CN105199046B - Responsive to temperature type molecular engram membrane material - Google Patents

Responsive to temperature type molecular engram membrane material Download PDF

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Publication number
CN105199046B
CN105199046B CN201510695413.0A CN201510695413A CN105199046B CN 105199046 B CN105199046 B CN 105199046B CN 201510695413 A CN201510695413 A CN 201510695413A CN 105199046 B CN105199046 B CN 105199046B
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monomer
type molecular
molecular engram
responsive
membrane material
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CN201510695413.0A
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CN105199046A (en
Inventor
郑学芳
廉琪
王东军
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Hebei Normal University of Science and Technology
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Hebei Normal University of Science and Technology
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Abstract

The present invention is prepared for a kind of responsive to temperature type molecular engram membrane material, and solvent, chitosan, monomer, initiator are sufficiently mixed, and the mass ratio of chitosan and monomer is 1:1~1:15, the volume ratio of solvent and monomer is 1:1~1:25, initiator content is the 0.001~20% of monomer mass, reacts 0.5 20h in 10 160 DEG C of reaction temperature, the atmospheric polymerization of pressure 1~100, obtains chitose graft copolymer, add template molecule into chitose graft copolymer again, the mass ratio of chitosan and template molecule is 10:1~1:20, be sufficiently mixed, seal, vibrate, polymerize 1~40h again, milky white liquid, standing and defoaming obtains casting solution, and by the horizontal casting film-forming of casting solution, the good responsive to temperature type molecular engram membrane material of memory performance is obtained after drying.This material has great application prospect in sensor field and bioactive materials field.

