CN114656404B - Amino acid gel factor, supermolecule hydrogel and preparation method thereof - Google Patents

Amino acid gel factor, supermolecule hydrogel and preparation method thereof Download PDF

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CN114656404B
CN114656404B CN202111628613.6A CN202111628613A CN114656404B CN 114656404 B CN114656404 B CN 114656404B CN 202111628613 A CN202111628613 A CN 202111628613A CN 114656404 B CN114656404 B CN 114656404B
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amino acid
rare earth
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CN114656404A (en
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王晓娟
林英武
李阳
魏传晚
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University of South China
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0065—Preparation of gels containing an organic phase
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide

Abstract

The invention provides a supermolecular hydrogel which is formed by an aqueous solution containing amino acid gel factors shown in a formula (I). Compared with the prior art, the supermolecule hydrogel provided by the invention has the advantages of good biocompatibility, degradability, low toxicity, good chemical stability and the like, and has wide application prospects in the fields of biological materials, medical treatment, agriculture, food and the like. Furthermore, the supermolecule hydrogel comprises rare earth ions as luminous factors, the rare earth ions are introduced into amino acid gel factors, fluorescent gel is formed under the crosslinking of the gel factors, the fluorescent gel has higher fluorescence intensity, and the amino acid gel factors have stronger selective response capability, so that the supermolecule hydrogel simultaneously has the characteristics of metal gel and hydrogel, combines the advantages of superior fluorescence performance of rare earth complexes, good biocompatibility of amino acid derivative main bodies, low toxicity and the like, and has wide application prospects in the fields of biological materials, medical treatment, agriculture, food, optical luminescence, technical anti-counterfeiting and the like.

Description

Amino acid gel factor, supermolecule hydrogel and preparation method thereof
Technical Field
The invention belongs to the technical field of supermolecular hydrogels, and particularly relates to an amino acid gel factor, a supermolecular hydrogel and a preparation method thereof.
Background
The supermolecular hydrogel constructed by the low molecular weight gel factor is an important soft material, contains a large number of water molecules in a three-dimensional fiber network, and has wide application prospect, especially in the biological field. These hydrogels are assembled by a variety of non-covalent interactions such as hydrogen bonding, pi-pi stacking, hydrophobic interactions, and van der Waals interactions. In addition to these interactions, metal hydrogels are formed by metal-ligand interactions, which are a branch of supramolecular hydrogels that contain metallic elements in the fiber as structural components. The introduction of metal ions enables the hydrogel to have the additional properties and functions of optics, electricity, magnetism, redox properties, catalysis and the like. Therefore, supramolecular hydrogels have become a hot spot of research in recent years. Functional groups such as carboxyl, pyridyl and the like are introduced into the gel factor, so that the gel has pH responsiveness; in addition, additives (e.g., metal ions, nanoparticles, etc.) may be added to alter the gel phase and properties.
Rare earth is a novel functional material with various characteristics of light, magnetism, electricity, biology and the like. Rare earth ions possess unique luminescent properties due to the unique structure of their 4f electron layer, which makes rare earth compounds widely used in medical, bioimaging, optical fibers, lighting devices, etc. The rare earth complex is obtained by coordination bonding of a ligand and rare earth ions, and the luminescence principle is that the ligand absorbs energy in the ultraviolet region, and then the ligand transmits the energy of an excited state to the emission energy level of the rare earth ions in a mode of energy transmission in molecules, so that the rare earth ions emit light. Fluorescent gels are a class of gels having fluorescent properties. Fluorescent gels may be accompanied by significant changes in fluorescence spectra during gel-sol or sol-gel phase transitions, which may provide important information for structural changes during phase transitions. Rare earth ions, because of their unique structure and properties, can be used as photosensitive molecules to be introduced into gel networks to prepare fluorescent gels. The rare earth compound is added into the corresponding polymer solution, and the coordination function of rare earth ions and the bonding function between ions are utilized to synthesize the rare earth polymer complex under certain conditions. The rare earth complex has the advantages of high luminous intensity, good fluorescence monochromaticity, good stability, long fluorescence life and the like.
