Spiropyrane-based dynamic photoresponse supramolecular lanthanide metal gel material as well as preparation method and application of spiropyrane-based dynamic photoresponse supramolecular lanthanide metal gel material

Abstract

The invention discloses a spiropyrane-based dynamic photoresponse supramolecular lanthanide series metal gel material as well as a preparation method and application of the spiropyrane-based dynamic photoresponse supramolecular lanthanide series metal gel material, and belongs to the technical field of dynamic luminescent materials. A plurality of non-covalent interactions (hydrogen bonds, pi-pi accumulation, Van der Waals force and metal coordination) are introduced for coordination and ordered self-assembly to form the spiropyrane-based dynamic photoresponse supramolecular lanthanide series metal gel material, and the spiropyrane-based dynamic photoresponse supramolecular lanthanide series metal gel material belongs to supramolecular gel. Fluorescence resonance energy transfer between lanthanide ions (Tb < 3 + >) and spiropyrane ligand double-luminescence centers realizes dynamic fluorescence change under supramolecular gel time dependence, and a microenvironment of gel similar to a solvent is beneficial to rapid ring opening isomerization of the spiropyrane ligand, so that the prepared dynamic supramolecular gel material has the characteristics of obvious fluorescence color change, high contrast ratio, high sensitivity, high sensitivity and the like. The method has the advantages of high response speed and the like, and has wide application potential and prospect in the advanced anti-counterfeiting field.

Description

Technical Field

[0001] The present invention belongs to the technical field of dynamic luminescent materials, and in particular relates to a spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material, and a preparation method and application thereof. Background Art

[0002] The booming development of globalization and the Internet has promoted the great prosperity of human economic society, but it has also led to an alarming increase in counterfeit and shoddy activities. At present, counterfeit and shoddy activities are widely present in all walks of life, causing huge economic losses and posing a serious threat to public safety. In order to resist and combat the increasingly rampant counterfeit and shoddy activities, it is necessary to develop higher-level anti-counterfeiting technologies and materials. Dynamic fluorescent anti-counterfeiting technology has attracted much attention due to its excellent safety performance and remarkable easy identification. Its fluorescent properties can change dynamically by changing the external stimulus, and the complexity and safety of anti-counterfeiting are higher. Supramolecular gel is a three-dimensional network structure formed by highly ordered self-assembly based on non-covalent bonds. It is easily affected by the external environment and changes. It is often used to construct smart materials that respond to external stimuli. Therefore, supramolecular gel and dynamic fluorescent material can be combined to prepare supramolecular dynamic fluorescent gel, which has the excellent characteristics of supramolecular gel such as stimulus responsiveness, flexibility, dynamic adjustability, reversibility, etc., while giving the gel dynamic fluorescent properties, which can be used in the field of advanced anti-counterfeiting.

[0003] At present, supramolecular dynamic fluorescent gel has been proven to have great development potential in the field of anti-counterfeiting, but it still faces many challenges. The non-covalent interaction force is weak, and it is difficult to self-assemble in an orderly manner to construct a stable supramolecular gel. There are relatively few studies on the combination of supramolecular gel and dynamic fluorescence, and there are problems such as low fluorescence color contrast, which also limits its advanced application in the field of anti-counterfeiting. Therefore, how to effectively use non-covalent interactions to construct supramolecular gels and at the same time make them have excellent dynamic luminescence ability is an urgent problem that researchers in this field need to solve. Summary of the invention

[0004] In order to solve the above technical problems, the present invention proposes a dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran and its preparation method and application. The present invention synthesizes two functionalized ligands (cholesterol ligand and spiropyran ligand), utilizes a variety of non-covalent interaction forces (hydrogen bond, π-π stacking, van der Waals force, metal coordination) to coordinate self-assembly to form supramolecular gel, introduces dual luminescent centers, and utilizes lanthanide ions (Tb 3+ ) and functionalized spiropyran derivatives to achieve time-dependent high-contrast dynamic fluorescence, thus achieving advanced anti-counterfeiting effects.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] One of the technical solutions of the present invention:

[0007] The present invention provides a spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material, the raw materials of which contain spiropyran ligands, cholesterol ligands and lanthanide metal compounds;

[0008] The structural formula of the spiropyran ligand is: The structural formula of the cholesterol ligand is The lanthanide metal compound is Tb(NO3)3·6H2O.

