embodiment 1138, wherein the substrate and / or material of the foil, film, thin plastic, and / or paper is suitable for being fixed to or embedded in an object.

[0456] Method according to any one of embodiments 1111 - 1135, further comprising incorporating HYSP into a substrate and / or material of a fiber, thread, yarn, and / or twine.

[0457] The method according to Embodiment 1140, wherein the base material, material, and / or surface of the fiber, thread, yarn, and / or twisted yarn is suitable for being woven into clothing, fabric, and / or a waterproof sheet.

[0458] Embodiment 1142. a) Providing the HYSP according to any one of Embodiments 1001 to 1110; b) Incorporating the HYSP into the base material and / or material of a fluid, suspension, ink, liquid film, and / or adhesive; and c) Applying the base material and / or material of the fluid, suspension, ink, liquid film, and / or adhesive to an object and / or surface. A method of using hollow yoke-shell particles (HYSP) according to any one of Embodiments 1001 to 1100.

[0459] Embodiment 1143. The method according to Embodiment 1142, wherein the application further includes spraying, adhesion, embedding, writing, printing, and / or absorption.

[0460] Embodiment 1144. The method according to Embodiment 1142 or 1143, wherein the object is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue.

[0461] Embodiment 1145. The method according to any one of Embodiments 1142 to 1144, wherein the object and / or surface exhibits the property of changing optical properties in response to the application of a magnetic field.

[0462] Embodiment 1146. a) Providing the HYSP according to any one of Embodiments 1001 to 1110; b) Incorporating the HYSP into the base material and / or material of a foil, film, thin plastic, and / or paper; and c) Applying the base material and / or material of the foil, film, thin plastic, and / or paper to an object and / or surface. A method of using hollow yoke-shell particles (HYSP) according to any one of Embodiments 1001 to 1110.

[0463] Embodiment 1147. The method according to Embodiment 1146, further comprising spraying, adhesion, embedding, writing, printing, and / or absorption.

[0464] Embodiment 1148. The method according to Embodiment 1146 or 1147, wherein the object is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue.

[0465] Embodiment 1149. The method according to any one of Embodiments 1146 to 1148, wherein the object and / or the surface exhibits a property of changing optical properties in response to the application of a magnetic field.

[0466] Embodiment 1150. a) Providing a HYSP according to any one of Embodiments 1001 to 1110; b) Incorporating the HYSP into a substrate and / or material of a fiber, thread, yarn, and / or twisted yarn; and c) Applying the substrate and / or material of the fiber, thread, yarn, and / or twisted yarn to an object and / or a surface. A method of using hollow yoke-shell particles (HYSP) according to any one of Embodiments 1001 to 1110.

[0467] Embodiment 1151. The method according to Embodiment 1150, wherein the application further comprises weaving and / or embedding.

[0468] Embodiment 1152. The method according to Embodiment 1150 or 1151, wherein the object is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue.

[0469] Embodiment 1153. The method according to any one of Embodiments 1150 to 1152, wherein the object and / or the surface exhibits a property of changing optical properties in response to the application of a magnetic field.

[0470] Providing a formulation of HYSP according to any one of Embodiments 1 to 14 (wherein the formulation comprises i) a base material and / or material of a fluid, suspension, ink, liquid film, and / or adhesive; ii) a base material and / or material of a foil, film, thin plastic, and / or paper; or iii) a base material and / or material of a fiber, thread, yarn, and / or twisted yarn); and c) tagging an object and / or surface with the formulation; and d) reading the tagging, a method for authenticating a material.

[0471] Embodiment 1155. The method according to Embodiment 1154, wherein the tagging is configured to be read by a sensor and / or an optical imaging device.

[0472] Embodiment 1156. The method according to Embodiment 1154 or 1155, wherein the reading comprises applying a magnetic field to determine a change in the optical properties of the object and / or surface due to the presence of HYSP.

[0473] Without further elaboration, it is believed that one of ordinary skill in the art can, based on the above description, make the fullest use of the present disclosure. Therefore, the following specific embodiments are to be construed as merely illustrative and not limiting in any way to the remainder of the disclosure.

Examples

[0474] Example 1: Synthesis of Encapsulated Magnetic Dye Particles This example describes, among other things, an exemplary core-shell HYSP synthesis.

[0475] Construction of Origami DNA: A 450-nm diameter monolayer flat DNA origami sheet with addressable nodes for binding cargo can be fabricated as described below: Wintersinger et al., (Wintersinger, C.M., et al., “Multi-micron crisscross structures grown from DNA-origami slats,” Nat. Nanotechnol. Vol. 18, 2023: pp. 281-289, doi: 0.1038 / s41565-022-01283-1), which uses 6-helix bundles 450 nm in length as described below: Mathieu et al. (Mathieu, et al., “Six-Helix Bundles Designed from DNA,” Nano Letters, Vol. 5, No. 4, 2005: pp. 661-665, doi: 10.1021 / nl050084f).

[0476] Functionalization and Attachment of Colloidal Gold Nanoparticles (AuNP): AuNPs (BBI International) with diameters of approximately 5 nm, 10 nm, and 15 nm can be processed by the citrate reduction method described below: Dai, et al., “DNA Origami-Directed, Discrete Three-Dimensional Plasmonic Tetrahedron Nanoarchitectures with Tailored Optical Chirality,” ACS Applied Materials & Interfaces, Vol. 6, No. 8, 2014: pp. 5388-5392, doi:10.1021 / am501599f. The processed AuNPs can be functionalized with thiolated DNA 5'-thiolated DNA oligonucleotides and / or 3'-thiolated DNA oligonucleotides. The thiolated DNA oligonucleotides can be added to the AuNP solution in a 200-fold molar excess, and the salt concentration can be increased stepwise to 600 mM NaCl. Next, the AuNPs can be purified from the excess DNA oligonucleotides by centrifugal filtration (AMICON, 100,000 MW cut-off spin filter). The thiolated DNA strands can be synthesized to be complementary to the DNA strands used in previous DNA origami constructs.

[0477] Preparation of DNA-decorated AuNPs: To form an AuNP-thiolated DNA mixture, additional thiolated DNA can be added to the AuNP solution at a molar ratio of approximately 300:1. The mixture can be placed on an orbital shaker at room temperature (about 20 °C) overnight (about 12 hours). Phosphate buffer (PB) (0.1 M, pH 7.4) can be added to the mixture such that the final phosphate concentration is 10 mM (pH 7.4). After a 30-minute incubation period, 2 M NaCl can be added (within about 30 minutes) such that the final concentration in the mixture is 100 mM NaCl. The resulting solution can be placed on an orbital shaker at room temperature (about 20 °C) overnight (about 12 hours). Next, the mixture can be centrifuged at 12,000 rpm for 20 minutes at 4 °C for 15 nm AuNPs, and at 14,000 rpm for 30 minutes at 4 °C for 5 nm and 10 nm AuNPs. Thereafter, the supernatant can be removed and the precipitate can be redispersed in a 10 mM PB solution (pH 7.4). This process can be repeated, for example, three times and redispersed in a solution with a final phosphate concentration of 10 nM (0.1 M NaCl, 10 mM PB, pH 7.4).

[0478] Hybridization of DNA-decorated AuNPs with DNA origami: Purified DNA-coated AuNPs can be added to the DNA origami structure at a 5-fold AuNP excess to the binding sites on the origami, and the MgCl2 concentration can be adjusted to 11 mM. The mixture can be incubated overnight for the DNA-coated AuNPs to hybridize to complementary, hybridizable single-stranded DNA oligonucleotide nodes on the origami structure. Next, the origami DNA structure can be hybridized with thiolated DNA-coated AuNPs to form DNA origami AuNPs.

[0479] Next, DNA origami AuNPs can be characterized using various techniques (e.g., transmission electron microscopy (TEM), atomic force microscopy (AFM), and spectroscopy). Data obtained from these experiments can provide details regarding the homogeneity of the sample, the size and symmetry of the particles, and / or the degree of DNA hybridization.

