CN1843598A - Method for preparing molecular engram CS/TEOS hybridized film by separation of phenylalanine isomer - Google Patents
Method for preparing molecular engram CS/TEOS hybridized film by separation of phenylalanine isomer Download PDFInfo
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- CN1843598A CN1843598A CN 200610013332 CN200610013332A CN1843598A CN 1843598 A CN1843598 A CN 1843598A CN 200610013332 CN200610013332 CN 200610013332 CN 200610013332 A CN200610013332 A CN 200610013332A CN 1843598 A CN1843598 A CN 1843598A
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Abstract
The invention discloses a method for preparing molecule print chitose/silicic acid carbethoxy hybridized film used to separate phenylalanine isomer of water solution. Said method comprises: adding chitose into acetate water solution whose content is 2%; mixing and filtering insoluble part with filter cloth to attain chitose solution; mixing and adding silicic acid carbethoxy into chitose solution; fully mixing, than adding L-phenylalanine water solution to be mixed for 12 hours; defoaming and filling casting liquid on the horizontally arranged clear organic glass plate horizontally to be extended and form transparent film; thermal treating the film and washing. The invention has the advantages that: the method is simple; attained molecule print chitose/silicic acid carbethoxy film has high density without significant phase separation, and it has better mechanical strength, and better separation function on phenylalanine isomer.
Description
Technical field
The present invention relates to a kind of separation isomers of phenylalanine (D, preparation method of molecular engram CS L-Phe)/TEOS hybridized film of being used for.The membrane technology that belongs to hybrid organic-inorganic film.
Background technology
Chirality is natural universals, the big molecule that constitutes the vital movement basis almost is a chirality as protein, polysaccharide, nucleic acid etc. entirely, also there are a large amount of chiral materials in artificial sintetics such as medicine etc., their physicochemical property is similar, but biologically active often has very big difference, therefore, the fractionation of chiral material has very important significance.Because the molecular formula of chiral material is identical, physicochemical properties are extremely similar, and the separating difficulty of chiral material is very big, and the fractionation of chiral material is considered to one of the most difficult process in compound separation field always.
Amino acid is the basis that constitutes protein and other, has chiral isomer mostly.At present, both at home and abroad the bibliographical information of the molecular imprinting that splits about chiral amino acids material is to adopt derive the earlier method of back trace of amino acid mostly, and preparation process is loaded down with trivial details.This is that solubility is very low in organic solvent because amino acid belongs to amphion, and at present molecular imprinting is confined to that non-aqueous system causes more.In fact, natural molecular recognition system mostly carries out in aqueous environments, for the biomolecule that comprises amino acid, trace and identification are except solubility in organic solvent, also have problems such as inactivation, thereby the molecular imprinting that exploitation is used for water trace and identification seems very urgent.Up to the present, the carrying out and report of research work of some this respects arranged, but effect is often unsatisfactory.As one of important research direction of separation field, molecular engram film comprises that aspect chiral resolution the water-based system chiral resolution has obtained some progress.Molecular imprinting, just by the existing this molecular recognition effect of simulating nature circle, in polymeric material, introduce the molecular recognition site, the polymer that preparation is mated with the target molecule perfection on space and binding site, be molecularly imprinted polymer (MIP), to realize specificity selection to target molecule.MIP also is widely used in numerous areas such as chromatographic isolation, SPE, bio-sensing, film separation, mimetic enzyme catalysis because of its remarkable performance, demonstrate good development and application prospect.
Molecular engram membrane material commonly used at present mainly is divided into inorganic material film, organic (macromolecule) membrane material and hybrid organic-inorganic film material.The molecular engram film of inorganic material preparation has the high advantage of recognition capability, but fragility is bigger, complicated process of preparation, and suitable microsphere is limited in scope.Organic film material has the advantage of the film forming of being easy to, but the good film of recognition performance often flux is too little, and the bigger organic film of flux, often swellbility is bigger, it is relatively poor that the structure of recognition site is kept ability, causes separating property to reduce.The method of hybrid inorganic-organic to the anti-swelling that improves the bigger high-polymer membrane of swellbility own can and mechanical strength be a kind of novelty and effective means.
Summary of the invention
The object of the present invention is to provide a kind of separation isomers of phenylalanine (D, preparation method of molecular engram CS L-Phe)/TEOS hybridized film of being used for.With the hybridized film of the method preparation mixture of separating chiral material D-Phe and L-Phe effectively, and its separating effect is better than corresponding non-trace hybridized film and the pure organic film of molecular engram.
