CN101363191B - Method for preparing chiral recognition functional fiber - Google Patents
Method for preparing chiral recognition functional fiber Download PDFInfo
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- CN101363191B CN101363191B CN2008101204797A CN200810120479A CN101363191B CN 101363191 B CN101363191 B CN 101363191B CN 2008101204797 A CN2008101204797 A CN 2008101204797A CN 200810120479 A CN200810120479 A CN 200810120479A CN 101363191 B CN101363191 B CN 101363191B
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- cyclodextrin
- cellulose fibre
- mass ratio
- fiber
- copper complex
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- 239000000835 fiber Substances 0.000 title claims abstract description 30
- 238000005557 chiral recognition Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 44
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 42
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000004699 copper complex Chemical class 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 18
- 238000006735 epoxidation reaction Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000009514 concussion Effects 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000008030 elimination Effects 0.000 claims description 6
- 238000003379 elimination reaction Methods 0.000 claims description 6
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 5
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 5
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 5
- 238000000926 separation method Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 1
- -1 aromatic amino acid Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a preparation method of chiral recognition functional fiber. In the method, cyclodextrin is prepared into binuclear copper complex with cyclodextrin. Then, the binuclear copper complex with cyclodextrin is grafted on cellulose fiber through chemical bonds to prepare the fiber with chiral recognition function which is used for the chiral recognition and separation of D/L type aromatic amino enantiomer. Compared with the prior art, the preparation method of the chiral recognition functional fiber is characterized by low separation cost, good effect, convenient separation of products, convenient recycling of materials, etc.
Description
Technical field
That the present invention relates to is a kind of preparation method of chiral recognition functional fiber, belongs to the preparing technical field of functional fibre material.
Background technology
The employed medicine overwhelming majority of people has chirality, and is referred to as chiral drug.Many medicines or its precursor contain a chiral centre at least, and usually be that an enantiomer has physiologically active, another is then opposite, there is not activity even poisonous on the contrary fully, wherein, amino acid is as the elementary cell of constitutive protein matter structure, and its chiral Recognition is not only significant to the chemical nature of further setting forth life process theoretically, but also split at enantiomer, tempting application prospect has been showed in the new specific drug and the aspects such as discovery of pharmaceutical carrier.But there are defectives such as productive rate is low, of a high price, energy consumption is big in chiral separation method commonly used such as pre-crystallisation, chromatography, electrophoresis etc., therefore, need set up the Chiral Separation method of easy cheapness.
Cyclodextrin and derivative thereof are the important supermolecule main block compounds of a class, have hydrophobic inner chamber and hydrophilic surface, and having a microenvironment of chirality, can the selectivity bonding various organic and inorganic and biomolecule form host-guest or supramolecular complexs.But the molecular structure of natural cyclodextrin rigidity and limited inclusion capabilities limits its application aspect molecular recognition.
Summary of the invention
It is low to the purpose of this invention is to provide a kind of separation costs, effective, the separation of product and recycling of materials be the preparation method of chiral recognition functional fiber easily, and this method is: be that 1: 25～250 to put into the pH value be that 12～14 sodium hydrate aqueous solution dissolves with cyclodextrin by mass ratio A); Mol ratio by cyclodextrin and copper sulphate is 1: 1～3 adding copper sulphate then, reacted 0.5～2 hour down at 20～30 ℃, stir, the elimination insoluble matter adds an amount of absolute ethyl alcohol, separates out blue acicular crystal, filter, with the crystal absolute ethanol washing that obtains, dry under 20～40 ℃, obtain cyclodextrin double-core copper complex; B) cellulose fibre is put into distilled water and soaked into 1～2 hour, 22～28 ℃ are dried; Cellulose fibre after will drying is that 1: 15～25 to put into mass percent concentration be in 30% the sodium hydroxide solution by mass ratio, stirs to press dry after 0.5～1.5 hour; C) will be that 1: 10～15 to put into mass percent concentration be in 30% the sodium hydroxide solution by mass ratio through the cellulose fibre of above-mentioned processing; Mass ratio by cellulose fibre and epoxychloropropane is that 1:2～4 add epoxychloropropane, and electronic stirring added an amount of distilled water after 15～30 hours, washing, filtration, till being neutrality to eluate, collect reacted fiber, obtain the epoxidation cellulose fibre 40～50 ℃ of oven dry down; D) be that 1: 45～60 to put into mass percent concentration be in 40% the sodium hydroxide solution with cyclodextrin double-core copper complex by mass ratio, stir, after treating that cyclodextrin double-core copper complex dissolves fully, mass ratio by cyclodextrin double-core copper complex and epoxidation cellulose fibre is 1: 0.8～1.5 adding epoxidation cellulose fibres, and the concussion reaction is 2 hours in 45～60 ℃ of water-baths; Stop concussion, add an amount of distilled water, washing, filtration are till eluate is neutrality; E) collect the fiber that obtains through above-mentioned processing,, obtain fiber with chiral Recognition function 40～50 ℃ of oven dry.
Cyclodextrin of the present invention is alpha-cyclodextrin or beta-schardinger dextrin-.