[0480] Quantum dot (QD) oligo particles: Quantum dot single-stranded oligonucleotide reagents can be prepared as described below: Shen, J., et al., “Valence-Engineering of Quantum Dots Using Programmable DNA Scaffolds,” Angewandte Chemie International Edition, Vol. 56, No. 50: 2017: pp. 16077-16081. doi: 10.1002 / anie.201710309. Reagents that can be used include organic QDs (OceanNanotech, Inc.) that emit light at 520 nm and 560 nm, chloroform (purity 99.8%), 3-mercaptopropionic acid (MAP) (99%), tetrabutylammonium bromide (TBAB, 98.0%), trioctylphosphine oxide (TOPO, 90%), 2,5,8,11,14,17,20-heptaoxadocosan-22-thiol ((mPEG), molecular weight (MW) 356.5 g / mol, purity 95%), and 3-(azidotetra(ethyleneoxy))propionic acid succinimidyl ester, HPLC-purified oligonucleotides, and ultrapure water (resistivity > 18.0 MΩ·cm).

[0481] QD can be transferred from the organic phase to the aqueous phase and used to perform ligand exchange to replace a portion of mercaptopropionic acid (MPA) with 2,5,8,11,14,17,20 - heptaoxadocosan - 22 - thiol (mPEG). Subsequently, the prepared MPA / mPEG co - decorated QDs can be incubated with DNA for functionalization, and QD (20 μL in 500 μL chloroform) and trioctylphosphine oxide (TOPO) (40 μL, 1 g / 10 mL) can be added. The mixture can be held under an inert atmosphere for 30 minutes. Next, MPA (500 μl, 11 mM in aqueous NaOH solution (0.2 M)) can be added. The mixture is vortexed and then incubated for 30 seconds to recover the aqueous layer. This procedure can be repeated 3 - 5 times, and each aqueous layer can be collected and concentrated. The QDs protected by MPA can be washed 3 times with ultrapure water. The QDs can be diluted in 2 mL of ultrapure water and incubated with mPEG (20 μL) at room temperature (about 20 °C) for 4 days. The reacted QDs can be concentrated and washed 3 times using a centrifugal device (30 kDa cut - off). Finally, for further use, the buffer can be exchanged with ultrapure water using a NAP desalting column (GE Healthcare). The QD concentration can be determined by absorbance at 350 nm (the extinction coefficients of QDs emitting at 520 nm and 560 nm are 1,590,000 M−1cm−1 and 3,500,000 M−1cm−1, respectively).

[0482] Preparation of monovalent quantum dots (QDs): 100 μL of QD solution (100 nM in 1×PBS buffer) can be added to monovalent DNA (the molar ratio of QD to DNA was 1:1.2). After a 2 - hour incubation, the mixture can be analyzed by gel electrophoresis.

[0483] Yoke-shell structure: Materials: tetraethyl orthosilicate (TEOS, 95%), titanium tetraisopropoxide (TTIP, 95%), acetonitrile (99.5%), aqueous ammonia solution (25 wt%), aqueous methylamine solution (40 wt%), ethanol (99.5%), styrene (St, 99%), sodium p-styrenesulfonate (NaSS, 80%), potassium persulfate (KPS, 95.0%), 3-methacryloxypropyltrimethoxysilane (MPTMS, 95.0%). Using an inhibitor removal column, polyvinylpyrrolidone (PVP, MW = 360,000 g / mol), poly(allylamine hydrochloride) (PAH, MW = 15,000 g / mol), and the silane coupling agent 3-aminopropyltrimethoxysilane (APTES, 95%), the inhibitor of the St monomer can be removed.

[0484] Synthesis Procedure of Hollow Silica Shell: The yolk-shell structure containing the silica shell as an example is shown in Figure 8. For example, as shown in Step A of Figure 8, when the silica core concentration is 0.15 vol% (in deionized water) at 35 °C, a sub-micrometer-sized silica core can be prepared using the surface of the silica core modified with MPTMS (2 mM). A suspension of the surface-modified core, styrene (St, 50 mM), and an aqueous solution of NaSS can be added (e.g., Step A→B in Figure 8). After stirring at 65 °C for 30 minutes, an aqueous solution of potassium persulfate (KPS) can be added to the suspension as an initiator. The formation of the PSt shell was carried out at [KPS] = 2 mM, [NaSS] = 0.25 mM, and a silica concentration of 0.15 vol%. To increase the PSt shell thickness, the polymerization of styrene (St) can be carried out one more time at a concentration of 100 mM or 200 mM using the KPS initiator (total concentration 2 mM). The second PSt shell formation can be carried out at a core / shell particle concentration of 0.05 vol%. In the second step (e.g., as shown in Step B→C of Figure 8), the doubly PSt-coated silica particles can be coated with silica. A suspension of the PSt-coated particles can be added to a solution containing PAH and NaCl. The concentrations of the doubly PSt-coated particles, PAH, and NaCl in the mixture were 0.15 vol%, 0.71 kg / m3, and 36 mol / m3, respectively. After two centrifugation steps to remove unadsorbed PAH and NaCl, the particles can be redispersed in an ethanol solution (40 mL) containing 0.20 g of polyvinylpyrrolidone (PVP). Two more centrifugation steps can be performed to remove excess PVP, and the particles were redispersed in 9.59 mL of ethanol. Next, 10.6 mL of ammonia solution can be added together with the silica precursor TEOS (1 mL) and APTES (37 μL). For example, as shown in Step B→C of Figure 8, the resulting mixed silica precursor can be used to form a low-density silica shell suitable for slight etching of the silica. The silica-coated PSt particles can be dried at 50 °C and then heat-treated in air in an oven at 500 °C for 4 hours (Figure 8, Step C→D).The particles obtained by heat treatment can be immersed in 30 mL of aqueous ammonia (15 - 20 mM, approximately pH 11) to slightly etch the silica component of the particles (Figure 8, Step D→E). This step can separate the core from the shell, resulting in, for example, a hollow silica shell as described below: Watanabe, et al., “Polyethylenimine-assisted synthesis of hollow silica spheres without shape deformation,” Mater. Chem. Phys. Vol. 262, No. 124267, 2021.

[0485] Yolk / shell particles incorporating a titania core: Yolk / shell particles can also be prepared using a titania core (titanium oxide core) in a similar manner as described above for incorporating a silica core. Sub-micrometer-sized titanium oxide cores can be prepared and surface-modified using MPTMS at 35 °C. After reacting for 1 hour with stirring, styrene monomer (St, 50 mM) and an aqueous solution of NaSS can be added to the suspension, and the mixture can be stirred for 1 hour. An aqueous solution of KPS can be added as an initiator to the suspension at 65 °C. Polymerization can be carried out at [MPTMS] = 2 mM, [KPS] = 2 mM, [NaSS] = 0.25 mM, and a titanium oxide concentration of 0.065 vol%.

[0486] Synthesis of Iron Oxide Core and Silica Shell Particles: Materials: Fe3O4 nanoparticles (NP) protected by oleylamine (OMA) and oleic acid (OA), hydrogen tetrachloroaurate (HAuCl4·H2O, 99.99%), sodium borohydride (NaBH4, 98%), cetyltrimethylammonium bromide (CTAB, 99%), silver nitrate (AgNO3), ascorbic acid (AA, 99.7%), tetraethyl orthosilicate (TEOS, 98%), 3-aminopropyltrimethoxysilane (APTMS, 95%), rhodamine B isothiocyanate (RITC), polyethyleneimine (PEI, branched, Mw 25000), and doxorubicin hydrochloride (DOX), N-hydroxysuccinimide (NHS), lactobionic acid (LA), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide HCl (EDC). Before the experiment, glassware was washed with aqua regia (volume ratio HCl / HNO3 = 3:1) and rinsed thoroughly with ultrapure water (resistivity 18.0 MΩ·cm).

