Supramolecular lanthanide phosphorescent four-dimensional assembly material as well as preparation method and application thereof

Abstract

The invention relates to an intelligent material, and particularly discloses a supramolecular lanthanide phosphorescent four-dimensional assembly material as well as a preparation method and application thereof. The supramolecular lanthanide phosphorescent four-dimensional assembly material has multicolor luminescence including white, specifically, time-resolved multicolor emission from colorless to purple to white is generated, and the preparation method is simple. Therefore, the material has a good application prospect in information multilevel logic anti-counterfeiting and efficient antibiotic selection.

Description

Technical Field

[0001] The present application relates to an intelligent material, and in particular to a supramolecular lanthanide phosphorescent four-dimensional assembly material and a preparation method and application thereof. Background Art

[0002] Dynamic self-assembly is common in various organisms in nature. In this process, weak non-covalent interactions between molecules accurately produce effective and complex biological functions on demand, such as the formation of actin filaments, DNA transcription and replication, and other life activities. Mimicking the ubiquitous dynamic self-assembly to achieve complex structures and functions can give materials intelligent bionic properties such as self-regulation, self-repair, and self-adaptation.

[0003] In recent years, it has been rapidly developed in the fields of bio-imaging, information encryption, sensors, etc. The supramolecular assembly strategy based on host-guest interaction is easy to prepare and avoids complex synthesis. More importantly, this method can easily adjust the different luminescent properties of organic room temperature phosphorescent RTP materials by changing the composition parameters, so it has attracted widespread attention from researchers.

[0004] However, multicolor lanthanide supramolecular RTP materials with time-dependent properties in aqueous solution still face great challenges. Summary of the invention

[0005] In view of the defects or shortcomings of the prior art, the purpose of the present application is to provide a supramolecular lanthanide phosphorescent four-dimensional assembly material and a preparation method and application thereof.

[0006] The first aspect of the present application is to provide a supramolecular lanthanide phosphorescent four-dimensional assembly material, comprising: a 4-(4-bromophenyl) pyridinium salt derivative G and an inorganic clay LP / Eu complex.

[0007] In some embodiments, the 4-(4-bromophenyl)pyridinium salt derivative G has the following structure:

[0008]

[0009] In some embodiments, the ratio between the amount of the 4-(4-bromophenyl)pyridinium salt derivative G and the mass of the inorganic clay LP / Eu complex is 0.01 mmol / 0.03-0.06 g.

[0010] In some embodiments, the above-mentioned material further comprises dipicolinic acid and its carboxylate.

[0011] In some embodiments, the dipyridine carboxylic acid includes pyridine-2,6-dicarboxylic acid.

[0012] In some embodiments, the ratio between the amount of the pyridinedicarboxylic acid and its carboxylate salt and the mass of the inorganic clay LP / Eu complex is 0.07 mmol / 0.006 g to 0.01 g.

[0013] The second aspect of the present application is to provide a method for preparing a supramolecular lanthanide phosphorescent four-dimensional assembly material, comprising the following preparation process:

[0014] providing a 4-(4-bromophenyl)pyridinium salt derivative G as a guest;

[0015] preparing LP / Eu host complex;

[0016] The above guest is assembled with the above LP / Eu host complex to prepare a four-dimensional assembly material.

[0017] In some embodiments, the above steps of preparing the LP / Eu host complex include:

[0018] dispersing LP in water to obtain LP dispersion;

[0019] dispersing a salt precursor of Eu into a LP dispersion;

[0020] Heat up and reflux for a period of time;

[0021] The LP / Eu main complex is obtained by cooling and post-treatment.

[0022] In some embodiments, the reflux temperature is 80° C. to 120° C., and the reflux time is 20 h to 36 h.

[0023] In some embodiments, the step of assembling the guest and the LP / Eu host complex to prepare a four-dimensional assembly material comprises:

[0024] At room temperature, the LP / Eu main complex is added to the guest, and the four-dimensional assembly material is obtained after the mixture reaches a dissolved state.

[0025] The third aspect of the present application is to provide an application of the four-dimensional assembly material described in the first aspect in information multi-level logic anti-counterfeiting.

[0026] The fourth aspect of the present application is to provide a use of the four-dimensional assembly material described in the first aspect in the preparation of a high-efficiency antibiotic selection sensor, characterized in that it includes selective detection of any one or more of nitrofurazone (NZO), metronidazole (MAZ) or sulfamethoxazole (SAZ).

[0027] The following is an explanation and description of the terms used in this application:

[0028] Inorganic clay LP: full name is lithium magnesium silicate It is a synthetic lithium magnesium silicate clay with a unique layered structure and excellent physical and chemical properties. Its chemical formula is Na 0.7 (Si 8 Mg 5.5 Li 0.3 ) 20 (OH) 4 -0.7 .

[0029] The structure of 4-(4-bromophenyl)pyridinium salt derivative G is:

[0030] Metronidazole (MAZ) is a commonly used antibacterial drug belonging to the nitroimidazole derivatives, mainly used to treat anaerobic bacterial infections and certain protozoan infections.

