CN114133596A - Preparation and application of a kind of ABA type photosensitive gel - Google Patents
Preparation and application of a kind of ABA type photosensitive gel Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003349 gelling agent Substances 0.000 claims abstract description 7
- 125000005647 linker group Chemical group 0.000 claims abstract 4
- 229920005615 natural polymer Polymers 0.000 claims description 10
- 229920000858 Cyclodextrin Polymers 0.000 claims description 8
- 239000001116 FEMA 4028 Substances 0.000 claims description 8
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 8
- 229960004853 betadex Drugs 0.000 claims description 8
- BEYOBVMPDRKTNR-BUHFOSPRSA-N 4-Hydroxyazobenzene Chemical compound C1=CC(O)=CC=C1\N=N\C1=CC=CC=C1 BEYOBVMPDRKTNR-BUHFOSPRSA-N 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 6
- 230000003993 interaction Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 4
- 229920002674 hyaluronan Polymers 0.000 claims description 4
- 229960003160 hyaluronic acid Drugs 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 2
- 230000002209 hydrophobic effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 230000007704 transition Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 230000004298 light response Effects 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 65
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- -1 azobenzene compound Chemical class 0.000 description 4
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- BCAGFJXMCZSAHD-UHFFFAOYSA-N 1,2-bis(2-iodoethoxy)ethane Chemical compound ICCOCCOCCI BCAGFJXMCZSAHD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 101100001672 Emericella variicolor andG gene Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- RGYOXKLCSIJDMU-UHFFFAOYSA-M sodium;phenoxide;hydrate Chemical compound [OH-].[Na+].OC1=CC=CC=C1 RGYOXKLCSIJDMU-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
- C08K5/235—Diazo and polyazo compounds
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
本发明属于新材料技术领域，具体涉及一种ABA型光敏感凝胶剂及其制备方法，并进一步将该凝胶剂用于光敏感凝胶的构筑。本发明将光敏感基团偶氮苯作为凝胶剂的主要构成单元。所述ABA型光敏感凝胶剂两端为偶氮苯基团，中间为亲水的柔性连接基团。由于偶氮苯基团在紫外光与可见光的照射下可实现构型的可逆转变，所得凝胶剂具有很好的光响应性。进一步，将本发明方法制备的凝胶剂用于凝胶的构筑。凝胶剂特殊的ABA型结构，使其在凝胶构筑过程中起到了交联剂的作用。由于偶氮苯基团可逆的光响应性，所得凝胶可实现可逆的溶胶‑凝胶转变，使其能够多次重复使用。本发明得到的凝胶剂光响应性好，具有很好的可逆性，且易于制备，应用灵活，可在智能凝胶的构筑、新材料设计等领域进行应用。The invention belongs to the technical field of new materials, in particular to an ABA-type light-sensitive gel and a preparation method thereof, and further uses the gel for the construction of light-sensitive gel. In the present invention, the photosensitive group azobenzene is used as the main structural unit of the gelling agent. The two ends of the ABA-type photosensitive gelling agent are azobenzene groups, and the middle is a hydrophilic flexible linking group. Because the azobenzene group can realize the reversible transformation of configuration under the irradiation of ultraviolet light and visible light, the obtained gelling agent has good photoresponsivity. Further, the gelling agent prepared by the method of the present invention is used for the construction of the gel. The special ABA-type structure of the gel makes it act as a cross-linking agent in the process of gel construction. Owing to the reversible photoresponsivity of the azobenzene groups, the resulting gel can achieve a reversible sol-gel transition, enabling it to be reused many times. The gelling agent obtained by the invention has good light response, good reversibility, easy preparation and flexible application, and can be applied in the fields of smart gel construction, new material design and the like.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to an ABA type photosensitive gel and application thereof.