The present invention earlier is prepared into cyclodextrin double-core copper complex with cyclodextrin, again with its by the chemical bond grafting to cellulose fibre, be prepared into fiber with chiral Recognition function, the chiral Recognition that is used for D/L type aromatic amino acid enantiomer with separate; Compared with prior art, it has characteristics such as separation costs is low, effective, and the separation of product and recycling of materials are very convenient.
The specific embodiment
The present invention will be described in detail below in conjunction with specific embodiment: the preparation method of chiral recognition functional fiber of the present invention, and this method is: be that 1: 25～250 to put into the pH value be that 12～14 sodium hydrate aqueous solution dissolves with cyclodextrin by mass ratio A); Mol ratio by cyclodextrin and copper sulphate is 1: 1～3 adding copper sulphate then, reacted 0.5～2 hour down at 20～30 ℃, stir, the elimination insoluble matter adds an amount of absolute ethyl alcohol, separates out blue acicular crystal, filter, with the crystal absolute ethanol washing that obtains, dry under 20～40 ℃, obtain cyclodextrin double-core copper complex; B) cellulose fibre is put into distilled water and soaked into 1～2 hour, 22～28 ℃ are dried; Cellulose fibre after will drying is that 1: 15～25 to put into mass percent concentration be in 30% the sodium hydroxide solution by mass ratio, stirs to press dry after 0.5～1.5 hour; C) will be that 1: 10～15 to put into mass percent concentration be in 30% the sodium hydroxide solution by mass ratio through the cellulose fibre of above-mentioned processing; Mass ratio by cellulose fibre and epoxychloropropane is that 1:2～4 add epoxychloropropane, and electronic stirring added an amount of distilled water after 15～30 hours, washing, filtration, till being neutrality to eluate, collect reacted fiber, obtain the epoxidation cellulose fibre 40～50 ℃ of oven dry down; D) be that 1: 45～60 to put into mass percent concentration be in 40% the sodium hydroxide solution with cyclodextrin double-core copper complex by mass ratio, stir, after treating that cyclodextrin double-core copper complex dissolves fully, mass ratio by cyclodextrin double-core copper complex and epoxidation cellulose fibre is 1: 0.8～1.5 adding epoxidation cellulose fibres, and the concussion reaction is 2 hours in 45～60 ℃ of water-baths; Stop concussion, add an amount of distilled water, washing, filtration are till eluate is neutrality; E) collect the fiber that obtains through above-mentioned processing,, obtain fiber with chiral Recognition function 40～50 ℃ of oven dry.
Described cyclodextrin is alpha-cyclodextrin or beta-schardinger dextrin-.
Embodiment 1, and it is: be that to put into the pH value at 1: 25 be that 12 sodium hydrate aqueous solution dissolves with cyclodextrin by mass ratio A); Mol ratio by cyclodextrin and copper sulphate is 1: 1 adding copper sulphate then, reacted 0.5 hour down at 20 ℃, stir, the elimination insoluble matter adds an amount of absolute ethyl alcohol, separates out blue acicular crystal, filter, with the crystal absolute ethanol washing that obtains, dry under 20 ℃, obtain cyclodextrin double-core copper complex; B) cellulose fibre is put into distilled water and soaked into 1 hour, 22 ℃ are dried; Cellulose fibre after will drying is that to put into mass percent concentration at 1: 15 be in 30% the sodium hydroxide solution by mass ratio, stirs to press dry after 0.5～1.5 hour; C) will be that to put into mass percent concentration at 1: 10 be in 30% the sodium hydroxide solution by mass ratio through the cellulose fibre of above-mentioned processing; Mass ratio by cellulose fibre and epoxychloropropane is that 1:2 adds epoxychloropropane, and electronic stirring added an amount of distilled water after 15 hours, washing, filtration, till being neutrality to eluate, collect reacted fiber, obtain the epoxidation cellulose fibre 40 ℃ of oven dry down; D) be that to put into mass percent concentration at 1: 45 be in 40% the sodium hydroxide solution with cyclodextrin double-core copper complex by mass ratio, stir, after treating that cyclodextrin double-core copper complex dissolves fully, mass ratio by cyclodextrin double-core copper complex and epoxidation cellulose fibre is 1: 0.8 adding epoxidation cellulose fibre, and the concussion reaction is 2 hours in 45 ℃ of water-baths; Stop concussion, add an amount of distilled water, washing, filtration are till eluate is neutrality; E) collect the fiber that obtains through above-mentioned processing,, obtain fiber with chiral Recognition function 40 ℃ of oven dry.