[0031] Nitrofurazone (NZO): has the following structural formula:

[0032]

[0033] Sulfadimethoxine (SAZ): has the following structural formula:

[0034]

[0035] Obviously, based on the above content of this application, in accordance with common technical knowledge and customary means in this field, without departing from the above basic technical ideas of this application, other various forms of modifications, replacements or changes can be made.

[0036] Beneficial technical effects of this application:

[0037] 1. The present application discloses a time-dependent supramolecular lanthanide phosphorescent four-dimensional assembly material composed of a 4-(4-bromophenyl)pyridinium salt derivative (G) and an inorganic clay (LP) / Eu complex, which has multicolor luminescence including white. Compared with the self-assembled nanoparticles G, the layered assembled G / LP shows dual emission of fluorescence at 380nm and phosphorescence at 516nm over time. Within 1 hour, due to the limitation of the "domino effect" driven by LP electrostatics, the phosphorescence lifetime and quantum yield increased from zero to 7.4ms and 27.53%, respectively, achieving time-dependent phosphorescence emission.

[0038] 2. The four-dimensional assembly of dipyridine carboxylic acid and its carboxylate (DPA) and G / LP / Eu of the present application produces time-resolved multicolor emission from colorless to purple to white, which has been successfully applied to information multi-level logic anti-counterfeiting and efficient antibiotic selection sensors.

[0039] 3. The four-dimensional assembly of DPA and G / LP / Eu of the present application achieves rapid ratio enhancement (the luminescence intensity at 616nm is increased by 7 times, and the partial quenching efficiency of blue and green light reaches about 60%), and the color changes from white to red. In addition, the four-dimensional assembly G / LP / Eu@DPA can selectively detect the antibiotics furacillin (NZO), metronidazole (MAZ) and sulfamethoxazole (SAZ). Among them, the quenching efficiency of NZO (70nM) at 616nM is about 70%, while the quenching efficiency of MAZ and SAZ is less than 30%. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 Test graphs provided for some embodiments of this application: (a) Absorption spectrum of LP (from 0wt% to 3wt%) added to G (0.01mM) at 298K; (b) Transmittance at 450nm when different LPs are added to G at 298K. Tyndall effect of G at different LP addition amounts (I) 0wt%, (II) 1wt% and (III) 2wt%; (c) Transient photoluminescence spectrum of G and LP (from 0wt% to 3wt%) in 298K (λex=300nm) water; (d) G / LP in water at 298K ([G]=0.01mM, LP=2wt%, λex=300nm)N 2 Phosphorescence emission spectra before and after addition (delay 0.1 s);

[0041] Figure 2 Test graphs provided for some embodiments of the present application: (a) dynamic photoluminescence spectra of G and LP (from 0wt% to 3wt%) in 298K (λex = 300nm) water; (b) dynamic photoluminescence emission intensity change graph of G and LP in 298K (λex = 300nm) water; (c) fluorescence dynamic lifetime decay curve of G / LP at 298K and 380nm; (d) phosphorescence dynamic lifetime decay curve of G / LP at 516nm and 298K; (e) CIE chromaticity diagram corresponding to the dynamic change spectra of G and LP in water at 298K (λex = 300nm);

[0042] Figure 3 Test electron microscope images provided for some embodiments of the present application: (a) transmission electron microscope (TEM) image of G, (b) transmission electron microscope (TEM) image of G / LP;

[0043] Figure 4Test graphs provided for some embodiments of the present application: (a) x-ray photoelectron spectroscopy XPS of LP and LP / Eu; (b) fluorescence spectrum of LP / Eu in water at 298K (λex=254nm); (c) dynamic prompt photoluminescence spectrum of G / LP / Eu in water at 298K (λex=254nm, LP=0.3wt%); (d) dynamic prompt photoluminescence spectrum of G / LP / Eu in water at 298K (λex=300nm, LP=0.3wt%); (e) CIE chromaticity diagram corresponding to the dynamic change spectra of G and LP / Eu in water at 298K (λex=254nm and λex=300nm, LP=0.3wt%) under different excitations; (f) transmission electron microscopy (TEM) of LP and (g) LP / Eu and corresponding mapping;

[0044] Figure 5 Test figures provided for some embodiments of the present application: (a) NZO, (b) MAZ, (c) SAZ instantaneous photoluminescence spectra added to G aqueous solution; (d) NZO, (e) MAZ and (f) SAZ corresponding to G / LP (λem=380nm and λem=516nm) luminescence quenching efficiency ([G]=0.01mM, LP=2wt%, [NZO]=70nm, [MAZ]=70nm, [SAZ]=70nm);

[0045] Figure 6 Test figures provided for some embodiments of the present application: (a) Fast photoluminescence spectra of NZO, (b) MAZ, and (c) SAZ added to LP / Eu aqueous solution; (d) Luminescence quenching efficiency of NZO, (e) MAZ, and (f) SAZ corresponding to LP / Eu (λem=616nm) (LP / Eu=0.5wt%, [NZO]=70nM, [MAZ]=70nM, [SAZ]=70nM);