The present invention is achieved through the following technical solutions, (1) preparation of casting solution: the mass content that 1g shitosan (CS) is joined 50ml is in 2% aqueous acetic acid, be stirred to the shitosan dissolving under 60 ℃ of water-baths, remove by filter insoluble part with filter cloth, obtain mass content and be 2% chitosan solution.The ethyl orthosilicate (TEOS) that adds 0.2～3g under the stirring condition in this chitosan solution again to the L-of the 0.1M that wherein the adds 6～18ml phenylalanine aqueous solution, promptly obtains casting solution after continuing to stir 12h after the stirring fully.
(2) preparation of film: to remove impurity, standing and defoaming is poured over casting solution on the clean poly (methyl methacrylate) plate of horizontal positioned the casting solution that step (1) is prepared then with screen filtration, curtain coating, behind at room temperature dry 24～36h, casting solution is thickness no longer, promptly makes smooth and transparent film.
(3) film that step (2) is prepared was heat-treated under 100～140 ℃ 1～3 hour, clean repeatedly with deionized water, cleaning fluid detects with high performance liquid chromatography, detects less than till the L-phenylalanine in cleaning solution, promptly obtains molecular engram CS/TEOS hybridized film.
The invention has the advantages that: the preparation method is easy, add inorganic material after, the anti-swelling energy of film and the fractionation ability of chiral isomer all is improved.
The specific embodiment
Embodiment one
The preparation of molecular engram CS/TEOS hybrid organic-inorganic film (film 1)
The shitosan (CS) of 1g is joined in the 2wt.% aqueous acetic acid of 50ml, be stirred to the shitosan dissolving under 60 ℃ of water-baths, remove by filter insoluble part, obtain the chitosan solution of 2wt.% with filter cloth.The ethyl orthosilicate (TEOS) that in this solution, adds 0.75g under the stirring condition, after stirring fully again to the L-phenylalanine aqueous solution that wherein adds 6ml 0.1M, continue to stir 12h, after the standing and defoaming, casting solution is poured on the clean poly (methyl methacrylate) plate of horizontal positioned, curtain coating, behind the at room temperature dry 24h, casting solution is thickness no longer, forms smooth and clear films on poly (methyl methacrylate) plate, peel off film this moment lentamente from substrate, obtain molecular engram CS/TEOS hybridized film.Then the gained film is put into drying box and heat-treated 2h at 100 ℃, clean repeatedly with deionized water, cleaning fluid detects with high performance liquid chromatography, detects less than till the L-Phe in cleaning solution.Promptly make required molecular engram CS/TEOS hybridized film.
Prepared molecular engram CS/TEOS hybridized film is through scanning electron microscope analysis, infrared spectrum analysis, and thermogravimetric analysis and X-ray diffraction analysis, this film have fine and close structure, and generation significantly is not separated between the organic and inorganic component.When being used to separate the L that concentration is 0.5mM, during the material liquid of D-Phe, separation factor reaches 1.04.
Embodiment two
The preparation of molecular engram CS/TEOS hybrid organic-inorganic film (film 2)
The shitosan (CS) of 1g is joined in the 2wt.% aqueous acetic acid of 50ml, be stirred to the shitosan dissolving under 60 ℃ of water-baths, remove by filter insoluble part, obtain the chitosan solution of 2wt.% with filter cloth.The ethyl orthosilicate (TEOS) that in this solution, adds 1.5g under the stirring condition, after stirring fully again to the L-phenylalanine aqueous solution that wherein adds 6ml 0.1M, continue to stir 12h, after the standing and defoaming, casting solution is poured on the clean poly (methyl methacrylate) plate of horizontal positioned, curtain coating, behind the at room temperature dry 24h, casting solution is thickness no longer, forms smooth and clear films on poly (methyl methacrylate) plate, peel off film this moment lentamente from substrate, obtain molecular engram CS/TEOS hybridized film.Then the gained film is put into drying box and heat-treated 2h at 100 ℃, clean repeatedly with deionized water, cleaning fluid detects with high performance liquid chromatography, detects less than till the L-Phe in cleaning solution.Promptly make required molecular engram CS/TEOS hybridized film.
Prepared molecular engram CS/TEOS hybridized film is through scanning electron microscope analysis, infrared spectrum analysis, and thermogravimetric analysis and X-ray diffraction analysis, this film have fine and close structure, and generation significantly is not separated between the organic and inorganic component.When being used to separate the L that concentration is 0.5mM, during the material liquid of D-Phe, separation factor reaches 1.14.