Background
The polymer gel is a three-dimensional network structure formed by physical or chemical interaction between polymer chains, can swell but not dissolve in liquid, and is a composite system of a solvent and a polymer network. The affinity of the liquid and the polymer network ensures that liquid molecules are enclosed in the polymer network and lose the fluidity, so that the gel can swell in a solvent to reach the balance, a stable shape is kept, and small molecular substances can permeate or diffuse in the network structure. In recent years, due to their abundant structure and easily controllable properties, polymer gels have attracted great interest in the field of material applications.
The dynamic reversible non-covalent bond interaction is introduced into the traditional polymer gel, so that the polymer gel is easy to regulate and control and has the characteristic of stimulus response. The azobenzene compound has cis-form and trans-form configurations, is a typical photoresponse material, and can be introduced into a gel system to obtain a photoresponse functional material. At present, in the construction of an azobenzene-based photoresponsive gel system, most of the adopted technologies are that azobenzene is modified on a macromolecular chain and then is further crosslinked into gel through the macromolecular chain, so that the flexibility of the design of a gel material is greatly limited.
Based on the preparation method, the preparation method of the ABA type photosensitive gel based on azobenzene is used for constructing the polymer gel, so that the flexible design of a gel system is realized while the polymer gel is endowed with good photosensitivity.
Disclosure of Invention
The invention aims to provide an ABA type photosensitive gel and a preparation method thereof, and a photoresponsive gel system is constructed by the interaction of a non-covalent bond between an azobenzene group and a natural polymer modified by beta-cyclodextrin. The photosensitive gel prepared by the method is simple in preparation method, and a gel system constructed by using the photosensitive gel has good photoresponse and has good application prospects in the fields of construction of intelligent gel, new material design and the like.
The invention solves the technical problems by the following technical scheme:
the preparation and application of the ABA type photosensitive gel comprise the following steps:
s1, mixing aniline, concentrated hydrochloric acid and sodium nitrite, dissolving in water to obtain diazonium salt, and performing nucleophilic substitution reaction with a sodium hydroxide solution of phenol to prepare 4-hydroxyazobenzene; the obtained 4-hydroxyazobenzene and 1, 2-bis (2-iodoethoxy) ethane are subjected to nucleophilic substitution reaction at a certain temperature according to a certain proportion to prepare ABA type photosensitive gel;
s2, carrying out N, N' -carbonyldiimidazole mediated conjugation reaction on beta-cyclodextrin and 1, 6-hexamethylenediamine in dimethyl sulfoxide to generate amino modified beta-cyclodextrin (marked as CD-NH)2). Thereafter, the mixture was passed through natural polymer chains and CD-NH in 4-morpholinoethanesulfonic acid buffer2The amidation reaction between the two is to graft the beta-cyclodextrin onto the natural high molecular main chain to obtain the high molecular monomer.
S3, dissolving the modified high molecular monomer in water, dissolving the gel in a certain solvent, respectively preparing homogeneous solutions with a certain concentration, stirring and heating the tetrahydrofuran solution of the gel while slowly dripping the tetrahydrofuran solution of the gel in the aqueous solution system of the high molecular monomer, mixing the high molecular monomer and the gel according to a certain mass ratio, and obtaining the gel through the non-covalent bond effect.
Preferably, the ratio in step S1 is in the range of 4-hydroxyazobenzene: 1, 2-bis (2-iodoethoxy) ethane is most preferred at a ratio of 2.4: 1.
Preferably, the temperature in step S1 is optimized to 80 ℃.
Preferably, the natural polymer in step S2 is a natural polymer containing a carboxyl group, such as hyaluronic acid or alginic acid.
Preferably, the solvent in step S3 is Tetrahydrofuran (THF) with a low boiling point.
Preferably, the concentration of the polymer aqueous solution in step S3 is 5 wt%.
Preferably, the concentration of the gelling agent solution described in step S3 is 0.34 wt%.
Preferably, the mass ratio in step S3 is gel: the ratio of the high molecular monomer is 0.5: 1.
Compared with the prior art, the invention has the following beneficial effects:
(1) the ABA type photosensitive gel is prepared by utilizing a simple two-step reaction, and the obtained gel has good photosensitivity.