[0046] Figure 7Test graphs provided for some embodiments of the present application: (a) transient photoluminescence spectrum of aqueous solution G / LP / Eu added with NZO at 298K (λex=254nm); (b) emission spectrum of G / LP / Eu in aqueous solution to different antibiotics (λex=254nm); (c) luminescence quenching efficiency of different antibiotics to G / LP / Eu at 380nm, 516nm and 616nm; (d) transient photoluminescence spectrum of aqueous solution G / LP / Eu at 298K (λex=254nm) after adding DPA; (e) 616nm / 380nm and 616nm / 516nm ratios of G / LP / Eu under 254nm and 300nm irradiation; (f) fast photoluminescence spectrum of NZO added after adding DPA to G / LP / Eu at 298K (λex=254nm); (g) graphical working mechanism of phosphorescence energy transfer process and induction;

[0047] Figure 8 Test images provided for some embodiments of the present application: (a) Combinatorial logic gate system based on component luminescent colors and corresponding truth tables (a and b represent the white light output and yellow light output of the logic gate, respectively); (b) Photos of supramolecular ink multilayer information storage under 254nm and 300nm irradiation ([G] = 0.01mM, [LP] = 2wt%, DPA = 60nm, NZO = 70nm); (c) Gel detection of the letters "NKU" and "IMMU" Schematic diagram and photograph of ZO ([G] = 0.01mM, [LP] = 2wt%, DPA = 60nM, NZO = 70nM); (d) the numbers "1-6" and "7-12" represent the R, G, B and R / B values ​​of the photos of "G, G / LP-0min, G / LP-60min, G / LP / Eu, G / LP / Eu / DPA, G / LP / Eu / DPA / NZO" under irradiation of 254nm and 300nm, respectively. DETAILED DESCRIPTION

[0048] In order to better understand the technical solution of the present application, the embodiments of the present application are described in detail below with reference to the accompanying drawings.

[0049] It should be clear that the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present application.

[0050] Unless expressly stated to the contrary, all ranges cited in this application are inclusive.

[0051] The term "a" or "an" used in this application is used to describe the elements and components described in this application. This is done only for convenience and to provide a general sense of the scope of this application. This description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that it is otherwise intended. "Multiple" means two or more.

[0052] The numbers in this application are approximate, regardless of whether the words "about" or "approximately" are used. The numerical values ​​of the numbers may vary by 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a number with a value of N is disclosed, any number with a value of N+ / -1%, N+ / -2%, N+ / -3%, N+ / -5%, N+ / -7%, N+ / -8% or N+ / -10% will be explicitly disclosed, where "+ / -" means plus or minus, and the range between N-10% and N+10% is also disclosed.

[0053] In the prior art, multicolor lanthanide supramolecular RTP materials with time dependence still face great challenges in aqueous solution.

[0054] In order to solve the above technical problems, the present application discloses a supramolecular lanthanide phosphorescent four-dimensional assembly material, which includes: a 4-(4-bromophenyl) pyridinium salt derivative G and an inorganic clay LP / Eu complex.

[0055] Supramolecular molecules in this application refer to molecular aggregates with specific structures and functions formed by the combination of two or more chemical species through intermolecular non-covalent bond interactions (such as hydrogen bonds, van der Waals forces, electrostatic forces, coordination bonds, etc.).

[0056] The lanthanide phosphorescent four-dimensional assembly material of the present application is a new type of material that combines the optical properties of lanthanide elements and supramolecular assembly technology, and has a unique structure and excellent optical properties. 3 +, etc.) can emit strong and stable fluorescence and phosphorescence due to their unique electronic structure. Four-dimensional assembly technology not only involves the construction of structures in three-dimensional space, but also introduces the dimension of time or dynamic regulation. For example, through supramolecular multivalent assembly, supramolecular structures with high temperature stability and excellent phosphorescence properties can be constructed.

[0057] The inorganic clay LP of this application is called lithium magnesium silicate. It is a synthetic lithium magnesium silicate clay with a unique layered structure and excellent physical and chemical properties. Its chemical formula is Na 0.7 (Si 8 Mg 5.5 Li 0.3 ) 20 (OH) 4 -0.7. It has a layered structure consisting of two tetrahedral silicate layers sandwiched by an octahedral magnesium ion layer. The magnesium ions can be partially replaced by lithium ions, making the surface negatively charged. The diameter of a single nanosheet is about 25-30nm and the thickness is about 1nm. After being dispersed in water, the surface negative charge is significant, and it can bind to a variety of molecules while maintaining a certain stability.

[0058] Eu (europium) in the present application belongs to the lanthanide series and has two valence states of +2 and +3. Its unique electronic structure enables it to exhibit excellent performance in luminescent materials.

[0059] In some embodiments, the 4-(4-bromophenyl)pyridinium salt derivative G has the following structure:

[0060]

[0061] The derivatives in the present application refer to the hydrochloride of 4-(4-bromophenyl)pyridinium salt.

[0062] In some embodiments, the ratio between the amount of the 4-(4-bromophenyl)pyridinium salt derivative G and the mass of the inorganic clay LP / Eu complex is 0.01 mmol / 0.03-0.06 g.