[0009] The molar ratio of the cholesterol ligand, the spiropyran ligand and the lanthanide metal compound is (99-91): (1-9): 50, wherein D 0.95 -SP 0.05 -Tb 3+ 0.5 It is the optimal molar ratio (ie, the molar ratio of the cholesterol ligand, the spiropyran ligand and the lanthanide metal compound is 95:5:50).

[0010] The preparation method of the cholesterol ligand is as follows:

[0011] Compound A1 and compound A2 are reacted by amidation to obtain an intermediate product B, wherein the structural formula of the compound A1 is The structural formula of the compound A2 is

[0012] The intermediate product B is hydrolyzed to obtain compound C, the structural formula of which is

[0013]

[0014] The compound C and the compound C1 are subjected to an amidation reaction to obtain the cholesterol ligand, and the structural formula of the compound C1 is

[0015] When preparing the intermediate product B: the solvent used is N,N-dimethylformamide (DMF), the catalyst is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCL), 1-hydroxybenzotriazole (HOBT) and 4-dimethylaminopyridine (DMAP), the protective gas of the reaction is nitrogen, the reaction temperature is room temperature, and the reaction time is 18h. Using compound A1 and compound A2 as raw materials, the route for preparing intermediate product B is as follows:

[0016]

[0017] When the intermediate product B is hydrolyzed to obtain compound C: the hydrolysis solution is trifluoroacetic acid (TFA), the solvent is dichloromethane (CH2Cl2), the protective gas of the reaction is nitrogen, the reaction temperature is room temperature, and the reaction time is 4h.

[0018] After obtaining the compound C, the method further includes a step of using a saturated sodium carbonate (Na2CO3) solution to adjust the pH to 10. The route of obtaining the compound C by hydrolyzing the intermediate product B is as follows:

[0019]

[0020] When the compound C reacts with the compound C1, the solvent is CH2Cl2, the catalyst is triethylamine (TEA), the protective gas of the reaction is nitrogen, the reaction temperature is room temperature, the reaction time is 18 hours, and the purification method is recrystallization from dichloromethane / methanol (volume ratio is 4:1). The route for preparing the cholesterol ligand (D) using the compound C and the compound C1 as raw materials is as follows:

[0021]

[0022] The preparation method of the spiropyran ligand is as follows:

[0023] Compound C and compound C2 are subjected to an amidation reaction to prepare the spiropyran ligand, wherein the structural formula of compound C is The structural formula of the compound C2 is

[0024] When preparing the spiropyran ligand: the solvent is CH2Cl2, the catalyst is EDCL, HOBT and DMAP, the protective gas of the reaction is nitrogen, the reaction temperature is room temperature, and the reaction time is 24h. Using compound C and compound C2 as raw materials, the route for preparing spiropyran ligand (SP) is as follows:

[0025]

[0026] The second technical solution of the present invention:

[0027] The present invention also provides a method for preparing the above-mentioned spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material, comprising adding cholesterol ligand and spiropyran ligand into toluene, heating and then standing to obtain a gel;

[0028] An acetonitrile solution of a lanthanide metal compound is added to the sol, and the sol is heated again and then allowed to stand to obtain the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material.

[0029] The preparation method of the acetonitrile solution of the lanthanide metal compound is as follows: dissolving Tb(NO3)3·6H2O in acetonitrile to obtain the acetonitrile solution of the lanthanide metal compound after dissolution.

[0030] The heating temperature is 75° C., and the cooling temperature is room temperature.

[0031] The volume ratio of toluene to acetonitrile is 4:1.