Description

Responsive to temperature type molecular engram membrane material
Technical field
The present invention relates to a kind of method of preparation temperature responsive type molecular engram membrane material.
Background technology
Molecular engram film has the characteristics of molecular recognition and UF membrane concurrently, and its principle is that trace point is added in polymerisation medium Son, microsphere is removed after film forming, the functional dimension of microsphere will be left in derivatized polymers, by this seperation film During for separating the mixture being made up of microsphere and other materials, it can recognize that microsphere, so as to will effectively print Mark molecule and other materials separate.Molecular engram film is that have single-minded knowledge to microsphere using molecular imprinting technology is artificial synthesized The novel separation film of other ability.Current product film such as ultrafiltration, micro-filtration and reverse osmosis membrane etc. can not all realize the choosing of single material Selecting property separates, and MIM be specific target molecules are separated from the mixture of its analogue provide it is feasible effectively Solution route;MIM can have molecular specific recognition capability, with conventional particle molecular engram as a kind of molecular imprinting technology Polymer MIPs is compared, and MIM has without cumbersome preparation process such as grindings, and diffusional resistance is small, be easy to using etc. it is unique excellent Point;Simultaneously more more stable than general biomaterial, anti-adverse environment ability is stronger, in sensor field and bioactive materials field Have great application prospect.Chitosan (chitosan) is the product of chitin deacetylation, is unique in natural polysaccharide Alkaline polysaccharide, there is many unique physicochemical characteristics and biological function, chitosan and profile of thermo sensitive polymers are carried out Graft copolymerization, it can assign chitosan more functions, binding molecule engram technology, preparation temperature responsive type molecular engram macromolecule Material, report is had no in this respect.
The content of the invention
Present invention aim to address prior art defect, there is provided one kind prepares temperature sensitive type molecular engram macromolecule member material Method.
The present invention prepares preferable responsive to temperature type shape-memory material using radical polymerization and a step blending method, its Specific preparation process is as follows:(1) preparation of chitose graft copolymer:Solvent, chitosan, monomer, initiator are sufficiently mixed, The mass ratio of chitosan and monomer is 1:1~1:15, the volume ratio of solvent and monomer is 1:1~1:25, initiator content is single The 0.001~20% of weight, in 10-160 DEG C of reaction temperature, the atmospheric polymerization of pressure 1~100 reaction 0.5-20h, obtain shell Polysaccharid graft copolymerization thing;(2) preparation of responsive to temperature type molecular engram membrane material:Template is added into chitose graft copolymer The mass ratio of molecule, chitosan and template molecule is 10:1~1:20, it is sufficiently mixed, seals, vibrates, polymerize 1~40h again, Milky white liquid, standing and defoaming obtains casting solution, and by the horizontal casting film-forming of casting solution, responsive to temperature type molecular engram is obtained after drying Membrane material.
One or more of mixtures of the solvent in acetic acid aqueous solution, aqueous formic acid.
The one kind or one of the monomer in methyl methacrylate, EMA or butyl methacrylate The mixture of the kind above.
The initiator is azodiisobutyronitrile, ABVN, persulfuric acid salt initiator or their mixture.
The one kind of the template molecule in bovine serum albumin, human albumin, amino acids.
Reaction temperature in the present invention is 20~100 DEG C.
Pressure in the present invention is 1~80 atmospheric pressure.
The reaction time of the chitose graft copolymer in the present invention is 2~10h;The temperature sensitive type molecular engram material The synthesising reacting time of material is 10~25h.
Described persulfuric acid salt initiator in the present invention in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate one Kind or more than one mixture.
Brief description of the drawings
Temperature sensitive type molecular engram membrane material prepared by Fig. 1 embodiments 1.
The restorability test result of Fig. 2 temperature sensitive type molecular engram spiral membranes.
Embodiment
Embodiment 1
1.0000g chitosans are dissolved in 3% acetic acid aqueous solution, and stirring is completely dissolved chitosan.Added at 40 DEG C 0.01g/mL ammonium persulfate 5mL, adds methyl methacrylate 3mL reaction 1h, and the bovine serum albumin for adding 0.2g/L is molten Liquid 10mL, 4h is reacted, obtains milky white liquid, standing and defoaming obtains casting solution.Casting solution is cast in horizontal positioned clean culture dish In, obtain responsive to temperature type molecular engram membrane material after drying.
Embodiment 2
1.0000g chitosans are dissolved in 3% acetic acid aqueous solution, and stirring is completely dissolved chitosan.Added at 60 DEG C 0.01g/mL ammonium persulfate 10mL, EMA 3mL reaction 5h are added, add 0.2g/L bovine serum albumin Solution 17mL, 10h is reacted, obtains milky white liquid, standing and defoaming obtains casting solution.Casting solution is cast and cultivated in horizontal positioned cleaning In ware, responsive to temperature type molecular engram membrane material is obtained after drying.
Embodiment 3
1.0000g chitosans are dissolved in 3% acetic acid aqueous solution, and stirring is completely dissolved chitosan.Added at 80 DEG C 0.01g/mL ammonium persulfate 20mL, methyl methacrylate 3mL reaction 9h are added, add 0.2g/L TYR solution 25mL, 15h is reacted, obtains milky white liquid, standing and defoaming obtains casting solution.Casting solution is cast in horizontal positioned clean culture dish In, obtain responsive to temperature type molecular engram membrane material after drying.
Embodiment 4
1.0000g chitosans are dissolved in 3% acetic acid aqueous solution, and stirring is completely dissolved chitosan.1mg is added at 40 DEG C Azodiisobutyronitrile, add methyl methacrylate 3mL reaction 5h, add 0.2g/L glycine solution 14mL, reaction 8h, obtains milky white liquid, and standing and defoaming obtains casting solution.Casting solution is cast in horizontal positioned clean culture dish, after drying Responsive to temperature type molecular engram membrane material.
Embodiment 5
1.0000g chitosans are dissolved in 3% acetic acid aqueous solution, and stirring is completely dissolved chitosan.1mg is added at 40 DEG C ABVN, butyl methacrylate 3mL reaction 16h are added, add 0.2g/L human albumin solution 22mL, instead 18h is answered, obtains milky white liquid, standing and defoaming obtains casting solution.Casting solution is cast in horizontal positioned clean culture dish, after drying Obtain responsive to temperature type molecular engram membrane material.