[0063] In these embodiments, the present application discloses that the ratio between the amount of the above-mentioned 4-(4-bromophenyl)pyridinium salt derivative G and the mass of the inorganic clay LP / Eu complex is any one of 0.01mmol / 0.03g, 0.01mmol / 0.04g, 0.01mmol / 0.05g, 0.01mmol / 0.06g or any one of the values ​​satisfying any two of the above ranges.

[0064] In some embodiments, the above materials further include dipicolinic acid.

[0065] In some embodiments, the aforementioned dipyridine carboxylic acid includes pyridine-2,6-dicarboxylic acid.

[0066] The pyridine-2,6-dicarboxylic acid of the present application can be used as an organic chromophore molecule of an electron-withdrawing group to obtain an organic two-photon absorption material with strong coordination ability.

[0067] In some embodiments, the ratio between the amount of dipicolinic acid and its carboxylate and the mass of the inorganic clay LP / Eu complex is 0.07 mmol / 0.006 g to 0.01 g.

[0068] In these embodiments, the present application discloses that the ratio between the amount of pyridinedicarboxylic acid and its carboxylate salt to the mass of the inorganic clay LP / Eu complex is any one of 0.07mmol / 0.006g, 0.07mmol / 0.007g, 0.07mmol / 0.008g, 0.07mmol / 0.009g, 0.07mmol / 0.01g or any one of the values ​​satisfying any two of the above ranges.

[0069] The second aspect of the present application is to provide a method for preparing a supramolecular lanthanide phosphorescent four-dimensional assembly material, the preparation method comprising the following preparation process:

[0070] providing a 4-(4-bromophenyl)pyridinium salt derivative G as a guest;

[0071] preparing LP / Eu host complex;

[0072] The above guest is assembled with the above LP / Eu host complex to prepare a four-dimensional assembly material.

[0073] In some embodiments, the above steps of preparing the LP / Eu host complex include:

[0074] dispersing LP in water to obtain LP dispersion;

[0075] dispersing a salt precursor of Eu into a LP dispersion;

[0076] Heat up and reflux for a period of time;

[0077] The LP / Eu main complex is obtained by cooling and post-treatment.

[0078] In some embodiments, the reflux temperature is 80° C. to 120° C., and the reflux time is 20 h to 36 h.

[0079] The present application discloses in these embodiments that the reflux temperature is any one of 80° C., 90° C., 100° C., 110° C., 120° C. or any one of the values ​​within the range of any two of the above.

[0080] The present application discloses in these embodiments that the reflux time is any one of 20 h, 24 h, 28 h, 32 h, 36 h or any one of the ranges satisfying any two of the above values.

[0081] In some embodiments, the step of assembling the guest and the LP / Eu host complex to prepare a four-dimensional assembly material comprises:

[0082] At room temperature, the LP / Eu main complex is added to the guest, and the four-dimensional assembly material is obtained after the mixture reaches a dissolved state.

[0083] The third aspect of the present application is to provide an application of the four-dimensional assembly material described in the first aspect in information multi-level logic anti-counterfeiting.

[0084] The fourth aspect of the present application is to provide a use of the four-dimensional assembly material described in the first aspect in the preparation of a high-efficiency antibiotic selection sensor, characterized in that it includes selective detection of any one or more of nitrofurazone (NZO), metronidazole (MAZ) or sulfamethoxazole (SAZ).

[0085] Reagents and Materials: All chemicals were commercially available unless otherwise stated. 4-(4-Bromophenyl)pyridine was purchased from bidepharm and ethyl bromide from heown. NMR spectra were recorded on a Bruker AV500 spectrometer. Steady-state fluorescence data were collected by a Varian Cary Eclipse fluorescence spectrometer and a Hitachi fluorescence spectrophotometer (F-4600S). UV-visible spectra and transmittance were recorded on a Shimadzu UV-3600 spectrophotometer equipped with a PTC-348WI thermostat using a quartz cell (path length, 10 mm). Photoluminescence spectra and fluorescence lifetimes were measured by time-correlated single photon counting on an FLS1000 instrument (edinburgh Instruments, Livingstone, UK). High-resolution transmission electron microscopy images were obtained using a Tecnai 20 high-resolution transmission electron microscope at an accelerating voltage of 200 keV; samples were prepared by dropping the solution on a copper grid and then air-drying it. Zeta potential was measured on a Nanobrook 90 Plus at 298 K. Ion exchange was tested using a Shimadzu X-ray photoelectron spectrometer. Electrospray ionization mass spectra were measured using an Agilent 6520Q-TOF-MS.

[0086] Example 1: Synthesis route of G

[0087] 3-Bromopropane-1-amine hydrobromide (0.23 g, 1.00 mmol) was added to a solution of 4-(4-bromophenyl)pyridine (0.47 g, 2.00 mmol) in acetonitrile (50 mL). The solution was heated under reflux for 2 h to produce a large amount of precipitation. The reaction mixture was cooled to room temperature and filtered, and the solid was thoroughly washed with acetonitrile to obtain a light yellow solid G (0.15 G, 67%). 1 HNMR (500MHz D 2 O 25℃) δ8.75(d J=7.0Hz,2h),8.35(d J=6.9Hz,2h),7.71--7.70(m,4h),4.60--4.57(m,2h),3.04--3.01(m,2h),2.34--2.28(m,2h). 13 C NMR (125MHz, D 2O, 25℃) δ156.09,144.24,132.78,132.75,129.61,126.71,125.23,57.68,36.20,28.32. C 14 H 16 Br 2 N 2 HRMS(ESI): Calculated. [M-HBr-Br] + :291.0497, measured molecular weight: 291.0497.