[0032] Furthermore, the preparation method of the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material is as follows:

[0033] The first step: preparing an acetonitrile solution of Tb(NO3)3·6H2O: dissolving Tb(NO3)3·6H2O in acetonitrile to obtain the acetonitrile solution of Tb(NO3)3·6H2O;

[0034] Step 2: Add cholesterol ligand and spiropyran ligand to toluene, heat at 75°C until the solution is completely clear, cool to room temperature, and form a gel after standing;

[0035] Step 3: Add the acetonitrile solution of Tb(NO3)3·6H2O to the above gel, heat the solution at 75°C until it is clear, cool it to room temperature, and prepare a dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran after standing.

[0036] Furthermore, the concentration of the acetonitrile solvent of Tb(NO3)3·6H2O prepared in the first step is 0.110 mol / L.

[0037] Furthermore, in the second step, the sum of the concentrations of the two ligands (spiropyran ligand and cholesterol ligand) in toluene is 0.055 mol / L, wherein the concentration of cholesterol ligand is (0.050-0.054) mol / L, and the concentration of spiropyran ligand is (0.005-0.001) mol / L.

[0038] Furthermore, the volume ratio of the acetonitrile added in the first step to the toluene used in the second step is 1:4.

[0039] The third technical solution of the present invention:

[0040] The present invention also provides the application of the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material in the field of advanced anti-counterfeiting. The spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material of the present invention has a fast color change speed and a high fluorescence color contrast. It can achieve a time-dependent dynamic change of the fluorescence color from green to yellow and then to orange in 3 minutes. Compared with most current anti-counterfeiting materials, it has better optical properties and a higher anti-counterfeiting level.

[0041] The principle of the present invention is that the supramolecular gel is assembled and formed through hydrogen bonding, π-π interaction, van der Waals force and metal coordination. The cholesterol ligand and the terpyridine group in the spiropyran ligand sensitize the lanthanide metal Tb3+ , emitting green fluorescence, the spiropyran ligand can be isomerized and ring-opened after ultraviolet irradiation, emitting red fluorescence, using the lanthanide metal Tb 3+ The fluorescence resonance energy transfer between the cholesterol ligand and the open-ring spiropyran ligand achieves a dynamic change in the fluorescence color of the supramolecular gel from green to orange-red. 3+ The final color of the gel can be adjusted by adjusting the ratio of

[0042] Compared with the prior art, the present invention has the following advantages and technical effects:

[0043] The present invention utilizes the coordinated effects of multiple non-covalent interaction forces (hydrogen bonds of amide bonds, π-π stacking of terpyridine, van der Waals forces of cholesterol, and metal coordination between lanthanide metal compounds and terpyridine) to successfully self-assemble into a dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran, which belongs to a supramolecular gel.

[0044] The present invention introduces a dual luminescence center and utilizes the lanthanide metal Tb 3+ The emission spectrum of the spiropyran was overlapped with the absorption spectrum of the open-ring spiropyran to achieve fluorescence resonance energy transfer, and a time-dependent dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran was successfully prepared with high color contrast. At the same time, the gel provides a solvent-like microenvironment for the isomerization of spiropyran, with a fast response speed and excellent color-changing performance.

[0045] The component prepared by the present invention is D 0.99 -SP 0.01 -Tb 3+ 0.5 The dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran, under the irradiation of ultraviolet light with a wavelength of 365nm, its fluorescence color changes from green to yellow-green within 3 minutes, indicating that the dynamic light-responsive supramolecular lanthanide gel material prepared by the present invention has a time-dependent dynamic change and a fast response speed;

[0046] The component prepared by the present invention is D 0.97 -SP 0.03 -Tb 3+ 0.5 The dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran has a fluorescence color from green to yellow under ultraviolet light with a wavelength of 365 nm, indicating that the dynamic light-responsive supramolecular lanthanide gel material prepared by the present invention has a dynamic change in time dependence;