Lanthanide metal complexes have attracted considerable attention due to their excellent optical properties, such as large stokes shift, narrow emission band, and long luminescence lifetime. The lanthanide coordination polymer has excellent photoluminescence and stimulus response performance, and is widely applied in the fields of illumination, imaging, sensing, anti-counterfeiting and the like. However, the luminescence of the rare earth complex is affected by various factors such as mechanical stimulus, temperature, preparation process and organic solvent requirements, and the application thereof is limited. To overcome these disadvantages, rare earth complexes are embedded in various matrices. But when the matrix is destroyed, the fluorescence disappears. Therefore, it is important to design a variety of ligands to construct a stable lanthanum containing fluorescent material.
In addition, in order to solve the optical instability problem of the rare earth fluorescent material, it can be solved by coating rare earth ions in a gel matrix as a structural component. Meanwhile, most of the reported lanthanide metal elements are formed in organic solvents, which limits their applications. Thus, how to design low molecular weight gel-based rare earth hydrogels with multiple stimuli-responsive properties that avoid the use of organic solvents remains a significant challenge.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide an amino acid gelator, a supermolecule hydrogel and a preparation method thereof, wherein the supermolecule hydrogel has the advantages of good biocompatibility, degradability, low toxicity, good chemical stability and the like.
The invention provides a supermolecular hydrogel, which is formed by an aqueous solution containing amino acid gel factors shown in a formula (I);
the R is selected from one of the formulas (1) to (3):
preferably, the aqueous solution further comprises rare earth ions; the rare earth ions are selected from europium ions and/or terbium ions.
Preferably, the molar ratio of the amino acid gel factor to the rare earth ion is (1-3): 1.
preferably, the pH of the aqueous solution is 8 to 11.
The invention also provides a preparation method of the supermolecule hydrogel, which comprises the following steps:
mixing an amino acid gel factor shown in a formula (I) with water, and regulating the pH value to obtain supermolecule hydrogel;
the R is selected from one of the formulas (1) to (3):
preferably, sodium hydroxide is added as a cosolvent when the amino acid gelator is mixed with water.
Preferably, the amino acid gel factor is mixed with water and then a rare earth compound is added; the rare earth compound is a rare earth europium compound and/or a rare earth terbium compound.
The invention also provides an amino acid gel factor, which is shown as a formula (I):
the R is selected from one of the formulas (1) to (3):
the invention also provides a preparation method of the amino acid gel factor, which comprises the following steps:
and (3) reacting phenylalanine, tyrosine or tryptophan with 1-H-indazole formaldehyde, and then reducing to obtain the amino acid gel factor.
The invention also provides application of the supermolecule hydrogel in anti-counterfeiting.
The invention provides a supermolecular hydrogel which is formed by an aqueous solution containing amino acid gel factors shown in a formula (I). Compared with the prior art, the supermolecule hydrogel provided by the invention has the advantages of good biocompatibility, degradability, low toxicity, good chemical stability and the like, and has wide application prospects in the fields of biological materials, medical treatment, agriculture, food and the like.
Furthermore, the supermolecule hydrogel comprises rare earth ions as luminous factors, the rare earth ions are introduced into amino acid gel factors, fluorescent gel is formed under the crosslinking of the gel factors, the fluorescent gel has higher fluorescence intensity, and the amino acid gel factors have stronger selective response capability, so that the supermolecule hydrogel simultaneously has the characteristics of metal gel and hydrogel, combines the advantages of superior fluorescence performance of rare earth complexes, good biocompatibility of amino acid derivative main bodies, low toxicity and the like, and has wide application prospects in the fields of biological materials, medical treatment, agriculture, food, optical luminescence, technical anti-counterfeiting and the like.