[0487] First, by preparing an RITC / APTMS / ethanol solution, Fe3O4-SiO2 core-shell NPs:RITC can be incorporated into the silica coating on the surface of Fe3O4 NPs. RITC (10 mg) can be covalently bonded to APTMS (44 mL) in ethanol (0.75 mL) in the dark for 2 days. The prepared RITC-APTMS stock solution can be stored at 48 °C. Fe3O4 NPs (400 mL of 10 mg / mL) in chloroform can be poured into a CTAB solution (8 mL of 0.2 M), and the solution can be mixed by stirring vigorously for 30 minutes. Next, the resulting solution can be heated to 60 °C for about 30 minutes to evaporate the chloroform, and the resulting turbid brown solution can be adjusted to a clear black Fe3O4 / CTAB solution. The CTAB-stabilized Fe3O4 NPs can be diluted with 20 mL of ultrapure water and then mixed with 5 mL of the RITC / APTMS solution. The pH of the mixture can be adjusted to pH 8 with 0.1 M NaOH. Fe3O4-SiO2 core-shell NPs with different shell thicknesses (18 nm and 35 nm, respectively) can be synthesized using 20% TEOS in ethanol (250 mL or 400 mL, respectively) injected at 30-minute intervals while gently stirring the reaction mixture for 24 hours. The Fe3O4-SiO2 core-shell NPs can be obtained from the reaction mixture, centrifuged, repeatedly washed with ethanol to remove excess precursors and CTAB molecules, and then dispersed in ethanol (8 mL).

[0488] This process can result in, for example, a metal-based core with a silica-based shell as described below: Zhang, L., et al., “General Route to Multifunctional Uniform Yolk / Mesoporous Silica Shell Nanocapsules: A Platform for Simultaneous Cancer-Targeted Imaging and Magnetically Guided Drug Delivery,” Chemistry-A European Journal, Vol. 18, No. 39, 2012: pp. 12512-12521. doi:10.1002 / chem.201200030.

[0489] Synthesis of PEI-coated SiO2 NPs: To control the hydrolysis and condensation of tetraethyl orthosilicate (TEOS) (the hydrolysis and condensation reaction of TEOS can be catalyzed by ammonia), the synthesis using an alcohol / water mixture can be carried out according to the Stcber method. To prepare SiO2 NPs, TEOS (2.3 mL) can be added to a mixed solution of ethanol (60 mL), ammonium hydroxide solution (3.0 mL), and water (1.0 mL). To synthesize SiO2 NPs, the sol-gel reaction can be carried out at 50 °C for 6 hours. The obtained SiO2 NPs can be collected and dispersed in ethanol. Next, SiO2 NPs (0.5 mg) can be mixed with polyethyleneimine (PEI) (1 mL, 10 mg / mL), incubated for 1 hour, and the resulting PEI-coated SiO2 NPs can be collected by centrifugation. The PEI-coated SiO2 NPs can be dispersed in water and etched at 50 °C for 90 minutes, and the resulting particles can be evaluated by TEM and / or spectroscopy to evaluate the homogeneity, size, symmetry, coating, etc. of the particles.

[0490] Example 2: DNA-functionalized magnetic particles For example, as described in Meyer et al., “Programmable Assembly of Iron Oxide Nanoparticles Using DNA Origami”, Nano Lett. Vol. 20, 2020: pp. 2799 - 2805, and as shown in, for example, FIG. 9, DNA-functionalized iron oxide nanoparticles can be prepared.

[0491] 10 mL of 10 mg / mL azide-coated magnetic particles (about 500 nm in diameter) can be incubated with a single-stranded DNA oligonucleotide modified with a dibenzylcyclooctyne (DBCO) group at one end. The magnetic particles can be mixed with DBCO-modified DNA at a surface area ratio of 1 DNA / nm 2 and incubated overnight at room temperature. The salt concentration of the reaction mixture can be increased stepwise by titrating with 5 M NaCl, increasing the total concentration by 100 mM every hour until a final concentration of 700 mM is reached, and the mixture can be left at room temperature overnight (12 hours at about 20 °C) for DNA functionalization. Next, the DNA-modified magnetic particles can be purified from excess DNA using three rounds of ultracentrifugation (18,200 xg, 1 hour) and resuspension in 1xTE (Tris-EDTA) buffer.

[0492] Example 3: Synthesis of DNA origami assembly using AuNP and AgNP as colorants. DNA-functionalized silica-coated silver nanoparticles (AgNP): For example, as described below, oligo-functionalized silica-coated Ag nanoparticles (50 nm in diameter) can be prepared: Liu et al., “Gram Scale Synthesis and Biofunctionalization of Silica-coated Silver Nanoparticles for Fast Colorimetric DNA Detection”, Anal. Chem. Vol. 77, 2005: pp. 2595 - 2600, DOI: 10.1021 / ac0482864 (entirely incorporated herein by reference).

[0493] Materials. AgNO3 (99.995%), sodium citrate dihydrate (99+%), tetraethyl orthosilicate (TEOS, 99%), 11-triethoxysilylundecanal (>99%), 5-(and-6)-((N-(5-aminopentyl)amino)carbonyl)tetramethylrhodamine (A-1318), sodium cyanoborohydride (95%), dithiothreitol (99.9%), and 30 wt% ammonia.

[0494] Synthesis of Ag-SiO2 NPs: While vigorously stirring, Ag NPs can be prepared by dropping a 38.8 mM aqueous sodium citrate solution (10 mL) into a boiling aqueous solution (490 mL) containing AgNO3 (90 mg) within 2 minutes. After boiling for 1 hour, the heat source can be removed, and the silver colloid reaction mixture can be cooled to room temperature (about 20 °C). The silver colloid can be centrifuged at 500 rpm for 1 hour to remove larger NPs, and the remaining silver NPs can be suspended in the solution and can have an average size of about 50 nm. The silver colloid can be evenly transferred to 10 500 mL conical glass flasks, each containing 200 mL of ethanol, and the pH can be adjusted to about 10 by adding 6.25 mL of about 30 wt% ammonia. Subsequently, a 10 mM TEOS ethanol solution (15 mL) can be added to each 500 mL flask at 30-minute intervals within 8 hours while shaking vigorously, and the resulting solution can be reacted at a constant temperature of 30 °C for 24 hours. Ag-SiO2 NPs can be collected by centrifuging at 3500 rpm for 30 minutes and can be washed, for example, 3 times with ethanol. For further characterization and functionalization, a sample (about 100 mg) of purified Ag-SiO2 NPs with a silica thickness of about 40 nm can be redispersed in deionized water (500 mL). Similarly, by silica coating 10 batches of silver colloids prepared using the above synthesis procedure, a sample of about 1000 mg of Ag-SiO2 NPs can be produced.

[0495] Aldehyde-functionalized Ag-SiO2 NPs: Approximately 6.6x10 12An Ag-SiO2 solution (100 mL) containing 12 of the particles can be mixed with 10 mM acetic acid buffer (pH 4.7, 10 mL) and 200 mL of ethanol, and subsequently, 10 mL of 11-triethoxysilylundecanal can be added dropwise for aldehyde functionalization. After shaking at room temperature (about 20 °C) for 2 hours, the reaction mixture can be heated at 50 °C for 1 hour and then cooled to room temperature (about 20 °C). Thereafter, the mixture can be washed thoroughly 4 times with 20 mL of ethanol, and subsequently, for further bioconjugation, the mixture can be dispersed in 4 mL of deionized water (containing about 6.6x10

[0496] Oligonucleotide-modified Ag-SiO 2 NP: An aliquot of 2 mL of an aqueous solution containing about 3.3x10 12 of aldehyde-modified Ag-SiO2 NPs can be mixed with an aqueous solution (1 mL) containing 3’ or 5’ amine-modified single-stranded DNA (300 nmol), 50 mM boric acid buffer (pH 9.2, 7 mL), and 5 mM sodium cyanoborohydride (2 mL). The reaction mixture can be incubated by shaking at room temperature (about 20 °C) for 2 hours. The supernatant can be removed by centrifuging at 4000 rpm for 10 minutes. The precipitate can be washed 3 times with PBS buffer at pH 7 (0.3 M NaCl, 10 mM phosphate) to obtain oligo-modified Ag-SiO2 NPs, which can be dispersed in 2 mL of PBS buffer for further use.