[0088]

[0089] Example 2: Preparation of G / LP assembly

[0090] Preparation process of G / LP assembly: Add 0.04g LP to 2ml G (0.01mM) at 25°C and dissolve it in 1min.

[0091] The positive charge of G makes it suitable for assembling with LPs with orthogonal surface (negative charge) and edge (positive charge). The optical properties of G-LP aqueous solution were studied by UV-visible spectroscopy and photoluminescence spectroscopy. The UV-visible spectrum of G showed that the maximum absorption intensity of G at 307nm gradually increased with the addition of LP, accompanied by a red shift of the maximum value to 330nm (Figure 2). Figure 1 (shown in a).

[0092] To further understand the assembly process after adding LP to G, the change in light transmittance was also monitored. Figure 1 As shown in Figure b, with pure water as the reference sample, the transmittance of G did not change. However, the addition of 1-2% LP to G causes a sharp drop in the transmittance of G / LP at 450nm, indicating that the electrostatic interaction between them is conducive to the formation of large nanostructures. G / LP and monomer G can also be easily distinguished by the Tyndall effect. After adding LP to G, the electrostatic interaction between LP and G and the hydrogen bonding and π-π stacking interactions between G molecules may change the electron density of the G molecule, thereby changing the excited state properties of the G molecule, thereby enhancing the absorption of the G molecule at a specific wavelength. Then, the formation of the G / LP assembly changes the electronic structure of the G molecule and causes changes in its luminescence properties.

[0093] By photoluminescence spectroscopy (Fig. Figure 1As shown in c), the present application found that after adding LP at concentrations of 0.5wt%, 1wt% and 2wt% to G, the fluorescence emission of G at 380nm continued to enhance. The luminescence intensity increased by 4 times, the quantum yield increased by 1.3 times, while the lifetime remained basically unchanged (1ns and 1.3ns, respectively). Combined with the delayed phosphorescence spectrum, an obvious new phosphorescence emission peak appeared at 516nm. When the LP addition amount was 2wt%, the phosphorescence quantum yield reached 7.93% and the lifetime was 2ms. After the introduction of N2 gas, the luminescence intensity increased by 2 times, the lifetime increased by 1.8 times, and the yield increased by 2.4 times, further proving the phosphorescence at 516nm ( Figure 1 d). However, when LP was added to 3 wt%, both the fluorescence at 380 nm and the phosphorescence at 516 nm began to be quenched, which may be caused by the competitive interaction of the excess charges.

[0094] Comparative Example 1

[0095] Quaternary ammonium salt cationic β-cyclodextrin (ACD) and ethyleneimine polymer (PEI) were added to the LP solution to neutralize the negative charge on LP, and then assembled with G. After further assembly with G, the luminescence of the assembly LP / ACD or LP / PEI was greatly suppressed, which was mainly due to the neutralization of the negative charge on LP by the positive charge of ACD or PEI. In addition, when negatively charged sodium carboxymethyl cellulose (CMC) and hyaluronic acid (HA) were added to the aqueous solution of G, there was no obvious emission peak at 516nm. This phenomenon proves that the non-covalent interaction between LP and G is mainly electrostatic interaction, and the strong rigid structure of LP is conducive to limiting the non-radiative transition of G molecules.

[0096] Example 3: Dynamic time-dependent study of the luminescence properties of the G / LP assembly

[0097] After 60 minutes of ultrasound action, the changes in the photoluminescence properties of 2wt% LP with the best photoluminescence performance were monitored. After the addition of LP, the fluorescence enhancement at 380nm increased with time. The 380nm fluorescence emission intensity reached the optimal state at 24 minutes and was stable for 60 minutes. The luminescence intensity increased by 4 times, the quantum yield increased by 2 times (from 7.32% to 14.85%), and the fluorescence lifetime was stable (from 1.3ns to 2ns). The new phosphorescence at 516nm also changed significantly. After 60 minutes, the luminescence intensity increased by 9.5 times, and the phosphorescence quantum yield reached 27.53%, an increase of 3.4 times. In addition, the phosphorescence lifetime increased to 7.4ms, which increased by 3.7 times (Figure 2 Figure 2 (as shown in a, b, c, and d).