Drawings
FIG. 1 is a photograph of the hydrogel obtained in example 2 of the present invention and a photograph thereof under an ultraviolet lamp;
FIG. 2 is an SEM image and a TEM image of the dried hydrogel obtained in example 2 and example 4 of the present invention;
FIG. 3 is an IR spectrum and XRD pattern of the dried hydrogel obtained in example 2 and example 4 of the present invention;
FIG. 4 is a photograph of hydrogel obtained in example 3 of the present invention and a photograph thereof under an ultraviolet lamp;
FIG. 5 is a graph showing rheological properties of the hydrogel obtained in example 4 of the present invention;
FIG. 6 is a digital image of hydrogels formed by different anions obtained in example 4 of the present invention under an ultraviolet lamp;
FIG. 7 is a digital chart of hydrogels formed by different rare earth ion ratios obtained in example 5 of the present invention under an ultraviolet lamp;
FIG. 8 is a photograph showing a hydrogel patch obtained in example 6 of the present invention and its exposure to an ultraviolet lamp;
FIG. 9 is a graph showing the acid-base response digital code and fluorescence spectrum of the hydrogel obtained in example 7 of the present invention;
FIG. 10 is a graph showing the experimental stability of the hydrogel obtained in example 8 of the present invention in air-space as fluorescent ink;
FIG. 11 is a graph showing the stability of the hydrogel obtained in example 9 of the present invention as fluorescent ink in different solvents;
fig. 12 is an experimental diagram of the hydrogel obtained in embodiment 10 of the present invention as a fluorescent ink anti-counterfeiting two-dimensional code;
FIG. 13 is an ASCII triple encryption chart of the hydrogel obtained in example 11 of the present invention as fluorescent ink.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an amino acid gel factor, which is shown as a formula (I):
the R is selected from one of the formulas (1) to (3):
preferably, as shown in formula (II):
further preferably, it is noted as IZF as follows:
the amino acid gel factor provided by the invention has good coordination capability and capability of providing various non-covalent interactions, can trigger coordination reaction, and can provide hydrogen bond and pi-pi stacking interaction, so that the formation requirements of a complex and hydrogel can be met, and the amino acid gel factor has the advantages of good biocompatibility, low toxicity, simple preparation method and the like.
The invention also provides a preparation method of the amino acid gel factor, which comprises the following steps: and (3) reacting phenylalanine, tyrosine or tryptophan with 1-H-indazole formaldehyde, and then reducing to obtain the amino acid gel factor.
The source of all the raw materials is not particularly limited, and the raw materials are commercially available.
Reacting phenylalanine, tyrosine or tryptophan with 1-H-indazole-formaldehyde; the 1-H-indazole formaldehyde is preferably 1-H-indazole-6-carbaldehyde; the reaction is preferably carried out in the presence of an acid-binding agent; the acid-binding agent is an alkaline substance well known to those skilled in the art, and is not particularly limited, and is preferably one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the reaction is preferably carried out in an alcoholic solvent; the alcohol solvent is preferably methanol and/or ethanol; the temperature of the reaction is preferably 50℃to 60℃and more preferably 50 ℃.
Reducing after the reaction, and then acidizing to obtain amino acid gel factors; the reducing agent used for the reduction is preferably sodium borohydride; the reduction is preferably carried out under ice bath conditions; the acidification is preferably carried out with HCl.
Taking phenylalanine as an example, the synthesis reaction formula of the amino acid gel factor is as follows:
the preparation method of the amino acid gel factor provided by the invention is simple.
The invention also provides a supermolecular hydrogel formed by an aqueous solution containing amino acid gel factors shown in a formula (I);
the R is selected from one of the formulas (1) to (3):
the supermolecular hydrogel provided by the invention has the advantages of good biocompatibility, degradability, low toxicity, good chemical stability and the like, and has wide application prospects in the fields of biological materials, medical treatment, agriculture, food and the like.
Wherein, the amino acid gel factor is the same as the above, and is not described herein.
In the present invention, the concentration of the water-soluble amino acid gelator represented by the formula (I) is preferably 0.05 to 0.5mol/L, more preferably 0.1 to 0.3mol/L, still more preferably 0.1 to 0.2mol/L.
When the aqueous solution contains only the amino acid gel factor represented by formula (I), the pH value of the aqueous solution is preferably 7 or less; the amino acid gel factor provided by the invention can form hydrogel under the condition of low pH value.
