Amyloid-like protein mediated substrate surface controllable functional modification method

Abstract

The invention discloses an amyloid-like protein mediated base material surface controllable functional modification method, which comprises the following steps of: dip-coating or spraying an aqueous solution containing protein, a photoinitiator, an anti-fouling monomer and an adhesive monomer on the surface of a base material, and irradiating by ultraviolet rays to form a uniform anti-fouling amyloid protein nano coating on the surface of the base material. Functional monomers and amyloid protein self-assembly are combined, and the effects of adhesion and stubborn stain resistance can be achieved by simultaneously constructing a dual-adhesion unit and a functional anti-fouling unit. The protein nano coating has high optical permeability, on the premise that the original appearance of a base material is not affected, the functions of surface stubborn stain resistance, self-cleaning, stable adhesion and the like are added, stains on the surface of the coating can be washed away through simple water flow washing, and the protein nano coating has wide application prospects in daily life.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional coatings, and particularly relates to a method for controllable functional modification of the surface of a substrate mediated by amyloid-like proteins. Background Art

[0002] With the continuous improvement of the demand for surface functionalization of materials, the development of coating technologies with anti-staining properties has become a research hotspot in fields such as medical devices, food packaging, marine anti-fouling, and the textile industry. Hydrophobic substrates (such as polytetrafluoroethylene, silicone rubber, hydrophobized metals or plastics) naturally have a certain ability to resist liquid infiltration due to their low surface energy characteristics and are widely used in medical devices, food packaging, and industrial equipment. However, traditional substrates face two core problems in practical applications: passive anti-fouling limitations and difficulties in surface modification. It is worth noting that protein-based coatings have received attention in recent years due to their environmental friendliness and biological activity. Existing research has mostly focused on the modification of hydrophilic substrates (such as cotton fibers, glass). For example, CN116144433A discloses a cleaning agent for the surface of materials, which prepares a protein product that can effectively remove oily stains on the surface of the substrate by polymerizing proteins and film-forming aids. However, when this product is applied, due to the large difference in surface energy between the protein and the substrate surface, there are the following key bottlenecks: (1) The adsorption ability of the protein on the surface of hydrophobic substrates (such as polypropylene, polydimethylsiloxane) is poor, and the coating is prone to peeling off due to the difference in interfacial energy; (2) Although it can adhere well on the surface of hydrophilic substrates (such as glass, cotton fibers), the mechanical strength of the coating is low and it is difficult to resist physical friction or chemical erosion; (3) Traditional cross-linking methods (such as glutaraldehyde treatment) may damage the active sites of proteins and reduce their anti-fouling function, resulting in limited application scenarios. Summary of the Invention

[0003] The purpose of the present invention is to provide a method for controllable functional modification of the surface of a substrate mediated by amyloid-like proteins with excellent anti-stubborn stain performance, stable adhesion, and biological safety, and to achieve efficient loading on the surfaces of hydrophilic and hydrophobic substrates by regulating the protein molecular conformation and interfacial interaction mechanism.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is: adding proteins, photoinitiators, anti-fouling monomers, and adhesion monomers into water, mixing well, and then dip-coating or spraying the obtained mixed solution on the surface of the substrate, and irradiating with ultraviolet light to form a uniform anti-stain amyloid protein nano-coating on the surface of the substrate.

[0005] In the above mixed solution, preferably, the concentration of the protein is 1 - 20 mg / mL, the concentration of the anti-fouling monomer is 50 - 400 mg / mL, the concentration of the adhesion monomer is 50 - 200 mg / mL, and the concentration of the photoinitiator is 1 - 10 mg / mL.

[0006] In the above-mentioned mixed solution, it is further preferably that the concentration of the protein is 2-10 mg / mL, the concentration of the anti-fouling monomer is 150-250 mg / mL, the concentration of the adhesion monomer is 80-120 mg / mL, and the concentration of the photoinitiator is 2-5 mg / mL.