[0098] Two-dimensional projection diagram of CIE's xy chromaticity diagram (see attached figure) Figure 2(as shown in Figure e), we can also observe the trend of the emission color change after LP was added to G for 60 minutes, from cyan (0.22, 0.36) to bright green (0.26, 0.49). Subsequently, in order to explore the assembly mode, the changes in zeta potential and morphology after assembly formation were studied. The potential of G was measured to be 7.64 mV, showing a positive charge, which can be assembled with negatively charged host compounds. LP is an orthogonally charged inorganic rigid silicate natural clay. Once LP (zeta potential of -50.34 mV) forms an assembly with G, the zeta potential increases to -38.42 mV, indicating that the positively charged G has an electrostatic interaction with the negatively charged LP surface (Figure S14). Transmission electron microscopy (TEM) was used to observe the morphological changes. The TEM image of the assembly G / LP shows many lamellar aggregates, which are very different from the spherical morphology of G, revealing the formation of the assembly (Figure Figure 3 ).

[0099] Example 4: Preparation of LP / Eu host complex

[0100] To obtain white-light emission, we prepared the LP / Eu host complex by replacing the sodium ions in LP with lanthanide europium ions through a simple ion exchange reaction.

[0101] The preparation process of LP / Eu main complex is as follows: 20 mL of water was added to 0.5 g of LP to dissolve it, and then 0.183 g of EuCl was added. 3 6H 2 O, refluxed at 100 °C for 24 hours, and finally centrifuged to obtain a LP / Eu gel.

[0102] The composition and chemical bonds of LP and LP / Eu were analyzed by XPS (Figure 2 Figure 3 a). The full spectrum peaks of LP are 49.72eV, 101.72eV, 531.72eV, 1071.73eV and 1303.73eV, corresponding to Li(1s), Si(2p), O(1s), Na(1s) and Mg(1s), respectively. In the XPS spectrum of LP / Eu complex, the Na 1s peak disappears and the Eu 3d peak appears, indicating that the LP / Eu complex is successfully prepared.

[0103] The TEM images of LP and LP / Eu both show a large number of lamellar aggregates. The TEM mapping images show that compared with LP, the Na + The content of Eu 3+ The content of LP / Eu increased significantly, proving that the exchange of LP / Eu was successful. The fluorescence emission spectrum of the LP / Eu complex was measured under 254nm excitation, as shown in the figure Figure 3As shown in Fig. 2a, the characteristic emission peaks of europium are 593 nm (5D0→7F1), 616 nm (5D0→7F2), 653 nm (5D0→7F3) and 701 nm (5D0→7F4). The fluorescence lifetime and quantum yield are 0.3 ms and 1.22% respectively.

[0104] Example 5: Preparation of component G / LP / Eu by guest G and host LP / Eu

[0105] The guest G and the host LP / Eu were prepared as follows: 0.04 g LP / Eu was added to 2 ml G (0.01 mM) at 25°C and dissolved in 1 min.

[0106] When 0.3wt% of LP / Eu is added, the blue fluorescence at 380nm and the green phosphorescence at 516nm are enhanced, indicating that the assembly of G / LP / Eu also has the same phenomenon. The characteristic emission peak of rare earth europium was also observed in this embodiment, indicating that the ion exchange host LP / Eu has no effect on the luminescence of g. After 60 minutes of ultrasonic dissolution, the luminescence at 380nm and 516nm is further enhanced. Since blue fluorescence, green phosphorescence and red rare earth luminescence are emitted after adding LP / Eu to the guest G, the luminescence of the assembly changes from blue to light pink under 254nm excitation, and gradually becomes a strong white light emission after 60 minutes, and the corresponding CIE coordinates are (0.16, 0.03), (0.37, 0.24) and (0.32, 0.34), respectively.

[0107] At an excitation wavelength of 300nm, since the rare earth europium cannot be excited to emit light, the component G / LP / Eu emits a weak blue-green light, and can emit green light after 60 minutes, corresponding to CIE coordinates (0.23, 0.35) and (0.21, 0.17), respectively. Adding an excess of LP / Eu to the G aqueous solution can emit a strong pink light at an excitation wavelength of 254nm, and can emit a light yellow light after 60 minutes, with CIE coordinates of (0.44, 0.32) and (0.39, 0.40), respectively. At an excitation wavelength of 300nm, the corresponding green light and bright green light are emitted, and their CIE coordinates are (0.25, 0.34) and (0.24, 0.40), respectively. By adjusting the time and the ratio of guest G to host LP / Eu, multi-color full-spectrum luminescence including white light can be achieved.

[0108] Example 6: Antibiotic Detection Application

[0109] As shown in the attached picture Figure 5 As shown in a, 5b, and 5c, different antibiotics (70 nM) (nitrofuranone NZO, nitrofuranone MAZ, sulfathiazine SAZ) were added to the G / LP aqueous solution. Figure 5d, 5e, and 5f calculated the quenching efficiency at 380 nm and 516 nm. The quenching efficiency of NZO (>95%, >70%) was higher than that of MAZ (<70%) and SAZ (<70%).

[0110] When the quenching efficiency was calculated by adding three antibiotics to LP / Eu, the quenching efficiency of NZO (quenching efficiency at 616nm was 70%) was also better than that of other antibiotics (MAZ < 20%, SAZ < 30%), as shown in the attached figure Figure 6 shown.

[0111] White light G / LP / Eu components have good selective detection effect on NZO, as shown in the attached figure Figure 7 a-7c. In G / LP / Eu, the quenching efficiency of NZO at 380nm, 516nm and 616nm reached 95%, 61% and 66% respectively, while the quenching efficiency of MAZ and SAZ was relatively weak (<50%).

