CN114133596A - Preparation and application of ABA type photosensitive gel - Google Patents

Preparation and application of ABA type photosensitive gel Download PDF

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Publication number
CN114133596A
CN114133596A CN202111533085.6A CN202111533085A CN114133596A CN 114133596 A CN114133596 A CN 114133596A CN 202111533085 A CN202111533085 A CN 202111533085A CN 114133596 A CN114133596 A CN 114133596A
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Prior art keywords
gel
aba type
group
type photosensitive
azobenzene
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CN202111533085.6A
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李相晔
毕子璇
高飞雪
李新进
董云会
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Shandong University of Technology
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Shandong University of Technology
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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)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention belongs to the technical field of new materials, and particularly relates to an ABA type photosensitive gel and a preparation method thereof, and the ABA type photosensitive gel is further used for construction of photosensitive gel. The invention takes photosensitive group azobenzene as the main constituent unit of the gel. The ABA type photosensitive gel has azobenzene groups at two ends and a hydrophilic flexible connecting group in the middle. The azobenzene group can realize reversible transformation of configuration under the irradiation of ultraviolet light and visible light, and the obtained gel has good photoresponse. Furthermore, the gel prepared by the method is used for constructing gel. The special ABA type structure of the gel enables the gel to play a role of a cross-linking agent in the gel construction process. Due to the reversible photoresponse of the azobenzene group, the obtained gel can realize reversible sol-gel transformation, so that the gel can be repeatedly used for many times. The gel prepared by the invention has good photoresponse, good reversibility, easy preparation and flexible application, and can be applied to the fields of intelligent gel construction, new material design and the like.

Description

Preparation and application of ABA type photosensitive gel
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.

Claims (9)

1. The preparation and application of the ABA type photosensitive gel are characterized in that two ends of the ABA type photosensitive gel are provided with hydrophobic photosensitive groups, and the middle of the ABA type photosensitive gel is provided with a hydrophilic flexible connecting group.
2. The photosensitive group of claim 1, wherein the photosensitive group is an azobenzene group.
3. The hydrophilic flexible linker of claim 1 wherein the hydrophilic flexible linker is a triethoxy group.
4. Preparation and application of ABA type photosensitive gel are characterized in that the preparation comprises the following steps: after diazotization, aniline reacts with phenol to obtain 4-hydroxy azobenzene.
5. The solvent of claim 4, wherein the solvent is N, N-dimethylformamide.
6. The catalyst of claim 4 wherein the catalyst is potassium carbonate.
7. Preparation and application of ABA type photosensitive gel are characterized in that the gel is applied to construct photoresponsive gel.
8. The photo-responsive gel according to claim 8, wherein the photo-responsive gel is constructed by using a natural polymer modified by β -cyclodextrin as a main body and using non-covalent bond interaction between azobenzene groups at both ends of the ABA type photo-sensitive gel and β -cyclodextrin on a natural polymer chain.
9. The natural polymer according to claim 9, wherein the natural polymer is a carboxyl group-containing natural polymer such as hyaluronic acid or alginic acid.
CN202111533085.6A 2021-12-15 2021-12-15 Preparation and application of ABA type photosensitive gel Withdrawn CN114133596A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702020A (en) * 2012-06-01 2012-10-03 吉林大学 Azo radical-substituted organic small molecular gel, preparation method thereof and application of azo radical-substituted organic small molecular gel to preparation of organic gel
CN103865083A (en) * 2014-03-05 2014-06-18 华东师范大学 Photosensitive hydrogel containing cyclodextrin and azobenzene and preparation method of photosensitive hydrogel
CN104140536A (en) * 2013-05-09 2014-11-12 江苏省农业科学院 Hyperbranched modified azobenzene and preparation method thereof
CN107434851A (en) * 2017-09-06 2017-12-05 阿里生物新材料（常州）有限公司 A kind of preparation method of Photosensitive hydrogel
CN107954894A (en) * 2017-11-25 2018-04-24 中北大学 A kind of gelator of azo-based phenyl group and preparation method thereof
CN112826791A (en) * 2021-01-13 2021-05-25 中国药科大学 Light-controlled hydrogel microneedle array patch and preparation method thereof
CN113583262A (en) * 2021-06-24 2021-11-02 四川大学 Near-infrared response hyaluronic acid hydrogel for articular cartilage repair and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702020A (en) * 2012-06-01 2012-10-03 吉林大学 Azo radical-substituted organic small molecular gel, preparation method thereof and application of azo radical-substituted organic small molecular gel to preparation of organic gel
CN104140536A (en) * 2013-05-09 2014-11-12 江苏省农业科学院 Hyperbranched modified azobenzene and preparation method thereof
CN103865083A (en) * 2014-03-05 2014-06-18 华东师范大学 Photosensitive hydrogel containing cyclodextrin and azobenzene and preparation method of photosensitive hydrogel
CN107434851A (en) * 2017-09-06 2017-12-05 阿里生物新材料（常州）有限公司 A kind of preparation method of Photosensitive hydrogel
CN107954894A (en) * 2017-11-25 2018-04-24 中北大学 A kind of gelator of azo-based phenyl group and preparation method thereof
CN112826791A (en) * 2021-01-13 2021-05-25 中国药科大学 Light-controlled hydrogel microneedle array patch and preparation method thereof
CN113583262A (en) * 2021-06-24 2021-11-02 四川大学 Near-infrared response hyaluronic acid hydrogel for articular cartilage repair and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Fabrication of multi-stimuli responsive supramolecular hydrogels based on host-guest inclusion complexation of a tadpole-shaped cyclodextrin derivative with the azobenzene dimer", 《POLYMER CHEMISTRY》 *
"基于偶氮苯的多刺激相应超分子水凝胶", 《中国优秀博硕士学位论文全文数据库 工程材料I辑》 *

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Application publication date: 20220304