[0047] The component prepared by the present invention is D 0.95 -SP 0.05 -Tb 3+ 0.5The dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran, under the irradiation of ultraviolet light with a wavelength of 365nm, its fluorescence color changes from green to yellow-orange within 3 minutes, indicating that the dynamic light-responsive supramolecular lanthanide gel material prepared by the present invention has a time-dependent dynamic change and a fast response speed;

[0048] The component prepared by the present invention is D 0.93 -SP 0.07 -Tb 3+ 0.5 The dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran, under the irradiation of ultraviolet light with a wavelength of 365nm, its fluorescence color changes from green to orange in 3min, indicating that the dynamic light-responsive supramolecular lanthanide gel material prepared by the present invention has a dynamic change in time dependence, a high fluorescence color contrast, and a fast response speed;

[0049] The component prepared by the present invention is D 0.91 -SP 0.09 -Tb 3+ 0.5 The dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran, under the irradiation of ultraviolet light with a wavelength of 365nm, its fluorescence color changes from green to dark orange within 3 minutes, indicating that the dynamic light-responsive supramolecular lanthanide gel material prepared by the present invention has dynamic changes in time dependence, high fluorescence color contrast, and fast response speed;

[0050] The dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran of the present invention has a fast color change speed and a high fluorescence color contrast. It can realize a time-dependent dynamic transition of fluorescence color from green to yellow and then to orange in 3 minutes. Compared with most current anti-counterfeiting materials, it has better optical properties and a higher anti-counterfeiting level. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0052] Figure 1 The components prepared in Example 2 of the present invention are D1-Tb 3+ 0.5 Fluorescence emission spectrum of supramolecular lanthanide metal gel material under 365nm ultraviolet irradiation (excitation wavelength 380nm);

[0053] Figure 2 The component prepared for Example 3 of the present invention is D 0.99 -SP 0.01 -Tb 3+ 0.5Fluorescence emission spectra of the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material at different times under 365nm ultraviolet irradiation (excitation wavelength 380nm);

[0054] Figure 3 The component prepared for Example 3 of the present invention is D 0.99 -SP 0.01 -Tb 3+ 0.5 Actual picture of the dynamic fluorescence changes of the dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran;

[0055] Figure 4 The component prepared for Example 3 of the present invention is D 0.97 -SP 0.03 -Tb 3+ 0.5 Fluorescence emission spectra of the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material at different times under 365nm ultraviolet irradiation (excitation wavelength 380nm);

[0056] Figure 5 The component prepared for Example 3 of the present invention is D 0.97 -SP 0.03 -Tb 3+ 0.5 Actual picture of the dynamic fluorescence changes of the dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran;

[0057] Figure 6 The component prepared for Example 3 of the present invention is D 0.95 -SP 0.05 -Tb 3+ 0.5 Fluorescence emission spectra of the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material at different times under 365nm ultraviolet irradiation (excitation wavelength 380nm);

[0058] Figure 7 The component prepared for Example 3 of the present invention is D 0.95 -SP 0.05 -Tb 3+ 0.5 Actual picture of the dynamic fluorescence changes of the dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran;

[0059] Figure 8 The component prepared for Example 3 of the present invention is D 0.93 -SP 0.07 -Tb 3+ 0.5 Fluorescence emission spectra of dynamic light-responsive supramolecular lanthanide gel materials at different times under 365nm ultraviolet irradiation (excitation wavelength 380nm);

[0060] Fig. 9 The component prepared for Example 3 of the present invention is D 0.93 -SP 0.07 -Tb 3+ 0.5 Actual picture of the dynamic fluorescence changes of the dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran;

[0061] Fig.10 The component prepared for Example 3 of the present invention is D 0.91 -SP 0.09 -Tb 3+ 0.5 Fluorescence emission spectra of the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material at different times under 365nm ultraviolet irradiation (excitation wavelength 380nm);

[0062] Fig.11 The component prepared for Example 3 of the present invention is D 0.91 -SP 0.09 -Tb 3+ 0.5 Actual image of the fluorescence changes of the spiropyran-based dynamic photoresponsive supramolecular lanthanide metal gel material. DETAILED DESCRIPTION

[0063] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0064] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0065] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0066] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0067] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0068] Unless otherwise specified, the room temperature in the present invention is 25±2°C.