Embodiment three
The preparation of molecular engram CS/TEOS hybrid organic-inorganic film (film 3)
The shitosan (CS) of 1g is joined in the 2wt.% aqueous acetic acid of 50ml, be stirred to the shitosan dissolving under 60 ℃ of water-baths, remove by filter insoluble part, obtain the chitosan solution of 2wt.% with filter cloth.The ethyl orthosilicate (TEOS) that in this solution, adds 2.5g under the stirring condition, after stirring fully again to the L-phenylalanine aqueous solution that wherein adds 10ml 0.1M, continue to stir 12h, after the standing and defoaming, casting solution is poured on the clean poly (methyl methacrylate) plate of horizontal positioned, curtain coating, behind the at room temperature dry 24h, casting solution is thickness no longer, forms smooth and clear films on poly (methyl methacrylate) plate, peel off film this moment lentamente from substrate, obtain molecular engram CS/TEOS hybridized film.Then the gained film is put into drying box and heat-treated 2h at 100 ℃, clean repeatedly with deionized water, cleaning fluid detects with high performance liquid chromatography, detects less than till the L-Phe in cleaning solution.Promptly make required molecular engram CS/TEOS hybridized film.
Prepared molecular engram CS/TEOS hybridized film is through scanning electron microscope analysis, infrared spectrum analysis, and thermogravimetric analysis and X-ray diffraction analysis, this film have fine and close structure, and generation significantly is not separated between the organic and inorganic component.When being used to separate the L that concentration is 0.5mM, during the material liquid of D-Phe, separation factor reaches 1.28.
Embodiment four
The preparation of molecular engram CS/TEOS hybrid organic-inorganic film (film 4)
The shitosan (CS) of 1g is joined in the 2wt.% aqueous acetic acid of 50ml, be stirred to the shitosan dissolving under 60 ℃ of water-baths, remove by filter insoluble part, obtain the chitosan solution of 2wt.% with filter cloth.The ethyl orthosilicate (TEOS) that in this solution, adds 1.5g under the stirring condition, after stirring fully again to the L-phenylalanine aqueous solution that wherein adds 6ml 0.1M, continue to stir 12h, after the standing and defoaming, casting solution is poured on the clean poly (methyl methacrylate) plate of horizontal positioned, curtain coating, behind the at room temperature dry 24h, casting solution is thickness no longer, forms smooth and clear films on poly (methyl methacrylate) plate, peel off film this moment lentamente from substrate, obtain molecular engram CS/TEOS hybridized film.Then the gained film is put into drying box and heat-treated 2h at 120 ℃, clean repeatedly with deionized water, cleaning fluid detects with high performance liquid chromatography, detects less than till the L-Phe in cleaning solution.Promptly make the required molecular engram CS of this experiment/TEOS hybridized film.
Prepared molecular engram CS/TEOS hybridized film is through scanning electron microscope analysis, infrared spectrum analysis, and thermogravimetric analysis and X-ray diffraction analysis, this film have fine and close structure, and generation significantly is not separated between the organic and inorganic component.When being used to separate the L that concentration is 0.5mM, during the material liquid of D-Phe, separation factor reaches 1.26.
Comparative Examples one
The preparation of molecular engram chitosan film (film 5)
The L-Phe that takes by weighing 1g CS and 0.1g joins in the 2wt% aqueous acetic acid of 50ml, and 6h is stirred in 60 ℃ of water-baths down, removes by filter insoluble part with filter cloth, obtains casting solution, standing and defoaming.Casting solution is poured on the clean glass plate of horizontal positioned, curtain coating, behind the at room temperature dry 24h, casting solution is thickness no longer, on glass plate, form smooth and clear films, peel off film this moment lentamente from substrate, obtain the molecular engram CS film, the gained film put into drying box heat-treat 2h at 120 ℃.Then film is placed the 0.5M sulfuric acid solution to soak 24h, clean to neutrality repeatedly with deionized water then.Promptly make the required molecular engram CS film of this experiment.
Prepared molecular engram CS film process scanning electron microscope analysis, infrared spectrum analysis, thermogravimetric analysis and X-ray diffraction analysis, this film has the structure of homogeneous phase densification.When being used to separate the L that concentration is 0.5mM, during the material liquid of D-Phe, separation factor reaches 1.03.
Comparative Examples two
The preparation of blank CS/TEOS hybridized film (film 6)
The shitosan (CS) of 1g is joined in the 2wt.% aqueous acetic acid of 50ml, be stirred to the shitosan dissolving under 60 ℃ of water-baths, remove by filter insoluble part, obtain the chitosan solution of 2wt.% with filter cloth.The ethyl orthosilicate (TEOS) that in this solution, adds 1.5g under the stirring condition, after fully stirring, standing and defoaming, casting solution is poured on the clean poly (methyl methacrylate) plate of horizontal positioned, curtain coating is behind the at room temperature dry 24h, casting solution is thickness no longer, form smooth and clear films on poly (methyl methacrylate) plate, peel off film this moment lentamente from substrate, obtain blank CS/TEOS hybridized film.Then the gained film is put into drying box and heat-treat 2h at 120 ℃.Promptly make required blank CS/TEOS hybridized film.