[0497] DNA-functionalized gold nanoparticles (AuNP): The synthesis of AuNP can be carried out, for example, as described below: Ma X, et al., “DNA-functionalized gold nanoparticles: Modification, characterization, and biomedical applications,” Front Chem. Vol. 10, No. 1095488, (2022) doi:10.3389 / fchem.2022.1095488. PMID: 36583149; PMCID: PMC9792995; Liu, et al., “Methods for DNA-functionalized gold nanoparticles, a key reagent of bioanalytical chemistry,” Analytical Methods, Vol. 9, No. 18, 2017: pp. 2633-43; Pal, et al., “DNA-Functionalized Gold Nanorods for Perioperative Optical Imaging and Photothermal Therapy of Triple-Negative Breast Cancer,” ACS Applied Nano Materials, Vol. 5, No. 7, 2022: 9159-69, DOI: 10.1021 / acsanm.2c01502; Liu, et al., Interface-Driven Hybrid Materials Based on DNA-Functionalized Gold Nanoparticles,” Matter, Vol. 1, 2019: pp. 825-57; Moros M, et al., “DNA-Coated Gold Nanoparticles for the Detection of mRNA in Live Hydra Vulgaris Animals,” ACS Appl Mater Interfaces, Vol. 11, No. 15, 2019: pp. 13905-13911. doi:10.1021 / acsami.8b17846. Epub 2018 Dec 11. PMID: 30525369; and Dai, et al.“DNA Origami-Directed, Discrete Three-Dimensional Plasmonic Tetrahedron Nanoarchitectures with Tailored Optical Chirality,” ACS Applied Materials & Interfaces, Vol. 6, No. 8, 2014: pp. 5388-5392, doi:10.1021 / am501599f (the entire content of which is incorporated herein by reference in its entirety).

[0498] 13.9 nm ± 1.4 nm AuNPs can be suspended in a solution of tetrachloroaurate (1 mM, 100 mL) and heated with stirring (700 rpm) until boiling. Sodium citrate (2% wt, 5 mL) can be added to the AuNP solution to initiate a color change while stirring (700 rpm) for 15 minutes. The reaction can be cooled to room temperature (about 20 °C), and a solution of bis-sulfonatophenylphosphine (BSPP, 42 mg in 2 mL of ultrapure water) can be added and stirred overnight to ensure successful ligand substitution. The resulting BSPP-coated spherical AuNPs can be filtered through a 0.45 μm filter to remove larger aggregates. Further, the solution can be purified by two centrifugations (10,000 rpm, 20 minutes). Purification can be facilitated by gradually adding concentrated NaCl solution until a color change from red to blue, indicating particle precipitation, is observed. The resulting synthetic AuNPs can be dispersed in 3 mL of ultrapure water and stored at 4 °C.

[0499] Construction of DNA Origami-Coated Gold and Silver NPs: For example, as described below, functionalization of AuNPs with DNA origami can be carried out: Knappe, et al., “Functionalizing DNA origami to investigate and interact with biological systems”, Nature Reviews Materials, Volume 8, February 2023, 123-138, on world wide web at: doi.org / 10.1038 / s41578-022-00517-x; Yang et al., “Programmable site-specific functionalization of DNA origami with polynucleotide brushes,” Angew. Chem. Int. Ed. 10.1002 / anie.202107829, on world wide web at: doi.org / 10.1002 / anie.202107829; Shaw et al., “Purification of Functionalized DNA Origami Nanostructures”, ACS Nano, Vol. 9, No. 5, 2015: pp. 4968-4975, on world wide web at: doi.org / 10.1021 / nn507035g; and Zhan, et al., “Recent Advances in DNA Origami-Engineered Nanomaterials and Applications, Chemical Reviews 2023 123 (7), 3976-4050, DOI: 10.1021 / acs.chemrev.3c00028 (the entire contents of which are hereby incorporated by reference in their entirety).

[0500] Referring to FIGS. 10 and 11, a solution containing both 10-fold stoichiometric excesses of DNA-coated AgNPs and DNA-coated AuNPs can be mixed with a DNA origami magnetic particle structure (e.g., as synthesized in Example 2) and incubated overnight at room temperature. The magnetic beads can be magnetically separated, decanted, and redispersed in phosphate buffer while gently mixing, and the process can be repeated until the decanted solution is visually optically clear to remove unbound AuNPs and AgNPs.

[0501] Example 4: Synthesis of DNA origami assemblies using quantum dots (QDs) and titania (titanium dioxide) nanoparticles as colorants. For example, as described below, quantum dot (QD)-oligo complexes: QD-oligo complexes can be synthesized: Deng, et al., “Robust DNA-Functionalized Core / Shell Quantum Dots with Fluorescent Emission Spanning from UV-vis to Near-IR and Compatible with DNA-Directed Self-Assembly,” Journal of the American Chemical Society, Vol. 134, No, 42, 2012: pp. 17424-17427, DOI: 10.1021 / ja3081023; Banerjee, et al., “Quantum dots-DNA bioconjugates: synthesis to applications,” Interface Focus, Vol. 6, No. 20160064, 2016, on world wide web at: dx.doi.org / 10.1098 / rsfs.2016.0064; Chen, et al., “Nanoscale 3D spatial addressing and valence control of quantum dots using wireframe DNA origami,” Nat Comm. Vol. 13, No. 4935, 2022; and Shen, J., et al., “Valence-Engineering of Quantum Dots Using Programmable DNA Scaffolds,” Angewandte Chemie International Edition, Vol. 56, No. 50: 2017: pp. 16077-16081.doi:10.1002 / anie.201710309 (the entire content of which is incorporated herein as is).

[0502] Materials: Cadmium nitrate tetrahydrate (Cd(NO3)2·4H2O, 99.8%), Zinc nitrate tetrahydrate (Zn(NO3)2·4H2O, 99.8%), Zinc oxide (ZnO, 99.9%, powder <5 microns), Cadmium oxide (CdO, 99.99+%, powder), Tellurium (Te, powder, 200 mesh, ≥99%, powder), Selenium (Se, powder, <100 mesh, 99.99%), Sulfur (S, 99.998% powder), Paraffin liquid (CnH2n+2, n = 16 - 22), Oleic acid (OLA, CH3(CH2)7CH=CH(CH2)7COOH, 90%), 2-Ethylhexanoic acid (EHA, CH3(CH2)3CH(C2H5)COOH, 99+%), Thiourea (NH2CSNH2, ≥99.0%), Sodium borohydride (NaBH4, powder, ≥99%), 3-Mercaptopropionic acid (HSCH2CH2CO2H, ≥99%), Isopropyl alcohol (IPA, 99%), Hexane (≥95%), Methanol (≥99.5%), Rhodamine 6G (QY = 95% (in ethanol)), and Rhodamine 101 (λem = 589 nm, QY = 100% (in ethanol + 0.01 HCl)).

[0503] Buffer: 1xPBS: 150 mM NaCl, 0.1 mM EDTA, 20 mM Sodium phosphate, pH 4.0, 7.0, 10.0; 1xTAE / Mg2+: 40 mM Tris acetate, 2 mM EDTA, and 12.5 mM Magnesium acetate, pH 8.0; 1xTBE / Mg2+: 50 mM Tris, 100 mM Boric acid, 10 mM EDTA, pH 8.2.

[0504] Synthesis of 1.6 nm CdTe core quantum dots (QDs): For example, as described below, CdTe core QDs with a diameter of 1.6 nm can be synthesized: Deng, et al., “Aqueous Synthesis of Zinc Blende CdTe / CdS Magic-Core / Thick-Shell Tetrahedral-Shaped Nanocrystals with Emission Tunable to Near-Infrared,” Journal of the American Chemical Society, Vol. 132, 2010: pp. 5592-5593 (the entire content of which is incorporated herein by reference). A NaHTe solution (Te 1.0 mol / L, 10 μL) can be injected with a syringe into a N2-saturated Cd(NO3)2 solution (Cd, 0.005 mol / L, 50 mL) at room temperature (about 20 °C) in the presence of 3-mercaptopropionic acid (MPA, 37 μL) as a stabilizer. By adding 1 M NaOH, the pH can be adjusted to about 12.2. The molar ratio of Cd2+ / MPA / NaHTe in the mixture can be fixed at 1:1.7:0.04. Then, the solution can be incubated overnight at 4 °C, and CdTe clusters with a photoluminescence emission peak at 480 nm were formed overnight. The diameter of the obtained CdTe QDs can be about 1.6 nm. These QDs can be purified by adding isopropyl alcohol (IPA) (volume ratio of 1:1), then centrifuging for 15 minutes (15,000 rpm), and then redispersing the QDs in deionized water. In some cases, the unpurified crude CdTe QD solution (without centrifugation and resuspension) can also be used directly as a stock solution for the next shell growth step. Both pure QDs and unpurified QDs can be used as cores for synthesizing oligonucleotide-conjugated CdTe / CdS core / shell QDs.

