CN105860098A - Preparation method and application of thermo-sensitive type porous semi-interpenetrating network hydrogel - Google Patents

Preparation method and application of thermo-sensitive type porous semi-interpenetrating network hydrogel Download PDF

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CN105860098A
CN105860098A CN201610248637.1A CN201610248637A CN105860098A CN 105860098 A CN105860098 A CN 105860098A CN 201610248637 A CN201610248637 A CN 201610248637A CN 105860098 A CN105860098 A CN 105860098A
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gel
interpenetrating network
hydrogel
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enzyme
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CN105860098B (en
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郭明
黄婧欣
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Zhejiang A&F University ZAFU
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    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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    • C08F8/00—Chemical modification by after-treatment
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
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    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Abstract

The invention discloses a preparation method and an application of a thermo-sensitive type porous semi-interpenetrating network hydrogel. The preparation method comprises the following five steps of 1, synthesizing linear PHEMA (poly-hydroxyethyl methacrylate); 2, preparing semi-interpenetrating network hydrogel HEMA-co-DEAAM; 3, using allyl to modify the hydrogel; 4, immobilizing papain. The thermo-sensitive type porous semi-interpenetrating network hydrogel has the advantages that an interpenetrating network porous structure is contained, the specific area is large, the temperature change can be quickly responded, and the hydrogel is an ideal immobilized enzyme carrier; the enzyme is immobilized by the methyl methacrylate double-bond structure on the carrier and the click reaction of sulfydryl on the enzyme molecule; the reaction selectivity is high, and only the enzyme containing sulfydryl is immobilized; the reaction condition is mild, and the reaction temperature is about 37 DEG C; the activity of immobilized enzyme after reaction is equal to 5.5 times of the activity of glutaraldehyde immobilized enzyme of traditional method, the stability is better, and the recycling effect is realized.

Description

A kind of preparation method and applications of temperature sensitive type porous semi-interpenetrating network aqueous gel
Technical field
The present invention relates to the preparation method of a kind of Novel temperature-sensitive semi-interpenetrating network aqueous gel, a kind of temperature sensitive The preparation method and applications of type porous semi-interpenetrating network aqueous gel.
Background technology
Enzyme immobilizatio (Immobilization of enzymes) is to use chemistry (covalently bonded legal, cross-linking method) Or the method such as physics (absorption method, investment), make water miscible enzyme combine with non-water-soluble carrier, system For both having kept enzyme to live, the most repeatable new function material utilizing enzyme.Immobilized enzyme is had at holding enzyme itself While the high selectivity, high efficiency and the mild condition feature that have, the advantage also presenting many, such as storage Stability is high, separation and recovery easily, can repeatedly use.In recent years, immobilized enzyme is chemistry, doctor The fields such as medicine, food, environmental project and commercial production have a wide range of applications, and become current research heat Point.But, the structure of enzyme immobilization carrier material and performance directly affect the performance of immobilized enzyme.Therefore, system The carrier material that standby structure is excellent is most important.
At present from document, enzyme immobilization carrier material organic and/or inorganic materials, macromolecular material, biological material Deng.In the recent period, the new results of materialogy are gradually applied in enzyme support material field.Wherein, before intellectual material is Edge and focus.Intelligence enzyme immobilization material divides from type, has pH response type, temperature response type, magnetic to ring Answer type etc., divide from material shape, have gel solids, vector resin etc..Wherein, temperature-sensitive hydrogel exists Immobilized enzyme aspect has reasonable advantage.The feature of temperature-sensitive hydrogel is containing certain proportion in its structure Hydrophilic group and hydrophobic group, when ambient temperature changes, the hydrophilic and hydrophobic of these groups and hydrogen Key effect will change accordingly.The hydrophilic of most temperature-sensitive hydrogel can be along with the increase of temperature And increase, but there is lowest critical solution temperature (Lower critical solution temperature, LCST) Hydrogel hydrophilic but along with temperature raise and reduce, this hydrogel is in the temperature less than LCST Time, hydrophilic group and hydrone, by hydrogen bonded, strengthen gel dissolubility in water；When temperature raises, Interaction between hydrophobic group is strengthened, and oxygen key dies down, gel shrinks.The LCST of temperature-sensitive hydrogel is permissible Being changed by the ratio of regulation hydrophobe group, generally, hydrophilic group content is the highest, hydrogel LCST is the highest, the most poly-N, N-diethyl-2-acrylamide (PDEAAM), by poly(ethylene oxide) (PEO) The block copolymer formed with poly(propylene oxide) (PPO) is respectively provided with temperature sensitivity, and LCST is close to human temperature Degree.So, can be by whether controlling the carrying out of controlling reaction temperature enzymic catalytic reaction.Meanwhile, LCST is mostly close to room temperature, and reaction condition is simply easily controlled.So, carry out this work highly significant.