In the present invention, the aqueous solution further includes rare earth ions; the rare earth ions are preferably europium ions and/or terbium ions; the rare earth ions are preferably formed from rare earth compounds; the rare earth compound is preferably one or more of europium nitrate, terbium nitrate, europium sulfate, terbium sulfate, europium chloride and terbium chloride; the molar ratio of the amino acid gel factor to the rare earth ion is preferably (1-3): 1, more preferably (1.5 to 2.5): 1, more preferably 2:1.
when the aqueous solution contains rare earth ions in addition to the amino acid gel factors, the pH value is preferably 8-11; the amino acid gel factor shown in the formula (I) can trigger gel to form gel under the action of rare earth ions and has the characteristics of hydrogel and metal gel, and the existence of the rare earth ions can improve the fluorescence intensity.
In the present invention, the aqueous solution preferably further includes carbon quantum dots.
The supermolecule hydrogel comprises rare earth ions as luminous factors, the supermolecule hydrogel is introduced into amino acid gel factors, fluorescent gel is formed under the crosslinking of the gel factors, the fluorescent gel has higher fluorescence intensity, and the amino acid gel factors have stronger selective response capability, so that the supermolecule hydrogel simultaneously has the characteristics of metal gel and hydrogel, combines the advantages of superior fluorescence performance of rare earth complexes, good biocompatibility, low toxicity and the like of amino acid derivative main bodies, and has wide application prospects in the fields of biological materials, medical treatment, agriculture, food and the like.
The invention also provides a preparation method of the supermolecule hydrogel, which comprises the following steps: mixing an amino acid gel factor shown in a formula (I) with water, and regulating the pH value to obtain supermolecule hydrogel;
the R is selected from one of the formulas (1) to (3):
the sources of all raw materials are not particularly limited, and the raw materials are commercially available; the amino acid gelator shown in (I) is the same as that described above, and is not described in detail here.
Mixing an amino acid gelator represented by formula (I) with water; in the present invention, in order to improve the solubility of the amino acid gelator represented by formula (I), sodium hydroxide is preferably added as a cosolvent; the added amount of the sodium hydroxide enables the amino acid gel factor to be dissolved.
When the system contains only the amino acid gel factor after mixing, it is preferable to adjust the pH to 7 or less; hydrochloric acid is preferably used for adjusting the pH value in the invention; amino acid gelator self-gelling.
When other substances are also added into the system, the pH value is preferably adjusted to 8-11; in the present invention, the pH value is preferably adjusted to be alkaline by using a sodium hydroxide solution; then preferably a rare earth compound is also added; the rare earth compound is preferably added in the form of an aqueous solution; the concentration of the aqueous rare earth compound solution is preferably 0.1 to 0.5mol/L, more preferably 0.2mol/L; the rare earth compound is preferably a rare earth europium compound and/or a rare earth terbium compound, more preferably one or more of europium nitrate, terbium nitrate, europium sulfate, terbium sulfate, europium chloride and terbium chloride; the molar ratio of the amino acid gel factor to the rare earth ions in the rare earth compound is preferably (1-3): 1, more preferably (1.5 to 2.5): 1, more preferably 2:1.
the rare earth compound is added, and the carbon quantum dots are preferably added.
The supermolecular hydrogel can be obtained by oscillation or ultrasonic treatment.
The preparation method provided by the invention is simple, strong in operability, short in reaction time, environment-friendly and suitable for industrial production.
The invention also provides an application of the supermolecule hydrogel in anti-counterfeiting; it can be used as fluorescent ink for anti-counterfeit.
In order to further illustrate the present invention, the following describes in detail an amino acid gelator, supramolecular hydrogel and a method for preparing the same according to the present invention.
The reagents used in the examples below are all commercially available.
Example 1
Weighing 0.92 g of phenylalanine and 0.34 g of potassium hydroxide, mixing the two in a round bottom flask, and adding 10 ml of water for dissolution; then 5 ml of 1-indazole-6-carbaldehyde (0.76 g) in ethanol was added and heated in a 50℃water bath for 4 hours; 0.23 g of sodium borohydride is added under ice bath cooling, and the reaction is continued for 4 hours; adding HCl to acidify to be neutral, and continuing to react for 2 hours; filtering, washing with ethanol and water, and oven drying to obtain yellow powder product, named IZF.