[0007] The above-mentioned anti-fouling monomers are selected from any one or more of methacryloylethylsulfobetaine (SBMA), 2-methacryloyloxyethylphosphorylcholine (MPC), 2-methacryloyloxyethylcarboxybetaine (CBMA), acryloyloxyethylcarboxybetaine (AECB), sulfopropylmethacrylamide betaine (SPPB), methacryloylpropylsulfobetaine (SPMA), vinylimidazolesulfobetaine (VIPS), vinylpyrrolidone (NVP), methacryloylbutylsulfobetaine (SBBA), acrylamidopropylsulfobetaine (APSB), methacryloylhydroxypropylsulfobetaine (HPSBMA), perfluorooctylsulfobetaine (PFOSB), polyethylene glycol (PEG), polyethylene glycol methacrylate (OEGMA), polyethylene glycol dimethacrylate (PEGDMA), methoxypolyethylene glycol methacrylate (mPEGMA), polyethylene glycol acrylate (PEGA), polyethylene glycol diacrylate (PEGDA), 2-hydroxyethyl methacrylate (HEMA), mussel adhesive protein-betaine hybrid monomer (MAP-SB), ethylene glycol dimethacrylate, methacryloylhydroxypropylsulfobetaine, N-(2-hydroxyethyl)acrylamide (HEAA), cellulose phosphate betaine (CPB).

[0008] The above-mentioned adhesion monomers are monomers containing carboxyl, phosphate ester, silane or catechol groups, and enhance interfacial adhesion through chemical bonding or physical adsorption. The adhesion monomers are selected from any one or more of acrylic acid (AA), methacrylic acid (MAA), itaconic acid (IA), 2-methacryloyloxyethyl phosphate (MEPA), 2-acryloyloxyethylphosphorylcholine (AEPHOS), sodium styrenesulfonate (SSS), 2-acrylamide-2-methylpropanesulfonic acid (AMPS), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylamide (HPAM), glycidyl methacrylate (GMA), glycidyl acrylate (AGA), acrylamide (AAm), N-vinylpyrrolidone (NVP), octadecyl acrylate (SA), butyl acrylate (BA), maleic anhydride (MA), citraconic acid (CA), N-(3,4-dihydroxyphenethyl) methacrylamide, 3-(3,4-dihydroxyphenyl) acrylate acrylate, vinyltriethoxysilane (VTES), γ-methacryloyloxypropyltrimethoxysilane (KH-570-MA), isocyanatoethyl methacrylate (IEM), pentaerythritol triacrylate (PETA), perfluoroalkyl ethyl acrylate (PFAEA), cellulose acrylate (CAc).

[0009] The above-mentioned proteins are selected from any one or more of lysozyme, bovine serum albumin, human serum albumin, lactoferrin, lactalbumin, insulin, α-lactalbumin, fibrinogen, β-lactoglobulin, ribonuclease A, cytochrome c, α-amylase, horseradish peroxidase, pepsin, myoglobin albumin, collagen, keratin, hemoglobin, DNA polymerase, casein, soy protein isolate, pea protein isolate, zein, gliadin, gluten, oat protein, potato protein, hemp seed protein, walnut protein, rapeseed protein, hazelnut protein, quinoa protein, sunflower seed protein, pumpkin seed protein, black sesame protein, mushroom protein, red algae protein, legumin, barley protein, wheat protein, glutenin, kidney bean protein, catalase, transferrin, thyroglobulin.

[0010] The photoinitiator is selected from any one or more of a free radical photoinitiator and a cationic photoinitiator. The free radical photoinitiator is selected from 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, benzoin ether, 4,4'-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzophenone, bisacylphosphine oxide, 4,4'-bis(diethylamino)benzophenone, benzoyldiphenylphosphine oxide, 2-chlorothioxanthone, ethyl-4-dimethylaminobenzoate, 4-methyldiphenyl any one or more of 2-phenylbenzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, methyl benzoylformate, 2-isopropylthioxanthone, and benzoin dimethyl ether; the cationic photoinitiator is selected from phenyl (2,4,6-trimethylbenzoyl) lithium phosphate, diphenyl iodonium p-toluenesulfonate, 1,2-diphenyl iodonium, tetrakis (phenyl) iodonium cation salt, 2-phenylphenyl triphenylsulfonium salt, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium hexafluorophosphate, (η 5 -cyclopentadienyl)(η 6 Any one or more of bis(4-tert-butylphenyl)iodonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, ferrocene hexafluorophosphate, tris(4-methylphenyl)sulfonium hexafluorophosphate, and phenylferrocene hexafluoroantimonate.