[0505] Oligonucleotide-functionalized CdTe / CdS core / shell QDs: The precipitated 1.6 nm CdTe QDs (from 100 μL of the stock solution) can be resuspended in 100 μL of ultrapure water. For example, as described below, the concentration of the core CdTe QDs and the amount of additional shell precursors can be calculated to obtain a specific shell thickness: Yu, et al., “Experimental determination of the extinction coefficient of CdTe, CdSe, and CdS nanocrystals,” Chem. Mater. Vol. 15, 2003: pp. 2854-2860 (which are hereby incorporated by reference in their entirety). To synthesize CdTe / 4CdS core / shell QDs with a 1.6 nm CdTe core diameter (0.25 nM in 100 μL of DI water), 4.5 μL of Cd2+ stock solution (25 mM) and 9.0 μL of MPA stock solution (25 mM) can be mixed with the core in a 1.5 mL plastic tube, vortexed, and gently sonicated. Next, 50 μL of the complementary oligo stock solution (100 nM) can be added and gently vortexed. Molar ratio of QDs:oligonucleotide was approximately 1:200. The pH can be adjusted to about 12.2 by adding 1 M NaOH. The reaction mixture can be incubated at 90 °C for 40 min in a heating block and then cooled by immersing the tube in a water bath at room temperature (about 20 °C). The reacted solution can be filtered through a 0.5 mL centrifugal filter (MWCO 30 KDa), 250 μL of deionized water can be added to the filter, and the sample can be centrifuged for 3 min (7000 rpm). After the first wash, the addition of deionized (DI) water (350 μL) and centrifugation can be repeated several more times (e.g., 4 times). This ultrafiltration process can remove free DNA and unreacted precursors from the QDs. Buffer exchange can also be performed using the centrifugal filtration method, in which 350 μL of buffer can be added instead of DI water. The final sample may be highly fluorescent and stable in buffer or DI water.

[0506] Quantum Dot (QD) Synthesis #2: Reagents that can be used include organic QDs (Ocean Nanotech, Inc.) that emit light at 520 nm and 560 nm, as well as PEG-coated QDs, chloroform (purity 99.8%), 3-mercaptopropionic acid (99%), tetrabutylammonium bromide (TBAB, 98.0%), trioctylphosphine oxide (TOPO, 90%), 2,5,8,11,14,17,20-heptaoxadocosan-22-thiol (mPEG thiol, molecular weight (MW) 356.5 g / mol, purity 95%), and 3-(azidotetra(ethyleneoxy))propionic acid succinimidyl ester, HPLC-purified oligonucleotides, and ultrapure water (resistivity >18.0 MΩ·cm). Commercially available QDs can be transferred from the organic phase to the aqueous phase and ligand exchange can be carried out to replace part of the MPA with mPEG. Then, the prepared MPA / mPEG co-decorated QDs can be incubated with DNA for functionalization. Organic QDs (20 μL in chloroform), chloroform (500 μL), and TOPO (40 μL, 1 g / 10 mL) can be added. The mixture can be kept under an inert atmosphere and incubated for 30 minutes. Next, MPA (500 μl, 11 mM in aqueous NaOH solution (0.2 M)) can be added. The mixture can be vortexed and incubated for 30 seconds, and then the aqueous layer can be recovered. The vortex incubation with MPA / NaOH can be repeated, for example, 5 times, and each aqueous layer can be collected and concentrated. Next, the QDs protected by MPA can be washed 3 times with ultrapure water. Next, the QDs can be diluted in 2 mL of ultrapure water and then incubated with mPEG (20 μL) at room temperature (about 20 °C) for 4 days. A centrifugal filter (MWCO of 30 kDa) can be used to concentrate the reacted QDs and wash them 3 times. For further use, the buffer can be exchanged to ultrapure water by a NAP desalting column (GE Healthcare). The QD concentration can be determined by the absorbance at 350 nm (the extinction coefficients of QDs that emit light at 520 nm and 560 nm are 1,590,000 M -1 cm -1, 3,500,000 M -1 cm -1 is).

[0507] To obtain monovalent DNA-functionalized QDs, monovalent DNA can be added to 100 μL of a QD solution (100 nM in 1×PBS buffer) at a molar ratio of QD to DNA of approximately 1:1.2. The mixture can be incubated for 2 hours and then analyzed by gel electrophoresis to measure DNA functionalization.

[0508] Synthesis of DNA-functionalization on titania NPs: For example, titanium oxide (titania) particles with a diameter of about 200 nm to 400 nm can be prepared as described below: Wang et al., “Synthetic Strategies Toward DNA-Coated Colloids that Crystallize,” J. Am. Chem. Soc. Vol. 137, 2015: pp. 10760 - 10766, DOI: 10.1021 / jacs.5b06607; and Tanaka et al., “Synthesis of highly-monodisperse spherical titania particles with diameters in the submicron range,” Journal of Colloid and Interface Science, Vol. 334, 2009: pp. 188 - 194, doi: 10.1016 / j.jcis.2009.02.060 (the entire contents of which are hereby incorporated by reference in their entirety).

[0509] Materials: Methanol, acetonitrile, ammonia solution (10 wt%), and titanium isopropoxide (TTIP), dodecylamine (DDA).

[0510] Titania particles can be prepared by hydrolyzing and condensing TTIP using ammonia or DDA as a catalyst in a methanol / acetonitrile co-solvent. The molar composition of the reaction mixture can range from methanol 714 / acetonitrile 271 / water 2.8 / TTIP 1 / ammonia 0 - 0.17 or methanol 714 / acetonitrile 271 / water 0.8 - 16 / TTIP 1 / DDA 0 - 6.4. In a steady preparation, water (0.18 mL) can be added to a methanol / acetonitrile solution (150 mL), and 0.28 g of DDA can be dissolved in the solution. After stirring for 10 minutes, TTIP (1 mL) can be added to allow the hydrolysis and condensation reactions to proceed, and it can be stirred for an incubation period of 12 hours to obtain a suspension of titania particles. The suspension was centrifuged at 1500 rpm for 10 minutes. The particles can be washed with methanol and centrifuged again; the process can be repeated, for example, 3 times. There is no need to perform other precipitation treatments for colloidal crystallization. Next, the product can be dried at 60 °C and then calcined at 400 °C for 5 hours.

[0511] Next, for surface functionalization, after adding 500 μL of (3-iodopropyl)trimethoxysilane, the particles (particle suspension (about 1% w / v, 5 mL)) can be transferred to a glass vial with a magnetic stir bar and anhydrous acetonitrile. The mixture can then be heated at 65 °C for 8 hours and then quenched by cooling to room temperature (about 20 °C).

[0512] To obtain azide functional groups, particles with halogen groups on the surface can be treated with sodium azide (NaN3). NaN3 (100 mg) can be added to a particle suspension (about 1% w / w, 20 mL) in an aqueous PLURONIC F127 solution (0.25% w / w) along with a trace amount of potassium iodide. The suspension can be heated at 70 °C overnight (about 12 hours). After washing by centrifugation / redispersion, the azide particles can be stored at 4 °C in a 0.1% w / w Triton X-100 solution.

[0513] By treating DNA with DBCO-sulfo-NHS (Click Chemistry Tool) in phosphate-buffered saline (PBS, 10 mM, pH 7.4, 100 mM sodium chloride), single-stranded 5-NH2 DNA oligonucleotides with sticky ends can be modified so that the amine groups can be converted to dibenzylcyclooctyne (DBCO) groups. 33.3 μL of amine ssDNA (300 μM) can be mixed with 1 mM DBCO-sulfo-NHS (50 μL) in PBS and stirred vigorously overnight (about 20 °C). The modified DNA can be purified by passing it through a MICROSPIN G-25 column (GE Healthcare), diluted to 100 μM, and stored in PBS at -20 °C.