Prepared blank CS/TEOS hybridized film is through scanning electron microscope analysis, infrared spectrum analysis, and thermogravimetric analysis and X-ray diffraction analysis, this film have fine and close structure, and generation significantly is not separated between the organic and inorganic component.When being used to separate the L that concentration is 0.5mM, during the material liquid of D-Phe, separation factor reaches 0.95.
Table 1 is depicted as the prepared film 1 of embodiment, film 2, film 3, the prepared film 5 of film 4 and Comparative Examples, film 6 be used to separate the L that concentration is 0.5mM, the separation factor the during material liquid of D-Phe.
Table 1
| Film | L-Phe quality (g) | TEOS quality (g) | Heat treatment temperature (K) | Separation factor |
| Film 1 film 2 films 3 films 4 films 5 films 6 | 0.1 0.1 0.1 0.1 0.1 0 | 0.75 1.5 2.5 1.5 0 1.5 | 373 373 373 393 393 393 | 1.04 1.14 1.28 1.26 1.03 0.95 |
Claims (1)
1, the preparation method of a kind of shitosan of separation isomers of phenylalanine/ethyl orthosilicate hybridized film is characterized in that this method may further comprise the steps:
(1) preparation of casting solution: the mass content that the 1g shitosan is joined 50ml is in 2% aqueous acetic acid, is stirred to shitosan dissolving under 60 ℃ of water-baths, removes by filter insoluble part with filter cloth, obtains mass content and be 2% chitosan solution.The ethyl orthosilicate that adds 0.2～3g under the stirring condition in this chitosan solution again to the L-phenylalanine aqueous solution that wherein adds 6～18ml 0.1M, continues stirring and promptly is made into casting solution after 12 hours after the stirring fully;
(2) preparation of film: to remove impurity, standing and defoaming is poured over casting solution on the clean poly (methyl methacrylate) plate of horizontal positioned the casting solution that step (1) is prepared then with screen filtration, curtain coating, after at room temperature dry 24～36 hours, casting solution is thickness no longer, promptly makes smooth and transparent film;
(3) film of step (2) preparation was heat-treated under 100～140 ℃ 1～3 hour, clean repeatedly with deionized water, cleaning fluid detects with high performance liquid chromatography, detects less than till the L-phenylalanine in cleaning solution, promptly obtains molecular engram shitosan/ethyl orthosilicate hybridized film.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298039B (en) * | 2008-01-18 | 2010-06-23 | 清华大学 | Preparation of chitosan molecular imprinting adsorbing agent |
| CN102166483A (en) * | 2011-03-04 | 2011-08-31 | 嘉兴学院 | Method for preparing molecular imprinted nanofiber membrane for detecting rhodamine B |
| CN101487822B (en) * | 2009-02-25 | 2012-10-24 | 中国科学院过程工程研究所 | L-phenylalanine analysis detection method based on molecular engram integral column |
| CN102872832A (en) * | 2012-09-28 | 2013-01-16 | 河海大学 | Preparation method of titanium dioxide loaded chitosan molecular imprinting adsorbent |
| CN105199046A (en) * | 2015-10-23 | 2015-12-30 | 河北科技师范学院 | Temperature-sensitive type molecularly imprinted membrane material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107532C (en) * | 2000-06-09 | 2003-05-07 | 清华大学 | Process for preparing compound polyelectrolyte (chitosan/sodium polyphosphate) membrane |
| US7238261B2 (en) * | 2003-11-26 | 2007-07-03 | Brown Technology Partnerships | Photo-formed metal nanoparticles and aerogel materials comprising the same |
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2006
- 2006-03-20 CN CNB2006100133329A patent/CN100351007C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298039B (en) * | 2008-01-18 | 2010-06-23 | 清华大学 | Preparation of chitosan molecular imprinting adsorbing agent |
| CN101487822B (en) * | 2009-02-25 | 2012-10-24 | 中国科学院过程工程研究所 | L-phenylalanine analysis detection method based on molecular engram integral column |
| CN102166483A (en) * | 2011-03-04 | 2011-08-31 | 嘉兴学院 | Method for preparing molecular imprinted nanofiber membrane for detecting rhodamine B |
| CN102166483B (en) * | 2011-03-04 | 2013-08-28 | 嘉兴学院 | Method for preparing molecular imprinted nanofiber membrane for detecting rhodamine B |
| CN102872832A (en) * | 2012-09-28 | 2013-01-16 | 河海大学 | Preparation method of titanium dioxide loaded chitosan molecular imprinting adsorbent |
| CN105199046A (en) * | 2015-10-23 | 2015-12-30 | 河北科技师范学院 | Temperature-sensitive type molecularly imprinted membrane material |
| CN105199046B (en) * | 2015-10-23 | 2018-01-05 | 河北科技师范学院 | Responsive to temperature type molecular engram membrane material |
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