Claims (5)

  1. A kind of 1. method of preparation temperature responsive type molecular engram membrane material, it is characterized in that being total to using radical polymerization and a step Mixed method prepares preferable responsive to temperature type molecular engram membrane material, and its specific preparation process is as follows:
    (1) preparation of chitose graft copolymer
    Solvent, chitosan, monomer, initiator are sufficiently mixed, the mass ratio of chitosan and monomer is 1:1~1:15, solvent and The volume ratio of monomer is 1:1~1:25, initiator content is the 0.001~20% of monomer mass, in 10-160 DEG C of reaction temperature, The atmospheric polymerization of pressure 1~100 reacts 0.5-20h, obtains chitose graft copolymer;
    (2) preparation of responsive to temperature type molecular engram membrane material
    Add template molecule into chitose graft copolymer, the mass ratio of chitosan and template molecule is 10:1~1:20, fill Divide mixing, sealing, vibration, polymerize 1~40h again, obtain milky white liquid, standing and defoaming obtains casting solution, and casting solution level is cast Film forming, responsive to temperature type molecular engram membrane material is obtained after drying;
    One or more of mixtures of the solvent in acetic acid aqueous solution, aqueous formic acid;
    One kind in methyl methacrylate, EMA or butyl methacrylate of the monomer or it is a kind of with On mixture;
    The initiator is azodiisobutyronitrile, ABVN, persulfuric acid salt initiator or their mixture;
    The one kind of the template molecule in bovine serum albumin, human albumin, amino acids.
  2. 2. method according to claim 1, it is characterized in that:The reaction temperature is 20~100 DEG C.
  3. 3. method according to claim 1, it is characterized in that:The pressure is 1~80 atmospheric pressure.
  4. 4. method according to claim 1, it is characterized in that:The reaction time of the chitose graft copolymer is 2~10h; The synthesising reacting time of the temperature sensitive type molecular engram material is 1~30h.
  5. 5. method according to claim 1, it is characterized in that:Described persulfuric acid salt initiator is selected from ammonium persulfate, over cure One or more kinds of mixtures in sour potassium, sodium peroxydisulfate.
CN201510695413.0A 2015-10-23 2015-10-23 Responsive to temperature type molecular engram membrane material Expired - Fee Related CN105199046B (en)

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722366B (en) * 2018-05-25 2021-03-16 海南大学 Preparation method of polysaccharide-based temperature-sensitive metal ion imprinted carbon quantum dot material
CN108929408B (en) * 2018-07-20 2020-05-22 中北大学 Preparation method and application of stevioside imprinted material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1843598A (en) * 2006-03-20 2006-10-11 天津大学 Method for preparing molecular engram CS/TEOS hybridized film by separation of phenylalanine isomer
CN101185856A (en) * 2007-08-29 2008-05-28 浙江大学 Preparation method and application of sulfonylureas herbicide molecular engram separating film
CN102764598A (en) * 2012-07-17 2012-11-07 西安建筑科技大学 Preparation method of molecular engram composite film for separating tryptophane isomer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1843598A (en) * 2006-03-20 2006-10-11 天津大学 Method for preparing molecular engram CS/TEOS hybridized film by separation of phenylalanine isomer
CN101185856A (en) * 2007-08-29 2008-05-28 浙江大学 Preparation method and application of sulfonylureas herbicide molecular engram separating film
CN102764598A (en) * 2012-07-17 2012-11-07 西安建筑科技大学 Preparation method of molecular engram composite film for separating tryptophane isomer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Preparation of chitosan-graft-(methyl)methacrylate/Ag nanocomposite with antimicrobial activity;Jing An,等;《Polymer International》;20100131;第59卷(第1期);全文 *
The synthesis of molecular imprinted chitosan-gels copolymerized with multiform functional monomers at three different temperatures and the recognition for the template ovalbumin;Ran Dan,等;《Analyst》;20130325;第138卷(第12期);第3434页右栏第2.3节,第3436页右栏第3.1.2节 *

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