CN103467680A - Intelligent photosensitive glycosyl hydrogel with block structure and preparation method of intelligent photosensitive glycosyl hydrogel - Google Patents
Intelligent photosensitive glycosyl hydrogel with block structure and preparation method of intelligent photosensitive glycosyl hydrogel Download PDFInfo
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- CN103467680A CN103467680A CN2013104268217A CN201310426821A CN103467680A CN 103467680 A CN103467680 A CN 103467680A CN 2013104268217 A CN2013104268217 A CN 2013104268217A CN 201310426821 A CN201310426821 A CN 201310426821A CN 103467680 A CN103467680 A CN 103467680A
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Abstract
The invention relates to intelligent photosensitive glycosyl hydrogel with a block structure and a preparation method of the intelligent photosensitive glycosyl hydrogel. The overall structure of the hydrogel is of a block type. According to the preparation method, small-molecule glucose is used as a raw material and is subjected to esterification reaction so as to firstly synthesize a glycosyl monomer with polymerizable double bonds; then, trithiocarbonate is used as a chain transfer agent and is polymerized with a photosensitive monomer through reversible addition fragmentation chain transfer agent-free radical polymerization method, thus preparing the intelligent photosensitive glycosyl hydrogel with a block structure. The molecular skeleton of the hydrogel prepared by using the method is of the block structure, the structure can be adjusted and controlled, and the raw material used in the method is carbohydrate, so that the biocompatibility is improved; and the photosensitive hydrogel prepared by using the method has excellent photostimulation response performance.
Description
Technical field
The present invention relates to photosensitive glycosyl intelligent aqueous gel capable of a kind of block structure and preparation method thereof.
Background technology
Hydrogel refers to that a kind of main chain or side chain contain a large amount of hydrophilic radicals and adsorb the cross-linked polymer with tridimensional network that large quantity of moisture is arranged.Hydrogel swelling but do not dissolve in water contains large quantity of moisture when keeping definite shape.According to environmental stimulus being replied to difference, can be divided into stimulating insensitive traditional hydrogel and producing to stimulating the environmental sensitive hydrogels responded, the latter claims again intelligent aqueous gel capable.So-called Intelligent Hydrogels, refer in extraneous physics and chemistry factor, as reversible change hydrogel can occur for own vol and shape under the stimulation of temperature, pH, light, electricity, magnetic, sound, power and chemical substance etc.Due to unique responsiveness of progress in Intelligent Hydrogel, at aspects such as fixing, the organizational project of chemical transformation device, memory cell switch, sensor, artificial muscle, chemical storage device, molecular separation system, organized enzyme, pharmaceutical carriers, there is good application prospect.
The characteristics that light source has clean and safe, easily uses and control, therefore photosensitive hydrogel all has broad application prospects at industrial circles such as chemical sensor, photoswitch, display unit, light-operated drug release, immobilized enzyme, organizational project or biomedical sector.With temperature sensitive, pH sensitive aqueous gel, compare, it is relatively late that ground is carried out in the research of photosensitive hydrogel.But because light stimulus can guarantee continuity and accuracy, therefore photosensitive hydrogel has its unique advantage: condition of molding gentleness, shape regulation and control arbitrarily, fast response time, can realize the target of localization response, the research of such hydrogel in recent years is subject to common concern.Such hydrogel volume changes generation under light (as UV-light, visible ray, infrared rays etc.) effect mutually, and response process has reversibility: after removing light stimulus, gel recovers original state.The Response Mechanism of current photosensitive hydrogel has three kinds: a kind of is to utilize Photoactive compounds to see photolysis, at a large amount of ions of the inner generation of gel, causes the sudden change that the gel internal penetration is pressed, and the diffusion of solvent ecto-entad, impel gel generation volume to change mutually.A kind of is that thermo-responsive hydro gel and photosensitive molecular form compound system, after the photon of the certain energy of gel absorption, photosensitive molecular is heat energy by light energy conversion, and the inner local temperature of gel is raise, when temperature is elevated to the phase transition temperature of gel, cause that the volume of gel changes mutually.More commonly at high polymer main chain or side chain, introduce photosensitive molecular, by the isomerization of photosensitive molecular, cause the variation of molecular configuration, and then make gel produce responsiveness.