[0112] Example 7: Detection of Bacillus anthracis pathogen

[0113] Dipicolinic acid (DPA) calcium salt constitutes 5-15% of the bacterial dry weight and is a specific biomarker for anthrax.

[0114] In the LP / Eu complex, as DPA was gradually added to 70nm nM, the luminescence of LP / Eu / DPA after secondary complexation gradually increased (from pink to bright red), the luminescence intensity increased by 234 times, the yield increased by 4 times, and the lifetime increased from 0.3ms to 0.4ms. When 70nM DPA was gradually added to the dynamic assembly LP / G, it was found that the luminescence at 380nM and 516nM was gradually quenched, and the quenching rates were 36% and 42%, respectively. Therefore, it was concluded that the white light luminescent component G / LP / Eu is conducive to the DPA secondary component to achieve high-selectivity detection of the ratio.

[0115] After DPA was gradually added to the G / LP / Eu component for four-dimensional assembly, the Eu 3+ The characteristic emission peaks (593nm, 616nm, 653nm and 701nm) of Eu increased dramatically (luminescence intensity increased by 7 times). 3+ The emission intensity at 616 nm doubled, while the fluorescence at 380 nm and the phosphorescence at 516 nm weakened, with the quenching efficiency surprisingly reaching 70% and 68%, respectively (Figure Figure 7 d, 7e), accompanied by a transition from white light to orange-red light. Therefore, the G / LP / Eu assembly can be effectively used for ratiometric detection even in the mildest anthrax risk.

[0116] Furthermore, the present application can use the four-dimensional component G / LP / Eu@DPA to further realize the selective detection of NZO in aqueous solution. The quenching efficiency at 616nm can reach 70% (Figure Figure 7 f), with the further quenching of blue fluorescence and green phosphorescence, the orange luminescence of the solution further approaches colorless.

[0117] Therefore, combined with the above data, this dramatic increase in fluorescence and phosphorescence properties over time may be due to the electrostatic interaction between LP and G in the assembled G / LP and the π-π stacking and hydrogen bonding between G, which increases the ISC process of guest G and restricts non-radiative transitions. At the same time, LP gradually dissolves, and the electrostatically driven "house of cards" between LP gradually assembles with G over time, forming a "domino effect" superimposed restriction effect and reducing collisions with oxygen in water to a certain extent (see Figure 2). Figure 7 g). The addition of DPA forms a coordination effect with rare earth ions, and energy transfer leads to enhanced luminescence. The quenching mechanism of DPA's fluorescence 380nm and phosphorescence 516nm may be caused by the interaction of photoinduced electron transfer PET and G / LP / Eu excited state co-absorption and energy transfer with rare earth ions. Similarly, antibiotics are also quenched by fluorescence, phosphorescence and rare earth ions caused by PET and co-absorption.

[0118] Example 8: Dynamic time-varying "domino effect" adjustable multicolor phosphorescent four-dimensional components can be applied to multi-layer logic gate anti-counterfeiting system

[0119] The device of the present application defines the different components of the assembly as input, and defines the white light emission with an excitation wavelength of 254 nm as output (Figure Figure 8 a). Based on the white light output recorded as "1" and the non-white light output recorded as "0", an inhibitory continuous logic gate system with light output is designed. The output "0" and "1" states of the current logic gate represent several different types of supramolecular assemblies.

[0120] In the logic gate system, when G / LP / Eu / 254nm coexist, the white light emission can be "locked" and 300nm is used as a NOT gate to "mute" the output signal, and then DPA and NZO are used to assemble the output white light respectively. This continuous logic gate system defines the fluorescence emission intensity of 616nm and the excitation of 254nm as the output. The fluorescence intensity of the upper 5×105 output is recorded as "2", and the fluorescence intensity of the lower 5×105 output is recorded as "0".

[0121] When G / LP / Eu / 254nm / DPA coexists, the yellow light emission can be "locked" and the output signal can be "muted" using NZO as a NOT gate, which is clearly shown in the truth table. This simple logic gate based on LP supramolecular assembly can output complex information after adding multiple input elements, providing great potential for the construction of complex logic gate circuits.

[0122] Example 9: LP supramolecular assembly suitable for multi-level information encryption