[0069] All raw materials used in the examples of the present invention are commercially available.

[0070] Supramolecular gel is a supramolecular network structure containing a large amount of solvent formed by self-assembly of low molecular weight gelling agent molecules through non-covalent interactions. This self-assembly process can form a three-dimensional network, effectively fix the solvent, and thus form a gel. Supramolecular gel is not only a soft material itself, but also can controllably obtain various nanostructures while forming the gel. They have structural diversity and can show unique responsiveness to different external stimuli (such as solvent selection, light, ultrasound, temperature changes and the introduction of other additives), achieve microstructural transformation, and even change the function of the gel.

[0071] The multi-level structure of supramolecular gel is often divided into primary structure, secondary structure and tertiary structure. The primary structure involves molecular recognition and anisotropic aggregation between gel factors, and the scale is generally within angstroms to tens of nanometers; the secondary structure involves the morphology of aggregates in molecular gels, such as networks, and the scale is between a few nanometers and hundreds of nanometers; the tertiary structure refers to the further aggregation of the aggregate network through interaction, and the scale is between tens of nanometers and micrometers.

[0072] Supramolecular gels have a wide range of applications in the biomedical field, including biosensors, cell culture, tissue engineering, genetic engineering, wound treatment, local drug delivery, etc. Their highly specific non-covalent interactions include host-guest interactions, ionic interactions, metal-ligand interactions, biomimetic interactions, hydrogen bonds, and stereocomplex interactions, which give supramolecular gels good biocompatibility, biodegradability, gel-sol interconversion properties, and good and stable controlled drug release properties. The three-dimensional network structure of supramolecular gels can not only be used as drug carriers, but also as scaffolds for cell culture, tissue engineering materials, and gene carriers.

[0073] The present invention designs two functionalized ligands (cholesterol ligand and spiropyran ligand) and introduces a variety of non-covalent interactions (hydrogen bonds, π-π stacking, van der Waals forces, metal coordination) to coordinate and orderly self-assemble to form a dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran, which belongs to supramolecular gel. Lanthanide ions (Tb 3+ ) and the fluorescence resonance energy transfer between the dual luminescent centers of the spiropyran ligand realizes the dynamic fluorescence change of the supramolecular gel in a time-dependent manner. The solvent-like microenvironment of the gel is conducive to the rapid ring-opening isomerization of the spiropyran ligand, which makes the prepared dynamic supramolecular gel material have the advantages of obvious fluorescence color change, high contrast, and fast response speed. It has broad application potential and prospects in the field of advanced anti-counterfeiting.

[0074] The present invention utilizes the green fluorescence of lanthanide terbium ions as a donor and spiropyran as an acceptor, and utilizes fluorescence resonance energy transfer to achieve dynamic changes. Lanthanide ions have the advantages of long excitation lifetime, large Stokes shift, high quantum yield, etc., and terbium ions are easily quenched in a solution state. The cholesterol ligand and the terpyridine group in the spiropyran ligand designed by the present invention can sensitize lanthanide terbium ions.

[0075] It should be pointed out that the matters not described in detail in the present invention are conventional operating means in the art and are not the focus of the present invention.

[0076] The technical solution of the present invention is further illustrated by the following embodiments.

[0077] Example 1

[0078] Synthesis of cholesterol ligand D:

[0079] Step 1: Synthesis of compound B. The reaction route is as follows:

[0080]

[0081] 0.710 g of compound A1 was added to a 100 mL three-necked flask, 40 mL of DMF was added to dissolve, and 420 μL of compound A2, 0.620 g of EDCL, 0.360 g of HOBT and 0.026 g of DMAP were added, and the mixture was evacuated, nitrogen was passed through, and the mixture was reacted at room temperature for 18 h. After the reaction was completed, 300 mL of deionized water was added to produce a precipitate, which was allowed to stand for a while before being filtered and dried in vacuo to obtain compound B.