[0011] The substrate is selected from a hydrophilic substrate or a hydrophobic substrate, wherein the hydrophilic substrate is selected from polyamide, polyacetal, polyetherimide, acrylonitrile-butadiene-styrene copolymer, polyoxyxylene resin, polymethyl methacrylate, photosensitive polyimide, cellulose film, nylon film, silicon, glass, quartz, mica, porcelain, various metals, stainless steel substrates, cotton cloth, polyester and other fabrics, and the hydrophobic substrate is selected from natural hydrophobic polymer materials (polyethylene, polyvinyl chloride, polypropylene, polystyrene, polytetrafluoroethylene , polymethylpentene, polyvinylidene fluoride, polyxylene oxide, polyxylene sulfide, polyether ketone, polyaromatic ester, polydimethylsiloxane), hydrophobically modified polymer materials (polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyvinyl chloride, polyether sulfone), hydrophobically treated substrates (quartz sheets, mica sheets, glass sheets, silicon sheets, aluminum sheets), hydrophobic fabrics (silk fabrics, hydrophobically modified polyester fabrics, modified vinyl fabrics, three-proof fabrics, twisted palm fabrics, jacquard fabrics or other hydrophobically treated fabrics).

[0012] The stains resistant to the above-mentioned coating include any one or more of solid stains (mud, dust, pollen, cement, metal filings, food residues, soot, carbon powder, plant debris, rubber particles, pigments, chalk dust, animal hair, dandruff), oil-soluble stains (chili oil, cooking oil, lubricating oil, cosmetics, engine oil, butter, shoe polish, sunscreen, asphalt, crayon marks), mixed stains (kitchen sauces, coffee stains, milk stains, ink), tannin pigment stains (grass juice, red wine, coffee, tea stains, fruit juice, traditional Chinese medicine stains, sap, tobacco juice), and protein stains (blood, urine).

[0013] Further, the wavelength of the above-mentioned ultraviolet irradiation is 200 - 400 nm, the intensity is 1000 - 3000 mW / cm 2 , and the time is 150 - 300 seconds.

[0014] The beneficial effects of the present invention are as follows:

[0015] 1. The present invention provides a method for controllable functional modification of the substrate surface mediated by amyloid-like proteins. Under the induction of ultraviolet light, the photoinitiator can generate free radicals, and the free radicals can simultaneously carry out the rapid self-assembly aggregation and monomer polymerization of proteins.

[0016] 2. The present invention combines functional monomers with the self-assembly of amyloid proteins. By simultaneously constructing dual adhesion units and functional anti-stain units, it breaks through the performance limitations of traditional bio-based coatings and can achieve the effect of both adhesion and resistance to stubborn stains.

[0017] 3. The method for controllable functional modification of the substrate surface of the present invention is simple. Its main components are proteins, photoinitiators, and functional monomers, which are non-toxic, non-irritating, and environmentally friendly.

[0018] 4. The method for controllable functional modification of the substrate surface of the present invention can quickly form a uniform coating on the substrate surface by a simple method of short-time ultraviolet irradiation, and has high application prospects.

[0019] 5. The surface of the functionalized substrate modified by the modification method of the present invention has excellent resistance to stubborn stains, and the stains on the coating surface can be washed off by simple water flow rinsing.

[0020] 6. The modification method of the present invention can form a coating on the surfaces of various regular or irregular substrates, and has universality. Description of the Drawings

[0021] Figure 1 is an optical photograph of the blank silk cloth (left) and the silk cloth with a uniform anti-stain amyloid protein nano-coating formed on the surface in Example 1 (right).

[0022] Figure 2This is an optical photograph of the anti-fouling amyloid protein nanocoating formed on the surface of the transparent glass sheet in Example 3.

[0023] Figure 3 This is the transmittance curve of the anti-stain amyloid protein nanocoating formed on the surface of the quartz plate in Example 4.

[0024] Figure 4 These are the optical contact angle images of anti-fouling amyloid protein nanocoatings formed on the surfaces of different substrates.

[0025] Figure 5 It is the anti-solid stain (mud and sand) performance of the anti-stain amyloid protein nano-coating formed on the surface of jacquard fabric and twisted brown fabric.

[0026] Figure 6 It is the anti-stain amyloid protein nano-coating formed on the surface of five kinds of fabrics: vinylon, silk, polyester, three-proof and hydrophobic polyester, which has the performance of resisting oil-soluble stains (chili oil).

[0027] Figure 7 It is an anti-stain amyloid protein nano-coating formed on the surface of five kinds of fabrics: vinylon, silk, polyester, three-proof and hydrophobic polyester, and has the performance of resisting mixed stains (bean paste).