Due to the synthetic high molecular biocompatibility of great majority and biological degradability poor, limited its application aspect biological medicine.So there is good biocompatibility, nontoxic, environmental friendliness, and the natural polymer with more active group becomes the ideal material for preparing hydrogel in recent years gradually.Corresponding, with synthetic polymer, to compare, natural polymer hydrogel has hypotoxicity, good biocompatibility, to environment sensitive and the cheap advantages such as price, however bad mechanical strength, unstable properties, the easily deficiency such as the degraded improvement that needs.See thus, hypotoxicity, good biocompatibility and biological degradability, good mechanical property and this some perfect adaptation of environmental sensitivity are got up, prepare the research direction that novel, green intelligent aqueous gel capable is effort from now on.Saccharide compound is as a class natural reproducible biomass resource, there is the not available good biocompatibility of petrochemical materials, biological degradability, the advantage such as nontoxic, non-stimulated, therefore, the photosensitive intelligent aqueous gel capable of introducing glycosyl has broad application prospects.
Summary of the invention
The objective of the invention is in order to obtain the photosensitive intelligent aqueous gel capable that a kind of biocompatibility is good, by introducing the glucose small molecules, prepared the controlled photosensitive intelligent aqueous gel capable of block structure of a class formation.
Technical solution of the present invention is:
The photosensitive glycosyl intelligent aqueous gel capable of a kind of block structure is block structure on the overall molecule structure; Glucose take in preparation as raw material, through with unsaturated carboxylic acid halides, carrying out esterification, prepare Monomer containing sugar moiety; The polymerization process adopted is reversible addition-fragmentation chain transfer free radical polymerization, and wherein, the esterifying reagent of polymerizable double bond is acrylate chloride, and the photaesthesia monomer is 4-acryloxy nitrogen benzide.
The preparation method of the photosensitive glycosyl intelligent aqueous gel capable of block structure, preparation process is as follows:
Step 1: glucose monomer is protected through OH, with the standby polymerizable Monomer containing sugar moiety that contains two keys of unsaturated acyl stew in soy sauce;
Step 2: trithiocarbonate chain transfer agent and the prepared polymerizable Monomer containing sugar moiety of previous step are joined in a certain amount of tetrahydrofuran (THF), under protection of inert gas, add the initiator Diisopropyl azodicarboxylate, under 70 ℃, carry out the polymerization of Monomer containing sugar moiety, after the Monomer containing sugar moiety polymerization completes, add the photosensitive monomer copolymerization, obtain block structure glycosyl polymkeric substance;
Step 3: by the block structure glycosyl polymkeric substance of preparation, in diluted acid, the free OH of hydrolysis, obtain the photosensitive glycosyl intelligent aqueous gel capable of target block structure.
The present invention compared with prior art has the following advantages: 1. having prepared the gel molecular skeleton is block structure, and its structure can regulate and control; 2. raw material used in the present invention is saccharide compound, has improved biocompatibility; 3. prepared photosensitive hydrogel has good light stimulus response performance.
the accompanying drawing explanation:
The schematic diagram that Fig. 1 is the photosensitive glycosyl intelligent aqueous gel capable of block structure.
embodiment:
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and the following example only, for explaining the present invention, does not form limiting the scope of the present invention.
The photosensitive glycosyl intelligent aqueous gel capable of a kind of block structure is block structure on the overall molecule structure; Glucose take in preparation as raw material, through with unsaturated carboxylic acid halides, carrying out esterification, prepare Monomer containing sugar moiety; The polymerization process adopted is reversible addition-fragmentation chain transfer free radical polymerization, and wherein, the esterifying reagent of polymerizable double bond is acrylate chloride, and the photaesthesia monomer is 4-acryloxy nitrogen benzide.