[0082] Step 2: Synthesis of compound C, the reaction formula is as follows:

[0083]

[0084] 0.671 g of compound B was added to a 100 mL three-necked flask, and 50 mL of CH2Cl2 was added to dissolve it. Compound TFA was then added and reacted at room temperature for 4 h. After the reaction was completed, the solution was distilled under reduced pressure, and a saturated aqueous solution of Na2CO3 was added dropwise to adjust the pH of the solution to 10. The solution was extracted with dichloromethane for 3 times and dried to obtain compound C.

[0085] Step 3: Synthesis of cholesterol ligand (D), the reaction route is as follows:

[0086]

[0087] 0.288 g of compound C was added to a 100 mL three-necked flask, 50 mL of CH2Cl2 was added to dissolve, 0.216 mL of LTEA and 0.450 g of compound C1 were added, vacuum was evacuated, nitrogen was passed, and the reaction was carried out at room temperature for 18 h. After the reaction was completed, it was washed with deionized water for 3 times, recrystallized with dichloromethane / methanol (volume ratio of 4:1), and dried to obtain cholesterol ligand (D).

[0088] The nuclear magnetic resonance hydrogen spectrum characterization data of cholesterol ligand (D) is: 1 H NMR(400MHz,Chloroform-d)δ8.79(s,2H),8.70(d,J=4.8,6.5Hz,2H),8.56(d,J=8.0Hz ,2H),7.86(td,J=7.8,1.9Hz,2H),7.53(s,1H),7.36(dd,J=7.4,4.9Hz,2H),5.34(d,J= 6.2Hz,1H),5.23(d,J=4.9Hz,1H),4.52(dt,J=12.0,6.3Hz,1H),3.66(q,J=5.8,5.8Hz, 2H), 2.24 (dd, J=24.9, 9.5Hz, 2H), 2.11-1.65 (m, 8H), 1.53-0.84 (m, 31H), 0.67 (s, 3H).

[0089] Example 2

[0090] Preparation of supramolecular lanthanide metal gels:

[0091] Weigh 0.4 g Tb(NO3)3·6H2O and dissolve it in 8 mL acetonitrile to prepare Tb 3+ / acetonitrile solution. Add 0.013 g of cholesterol ligand to 0.32 mL of toluene, heat at 75 °C for 10 min to completely dissolve it, let it stand at room temperature for 5 min to form a gel, and add 0.08 mL of Tb 3+ / acetonitrile solution, heated and stirred at 75°C until the solution was completely clear, and then allowed to stand at room temperature for 10 min to obtain supramolecular lanthanide metal gel D1-Tb 3+0.5 .

[0092] Example 3

[0093] Preparation of dynamic photoresponsive supramolecular lanthanide metal gel materials based on spiropyran:

[0094] The synthesis of spiropyran ligand (SP) is as follows:

[0095]

[0096] 0.344 g of compound C2, 0.252 g of EDCL, 0.148 g of HOBT and 0.011 g of DMAP were added to a 100 mL three-necked flask, 40 mL of CH2Cl2 was added to dissolve, vacuumed, nitrogen was passed, ice-water bath was placed for 1 h, and then 0.32 g of compound C was added, and the mixture was reacted at room temperature for 24 h. After the reaction was completed, the mixture was washed with deionized water and saturated brine for 3 times each, recrystallized with dichloromethane / petroleum ether (volume ratio of 3:1), the precipitate was filtered, and the spiropyran ligand (SP) was obtained after vacuum drying.

[0097] The nuclear magnetic resonance hydrogen spectrum characterization data of spiropyran ligand (SP) are: 1 H NMR(400MHz,Chloroform-d)δ8.61(d,J=4.7Hz,2H),8.50(s,2H),8.35(d,J=7.9Hz,2H),7 .85-7.76(m,3H),7.71(d,J=2.5Hz,2H),7.35(dd,J=7.3,4.9Hz,2H),7.08(t,J=7.7Hz,1H ),7.01(s,1H),6.97(d,J=7.7Hz,1H),6.79(t,J=7.4Hz,1H),6.56(dd,J=16.7,8.8Hz,3H) ,5.68(d,J=10.3Hz,1H),3.73-3.35(m,6H),2.63-2.39(m,2H),1.10(s,3H),1.01(s,3H).