Example 2
A certain amount of IZF sample is weighed, a small amount of sodium hydroxide is added for dissolution assistance, and a 0.1M IZF aqueous solution is prepared, and the solution is yellow and transparent. The acidity of IZF (pH 7 or less) was adjusted with hydrochloric acid to give a yellow hydrogel instantaneously by shaking or ultrasonic treatment, and no fluorescence was observed under ultraviolet light as shown in FIG. 1.
The hydrogel obtained in example 2 was dried and analyzed by a scanning electron microscope and a transmission electron microscope to obtain an SEM image as shown in fig. 2 (a) and a TEM image as shown in fig. 2 (b).
The hydrogel obtained in example 2 was dried and analyzed by infrared spectrum and X-ray diffraction to obtain an infrared spectrum as shown in fig. 3 (a) and an XRD pattern as shown in fig. 3 (b).
Example 3
200 μl of 0.1M IZF aqueous solution was removed, and the pH of the solution was adjusted to 10,0.2M to obtain each ion solution (e.g. La (NO) 3 ) 3 、Er(NO 3 ) 3 、Eu(NO 3 ) 3 、HoCl 3 、Pr(NO 3 ) 3 、Lu(NO 3 ) 3 、Dy(NO 3 ) 3 、TmCl 3 、Ce(NO 3 ) 3 、Gd(NO 3 ) 3 、Sm(NO 3 ) 3 、Tb(NO 3 ) 3 、Yb(NO 3 ) 3 、Nd(NO 3 ) 3 ) The lanthanide metal hydrogels formed were observed for fluorescence at 254nm by mixing the ligand with metal in a 2:1 molar equivalent in a glass jar, shaking or sonicating. As a result, it was found that Eu (NO) alone 3 ) 3 And Tb (NO) 3 ) 3 When assembled with IZF, respectively, red and green light were emitted at 254nm, as shown in fig. 4.
Example 4
200. Mu.L of a 0.1M aqueous IZF solution was removed, the pH of the solution was adjusted to 8, and the solution was mixed with a 0.2M trivalent europium or terbium ion solution (e.g., eu (NO) 3 ) 3 、Eu 2 (SO 4 ) 3 、EuCl 3 、Tb(NO 3 ) 3 、Tb 2 (SO 4 ) 3 ，TbCl 3 ) Mixing the ligand and metal in a molar ratio of 2:1, shaking or ultrasonic treatment, and observing whether metal hydrogel is formed. As a result, it was found that the different anions had no effect on the gelling properties and the fluorescence intensity, as shown in FIG. 6.
The raw material is Tb (NO) 3 ) 3 The prepared hydrogel was dried and analyzed by scanning electron microscopy and transmission electron microscopy to obtain an SEM image as shown in fig. 2 (c) and a TEM image as shown in fig. 2 (d).
The raw material is Tb (NO) 3 ) 3 The prepared hydrogel is dried and analyzed by infrared spectrum and X-ray diffraction, the infrared spectrum is shown in figure 3 (a), and the XRD pattern is shown in figure 3 (b).
The starting material in example 4 was Tb (NO) 3 ) 3 The prepared hydrogel was analyzed to obtain a rheological property graph, as shown in fig. 5, in which (a) is a dynamic frequency sweep curve and (b) is a dynamic time sweep curve.
Example 5
200. Mu.L of a 0.1M IZF aqueous solution was removed, the pH of the solution was adjusted to 10, and a mixed solution of 0.2M europium ion and 0.2M terbium ion was mixed in a glass bottle in a molar equivalent of 2:1 of the ligand to the metal (the mixed solution of europium ion and terbium ion was mixed in a ratio of 10:0, 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 1:9, 0:10 mass), and the fluorescence color change was observed by ultrasound. As a result, it was found that the above-mentioned mixtures were all gelled, and the light emission was observed at 254nm, and the gradual transition from red light to yellow light to green light was found, as shown in FIG. 7.