The preparation method of the photosensitive glycosyl intelligent aqueous gel capable of a kind of block structure, preparation process is as follows:
Step 1: glucose monomer is protected through OH, with the standby polymerizable Monomer containing sugar moiety that contains two keys of unsaturated acyl stew in soy sauce;
Step 2: trithiocarbonate chain transfer agent and the prepared polymerizable Monomer containing sugar moiety of previous step are joined in a certain amount of tetrahydrofuran (THF), under protection of inert gas, add the initiator Diisopropyl azodicarboxylate, under 70 ℃, carry out the polymerization of Monomer containing sugar moiety, after the Monomer containing sugar moiety polymerization completes, add the photosensitive monomer copolymerization, obtain block structure glycosyl polymkeric substance;
Step 3: by the block structure glycosyl polymkeric substance of preparation, in diluted acid, the free OH of hydrolysis, obtain the photosensitive glycosyl intelligent aqueous gel capable of target block structure, as shown in Figure 1.
Embodiment 1:
Synthesizing of diacetoneglucose acrylate: in the four-hole boiling flask of 250 mL that the thermometer reflux condensing tube is housed, add dry anhydrous propanone 150 mL and pulverize and dry glucose 9.0 g (0.05 mol), adding the anhydrous FeCl of catalyzer
3(1.7g, 0.01 mol).Back flow reaction 2h under ultrasound condition.Then add rare Na
2cO
3solution 300 ml, CHCl
3extract three times (50 mL * 3), merge organic phase and, with saturated common salt water washing (50 mL * 3), use anhydrous Na
2sO
4drying, filter underpressure distillation, obtains crude product, and yield is 75.8%, with the hexanaphthene recrystallization, obtains white crystals diacetoneglucose DAG.In the there-necked flask of 250 mL dried and clean; add DAG(10 g, 0.04mol) and 80 mL dry tetrahydrofuran stirring and dissolving, under nitrogen protection; by 60% sodium hydride (2.4g; 0.052 mol), then under 40 ℃ of conditions, stirring reaction 1h; slowly drip acrylate chloride (5.45g; 0.045 mol), after dripping end, continue reaction 3h.Remove by filter insolubles, removal of solvent under reduced pressure, obtain the diacetoneglucose acrylate, and yield is 92.3%.
Embodiment 2:
S, S '-bis-(α, α '-dimethyl-α "-acetic acid)-trithiocarbonate (CMP) synthetic: by dithiocarbonic anhydride (7.61 g; 0.1mol); trichloromethane (29.85 g; 0.25mol); acetone (14.52 g; 0.25 mol) and tetrabutylammonium iodide (0.74 g, 0.002mol), normal hexane (50 mL) joins in the there-necked flask of 500 mL, plugs respectively constant pressure funnel, thermometer, spherical condensation tube (with threeway) in there-necked flask, 50% sodium hydroxide (56 g, 0.7 mol) is added in constant pressure funnel simultaneously.Cooling with ice-water bath, keep temperature lower than 25 ℃.By threeway, balloon (interior inflated with nitrogen), with water circulating pump, bleed, then open the threeway inflation, so 3-4 time, make device under nitrogen protection.Open constant pressure funnel, keep dripping speed 2 seconds/drip left and right, control temperature lower than 25 ℃.Reaction overnight.After having reacted, add distilled water (300 mL) to dissolve the solid generated, then add concentrated hydrochloric acid (35 mL) to constant pressure funnel, to open piston, drip concentrated hydrochloric acid, the acidifying water layer, note controlling temperature lower than 25 ℃.After dripping, then stir 30 min, responseless volatility of raw material is fallen.By the solid filtering in solution out, and wash with water, obtain khaki color crude product solid, claim to obtain thick CMP 16.81g, thick productive rate is 89.3%.Thick CMP is carried out to recrystallization with 60% isopropanol water solution.