[0028] Figure 8 It is an anti-stain amyloid protein nano-coating formed on the surface of five kinds of fabrics: vinylon, silk, polyester, three-proof and hydrophobic polyester, which has the performance of resisting tannin pigment stains (grass juice). DETAILED DESCRIPTION

[0029] In order to facilitate the understanding of the present invention, the present invention will be described in more comprehensive and detailed manner below in conjunction with the accompanying drawings and experimental examples, but the protection scope of the present invention is not limited to the following specific embodiments.

[0030] Example 1

[0031] 25 mg of lysozyme and 12.5 mg of phenyl (2,4,6-trimethylbenzoyl) lithium phosphate were dissolved in 2.5 mL of ultrapure water, and then the two solutions were mixed, and 1.0 g of methacryloylethyl sulfobetaine and 0.5 g of acrylic acid were added to prepare a uniform mixed solution. The mixed solution was sprayed on a square silk cloth with a size of 50 mm × 50 mm, using a wavelength of 365 nm and an intensity of 1000 mW / cm 2 The silk cloth was irradiated with LED light for 200 seconds to form a uniform anti-fouling amyloid protein nanocoating on the silk cloth. Optical photos of a blank silk cloth and a silk cloth with a uniform anti-fouling amyloid protein nanocoating on the surface are shown in Figure 1. Figure 1 As shown, the antifouling coating will spread evenly on the fabric surface without changing the color of the fabric itself, and the coating surface is hydrophilic.

[0032] Example 2

[0033] Dissolve 50 mg of bovine serum albumin and 25 mg of phenyl (2,4,6-trimethylbenzoyl) lithium phosphate in 2.5 mL of ultrapure water, then mix the two solutions, add 1.2 g of sulfopropyl methacrylamide betaine and 0.6 g of acrylic acid to prepare a uniform mixed solution. Spray the mixed solution on a square three-proof fabric with a size of 50 mm × 50 mm at a wavelength of 365 nm and an intensity of 1200 mW / cm 2 The LED light was irradiated for 150 seconds to form a uniform anti-stain amyloid protein nano-coating on the triple-proof fabric.

[0034] Example 3

[0035] 25 mg of ovalbumin and 12.5 mg of phenyl (2,4,6-trimethylbenzoyl) lithium phosphate were dissolved in 2.5 mL of ultrapure water, and then the two solutions were mixed, and 1.0 g of dopamine sulfobetaine and 0.4 g of sodium styrene sulfonate were added to prepare a uniform mixed solution. The mixed solution was sprayed on a rectangular transparent glass sheet with a size of 15 mm × 50 mm, using a wavelength of 365 nm and an intensity of 1000 mW / cm 2 After irradiation with LED light for 180 seconds, a uniform anti-fouling amyloid protein nanocoating was formed on the transparent glass sheet. The optical photograph of the coating is shown in FIG. Figure 2 As shown, the coating does not change the high transmittance of the blank glass sheet and has excellent optical transmittance.

[0036] Example 4

[0037] 12.5 mg lactoferrin and 12.5 mg phenyl (2,4,6-trimethylbenzoyl) lithium phosphate were dissolved in 2.5 mL ultrapure water, and then the two solutions were mixed, and 1.1 g methacryloylethyl sulfobetaine and 0.5 g acrylamide were added to prepare a uniform mixed solution. The mixed solution was sprayed on a rectangular transparent quartz plate with a size of 10 mm × 40 mm, using a wavelength of 365 nm and an intensity of 1500 mW / cm 2 After irradiation with LED light for 160 seconds, a uniform anti-fouling amyloid protein nanocoating (denoted as PTL-PSBMA-PAA) was formed on the transparent quartz plate. The transmittance curve of the coating is shown in FIG. Figure 3 As shown, the results show that the coating will not change the high transmittance of the blank quartz plate and has broad application prospects.

[0038] Example 5

[0039] Dissolve 25 mg of lysozyme and 12.5 mg of lithium phenyl(2,4,6-trimethylbenzoyl)phosphate in 2.5 mL of ultrapure water respectively, then mix the two solutions, and add 1.0 g of acryloyloxyethyl carboxybetaine and 0.5 g of itaconic acid to obtain a homogeneous mixed solution. Spray the mixed solution on a polycarbonate (PC) sheet with a specification of 20 mm × 20 mm, and irradiate it with LED light with a wavelength of 365 nm and an intensity of 1200 mW / cm 2 for 180 seconds to form a uniform anti-stain amyloid protein nano-coating on the PC sheet.