Example 6
500. Mu.L of a 0.1M aqueous IZF solution was removed, the pH of the solution was adjusted to 10, and the solution was mixed with a lanthanide metal solution (Eu (NO) 3 ) 3 ：Tb(NO 3 ) 3 =8: 2, initial concentrations of europium ion and terbium ion are 0.2M), uniformly mixing the materials in an EP tube according to the molar equivalent of the ligand and the metal of 2:1 to obtain yellow light, adding 50 microliters of blue light carbon quantum dots CDs with the pH adjusted, shaking or ultrasonic, and observing 254Fluorescence generated at nm. As a result, the above mixture was found to emit white light at 254nm, as shown in FIG. 8.
Example 7
200 mu L of a 0.1M IZF aqueous solution is respectively removed, the pH value of the solution is adjusted to 10, and the solution is mixed with a 0.2M terbium nitrate solution according to the molar equivalent of the ligand to the metal of 2:1 in a cuvette, and the mixture is subjected to ultrasonic gel forming. HCl is added into a cuvette until gel collapses, and the phenomenon change is observed under 254 nanometers; then adding the same amount of NaOH, and observing the phenomenon change under 254 nanometers; 10 microliters of the mixture was placed on a round quartz plate, and the mixture was exposed to HCl vapor for 10 minutes, and observed for a change in phenomenon at 254 nm; then exposed to NH 3 The steam, at 254nm, was observed for its change in phenomenon. As a result, acidity was found to quench the mixed gel fluorescence, and the addition of alkali was also able to restore its fluorescence, and the process was able to cycle at least 4 times as seen by fluorescence spectrum, and both macroscopic and microscopic were able to demonstrate its pH responsiveness, as shown in FIG. 9.
Example 8
200 mu L of a 0.1M IZF aqueous solution is respectively removed, the pH of the solution is adjusted to 10, the solution is mixed with a 0.2M europium nitrate or terbium nitrate solution according to the molar equivalent of the ligand to the metal of 2:1 in a cuvette, IZF-Eu and IZF-Tb solutions are respectively dipped by a writing brush to draw small flowers (IZF-Eu for petals and IZF-Tb for stems and leaves), and the small flowers are placed for two weeks without changing fluorescence, so that IZF-Eu and IZF-Tb have fluorescence stability, as shown in figure 10.
Example 9
200 mu L of a 0.1M IZF aqueous solution is respectively removed, the pH of the solution is adjusted to 10, the solution is mixed with a 0.2M europium nitrate or terbium nitrate solution according to the molar equivalent of the ligand to the metal of 2:1 in a cuvette, the writing brush is used for dipping IZF-Eu and IZF-Tb solutions to write Eu and Tb letters respectively, the Eu and Tb letters are exposed to different solvents (a methanol, bN, N-dimethylformamide, c dichloromethane, d ethylene glycol, e ethanol and f dimethyl sulfoxide), and fluorescent conditions before and after the exposure are respectively observed, so that the result shows that the fluorescent ink is not greatly changed, and the IZF-Eu and IZF-Tb are stable in different organic solvents as fluorescent ink.
Example 10
Respectively transferring 200 mu L of a 0.1M IZF aqueous solution, adjusting the pH of the solution to 10, mixing the solution with a 0.2M terbium nitrate solution according to the molar equivalent of a ligand to metal 2:1 in a cuvette, dipping IZF-Tb solution by using a seal, printing on A4 paper, and identifying two-dimensional code information- "Eu and Tb" printed on the A4 paper by using the QR function of an intelligent machine under a 254 nanometer ultraviolet lamp without any information visible in sunlight, as shown in FIG. 12.
Example 11
200 mu L of a 0.1M IZF aqueous solution is respectively removed, the pH of the solution is adjusted to 10, the mixed solution is mixed with a 0.2M mixed solution of europium nitrate or terbium nitrate according to the molar equivalent of the ligand and metal of 2:1 in a cuvette, 10 microliters of IZF-Eu and IZF-Tb mixed solutions are respectively taken on A4 paper for multiple times and are arranged into a matrix according to the pre-designed positions, then under a 254 nanometer ultraviolet lamp, IZF-Eu emitting red light represents the number of 0, IZF-Tb emitting green light represents the number of 1, and then ACSII is utilized to compile "IOUSC", which is an English abbreviation of "I Aihua university", as shown in figure 13.