[0123] On a multi-well plate (Fig. Figure 8 b), under irradiation of 254nm, the addition of G to the main LP, the addition of LP / Eu to aqueous solution and G, and the addition of excess LP / Eu to G can emit dark green, red, light red and light purple luminescent characters "1919", respectively. The G / LP / Eu assembly was added to the small "1", and after 60 minutes, the "1958" character was given different colors of luminescence (bright green, red, white and light yellow, respectively). With the further addition of DPA, "1958" can turn into light green, bright red, yellow and orange light, respectively. Finally, after the addition of NZO, almost all of them were quenched, and only 9 could vaguely show a weak red color. The porous plate on each step can emit luminescent characters "119" of different colors under irradiation of 300nm, namely light green "1" and light blue "1" and "9", respectively. After standing for 3 hours, the numbers showed a brighter "119", and with the continuous addition of DPA and NZO, the numbers gradually darkened. As shown in the attached figure Figure 8 As shown in c, we used agarose to further form modular gels of different assemblies G, G / LP, LP / Eu, G / LP / Eu, LP / Eu@DPA, and G / LP / Eu@DPA aqueous solutions to spell out "NKU" and "IMMU". Under 254nm irradiation, the different colored letters of "NKU" were blue "N" (G), light green "K" (G / LP), and light yellow "U" (LP / Eu), and the letters of "IMMU" were white "I" (G / LP / Eu@1h), bright red "M" (G / LP / Eu@1hDPA), and orange "U" (LP / EuDPA). Under 300nm irradiation, the different colored letters of "NKU" were light green "N", bright green "K", and "U", and the letters of "IMMU" were bright green "I", colorless "M", and bright green "U", writing NKU@IU. After adding the antibiotic NZO, the luminescence at 254nm and 300nm was almost completely quenched, but different weak colors were still present.

[0124] A series of pictures excited at 254nm and 300nm were collected with a smartphone and analyzed with color recognition software to obtain their RGB values. By calculating the R / G value, the addition of LP, 60 minutes later, and the addition of DPA all showed a good linear relationship with the R / G value. The R / G value dropped sharply after the addition of NZO (see Figure 2). Figure 8 d).

[0125] In summary, the material provided in this application has good application prospects in information multi-level logic anti-counterfeiting and efficient antibiotic selection.

[0126] The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for a person skilled in the art, according to the idea of ​​the present application, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

[0127] For example, certain words are used in the specification and claims to refer to specific components. Those skilled in the art should understand that hardware manufacturers may use different nouns to refer to the same component. This specification and claims do not use differences in names as a way to distinguish components, but use differences in the functions of components as the criteria for distinction. As mentioned throughout the specification and claims, "including" and "comprising" are open-ended terms, so they should be interpreted as "including / including but not limited to". "Approximately" means that within an acceptable error range, those skilled in the art can solve the technical problem within a certain error range and basically achieve the technical effect. The subsequent description of the specification is a preferred embodiment of the present application, but the description is for the purpose of illustrating the general principles of the present application, and is not used to limit the scope of the present application. The scope of protection of the present application shall be determined by the definition of the attached claims.

[0128] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a product or system including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such a product or system. In the absence of more restrictions, the elements defined by the sentence "comprises a ..." do not exclude the existence of other identical elements in the product or system including the elements.

[0129] It should be understood that the term "and / or" used in this article is only a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0130] The above is only a preferred specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A supramolecular lanthanide phosphorescent four-dimensional assembly material, characterized in that: include: 4-(4-Bromophenyl)pyridinium salt derivative G and inorganic clay LP / Eu complex.

2. The four-dimensional assembly material according to claim 1, characterized in that: The 4-(4-bromophenyl)pyridinium salt derivative G has the following structure:

3. The four-dimensional assembly material according to any one of claims 1 to 2, characterized in that: The ratio between the amount of the 4-(4-bromophenyl)pyridinium salt derivative G and the mass of the inorganic clay LP / Eu complex is 0.01 mmol / 0.03-0.06 g.

4. The four-dimensional assembly material according to any one of claims 1 to 2, characterized in that: The materials also include dipicolinic acid and its carboxylate salts.

5. The four-dimensional assembly material according to claim 4, characterized in that: The dipyridine carboxylic acid includes pyridine-2,6-dicarboxylic acid; and / or; The ratio between the amount of the pyridine dicarboxylic acid and its carboxylate and the mass of the inorganic clay LP / Eu complex is 0.07mmol / 0.006g-0.01g.

6. A method for preparing a supramolecular lanthanide phosphorescent four-dimensional assembly material, characterized in that: The preparation process includes the following: providing a 4-(4-bromophenyl)pyridinium salt derivative G as a guest; preparing LP / Eu host complex; The guest is assembled with the LP / Eu host complex to produce a four-dimensional assembly material.

7. The preparation method according to claim 6, characterized in that: The steps of preparing the LP / Eu main complex include: dispersing LP in water to obtain LP dispersion; dispersing a salt precursor of Eu into a LP dispersion; Heat up and reflux for a period of time; Cooling and post-treatment to obtain LP / Eu main complex; Preferably, the reflux temperature is 80° C. to 120° C., and the reflux time is 20 h to 36 h.

8. The preparation method according to any one of claims 6 to 7, characterized in that: The step of assembling the guest and the LP / Eu host complex to prepare a four-dimensional assembly material comprises: At room temperature, the LP / Eu main complex is added to the guest, and the four-dimensional assembly material is obtained after the complex reaches a dissolved state.

9. Use of the four-dimensional assembly material according to any one of claims 1 to 5 in information multi-level logic anti-counterfeiting.

10. Use of the four-dimensional assembly material according to any one of claims 1 to 5 in preparing a highly efficient antibiotic selection sensor, characterized in that: Included are selective detection for any one or more of nitrofurazone (NZO), metronidazole (MAZ) or sulfamethazine (SAZ).

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