[0040] Example 6

[0041] Dissolve 20 mg of lysozyme and 15 mg of lithium phenyl(2,4,6-trimethylbenzoyl)phosphate in 2.5 mL of ultrapure water respectively, then mix the two solutions, and add 0.8 g of methacryloylethyl sulfobetaine and 0.4 g of glycidyl methacrylate to obtain a homogeneous mixed solution. Spray the mixed solution on a silicon (Si) wafer with a specification of 10 mm × 10 mm, and irradiate it with LED light with a wavelength of 365 nm and an intensity of 1500 mW / cm 2 for 170 seconds to form a uniform anti-stain amyloid protein nano-coating on the Si wafer.

[0042] Example 7

[0043] Dissolve 25 mg of lysozyme and 12.5 mg of lithium phenyl(2,4,6-trimethylbenzoyl)phosphate in 2.5 mL of ultrapure water respectively, then mix the two solutions, and add 0.8 g of methacryloyloxyethyl phosphorylcholine and 0.4 g of acrylamide to obtain a homogeneous mixed solution. Spray the mixed solution on a polyethylene (PE) substrate with a specification of 20 mm × 50 mm, and irradiate it with LED light with a wavelength of 365 nm and an intensity of 1500 mW / cm 2 for 180 seconds to form a uniform anti-stain amyloid protein nano-coating on the PE substrate sheet.

[0044] Example 8

[0045] Dissolve 25 mg of lysozyme and 12.5 mg of lithium phenyl(2,4,6-trimethylbenzoyl)phosphate in 2.5 mL of ultrapure water respectively, then mix the two solutions, and add 0.8 g of methacryloylethyl sulfobetaine and 0.4 g of acrylamide to obtain a homogeneous mixed solution. Spray the mixed solution on a hydrophobic polyester fabric with a specification of 50 mm × 50 mm, and irradiate it with LED light with a wavelength of 365 nm and an intensity of 1500 mW / cm 2 for 180 seconds to form a uniform anti-stain amyloid protein nano-coating on the hydrophobic polyester fabric.

[0046] Example 9

[0047] Dissolve 30 mg of lysozyme and 12.5 mg of lithium phenyl(2,4,6 - trimethylbenzoyl)phosphate in 2.5 mL of ultrapure water respectively. Then mix the two solutions, and add 1.0 g of methacryloylethyl sulfobetaine and 0.4 g of acrylic acid to obtain a uniform mixed solution. Spray the mixed solution on a polyester fabric with a specification of 50 mm×50 mm, and irradiate it with LED light with a wavelength of 365 nm and an intensity of 1800 mW / cm 2 for 180 seconds to form a uniform stain - resistant amyloid protein nano - coating on the polyester fabric.

[0048] Example 10

[0049] Dissolve 20 mg of bovine serum albumin and 12.5 mg of lithium phenyl(2,4,6 - trimethylbenzoyl)phosphate in 2.5 mL of ultrapure water respectively. Then mix the two solutions, and add 1.0 g of methacryloylethyl sulfobetaine and 0.4 g of butyl acrylate to obtain a uniform mixed solution. Spray the mixed solution on a vinylon fabric with a specification of 50 mm×50 mm, and irradiate it with LED light with a wavelength of 365 nm and an intensity of 2000 mW / cm 2 for 180 seconds to form a uniform stain - resistant amyloid protein nano - coating on the vinylon fabric.

[0050] Example 11

[0051] Dissolve 37.5 mg of lysozyme and 20 mg of lithium phenyl(2,4,6 - trimethylbenzoyl)phosphate in 2.5 mL of ultrapure water respectively. Then mix the two solutions, and add 1.0 g of methacryloylethyl sulfobetaine and 0.4 g of acrylic acid to obtain a uniform mixed solution. Spray the mixed solution on a jacquard fabric with a specification of 30 mm×30 mm, and irradiate it with LED light with a wavelength of 365 nm and an intensity of 2000 mW / cm 2 for 200 seconds to form a uniform stain - resistant amyloid protein nano - coating on the jacquard fabric.