Taken together, IZF self-assembles to form a hydrogel under acidic conditions, and IZF is capable of reacting with Eu at high pH 3+ And Tb 3+ Co-assembly forms a metal hydrogel with red/green fluorescence. Furthermore, by adjusting Eu 3+ And Tb 3+ Can prepare bimetallic hydrogel with different luminous performances; the IZF-Eu/Tb-CDs hybridized metal hydrogel with white luminescence can be constructed by doping the carbon quantum dots. Taking IZF-Tb gel as an example, multiple stimulus reactivity, rheological property and gel forming mechanism are systematically researched through testing means such as a scanning electron microscope, a transmission electron microscope, an infrared spectrum, an ultraviolet spectrum, a transmission electron microscope and the like. The results show that the IZF-Tb gel has good pH response and thermal response properties. IZF-Eu and IZF-Tb can be used as fluorescent ink with good light stability, so that information storage and encryption are realized. Especially, the double encryption and the triple encryption greatly improve the anti-counterfeiting level of the luminescent ink. Therefore, the IZF-Ln metal hydrogel provided by the invention has a wide application prospect.
Furthermore, the invention uses small molecule IZF as ligand to react with Eu 3+ Or Tb (Tb) 3+ Mixing and sonicating the ionic solution, self-assembling by multiple non-covalent interactionsAnd emits red or green light at 254nm, respectively. Under the same conditions, IZF cannot form metal hydrogels with fluorescence emission (such as La (NO) 3 ) 3 、Er(NO 3 ) 3 、Eu(NO 3 ) 3 、Eu 2 (SO 4 ) 3 、EuCl 3 、HoCl 3 、Pr(NO 3 ) 3 、Lu(NO 3 ) 3 、Dy(NO 3 ) 3 、TmCl 3 、Ce(NO 3 ) 3 、Gd(NO 3 ) 3 、Sm(NO 3 ) 3 、Tb(NO 3 ) 3 、Tb 2 (SO 4 ) 3 ,TbCl 3 Yb(NO 3 ) 3 、Nd(NO 3 ) 3 ). By changing Eu 3+ /Tb 3+ The proportion can form bimetallic gel which emits light with different colors, and the carbon quantum dots are doped in the bimetallic gel to prepare the composite metal hydrogel which emits white light. And IZF-Tb and IZF-Eu can be used as fluorescent ink, and can be applied to information storage and anti-counterfeiting.

Claims (10)

1. A supramolecular hydrogel formed from an aqueous solution comprising an amino acid gelator represented by IZF;
2. the supramolecular hydrogel according to claim 1, wherein the aqueous solution further comprises rare earth ions; the rare earth ions are selected from europium ions and/or terbium ions.
3. The supramolecular hydrogel according to claim 2, wherein the molar ratio of amino acid gelator to rare earth ion is (1-3): 1.
4. the supramolecular hydrogel according to claim 2, wherein the pH of the aqueous solution is between 8 and 11.
5. A method for preparing a supramolecular hydrogel, comprising:
mixing the amino acid gel factor shown in IZF with water, and regulating the pH value to obtain supermolecule hydrogel;
6. the method according to claim 5, wherein sodium hydroxide is added as a cosolvent when the amino acid gelator is mixed with water.
7. The method according to claim 5, wherein a rare earth compound is further added when the amino acid gelator is mixed with water; the rare earth compound is a rare earth europium compound and/or a rare earth terbium compound.
8. An amino acid gelator, comprising, as shown in IZF:
9. a method for producing the amino acid gelator according to claim 8, comprising:
and (3) reacting phenylalanine with 1-H-indazole formaldehyde, and then reducing to obtain the amino acid gel factor.
10. The use of the supramolecular hydrogel of claim 2 or the supramolecular hydrogel prepared by the preparation method of claim 7 in anti-counterfeiting.
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