In recent years, with new and high technology in the present age for according to designing synthesizing new carrier, developing novel process for fixation And both combinations are the research directions that many scholars are devoted in recent years, the novel of exploitation is fixed Change method must comply with following principle: enzyme immobilizatio is the gentleest, to reduce to greatest extent or to keep away Exempt from loss of enzyme activity, and temperature-sensitive hydrogel causes numerous researchers as the mode of a kind of new immobilized enzyme Extensive concern.Gotoh etc. respectively with NIPAm and N, N-diethyl acrylamide (DEAAm) for monomer, Temperature higher than utilize under conditions of LCST radical polymerization be prepared for Thermo-sensitive porous PNIPAm and PDEAAm hydrogel.Zhang etc. are prepared for PNIPAm macropore temperature sensitive type water-setting with PEG for perforating agent Glue, can regulate the structure of hydrogel by changing PEG consumption.Alves etc. are with isopropyl propionic acid amide., sea Calcium alginate is prepared for pH/ temperature sensitive Semi-IPN hydrogel.Guo etc. are with carboxymethyl chitosan and gather (NIPA) is prepared for Semi-IPN aquogel polymer, and have studied this polymer Medicine-releasing performance.Cheng etc. utilize perforating agent to be prepared for PNIPAm super porous hydrogel, and carry out Sanguis Bovis seu Bubali Albumin controlled release is studied, and controlled release rate and the controlled release rate of medicine are higher.Hu Lin etc. utilize plasma filling perforation to be grafted PNIPAm is grafted on polyvinylidene fluoride film (PVDF) fenestra by polymerization technique, then with crosslinking PNIPAm hydrogel combination is made for a kind of temperature sense and controls release membranous system, and this system has good Temperature-responsive.Lee etc. utilize PNIPAm and several different ion monomer polymerizations, with different molecular weight PEG be that perforating agent is prepared for a series of hydrogel, have studied caffeine releasing mechanism in hydrogel. From the known references given, utilize DEAAm and linear methyl 2-(Acryloyloxy)ethanol many for raw material preparation Hole semi-interpenetrating network aqueous gel the research carrying out modifying with methyl methacrylate double bond structure there is no people and completes, Having certain novelty, research work is significant.
The present invention is that raw material prepares porous semi-intercrossing network with linear methyl 2-(Acryloyloxy)ethanol based on DEAAm Hydrogel, utilizes this New-type matrix material and the fixing sulfydryl enzyme of sulfydryl reaction, has extremely strong selectivity and pole Good temperature-responsive.Knowable to fixed papain eligible result, immobilized papain is repeatable Utilizing, activity recovery 6.5%, temperature-responsive scope is 35～39 DEG C, and heat stability 85% has excellence Character.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation of a kind of temperature sensitive type porous semi-interpenetrating network aqueous gel Method, and the application with this new type gel fixed papain.
Solve above-mentioned technical problem and be the technical scheme is that a kind of temperature sensitive type porous semi-intercrossing network water-setting The preparation method of glue, is carried out as follows:
(1) synthesis of PHEMA: by the initiator azodiisobutyronitrile (2,2'-Azobis (2-of 5mg Methylpropionitrile), AIBN), the monomers hydroxy ethyl ester (Hydroxyethyl of 2mL Methacrylate, HEMA) be added to 4mL solvent dimethyl sulfoxide (Dimethyl sulfoxide, DMSO), in, reflux in 60 DEG C of water-baths 8h in a nitrogen environment, obtains PHEMA weak yellow liquid.With Ether sedimentation, filters, and dries and obtains PHEMA powder.