(2) The ABA type photosensitive gel prepared by the invention can construct a gel system with beta-cyclodextrin modified natural polymers through flexible non-covalent bond interaction, and the obtained gel has good photosensitivity and can realize reversible sol-gel conversion.
(3) The invention adopts natural polysaccharide macromolecules produced by animals, plants and microorganisms in nature as gel construction units, and has the advantages of simplicity, easy obtainment and low cost.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of the ABA type gel
FIG. 2 is a schematic diagram showing the changes of UV-VIS absorption spectrum of the obtained ABA type gel-THF solution with the irradiation time of UV (a) and visible (b)
FIG. 3 is a schematic diagram showing the trend of the absorption value of the obtained ABA type gel-THF solution at 330nm after cyclic and alternate irradiation of ultraviolet light and visible light
FIG. 4 is a schematic diagram of the reversible sol-gel transition of the resulting gel
FIG. 5 shows the gel obtainedG' andGschematic diagram of frequency scanning curve before and after ultraviolet light irradiation
Detailed Description
The invention will now be described in further detail with reference to specific examples, but it should be understood that the description is only intended to illustrate the invention and not to limit the claims.
The reagents or instruments used in the present invention are not indicated by manufacturers, and are all conventional products commercially available. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1: preparation of ABA type photosensitive gel
Weighing 6.5g of aniline in a 250ml round bottom flask, placing at-10 ℃, dropwise adding 24ml of concentrated hydrochloric acid while stirring, weighing 5.3g of sodium nitrite, dissolving in 20ml of water, dropwise adding into the reaction system within 40min, gradually clarifying the reaction system, raising the temperature to-5 ℃, and adding the prepared phenol sodium hydroxide solution (weighing 7.9g of phenol and 8.4g of sodium hydroxide in 30ml of water) into the reaction system within 5min for reacting for 2 hours. The reaction was terminated by thin layer chromatography. Adding a little NaI solution, extracting with petroleum ether and water, taking supernatant liquor, and spin-drying to obtain 4-hydroxyazobenzene;
in N2Under the condition, 3.3g of potassium carbonate and 4.7g of 4-hydroxyazobenzene are dissolved in 60ml of DMF, 3.6g of 1, 2-bis (2-iodoethoxy) ethane is slowly dropped into the DMF, the mixture reacts for 15 hours at the temperature of 80 ℃, dichloromethane and water are used for extraction and then spin-drying the mixture, 8ml of ethyl acetate is added for pulping, and the ABA type photosensitive gel is obtained after suction filtration and drying.
The structure of 4-hydroxyazobenzene is determined by nuclear magnetic resonance hydrogen spectrum (1H NMR). 1H NMR (400 MHz, CDCl)3): δ 7.88 (d, J = 7.88 Hz, 4H), 7.52-7.42 (m, 3H), 6.95 (d, J = 6.94 Hz, 2H), 5.56 (s, 1H)。
The structure of the gel is determined by NMR (hydrogen NMR)1H NMR). 1H NMR (400 MHz, CDCl)3): δ 7.88 (t, J = 9.6 Hz, 8H), 7.50-7.40 (m, 6H), 7.01 (d, J = 8.4 Hz, 4H), 4.19 (s, 4H), 3.89 (s, 4H), 3.76 (s, 4H)。
Azobenzene is the most common photoisomerization group, fig. 2 shows that under ultraviolet irradiation (λ =365 nm) of a tetrahydrofuran solution of the gel, the absorption intensity of a trans configuration at about 330nm is gradually reduced, but a remarkable blue shift is shown, and the azobenzene group in the gel is changed from the trans configuration to a cis configuration; under visible light irradiation (lambda =470 nm), the absorption peak caused by symmetrically allowed pi-pi transition at 330nm in the ultraviolet-visible absorption spectrum is rapidly enhanced, the peak position is red shifted, meanwhile, the absorption peak caused by symmetrically forbidden n-pi transition at 440 nm is gradually weakened, and the azobenzene group in the gel is gradually converted into a trans configuration from the cis configuration, which indicates that the photocis-trans isomerization behavior of the gel molecule is a reversible process.