[0098] Preparation of dynamic photoresponsive supramolecular lanthanide metal gel materials based on spiropyran:

[0099] Weigh 0.4 g Tb(NO3)3·6H2O and dissolve it in 8 mL acetonitrile to prepare Tb 3+ / acetonitrile solution. Add 0.061 g (0.0083 mmol) of cholesterol ligand and 0.003 g (0.0044 mmol) of spiropyran ligand into 1.6 mL of toluene, heat at 75 °C for 10 min to completely dissolve them, and let stand at room temperature for 5 min to form a gel. Add 0.4 mL of prepared Tb 3+ / acetonitrile solution, heated and stirred at 75°C until the solution was completely clear, and allowed to stand at room temperature for 10 minutes to prepare component D 0.95 -SP 0.05 -Tb 3+ 0.5 Dynamically photoresponsive supramolecular lanthanide metal gel materials based on spiropyran.

[0100] Only the molar ratio of cholesterol ligand to spiropyran ligand was changed, and the component D was prepared in the same way. 0.99 -SP 0.01 -Tb 3+ 0.5 , D 0.97 -SP 0.03 -Tb 3+ 0.5 , D 0.93 -SP 0.07 -Tb 3+ 0.5 , D 0.91 -SP 0.09 -Tb 3+ 0.5 Dynamically photoresponsive supramolecular lanthanide metal gel materials based on spiropyran.

[0101] Results: After irradiation with 365nm ultraviolet light, the components are D1-Tb 3+ 0.5 The fluorescence emission spectrum of supramolecular lanthanide metal gel (excitation wavelength: 380nm) is shown in Figure 1 shown.

[0102] 365nm ultraviolet light irradiation for different time, component D 0.99 -SP 0.01 -Tb 3+ 0.5 The fluorescence emission spectra of the dynamic light-responsive supramolecular lanthanide metal gel materials based on spiropyran (excitation wavelength: 380 nm) are shown in Figure 2. Figure 2 As shown in the figure, the fluorescence change diagram is as follows Figure 3 shown.

[0103] 365nm ultraviolet light irradiation for different time, component D 0.97 -SP 0.03 -Tb 3+ 0.5 The fluorescence emission spectrum of the dynamic light-responsive supramolecular lanthanide metal gel material (excitation wavelength: 380 nm) is shown in Figure 4 As shown in the figure, the fluorescence change diagram is as follows Figure 5 shown.

[0104] 365nm ultraviolet light irradiation for different time, component D 0.95 -SP 0.05 -Tb3+ 0.5 The fluorescence emission spectrum (excitation wavelength 380nm) of the dynamic light-responsive supramolecular lanthanide metal gel material is shown in Figure 6 As shown in the figure, the fluorescence change diagram is as follows Figure 7 shown.

[0105] 365nm ultraviolet light irradiation for different time, component D 0.93 -SP 0.07 -Tb 3+ 0.5 The fluorescence emission spectrum (excitation wavelength 380nm) of the dynamic light-responsive supramolecular lanthanide metal gel material is shown in Figure 8 As shown in the figure, the fluorescence change diagram is as follows Fig. 9 shown.

[0106] 365nm ultraviolet light irradiation for different time, component D 0.91 -SP 0.09 -Tb 3+ 0.5 The fluorescence emission spectrum (excitation wavelength 380nm) of the dynamic light-responsive supramolecular lanthanide metal gel material is shown in Fig.10 As shown in the figure, the fluorescence change diagram is as follows Fig.11 shown.

[0107] Depend on Figure 1 The composition is D1-Tb 3+ 0.5 The fluorescence emission spectrum of supramolecular lanthanide metal gel (excitation wavelength: 380nm) shows that after ultraviolet irradiation, Tb appears at 489nm, 542nm, 582nm and 621nm in the spectrum. 3+ The gel showed green fluorescence.