(2) preparation of the Semi-IPN hydrogel of network: by the perforating agent Polyethylene Glycol PEG20000 of 0.1g, The N of 1.8mL, N-acrylamide (N, N-diethyl-Acrylamide, DEAAm), the crosslinking of 0.04g Agent N,N methylene bis acrylamide (Methylene-Bis-Acrylamide, Bis) and 0.075g's PHEMA powder is dissolved in the DMSO of 6mL, and water-bath backflow 6h, obtains gel in a nitrogen environment.
(3) gel modified by acrylate: gel is placed in distilled water immersion 14 days, after weighing 1g immersion Gel, be dissolved in the DMF (N, N-Dimethylformamide, DMF) of 10mL In, add the Feldalat NM of 0.01～0.05g, drip the ethylaminoethanol of 0.11g under stirring condition, on 150 DEG C of left sides The right side is stirred at reflux 4h.After reaction terminates, it is cooled to 80 DEG C, adds the hydroquinone of 0.005g, dropping The methyl methacrylate of 0.18g, water-bath backflow 1h, obtain transparent gel-form solid.After reaction terminates, Wash solid several times with water, obtain temperature sensitive type porous semi-interpenetrating network aqueous gel.
The application of a kind of temperature sensitive type porous semi-interpenetrating network aqueous gel, described application is: by temperature sensitive type porous half Interpenetration network hydrogel is for the fixing enzyme containing sulfydryl.
The invention has the beneficial effects as follows that the temperature-sensitive hydrogel prepared by this method contains the porous mutually run through Structure, has big specific surface area, can quickly respond variations in temperature, is a kind of more satisfactory immobilization The carrier of enzyme.Utilize the methyl methacrylate double bond structure on carrier and the click-reaction of sulfydryl on enzyme molecule Carrying out enzyme immobilizatio, have reaction selectivity high, reaction condition is gentle, the advantage that method is easily operated, The activity of the immobilized enzyme that reaction obtains is 5.5 times that traditional method passes through glutaraldehyde immobilized enzyme, and it is stable Property preferable, recoverable.
Accompanying drawing explanation
Accompanying drawing 1 is the Novel temperature-sensitive semi-interpenetrating network aqueous gel technology of preparing route map of the present invention, in figure, 1. Initiator A IBN 2. solvent DMSO 3. crosslinking agent B is 4. perforating agent PEG20000 5. DEAAm monomer ⑥CH3ONa⑦NH2C2H4OH 8. hydroquinone 9. methyl methacrylate
Accompanying drawing 2 is the Novel temperature-sensitive semi-interpenetrating network aqueous gel infrared spectrogram of the present invention.
Accompanying drawing 3 is the Novel temperature-sensitive semi-interpenetrating network aqueous gel of the present invention13C nuclear magnetic spectrogram.
Accompanying drawing 4 is the Novel temperature-sensitive semi-interpenetrating network aqueous gel of the present invention1H nuclear magnetic spectrogram.
Accompanying drawing 5 is the electron-microscope scanning figure of the Novel temperature-sensitive semi-interpenetrating network aqueous gel of the present invention.
Detailed description of the invention
The present invention below in conjunction with embodiment and is further elaborated referring to the drawings:
First buy following raw material: hydroxyethyl methylacrylate (HEMA), azodiisobutyronitrile (AIBN), Dimethyl sulfoxide (DMSO), Polyethylene Glycol (PEG20000), N, N-acrylamide (DEAAm), N,N methylene bis acrylamide (Bis), methyl methacrylate, ethylaminoethanol, Dimethylformamide (DMF), Feldalat NM, hydroquinone.The present embodiment g makees unit of weight, mL For volume unit.
Embodiment 1
1. the preparation method of the Semi-IPN temperature-sensitive hydrogel of porous, is characterized in that carrying out as follows:
(1) synthesis of PHEMA: the monomer HEMA of initiator A IBN, 2mL of 5mg is added to In the solvent DMSO of 4mL, logical nitrogen, water-bath backflow 8h in 60 DEG C.After reaction terminates, use ether Precipitation, filters, the PHEMA powder of drying.Synthetic reaction principle is as follows:
(2): the preparation of the Semi-IPN hydrogel of porous network: by the perforating agent PEG20000 of 0.1g, Crosslinking agent B is of DEAAm, 0.04g of 1.8mL and the PHEMA of 0.075g are dissolved in 6mL's In DMSO, logical nitrogen, water-bath backflow 6h.After reaction terminates, obtain gel.Synthetic reaction principle is as follows:
(3) gel modified by acrylate: gel is placed in distilled water immersion 14 days, after weighing 1g immersion Gel, be dissolved in the DMF of 10mL, add 0.01～0.05g Feldalat NM, stir and drip 0.11g's Ethylaminoethanol, is stirred at reflux 4h at about 150 DEG C.After reaction terminates, it is cooled to 80 DEG C, adds 0.005g Hydroquinone, is slowly added dropwise the methyl methacrylate of 0.18g, water-bath backflow 1h.After reaction terminates, use Water washs for several times, obtains temperature sensitive type porous semi-interpenetrating network aqueous gel.