Subjecting tetrahydrofuran solution of gel to alternate irradiation of ultraviolet light (30 min) and visible light (30 min), and recording maximum absorption peak in ultraviolet absorption regionλ maxThe absorption value at (330nm) is shown in FIG. 3. After multiple cycles of irradiation, the gel has a maximum absorption peakλ maxThe absorption value at the (330nm) position can realize good reproducibility, which shows that the photosensitivity of the gel has good reversibility.
Example 2: preparation method of beta-cyclodextrin modified hyaluronic acid
S1, weighing 5g of beta-Cyclodextrin (CD) in N2Placing in a single-mouth bottle under protection, dropwise adding 20ml of dry dimethyl sulfoxide into the bottle, dissolving 1.5g of N, N' -carbonyldiimidazole in 10ml of dimethyl sulfoxide, dropwise adding into the system, reacting at 30 ℃ for 4 hours, subsequently adding 5g of 1, 6-hexamethylene diamine into the system, stirring at 30 ℃ for 48 hours, precipitating the mixture with ethyl acetate, further purifying the product by using a dialysis membrane (1 KMWCO), and freeze-drying to obtain CD-NH2。
S2, weighing 2.5g of hyaluronic acid and 4g of CD-NH23.5g4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholine chloride was dissolved in 250ml 4-morpholinoethanesulfonic acid buffer, after stirring at 56 ℃ for 12 hours, the product was further purified using dialysis membrane (1 KMWCO) and freeze dried to give white floc as beta-cyclodextrin modified hyaluronic acid, noted HA-CD.
CD-NH2The structure of (a) was identified by nuclear magnetic resonance hydrogen spectroscopy (1H NMR). 1H NMR (400 MHz, D)2O). Peaks (. delta.3.08 ppm),. delta.2.90 ppm and (. delta.1.32-1.60 ppm) characterize the protons of the alkyl groups. The peak (. delta.5.08 ppm) is derived from protons with CD chiral carbon structure.
The HA-CD structure was identified by nuclear magnetic resonance hydrogen spectroscopy (1H NMR). 1H NMR (400 MHz, D)2O). The peaks (. delta.1.39-1.70 ppm) represent protons of alkyl groups. The peak (. delta.5.09 ppm) originates from protons with CD chiral carbon structure. The peak (. delta.2.03 ppm) represents the proton of the methyl group of hyaluronic acid.
Example 3: preparation of photosensitive gels
S1, weighing 0.05g of modified high molecular monomer (HA-CD) and dissolving in 1ml of deionized water, weighing 0.0034g of gel and dissolving in 300 mu l of THF, heating the gel-THF solution while stirring and slowly dripping into the high molecular monomer-water solution until the system is viscous and HAs no fluidity.
S2. gel formation was confirmed by inverted vial method (as shown in FIG. 4). Further, by analyzing the system storage modulus: (G') and loss modulus: (G") verified the formation of a gel (curve after gelling as shown in figure 5). After the gel is formed, the systemG'＞G", exhibits elastic properties, which are expressed as solid, in the gel state, further verifying the formation of the gel.
After 20min irradiation of the gel with ultraviolet light (λ =365 nm), the gel network collapsed, resulting in fluidity, as shown in fig. 4. This is because the azobenzene group in the gel is changed from a trans configuration to a cis configuration under the irradiation of ultraviolet light, and the non-covalent bond interaction in the gel network is destroyed. At the same time, fromG' andG"frequency sweep curve of the system after UV irradiationG' andG"significantly reduced in value, andG"gradually greater thanG' it is explained that the system exhibits more viscous properties, which are liquid properties, and is converted into a sol state. The system converted into the sol can be placed away from the sun or irradiated by visible light, and the gel can be formed again, which shows that the gel constructed by using the obtained gel has good photoresponse and can realize reversible sol-gel conversion for many times.
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