Embodiment 3:
In the four-hole boiling flask of 250 mL that thermometer is housed, add tetrahydrofuran (THF) 100 ml, then add diacetoneglucose methacrylic ester 10.0 g and trithiocarbonate 0.2 g, under nitrogen protection, add initiator Diisopropyl azodicarboxylate AIBN 0.05 g, in 70 ℃ of water-baths, reaction 2h, adopt TLC to detect the polymerization of diacetoneglucose acrylate monomer complete; Add subsequently comonomer 4-acryloxy nitrogen benzide 10.0 g, continue polyreaction 5h under 70 ℃.Add the be hydrolyzed acetone of deprotection of the hydrochloric acid of 2 mol/L, hydrolysis 2h, methanol extraction, drying, obtain photosensitive glycosyl hydrogel 11.4 g of " glycosyl-4-acryloxy nitrogen benzide " block structure.
Embodiment 4:
In the four-hole boiling flask of 250 mL that thermometer is housed, add tetrahydrofuran (THF) 100 ml, then add diacetoneglucose acrylate 5.0 g and trithiocarbonate 0.1 g, under nitrogen protection, add initiator Diisopropyl azodicarboxylate AIBN 0.025 g, in 70 ℃ of water-baths, reaction 2h, adopt TLC to detect the polymerization of diacetoneglucose acrylate monomer complete; Add subsequently comonomer 4-acryloxy nitrogen benzide 10.0 g, continue polyreaction 5h under 70 ℃.Add the be hydrolyzed acetone of deprotection of the hydrochloric acid of 2 mol/L, hydrolysis 2h, methanol extraction, drying, obtain photosensitive glycosyl hydrogel 9.1 g of " glycosyl-4-acryloxy nitrogen benzide " block structure.
Embodiment 5:
In the four-hole boiling flask of 250 mL that thermometer is housed, add tetrahydrofuran (THF) 100 ml, then add diacetoneglucose acrylate 10.0 g and trithiocarbonate 0.2 g, under nitrogen protection, add initiator Diisopropyl azodicarboxylate AIBN 0.05 g, in 70 ℃ of water-baths, reaction 2h, adopt TLC to detect the polymerization of diacetoneglucose acrylate monomer complete; Add subsequently comonomer 4-acryloxy nitrogen benzide 5.0 g, continue polyreaction 5h under 70 ℃.Add the be hydrolyzed acetone of deprotection of the hydrochloric acid of 2 mol/L, be hydrolyzed 2 h, methanol extraction, drying, obtain photosensitive glycosyl hydrogel 8.2 g of " glycosyl-4-acryloxy nitrogen benzide " block structure.
It is block structure that the present invention has prepared the gel molecular skeleton, and its structure can regulate and control; Raw material used in the present invention is saccharide compound, has improved biocompatibility; The prepared photosensitive hydrogel of the present invention has good light stimulus response performance.
Claims (5)
1. the photosensitive glycosyl intelligent aqueous gel capable of block structure, is characterized in that: on the overall molecule structure, be block structure; Glucose take in preparation as raw material, through the unsaturated carboxylic acid halides with containing two keys, carry out esterification, prepare Monomer containing sugar moiety; By Monomer containing sugar moiety and photosensitive monomer, by the RAFT agent, through reversible addition-fragmentation chain transfer free radical polymerization, prepare the photosensitive glycosyl intelligent aqueous gel capable of block structure.
2. the photosensitive glycosyl intelligent aqueous gel capable of block structure according to claim 1 is characterized in that: the described unsaturated carboxylic acid halides that contains two keys is acrylate chloride.
3. the photosensitive glycosyl intelligent aqueous gel capable of block structure according to claim 1, it is characterized in that: described photosensitive monomer is 4-acryloxy nitrogen benzide.