[0514] First, azide-functionalized particles can be dispersed in PBS (400 μL) containing Triton X-100 (0.1% w / w) with a particle concentration of about 0.1% w / w, after which 20 μL of DBCO-DNA (100 μM) can be added and the reaction mixture can be stirred at 55 °C for 24 hours. For further use, the resulting particles can be washed and stored in PBS containing 1% w / w PLURONIC F127.

[0515] As shown in FIGS. 9 and 11, a solution containing 10-fold stoichiometric excess of DNA-coated QDs can be mixed with the DNA origami magnetic particle structure and incubated overnight (about 12 hours at 20° C.) at room temperature. The magnetic beads can be magnetically separated, decanted, and redispersed while gently mixing in phosphate buffer, and this process can be repeated until the decanted solution becomes optically clear by UV-Vis to remove unbound QDs. The QD-magnetic particle-origami assembly can be mixed with 10-fold stoichiometric excess of DNA-coated titania and then incubated overnight (about 12 hours at 20° C.) at room temperature. The magnetic beads can be magnetically separated, decanted, and redispersed while gently mixing in phosphate buffer, and this process can be repeated until the decanted solution becomes optically clear by UV-Vis to remove unbound QDs.

[0516] Growth of silica on DNA origami particle assemblies: The growth of silica on nanoparticles and microparticles can be carried out, for example, as described below: Pastoriza-Santos and Liz-Marzan. (2013). Chapter 6: “Reliable Methods for Silica Coating of Au Nanoparticles,” In: Bergese, P., Hamad-Schifferli, K. (eds) Nanomaterial Interfaces in Biology. Methods in Molecular Biology, Vol. 1025. Humana Press, Totowa, NJ. on world wide web at: doi.org / 10.1007 / 978-1-62703-462-3_6; Moreira et al., “Gold-core silica shell nanoparticles application in imaging and therapy: A review”, Microporous and Mesoporous Materials, Volume 270, 1 November 2018, pp. 168-179, on world wide web at: doi.org / 10.1016 / j.micromeso.2018.05.022; Hankse et al. “Silica-Coated Plasmonic Metal Nanoparticles in Action”, Adv. Mater. 2018, 1707003, DOI: 10.1002 / adma.201707003; and Sharafi et al. “Synthesis of Silica-coated Iron Oxide Nanoparticles: Preventing Aggregation without Using Additives or Seed Pretreatment”, Iranian Journal of Pharmaceutical Research (2018), 17(1): 386-395. PMID: 29755569; PMCID: PMC5937108, (the entire contents of which are hereby incorporated by reference).

[0517] In order to simultaneously grow silica around the entire structure, a modification of the protocol of the conventional Stcber method can be carried out using polyvinylpyrrolidone, a widely used particle stabilizer. 1 mL of the solution containing the particle-paper assembly (e.g., synthesized in Example 1 or 3) can be mixed with 5 mL of an ultrasonically treated aqueous solution of the polymer poly(vinylpyrrolidone) (PVP). The mixture can be gently stirred at room temperature overnight (about 12 hours at 20 °C). The polymer-coated particles can be centrifuged, the supernatant collected and discarded, and then replaced with water. The process can be repeated until the supernatant becomes clear upon visual observation. Next, the particles can be resuspended in 8.25 mL of isopropanol, 1.44 mL of ultrapure water, 0.106 mL of NH4OH (30% in water), and 0.204 mL of tetraethyl orthosilicate (TEOS) (5 vol% TEOS in isopropanol) with gentle stirring. The solution can be further incubated and stirred for 2 hours.

[0518] Etching of silica to produce a yolk-shell structure: The generation of yolk-shell particles by etching can be carried out, for example, as described below: Purbia and Paria, “Yolk / shell nanoparticles: classifications, synthesis, properties, and applications,” Nanoscale, Vol. 7, 2015: pp. 19789-19873, on world wide web at: doi.org / 10.1039 / C5NR04729C; Priebe et al. “Nanorattles or Yolk-Shell Nanoparticles-What Are They, How Are They Made, and What Are They Good For?” Chemistry Europe, Vol. 21, 2015: pp. 3854-3874, on world wide web at: doi.org / 10.1002 / chem.201405285; Zhang, L., et al., “General Route to Multifunctional Uniform Yolk / Mesoporous Silica Shell Nanocapsules: A Platform for Simultaneous Cancer-Targeted Imaging and Magnetically Guided Drug Delivery,” Chemistry-A European Journal, Vol. 18, No. 39, 2012: pp. 12512-12521. doi:10.1002 / chem.201200030; and Watanabe, et al., “Polyethylenimine-assisted synthesis of hollow silica spheres without shape deformation,” Mater. Chem. Phys. Vol. 262, No. 124267, 2021 (the entire contents of which are hereby incorporated by reference in their entirety).

[0519] The protocol for using polyethyleneimine (PEI) as a low-temperature etchant for silica (which can be used to generate hollow particles through the formation of hydroxides by the amino groups of PEI) is as follows. This process can result in hydrolysis inside the particles, generating soluble silicate species, which can then be re-concentrated on the silica-PEI+ structure. The result is hollow silica particles with a slightly enlarged diameter.

[0520] The silica-coated particle origami assemblies obtained from the above examples can be dispersed in an ethanol solution of polyethyleneimine (PEI) (0.0025 - 0.01 g / L) for surface modification of the particles. The volume fraction of silica particles in the surface modification process can be in the range of 1.0×10 -3 ~5.0×10 -3 vol%. The particle solution can be sonicated for 15 minutes and then stirred at ambient temperature for 30 minutes (about 20 °C). Before dissolving the silica, the suspension of PEI-modified silica particles can be centrifuged twice (8000 rpm) for 15 minutes with ethanol and water to remove excess PEI molecules and then redispersed in water. To dissolve the inside of the particles, the aqueous suspension of PEI-modified silica particles can be stirred at 50 °C for 18 hours. The volume fraction of PEI-modified particles in the silica dissolution process can be made the same as that in the surface modification process. After centrifuging at 8000 rpm for 15 minutes, the obtained hollow particles can be dispersed in water.

[0521] Definitions In connection with the disclosure presented herein, the following definitions are used. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0522] As used herein, "a", "an", or "the" can mean one or more.

[0523] Furthermore, when the term "about" is used in connection with a recited numerical indication, it means the recited numerical indication ± up to 10% of the recited numerical indication. For example, the phrase "about 50" encompasses the range from 45 to 55.

[0524] As used herein, all composition percentages are by weight of the total composition unless otherwise specified. As used herein, the term "comprising" and variations thereof are intended to be non-limiting such that the recitation of items in a list does not exclude other like items that may be useful in the compositions and methods of this technology. Similarly, the terms "can" and "may" and variations thereof are intended to be non-limiting such that the recitation that an embodiment can or may include a particular element or feature does not exclude other embodiments of this technology that do not contain that element or feature.

[0525] For purposes of describing and claiming the present disclosure, the open-ended term "comprising" is used herein as a synonym for terms such as including, containing, or having, but the present disclosure or embodiments thereof may alternatively be described using alternative terms such as "consisting of" or "consisting essentially of".

[0526] In embodiments, as used herein, the terms "preferred" and "preferably" refer to embodiments of the technology that provide certain advantages under certain circumstances. However, in the same or other circumstances, other embodiments may also be preferred. Further, the recitation of one or more preferred embodiments does not mean that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the technology.

[0527] Equivalents Although the present disclosure has been described in connection with its particular embodiments, further modifications are possible, and this application is generally intended to cover any variations, uses, or adaptations of the present disclosure that depart from the present disclosure, including those that come within the scope of the principles of the present disclosure and within the scope of the known or customary in the technical field to which the present disclosure pertains, as applied to the essential features described above, and as defined by the scope of the above and the appended claims.

[0528] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific embodiments described herein. Such equivalents are intended to be encompassed by the following claims.

[0529] Incorporation by reference All patents and publications referred to herein are hereby incorporated by reference in their entirety.

[0530] The publications discussed herein are presented only to set forth the disclosure prior to the filing date of this application. Nothing in this specification should be construed as an admission that the present disclosure is not entitled to antedate such publications by virtue of prior disclosure.