[0108] Depend on Figure 2 , Figure 4 , Figure 6 , Figure 8 and Fig.10 From the fluorescence emission spectrum, we can see that the component is D 0.99 -SP 0.01 -Tb 3+ 0.5 , D 0.97 -SP 0.03 -Tb 3+ 0.5 , D 0.95 -SP 0.05 -Tb 3+ 0.5， D 0.93 -SP 0.07 -Tb 3+ 0.5 , D 0.91 -SP0.09 -Tb 3+ 0.5 The dynamic photoresponsive supramolecular gel of lanthanide metal Tb after UV irradiation 3+ The four characteristic emission peaks (489nm, 542nm, 582nm and 621nm) of the lanthanide metal Tb decreased to varying degrees with the irradiation time, indicating that under ultraviolet light, 3+ Obvious energy resonance transfer occurs between spiropyran and the material, achieving a variety of dynamic fluorescence color responses.

[0109] Figure 3 , Figure 5 , Figure 7 , Fig. 9 and Fig.11 The fluorescence change diagram intuitively shows the dynamic change of the fluorescence color of the dynamic light-responsive supramolecular lanthanide metal gel material, showing a change trend from green to orange-red, with fast response speed and high contrast.

[0110] The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention 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 by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A dynamic light-responsive supramolecular lanthanide metal gel material based on spiropyran, characterized in that: The raw materials contain spiropyran ligands, cholesterol ligands and lanthanide metal compounds; The structural formula of the spiropyran ligand is: The structural formula of the cholesterol ligand is The lanthanide metal compound is Tb(NO3)3·6H2O.

2. The spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to claim 1, characterized in that: The preparation method of the cholesterol ligand is as follows: Compound A1 and compound A2 are reacted by amidation to obtain an intermediate product B, wherein the structural formula of the compound A1 is The structural formula of the compound A2 is The intermediate product B is hydrolyzed to obtain compound C, the structural formula of which is The compound C and the compound C1 are subjected to an amidation reaction to obtain the cholesterol ligand, and the structural formula of the compound C1 is 3. The spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to claim 2, characterized in that: When preparing the intermediate product B: the solvent used is N,N-dimethylformamide, the catalyst is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole and 4-dimethylaminopyridine, and the protective gas of the reaction is nitrogen.

4. The spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to claim 2, characterized in that: When the intermediate product B is hydrolyzed to obtain compound C, the hydrolysis solution is trifluoroacetic acid, the solvent is dichloromethane, and the protective gas for the reaction is nitrogen.

5. The spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to claim 4, characterized in that: After obtaining the compound C, the method further comprises the step of adjusting the pH value to 10 using a saturated sodium carbonate solution.

6. The spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to claim 2, characterized in that: When the compound C reacts with the compound C1, the solvent is dichloromethane, the catalyst is triethylamine, and the protective gas of the reaction is nitrogen.

7. The spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to claim 1, characterized in that: The preparation method of the spiropyran ligand is as follows: Compound C and compound C2 are subjected to an amidation reaction to prepare the spiropyran ligand, wherein the structural formula of compound C is The structural formula of the compound C2 is 8. The spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to claim 7, characterized in that: When preparing the spiropyran ligand, the solvent is dichloromethane, the catalyst is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole and 4-dimethylaminopyridine, and the protective gas of the reaction is nitrogen.

9. A method for preparing a spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to any one of claims 1 to 8, characterized in that: The cholesterol ligand and the spiropyran ligand are added to toluene, heated, cooled and allowed to stand to obtain a gel; An acetonitrile solution of a lanthanide metal compound is added to the sol, heated again, cooled and then allowed to stand to obtain the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material.

10. Application of the spiropyran-based dynamic light-responsive supramolecular lanthanide metal gel material according to any one of claims 1 to 8 in the field of advanced anti-counterfeiting.

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