4. the photosensitive glycosyl intelligent aqueous gel capable of block structure according to claim 1, it is characterized in that: described RAFT agent is S, S '-bis-(α, α '-dimethyl-α "-acetic acid)-trithiocarbonate.
5. a method for preparing the photosensitive glycosyl intelligent aqueous gel capable of block structure as described as any one in claim 1-4, it is characterized in that: preparation process is as follows:
A: glucose monomer is protected through OH, with the standby polymerizable Monomer containing sugar moiety that contains two keys of unsaturated acyl stew in soy sauce;
B: by chain-transfer agent S, S '-bis-(α, α '-dimethyl-α "-acetic acid)-trithiocarbonate and the prepared polymerizable Monomer containing sugar moiety of previous step join in tetrahydrofuran (THF), and described polymerizable glycosyl proportion in whole molecular chain is 10-70%, under protection of inert gas; add the initiator Diisopropyl azodicarboxylate; under 70 ℃, carries out the polymerization of Monomer containing sugar moiety, after the Monomer containing sugar moiety polymerization completes; add the photosensitive monomer copolymerization, obtains block structure glycosyl polymkeric substance;
C: by the block structure glycosyl polymkeric substance of preparation, in diluted acid, the free OH of hydrolysis, obtain the photosensitive glycosyl intelligent aqueous gel capable of target product block structure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670039A (en) * | 2017-10-19 | 2018-02-09 | 苏州杰纳生物科技有限公司 | A kind of catalase and photosensitive molecular compound and its preparation method and application |
| CN110327056A (en) * | 2019-05-24 | 2019-10-15 | 武汉大学 | A kind of intelligent aqueous gel and preparation method thereof for visualizing blood sugar test |
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| CN101824124A (en) * | 2010-04-20 | 2010-09-08 | 常州杰森化工材料科技有限公司 | Preparation method of photoresponse hydrogel containing azo monomers |
| CN102432497A (en) * | 2011-09-23 | 2012-05-02 | 北京化工大学 | Synthesis and application of bis-o-substituted acrylate azobenzene containing intramolecular hydrogen bonds |
| CN102964547A (en) * | 2012-12-05 | 2013-03-13 | 南通大学 | PH response glycosyl intelligent hydrogel with segmented structure and preparation method thereof |
| CN103289102A (en) * | 2013-06-08 | 2013-09-11 | 长春理工大学 | Dual-response magnetic nano particle with fluorescence and preparation method thereof |
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Patent Citations (4)
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| CN101824124A (en) * | 2010-04-20 | 2010-09-08 | 常州杰森化工材料科技有限公司 | Preparation method of photoresponse hydrogel containing azo monomers |
| CN102432497A (en) * | 2011-09-23 | 2012-05-02 | 北京化工大学 | Synthesis and application of bis-o-substituted acrylate azobenzene containing intramolecular hydrogen bonds |
| CN102964547A (en) * | 2012-12-05 | 2013-03-13 | 南通大学 | PH response glycosyl intelligent hydrogel with segmented structure and preparation method thereof |
| CN103289102A (en) * | 2013-06-08 | 2013-09-11 | 长春理工大学 | Dual-response magnetic nano particle with fluorescence and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107670039A (en) * | 2017-10-19 | 2018-02-09 | 苏州杰纳生物科技有限公司 | A kind of catalase and photosensitive molecular compound and its preparation method and application |
| CN107670039B (en) * | 2017-10-19 | 2020-06-05 | 苏州杰纳生物科技有限公司 | Catalase and photosensitive molecule compound and preparation method and application thereof |
| CN110327056A (en) * | 2019-05-24 | 2019-10-15 | 武汉大学 | A kind of intelligent aqueous gel and preparation method thereof for visualizing blood sugar test |
| CN110327056B (en) * | 2019-05-24 | 2021-01-01 | 武汉大学 | Intelligent hydrogel for visual blood glucose detection and preparation method thereof |
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Application publication date: 20131225 |