[0531] As used herein, all headings are for organizational purposes only and are not intended to limit the disclosure in any way. The content of any individual section may be equally applicable to all sections.

Claims

Claim 1 A stimulus-responsive hollow yoke-shell particle (HSP), comprising: a) at least one orientation-controllable polyphase yoke comprising at least two colorants and at least one stimulus-responsive element; and b) at least one shell encapsulating the orientation-controllable polyphase yoke, wherein at least a portion of the shell comprises a material that is transparent to at least a portion of the visible electromagnetic spectrum from about 380 nm to about 800 nm; wherein the orientation-controllable polyphase yoke is configured to move within the shell in response to an applied force. The stimulus-responsive hollow yoke-shell particle Claim 2 The stimulus-responsive HSP according to claim 1, wherein the applied force is a magnetic field, and the at least one orientation-controllable polyphase yoke is configured to rotate about its own axis when exposed to the magnetic field. Claim 3 The HYP has dimensions of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 50 μm, and The at least one orientation-controllable polyphase yoke includes dimensions of about or at least about 2 nm, about or at least about 3 nm, about or at least about 4 nm, about or at least about 5 nm, about or at least about 6 nm, about or at least about 7 nm, about or at least about 8 nm, about or at least about 9 nm, about or at least about 10 nm, about or at least about 20 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 60 nm, about or at least about 70 nm, about or at least about 80 nm, about or at least about 90 nm, about or at least about 100 nm, about or at least about 150 nm, about or at least about 200 nm, about or at least about 250 nm, about or at least about 300 nm, about or at least about 350 nm, about or at least about 400 nm, about or at least about 450 nm, about or at least about 500 nm, about or at least about 550 nm, about or at least about 600 nm, about or at least about 650 nm, about or at least about 700 nm, about or at least about 750 nm, about or at least about 800 nm, about or at least about 850 nm, about or at least about 900 nm, about or at least about 950 nm, about or at least about 1000 nm (1 μm), about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 6 μm, about or at least about 7 μm, about or at least about 8 μm, about or at least about 9 μm, about or at least about 10 μm, about or at least about 20 μm, or about or at least about 50 μm, and / or The at least one layer of shell of the stimulus-responsive HYP of claim 1 or 2 comprises a thickness of about or at least about 1 nm, about or at least about 5 nm, about or at least about 10 nm, about or at least about 15 nm, about or at least about 20 nm, about or at least about 25 nm, about or at least about 30 nm, about or at least about 40 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 200 nm, about or at least about 300 nm, about or at least about 400 nm, about or at least about 500 nm, about or at least about 600 nm, about or at least about 700 nm, about or at least about 800 nm, about or at least about 900 nm, about or at least about 1 μm, about or at least about 2 μm, about or at least about 3 μm, about or at least about 4 μm, about or at least about 5 μm, about or at least about 10 μm, about or at least about 15 μm, about or at least about 20 μm, about or at least about 25 μm, about or at least about 30 μm, about or at least about 35 μm, about or at least about 40 μm.

4. The HYP comprises one or more of the shapes, geometric shapes, and / or morphologies of spherical, elliptical, spindle-shaped, rod-shaped, cubic, star-shaped, cylindrical, plate-shaped, tetrahedral, and dodecahedral, and / or the at least one orientation-controllable polyphase yoke comprises a shape, geometric shape, and / or morphology that conforms to the congruent shape, geometric shape, or morphology of the inner surface of at least one layer of the shell, the stimulus-responsive HYP according to any one of the preceding claims.

5. The at least one orientation-controllable polyphase yoke comprises a material comprising one or more of metals, metal oxides, silica, organic polymers, inorganic polymers, biological polymers, synthetic polymers, and combinations thereof. Optionally, the one or more biological polymers comprise nucleic acids (DNA, RNA), amino acids (peptides, proteins), polysaccharides, and / or lipids, the stimulus-responsive HYP according to any one of the preceding claims.

6. The at least one orientation-controllable polyphase yoke is coated with a protective coating. The protective coating includes chemical functionalization, lubricants, surface treatments, coatings, abrasives, and / or combinations thereof, Optionally, the protective coating includes silica, polymeric materials, inorganic oxides, carbon materials, polytetrafluoroethylene (PTFE), hydroxylated self-assembled monolayers, vitreous enamels, ceria (cerium oxide), ceramics, anodized metals, and / or combinations thereof, the stimulus-responsive HYP of any one of the preceding claims. **Claim 7** The at least one orientation-controllable polyphase yoke is a solid nanoparticle, optionally suspended in a fluid medium, semi-solid medium, non-Newtonian fluid or medium, and / or combinations thereof and configured to move in response to a magnetic field, or the at least one orientation-controllable polyphase yoke includes a fluid, ferromagnetic fluid, semi-solid, and / or non-Newtonian fluid, the stimulus-responsive HYP of any one of the preceding claims. **Claim 8** The at least one stimulus-responsive element includes a magnetic material and / or a material configured to be magnetized and / or generate a magnetic field, Optionally, the magnetic material is ferromagnetic, ferrimagnetic, antiferromagnetic, diamagnetic, paramagnetic, superparamagnetic, and / or antiferromagnetic, Optionally, the magnetic material is iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), manganese (Mn), chromium (Cr), samarium (Sm), gold (Au), silver (Ag), their alloys or oxides; alloys, intermetallic compounds, and / or oxides of Fe, Co, Ni, Zn, Mn, Sm, Ag, Au; iron, Fe ２ O ３ , FeO, and / or Fe ３ O ４ oxides; ferrite materials and / or doping materials of Co, Ni, Zn, and / or Mn; FexOy, and / or magnetite; and / or Optionally, the magnetic material is organic, carbon-based, and / or biomolecular-based, the stimulus-responsive HYP of any one of the preceding claims. **Claim 9** The magnetic material includes magnetic particles and / or beads, and optionally, the magnetic particles and / or beads have dimensions of about or at least about 5 nm, about or at least about 10 nm, about or at least about 50 nm, about or at least about 100 nm, about or at least about 500 nm, about or at least about 1 μm, about or at least about 5 μm, about or at least about 10 μm, about or at least about 50 μm, or dimensions in the range of about or at least about 5 nm to about or at least about 50 nm, about or at least about 5 nm to about or at least about 100 nm, about or at least about 5 nm to about or at least about 500 nm, about or at least about 5 nm to about or at least about 1,000 nm, about or at least about 5 nm to about or at least about 2,000 nm, about or at least about 5 nm to about or at least about 5,000 nm, about or at least about 10 nm to about or at least about 5,000 nm, about or at least about 100 nm to about or at least about 5,000 nm, about or at least about 1,000 nm to about or at least about 5,000 nm, the stimulus-responsive HYP of claim 8.

10. The magnetic material is configured to generate a magnetic field of about or at least about 200 gauss, about or at least about 500 gauss, about or at least about 800 gauss, about or at least about 1,000 gauss, about or at least about 2,500 gauss, about or at least about 12,500 gauss, about or at least about 15,000 gauss, about or at least about 20,000 gauss, or about or at least about 25,000 gauss, or a magnetic field having a range of about or at least about 200 gauss to about or at least about 25,000 gauss, the stimulus-responsive HYP of claim 8 or 9.

11. The at least two colorants include colors of the visible electromagnetic spectrum including, at approximately or at least approximately 350 nm to approximately or at least approximately 800 nm wavelength, attenuation, absorption, emission, reflection, scattering, and / or interference, and optionally, the color includes one or more of white, black, red, orange, yellow, green, blue, indigo, violet, and variations in hue, shade, and intensity therebetween, the stimulus-responsive HYSP according to any one of the preceding claims.

12. The at least two colorants include dyes, pigments, stains, phosphors, metal salts, and / or chromophores, and optionally, the at least two colorants include one or more of transparent effect pigments, goniochromatic pigments, nacreous pigments, metallic pigments, interference pigments, metallic effect pigments, fluorescent pigments, luminescent pigments, phosphorescent pigments, magnetic pigments, and anticorrosive pigments, the stimulus-responsive HYSP according to any one of the preceding claims.