Temperature sensitive type porous semi-interpenetrating network aqueous gel is carried out infrared,13C nuclear magnetic resonance, NMR,1H nuclear magnetic resonance, NMR, Scanning electron microscope scans.Result is as follows: infared spectrum as in figure 2 it is shown, wherein, 3080-2870cm-1For gel The stretching vibration absworption peak of methylmethylene C-H, 1469-1380cm at carbon-carbon double bond-1Curved for methyl C-H Bent vibration absorption peak, 895cm-1For methylene C-H bending vibration absworption peak, 1650cm-1Stretching for C=O Contracting vibration absorption peak.In gel, 3600cm-1Place, without characteristic peak, shows that methyl methacrylate modifies water-setting Glue success, i.e. the Semi-IPN hydrogel of Novel temperature-sensitive type porous synthesizes successfully.13C nuclear magnetic spectrum (NMR) such as Fig. 3,1H nuclear magnetic spectrum (NMR) such as Fig. 4, is understood the Semi-IPN hydrogel of temperature sensitive type porous by it and synthesizes successfully.Scanning Electronic Speculum figure such as Fig. 5, it is known that for the loose structure mutually run through in hydrogel, hole size and distribution are more equal Even.
Embodiment 2
Temperature sensitive type porous semi-interpenetrating network aqueous gel embodiment 1 prepared is used for the fixing enzyme containing sulfydryl, presses Following steps are carried out:
Sulfydryl click-reaction fixed papain: weigh the temperature sensitive type porous semi-intercrossing network water that 0.1g prepares Gel, adds it in enzymatic solution, is heated to 30 DEG C, and gel starts to absorb enzymatic solution and occurs swelling, enzyme Molecule crosslinks reaction in gel inside with gel, prepares immobilized enzyme.By prepared immobilization Fructus Chaenomelis egg White enzyme is saved in (pH=7) 4 DEG C of preservations of 0.1mol/L phosphate buffer.
Through Experimental comparison, show that the enzymatic activity of obtained immobilized enzyme is to use consolidating of glutaraldehyde cross-linking gained Surely change enzyme about 5.5 times.
Embodiment 3
The preparation method of a kind of temperature sensitive type porous semi-interpenetrating network aqueous gel, is carried out as follows:
(1) synthesis of PHEMA: 5mg initiator A IBN, 2mL monomer HEMA is added to 4mL In solvent DMSO, logical nitrogen, water-bath backflow 8h in 60 DEG C.After reaction terminates, with ether sedimentation, Filter, dry and obtain PHEMA powder.
(2) preparation of the Semi-IPN hydrogel of porous network: by perforating agent PEG20000,1.8mL of 0.1g Crosslinking agent B is of DEAAm, 0.04g and the PHEMA of 0.075g be dissolved in the DMSO of 6mL, Logical nitrogen, water-bath backflow 6h.After reaction terminates, obtain gel.
(3) gel modified by acrylate: gel is placed in distilled water immersion 14 days, after weighing 1g immersion Gel, be dissolved in the DMF of 10mL, add 0.01～0.05g Feldalat NM, stir and drip 0.11g Ethylaminoethanol, be stirred at reflux 4h 1 time in temperature.After reaction terminates, it is cooled to temperature 2, adds The hydroquinone of 0.005g, the methyl methacrylate of dropping 0.18g, water-bath backflow 1h.After reaction terminates, Wash with water for several times, obtain temperature sensitive type porous semi-interpenetrating network aqueous gel a～f.
The impact on gel characteristic of table 1 temperature
As shown in Table 1, when temperature 1 is 150 DEG C, temperature 2 is 80 DEG C, gained hydrogel is optimum.Temperature Time too high, a large amount of by-product can be produced and make productivity relatively low, and when temperature is relatively low, have a large amount of reactant residue. So, temperature is too high or too low all can make hydrogel impurity too much and reduce the effectiveness of hydrogel.