[0052] Example 12

[0053] Dissolve 37.5 mg of lysozyme and 20 mg of lithium phenyl(2,4,6 - trimethylbenzoyl)phosphate in 2.5 mL of ultrapure water respectively. Then mix the two solutions, and add 1.0 g of methacryloylethyl sulfobetaine and 0.4 g of acrylic acid to obtain a uniform mixed solution. Spray the mixed solution on a twill - brown fabric with a specification of 30 mm×30 mm, and irradiate it with LED light with a wavelength of 365 nm and an intensity of 2000 mW / cm 2The LED light was irradiated for 200 seconds to form a uniform anti-stain amyloid protein nano-coating on the twisted brown fabric.

[0054] Example 13

[0055] 25 mg of lysozyme and 12.5 mg of phenyl (2,4,6-trimethylbenzoyl) lithium phosphate were dissolved in 2.5 mL of ultrapure water, and then the two solutions were mixed, and 1.0 g of acryloyloxyethyl carboxybetaine and 0.5 g of itaconic acid were added to prepare a uniform mixed solution. The mixed solution was sprayed on a mica sheet with a size of 20 mm × 20 mm, using a wavelength of 365 nm and an intensity of 1200 mW / cm 2 The PC sheet was irradiated with LED light for 180 seconds to form a uniform anti-fouling amyloid protein nanocoating.

[0056] The performance of the anti-fouling amyloid protein nano-coatings formed on the surfaces of different hydrophobic substrates in the above Examples 1 to 13 was tested, and the specific experiments are as follows:

[0057] 1. Optical contact angle test

[0058] The substrates with uniform anti-fouling amyloid protein nanocoating (PTL-PSBMA-PAA) formed on the surface in Examples 1 to 3, 5 to 10, and 13 were taken for contact angle characterization. The volume of water dropped on the coating surface was controlled to be 4 μL by using an optical contact angle measuring instrument syringe, and the static contact angle of the surface was measured. Each surface was measured at least three times. The results are as follows: Figure 4 shown.

[0059] The results show that the anti-fouling amyloid protein nanocoating of the present invention is universal and can form a uniform coating on the surface of any substrate. These substrates include various fabrics (vinylon cloth, silk cloth, polyester cloth, three-proof cloth and hydrophobic polyester cloth), inorganic non-metallic materials (glass sheets, silicon sheets and mica sheets) and polymer materials (PC and PE), etc. By modifying the surface of these materials with protein coating, a uniform anti-fouling coating with a contact angle of about 80° can be obtained.

[0060] 2. Solid stain resistance test

[0061] The anti-solid stain performance of the skein and jacquard fabrics formed with the anti-stain amyloid protein nanocoating (PTL-PSBMA-PAA) on the surface in Examples 11 and 12 was characterized. The solid stain was selected as mud and sand. The surfaces of the blank fabric and the fabric formed with the anti-stain amyloid protein nanocoating were contaminated, and the contaminated fabrics were dried in an oven at 70°C for 2 hours, rinsed under running water for 60 seconds, and dried again. Microscopic photos were taken with a microscope. The results are as follows Figure 5 shown.

[0062] From Figure 5 It can be seen that the stain-resistant amyloid protein nano-coating has good performance against solid stains (mud and sand). After being contaminated and washed, the fabric with the stain-resistant amyloid protein nano-coating on its surface is cleaner than the blank fabric after washing, and there is less residue of solid stains microscopically.

[0063] 3. Test of oil-soluble stain resistance

[0064] Take the fabrics with the stain-resistant amyloid protein nano-coating (PTL-PSBMA-PAA) formed on the surface in Examples 1, 2, 8, 9, and 10 for the characterization of oil-soluble stain resistance. The oil-soluble stain selected is chili oil. Contaminate the surfaces of the blank fabric and the fabric with the stain-resistant amyloid protein nano-coating formed on the surface, and dry the contaminated fabric in an oven at 70 °C for 2 hours. Rinse the fabric under running water for 60 seconds, and record the optical photo of the fabric after drying again. The results are as Figure 6 shown.

[0065] From Figure 6 It can be seen that the stain-resistant amyloid protein nano-coating has good performance against oil-soluble stains (chili oil). After being contaminated and washed, the fabric with the stain-resistant amyloid protein nano-coating formed on the surface has less residue of oil-soluble stain pigments than the blank fabric.