13. The at least one shell layer is optically opaque and includes at least a portion that absorbs, deflects, blocks, and / or scatters at least a portion of light in the visible electromagnetic wave range of approximately 380 nm to approximately 800 nm, the stimulus-responsive HYSP according to any one of the preceding claims.

14. The at least one shell layer includes a material including one or more of glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), nylon, thermoresponsive polymer, and combinations thereof, optionally, the at least one shell layer is composed of and / or disposed on one or more of polysaccharides, lipids, amino acids, DNA, RNA, plastic, thermoresponsive polymer, hydrocarbon, crude oil, or petroleum derivative, and combinations thereof, optionally, the at least one shell layer includes one or more depressions, grooves, and spaces disposed on an inner surface for fixing the at least one orientation-controllable polyphase yoke, and / or Optionally, in any one of the preceding claims, the at least one shell layer comprises one or more materials for reducing friction between the inner surface and the at least one orientation-controllable polyphase yoke, the stimulus-responsive HYP.

15. i) preparing the at least one orientation-controllable polyphase yoke, wherein the at least one orientation-controllable polyphase yoke comprises at least two colorants and at least one stimulus-responsive element; ii) forming a dissolution layer disposed on the at least one orientation-controllable polyphase yoke; iii) forming at least one shell layer enclosing the orientation-controllable polyphase yoke, wherein the at least one shell layer comprises pores; iv) repositioning the dissolution layer through the pores of the at least one shell layer to form a cavity between the at least one orientation-controllable polyphase yoke and the at least one shell layer; and v) curing the at least one shell layer to form a non-porous shell, a method for manufacturing hollow yoke-shell particles (HYP) according to any one of claims 1 to 14, wherein the orientation-controllable polyphase yoke is configured to move within the shell in response to an applied force.

16. The method according to claim 15, wherein the applied force is a magnetic field, and the at least one orientation-controllable polyphase yoke is configured to rotate about its own axis when exposed to the magnetic field.

17. The method according to claim 15 or 16, further comprising coating the at least one orientation-controllable polyphase yoke before forming the dissolution layer, and optionally, the coating comprises one or more of a protective coating, chemical functionalization, lubricant, surface treatment, and / or abrasive.

18. The method according to any one of claims 15 to 17, further comprising forming one or more additional shells enclosing the at least one shell layer.

19. The method according to any one of claims 15 to 18, further comprising disposing one or more materials within the cavity formed by the removal, and optionally, the one or more materials comprise a thermoresponsive polymer and / or a fluid medium.

20. ​ One or more of (i) preparing at least one orientation-controllable polyphase yoke, (ii) forming a dissolution layer, and (iii) forming at least one shell layer is / are the assembly, adhesion, and / or fixation of two or more components; injection molding and / or micro-injection molding; self-assembly, adsorption, coacervation, and / or mixing; polymerization, extrusion, and / or manipulation of polymers; additive manufacturing, CNC machining (computer numerical control machining), urethane casting, microcontact printing, dip-pen lithography, beam-pen lithography, photolithography, electron-beam lithography, and / or 3D printing, according to any one of claims 15 to 19.

21. Forming the at least one shell layer includes performing one or more of synthesis of mesoporous materials, soft templating, calcination, and / or extraction, and optionally, the at least one shell layer containing pores contains mesoporous silica and / or a porous organic framework, according to any one of claims 15 to 20.

22. The rearrangement of the dissolution layer includes dissolving, removing, and / or etching the dissolution layer, according to any one of claims 15 to 21.

23. Hardening the at least one shell layer to form a non-porous shell includes forming by compressing a solid mass of the shell material by heat and / or pressure, according to any one of claims 15 to 22.

24. Preparing the at least one orientation-controllable polyphase yoke includes the DNA origami technique, and optionally, the DNA origami technique includes self-assembly of at least two DNA-coated colorants and at least one DNA-coated stimulus-responsive element, according to any one of claims 15 to 23.

25. One or more of the at least one orientation controllable polyphase yoke, the dissolution layer, and the at least one shell layer include one or more of a thermoresponsive polymer, resin, metal, ceramic, glass, quartz, plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate (acrylic), polyethylene, polyurethane, polypropylene, thermoplastic elastomer (TPE), acrylonitrile butadiene styrene (ABS), epoxy and epoxy-based photoresist, hydrogel, cyclic olefin copolymer (COC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS), polyether ester ketone (PEEK), polyether imide (ULTEM), nylon, and combinations thereof, and optionally, the one or more thermoresponsive polymers and resins include one or more of poloxamer, styrene butadiene block copolymer, polymethyl methacrylate, polybutyl methacrylate, plasticized polyvinyl chloride, plasticized nylon, plasticized polyethylene terephthalate, polyethylene, polyacrylonitrile, polychlorotrifluoroethylene, poly-4,4'-isopropylidenediphenylene carbonate, polyethylene vinyl ester, polyvinyl chloride-diethyl fumarate, and combinations thereof, the method according to any one of claims 15 to 24.

26. Preparing the at least one orientation-controllable polyphase yoke includes forming Janus particles, optionally, the Janus particles being poly(tert-butyl acrylate)-poly(3-(triethoxysilyl)propyl methacrylate) (PtBA-PTPM), polystyrene latex polymer, carboxylated latex polymer, aminated latex polymer, colored polystyrene polymer (dye injection and / or pigment injection), colored polystyrene-based carboxylated latex polymer (dye injection and / or pigment injection), fluorescent polystyrene-based polymer, fluorescent polystyrene-based carboxylated latex polymer, fluorescent aminated polystyrene-based polymer, surfactant-free polystyrene, carboxylated surfactant-free polymer, polymethyl methacrylate (PMMA) latex polymer, divinylbenzene (DVB) crosslinked polystyrene latex polymer, and combinations thereof, according to any one of claims 15 to 25.

27. Furthermore, the HYSP is optionally, the fluid, suspension, ink, liquid film, and / or adhesive substrate and / or material, where the fluid, suspension, ink, liquid film, and / or adhesive substrate and / or material is suitable for application to the surface of an object, optionally, the foil, film, thin plastic, and / or paper substrate and / or material, where the foil, film, thin plastic, and / or paper substrate and / or material is suitable for being attached to or embedded in an object, or optionally, the fiber, thread, yarn, and / or twisted yarn substrate, material, and / or surface, where the fiber, thread, yarn, and / or twisted yarn substrate and / or material is suitable for being woven into a clothing item, fabric, and / or waterproof sheet, including incorporating into, according to any one of claims 15 to 26.

28. a) providing the HYSP according to any one of claims 1 to 14, b) the HYSP is i) the fluid, suspension, ink, liquid film, and / or adhesive substrate and / or material, ii) the foil, film, thin plastic, and / or paper substrate and / or material, or iii) the fiber, thread, yarn, and / or twisted yarn substrate and / or material, incorporating, and c) applying the complex to the object and / or surface, A method of using the hollow yoke-shell particles (HYSP) according to any one of claims 1 to 14, wherein the object and / or surface exhibits the property of changing optical properties in response to the application of a magnetic field. **Claim 29** The method according to claim 28, wherein the applying further includes spraying, adhesion, weaving, embedding, writing, printing, and / or absorption. **Claim 30** The method according to claim 28 or 29, wherein the object is a polymer, paper, fabric, metal, clay plate, ceramic, window, glass, plastic, computer chip, wood, building material, and / or human or animal tissue. **Claim 31** A method for authenticating a material, comprising: a) providing a formulation of HYSP according to any one of claims 1 to 14, wherein the formulation comprises: i) a substrate and / or material of a fluid, suspension, ink, liquid film, and / or adhesive, ii) a substrate and / or material of a foil, film, thin plastic, and / or paper, or iii) a substrate and / or material of a fiber, thread, yarn, and / or spun yarn, and the method comprises: c) tagging the object and / or surface with the formulation, and d) reading the tagging, **Claim 32** The method according to claim 31, wherein the tagging is configured to be read by a sensor and / or an optical imaging device. **Claim 33** The method according to claim 31 or 32, wherein the reading includes applying a magnetic field to determine a change in the optical properties of the object and / or surface due to the presence of the HYSP.

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