Claims (2)

1. a preparation method for temperature sensitive type porous semi-interpenetrating network aqueous gel, is characterized in that, by following step Suddenly carry out:
(1) synthesis of PHEMA: by the initiator azodiisobutyronitrile (2,2'-Azobis (2-of 5mg Methylpropionitrile), AIBN), the monomers hydroxy ethyl ester (Hydroxyethyl of 2mL Methacrylate, HEMA) be added to 4mL solvent dimethyl sulfoxide (Dimethyl sulfoxide, DMSO), in, reflux in 60 DEG C of water-baths 8h in a nitrogen environment, obtains PHEMA weak yellow liquid.With Ether sedimentation, filters, and dries and obtains PHEMA powder.
(2) preparation of the Semi-IPN hydrogel of network: by the perforating agent Polyethylene Glycol PEG20000 of 0.1g, The N of 1.8mL, N-acrylamide (N, N-diethyl-Acrylamide, DEAAm), the crosslinking of 0.04g Agent N,N methylene bis acrylamide (Methylene-Bis-Acrylamide, Bis) and 0.075g's PHEMA powder is dissolved in the DMSO of 6mL, and water-bath backflow 6h, obtains gel in a nitrogen environment.
(3) gel modified by acrylate: gel is placed in distilled water immersion 14 days, after weighing 1g immersion Gel, be dissolved in the DMF (N, N-Dimethylformamide, DMF) of 10mL In, add the Feldalat NM of 0.01～0.05g, drip the ethylaminoethanol of 0.11g under stirring condition, on 150 DEG C of left sides The right side is stirred at reflux 4h.After reaction terminates, it is cooled to 80 DEG C, adds the hydroquinone of 0.005g, dropping The methyl methacrylate of 0.18g, water-bath backflow 1h, obtain transparent gel-form solid.After reaction terminates, Wash solid several times with water, obtain temperature sensitive type porous semi-interpenetrating network aqueous gel.
2. the application of the temperature sensitive type porous semi-interpenetrating network aqueous gel that prepared by method as described in right 1, it is special Levying and be, described application is: temperature sensitive type porous semi-interpenetrating network aqueous gel is used for the fixing enzyme containing sulfydryl.
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CN107163282A (en) * 2017-07-19 2017-09-15 中国科学院长春应用化学研究所 Macroporous polymer resin of fast temperature response and preparation method thereof
CN109989679A (en) * 2017-12-30 2019-07-09 长沙星纳气凝胶有限公司 A kind of temperature sensitive heat insulation glass of aerogel-congtg and preparation method thereof
CN109989684A (en) * 2017-12-30 2019-07-09 长沙星纳气凝胶有限公司 A kind of temperature sensitive heat-insulation and heat-preservation daylighting glass of aerogel-congtg and preparation method thereof
CN109989685A (en) * 2017-12-30 2019-07-09 长沙星纳气凝胶有限公司 A kind of temperature sensitive heat insulation glass of aerogel-congtg and preparation method thereof
CN110776667A (en) * 2019-11-11 2020-02-11 浙江农林大学 Piezoresistive sensing device material and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN107163282A (en) * 2017-07-19 2017-09-15 中国科学院长春应用化学研究所 Macroporous polymer resin of fast temperature response and preparation method thereof
CN109989679A (en) * 2017-12-30 2019-07-09 长沙星纳气凝胶有限公司 A kind of temperature sensitive heat insulation glass of aerogel-congtg and preparation method thereof
CN109989684A (en) * 2017-12-30 2019-07-09 长沙星纳气凝胶有限公司 A kind of temperature sensitive heat-insulation and heat-preservation daylighting glass of aerogel-congtg and preparation method thereof
CN109989685A (en) * 2017-12-30 2019-07-09 长沙星纳气凝胶有限公司 A kind of temperature sensitive heat insulation glass of aerogel-congtg and preparation method thereof
CN110776667A (en) * 2019-11-11 2020-02-11 浙江农林大学 Piezoresistive sensing device material and preparation method and application thereof
US11897162B2 (en) 2019-11-11 2024-02-13 Zhejiang A & Funiversity Piezoresistive sensor material and preparation method and use thereof

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