[0066] 4. Test of mixed stain resistance

[0067] Take the fabrics with the stain-resistant amyloid protein nano-coating (PTL-PSBMA-PAA) formed on the surface in Examples 1, 2, 8, 9, and 10 for the characterization of mixed stain resistance. The mixed stain selected is broad bean paste. Contaminate the surfaces of the blank fabric and the fabric with the stain-resistant amyloid protein nano-coating formed on the surface, and dry the contaminated fabric in an oven at 70 °C for 2 hours. Rinse the fabric under running water for 60 seconds, and record the optical photo of the fabric after drying again. The results are as Figure 7 shown.

[0068] From Figure 7 It can be seen that the stain-resistant amyloid protein nano-coating has good performance against mixed stains (broad bean paste). After being contaminated and washed, the fabric with the stain-resistant amyloid protein nano-coating formed on the surface has less residue of mixed stain pigments than the blank fabric and has stronger detergency.

[0069] 5. Test of tannin pigment stain resistance

[0070] The fabrics with anti-stain amyloid protein nano-coatings (PTL-PSBMA-PAA) formed on the surface in Examples 1, 2, 8, 9, and 10 were characterized for their performance against tannin pigment stains. The mixed stain selected was grass juice. The surfaces of the blank fabric and the fabric with the anti-stain amyloid protein nano-coating formed on the surface were contaminated, and the contaminated fabric was dried in an oven at 70 °C for 2 hours, rinsed under running water for 60 seconds, and the optical photograph of the fabric was recorded after drying again. The results are as Figure 8 shown.

[0071] As Figure 8 can be seen, the anti-stain amyloid protein nano-coating has good performance against tannin pigment stains (grass juice). After contamination and cleaning, the fabric with the anti-stain amyloid protein nano-coating formed on the surface has less tannin pigment stain residue, stronger detergency, and higher whiteness than the blank fabric.

[0072] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for controllable functional modification of the surface of a substrate mediated by amyloid-like proteins, characterized in that: A protein, a photoinitiator, an anti-fouling monomer and an adhesive monomer are added to water and thoroughly mixed. Then, the resulting mixed solution is dip-coated or spray-coated on the surface of a substrate, and a uniform anti-fouling amyloid protein nano-coating is formed on the surface of the hydrophobic substrate by ultraviolet irradiation; The anti-fouling monomer is selected from any one or more of methacryloylethyl sulfobetaine, 2-methacryloyloxyethyl phosphorylcholine, methacryloyloxyethyl carboxybetaine, 2-acryloyloxyethyl carboxybetaine, sulfopropyl methacrylamide betaine, methacryloylpropyl sulfobetaine, vinylimidazole sulfobetaine, triethylene glycol methacrylate, N-(2-hydroxyethyl)acrylamide, vinylpyrrolidone, methacryloylbutyl sulfobetaine, acrylamidepropyl sulfobetaine, polyethylene glycol, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, methoxypolyethylene glycol methacrylate, polyethylene glycol acrylate, polyethylene glycol diacrylate, 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, methacryloylhydroxypropyl sulfobetaine, perfluorooctyl sulfobetaine, cellulose phosphate betaine, mussel adhesive protein-betaine hybrid monomer; The adhesive monomer is selected from any one or more of acrylic acid, methacrylic acid, itaconic acid, 2-methacryloyloxyethyl phosphate, 2-acryloyloxyethyl phosphorylcholine, sodium styrene sulfonate, 2-acrylamide-2-methylpropanesulfonic acid, hydroxyethyl methacrylate, hydroxypropyl acrylamide, glycidyl methacrylate, glycidyl acrylate, acrylamide, N-vinylpyrrolidone, octadecyl acrylate, butyl acrylate, maleic anhydride, citraconic acid, N-(3,4-dihydroxyphenethyl)methacrylamide, 3-(3,4-dihydroxyphenyl)acrylate acrylate, vinyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, isocyanatoethyl methacrylate, pentaerythritol triacrylate, perfluoroalkyl ethyl acrylate, cellulose acrylate; 2. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to claim 1, wherein: In the mixed solution, the concentration of the protein is 1-20 mg / mL, the concentration of the anti-fouling monomer is 50-400 mg / mL, the concentration of the adhesive monomer is 50-200 mg / mL, and the concentration of the photoinitiator is 1-10 mg / mL.

3. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to claim 1, wherein: In the mixed solution, the concentration of the protein is 2-10 mg / mL, the concentration of the anti-fouling monomer is 150-250 mg / mL, the concentration of the adhesive monomer is 80-120 mg / mL, and the concentration of the photoinitiator is 2-5 mg / mL.

4. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to any one of claims 1 to 3, characterized in that: The protein is selected from any one or more of lysozyme, bovine serum albumin, human serum albumin, lactoferrin, lactalbumin, insulin, α-lactalbumin, fibrinogen, β-lactoglobulin, ribonuclease A, cytochrome c, α-amylase, horseradish peroxidase, pepsin, myoglobin albumin, collagen, keratin, hemoglobin, DNA polymerase, casein, soy protein isolate, pea protein isolate, zein, gliadin, gluten, oat protein, potato protein, hemp seed protein, walnut protein, rapeseed protein, hazelnut protein, quinoa protein, sunflower seed protein, pumpkin seed protein, black sesame protein, mushroom protein, red algae protein, legumin, barley protein, wheat protein, glutenin, kidney bean protein, catalase, transferrin, and thyroglobulin.

5. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to any one of claims 1 to 3, characterized in that: The photoinitiator is selected from any one or more of free radical photoinitiators and cationic photoinitiators.

6. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to claim 5, characterized in that: The free radical photoinitiator is selected from any one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, benzoin ether, 4,4'-dichlorobenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzophenone, bisacylphosphine oxide, 4,4'-bis(diethylamino)benzophenone, benzoyl diphenylphosphine oxide, 2-chlorothioxanthone, ethyl-4-dimethylaminobenzoate, 4-methoxybenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, methyl benzoylformate, 2-isopropylthioxanthone, and benzoin dimethyl ether.

7. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to claim 5, characterized in that: The cationic photoinitiator is selected from any one or more of lithium phenyl(2,4,6-trimethylbenzoyl)phosphate, diphenyliodonium p-toluenesulfonate, 1,2-diphenyliodene, tetrakis(phenyl)iodonium cation salt, 2-phenylphenyldiphenylsulfonium salt, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, (η 5 -cyclopentadienyl)(η 6 -cumene)iron(II) hexafluorophosphate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, ferrocene hexafluorophosphate, tris(4-methylphenyl)thiolanium hexafluorophosphate, phenylferrocene hexafluoroantimonate.

8. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to claim 1, wherein: The wavelength of the ultraviolet irradiation is 200 - 400 nm, the intensity is 1000 - 3000 mW / cm 2 , and the time is 150 - 300 seconds.

9. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to claim 1, wherein: The stains include any one or more of sediment, dust, pollen, cement, metal filings, food residues, soot, carbon powder, plant debris, rubber particles, pigments, chalk dust, animal hair, dandruff, chili oil, cooking oil, lubricating oil, cosmetics, engine oil, butter, shoe polish, sunscreen, asphalt, crayon marks, kitchen sauces, coffee stains, milk stains, ink, grass juice, red wine, coffee, tea stains, fruit juice, traditional Chinese medicine stains, sap, tobacco juice, blood, and urine.

10. The method for controllable functional modification of the substrate surface mediated by amyloid-like proteins according to claim 1, wherein: The substrate is a hydrophilic substrate or a hydrophobic substrate; the hydrophilic substrate is selected from any one of polyamide, polyacetal, polyetherimide, acrylonitrile-butadiene-styrene copolymer, polyoxylene resin, polymethyl methacrylate, photosensitive polyimide, cellulose film, nylon film, silicon, glass, quartz, mica, porcelain, metal, stainless steel substrate, cotton cloth, and polyester; the hydrophobic substrate is selected from any one of polyethylene, polyvinyl chloride, polypropylene, polystyrene, polytetrafluoroethylene, polymethylpentene, polyvinylidene fluoride, polyoxylene, polysulfide dimethylbenzene, polyether ketone, polyarylate, polydimethylsiloxane, hydrophobically modified polycarbonate, hydrophobically modified polymethyl methacrylate, hydrophobically modified polyethylene terephthalate, hydrophobically modified polyvinyl chloride, hydrophobically modified polyethersulfone, hydrophobically treated quartz wafer, hydrophobically treated mica wafer, hydrophobically treated glass wafer, hydrophobically treated silicon wafer, hydrophobically treated aluminum sheet, silk fabric, hydrophobically modified polyester fabric, modified vinylon fabric, three-proof fabric, twisted palm fabric, and jacquard fabric.

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