Embodiment 2, and it is: be that to put into the pH value at 1: 250 be that 14 sodium hydrate aqueous solution dissolves with alpha-cyclodextrin by mass ratio A); Mol ratio by alpha-cyclodextrin and copper sulphate is 1: 3 adding copper sulphate then, reacted 2 hours down at 30 ℃, stir, the elimination insoluble matter adds an amount of absolute ethyl alcohol, separates out blue acicular crystal, filter, with the crystal absolute ethanol washing that obtains, dry under 40 ℃, obtain cyclodextrin double-core copper complex; B) cellulose fibre is put into distilled water and soaked into 2 hours, 28 ℃ are dried; Cellulose fibre after will drying is that to put into mass percent concentration at 1: 25 be in 30% the sodium hydroxide solution by mass ratio, stirs to press dry after 1.5 hours; C) will be that to put into mass percent concentration at 1: 15 be in 30% the sodium hydroxide solution by mass ratio through the cellulose fibre of above-mentioned processing; Mass ratio by cellulose fibre and epoxychloropropane is that 1:2～4 add epoxychloropropane, and electronic stirring added an amount of distilled water after 30 hours, washing, filtration, till being neutrality to eluate, collect reacted fiber, obtain the epoxidation cellulose fibre 50 ℃ of oven dry down; D) be that to put into mass percent concentration at 1: 60 be in 40% the sodium hydroxide solution with cyclodextrin double-core copper complex by mass ratio, stir, after treating that cyclodextrin double-core copper complex dissolves fully, mass ratio by cyclodextrin double-core copper complex and epoxidation cellulose fibre is 1: 1.5 adding epoxidation cellulose fibre, and the concussion reaction is 2 hours in 60 ℃ of water-baths; Stop concussion, add an amount of distilled water, washing, filtration are till eluate is neutrality; E) collect the fiber that obtains through above-mentioned processing,, obtain fiber with chiral Recognition function 50 ℃ of oven dry.
Embodiment 3, and it is: be that to put into the pH value at 1: 125 be that 13 sodium hydrate aqueous solution dissolves with beta-schardinger dextrin-by mass ratio A); Mol ratio by beta-schardinger dextrin-and copper sulphate is 1: 2 adding copper sulphate then, reacted 1.5 hours down at 25 ℃, stir, the elimination insoluble matter adds an amount of absolute ethyl alcohol, separates out blue acicular crystal, filter, with the crystal absolute ethanol washing that obtains, dry under 30 ℃, obtain cyclodextrin double-core copper complex; B) cellulose fibre is put into distilled water and soaked into 1.5 hours, 25 ℃ are dried; Cellulose fibre after will drying is that to put into mass percent concentration at 1: 22 be in 30% the sodium hydroxide solution by mass ratio, stirs to press dry after 1 hour; C) will be that to put into mass percent concentration at 1: 12 be in 30% the sodium hydroxide solution by mass ratio through the cellulose fibre of above-mentioned processing; Mass ratio by cellulose fibre and epoxychloropropane is that 1:2～4 add epoxychloropropane, and electronic stirring added an amount of distilled water after 22 hours, washing, filtration, till being neutrality to eluate, collect reacted fiber, obtain the epoxidation cellulose fibre 45 ℃ of oven dry down; D) be that to put into mass percent concentration at 1: 50 be in 40% the sodium hydroxide solution with cyclodextrin double-core copper complex by mass ratio, stir, after treating that cyclodextrin double-core copper complex dissolves fully, mass ratio by cyclodextrin double-core copper complex and epoxidation cellulose fibre is 1: 1 adding epoxidation cellulose fibre, and the concussion reaction is 2 hours in 50 ℃ of water-baths; Stop concussion, add an amount of distilled water, washing, filtration are till eluate is neutrality; E) collect the fiber that obtains through above-mentioned processing,, obtain fiber with chiral Recognition function 45 ℃ of oven dry.
Claims (2)
1. the preparation method of a chiral recognition functional fiber, this method is:
A) be that 1: 25～250 to put into the pH value be that 12～14 sodium hydrate aqueous solution dissolves with cyclodextrin by mass ratio; Mol ratio by cyclodextrin and copper sulphate is 1: 1～3 adding copper sulphate then, reacted 0.5～2 hour down at 20～30 ℃, stir, the elimination insoluble matter adds an amount of absolute ethyl alcohol, separates out blue acicular crystal, filter, with the crystal absolute ethanol washing that obtains, dry under 20～40 ℃, obtain cyclodextrin double-core copper complex;
B) cellulose fibre is put into distilled water and soaked into 1～2 hour, 22～28 ℃ are dried; Cellulose fibre after will drying is that 1: 15～25 to put into mass percent concentration be in 30% the sodium hydroxide solution by mass ratio, stirs to press dry after 0.5～1.5 hour;
C) will be that 1: 10～15 to put into mass percent concentration be in 30% the sodium hydroxide solution by mass ratio through the cellulose fibre of above-mentioned processing; Mass ratio by cellulose fibre and epoxychloropropane is that 1:2～4 add epoxychloropropane, and electronic stirring added an amount of distilled water after 15～30 hours, washing, filtration, till being neutrality to eluate, collect reacted fiber, obtain the epoxidation cellulose fibre 40～50 ℃ of oven dry down;
D) be that 1: 45～60 to put into mass percent concentration be in 40% the sodium hydroxide solution with cyclodextrin double-core copper complex by mass ratio, stir, after treating that cyclodextrin double-core copper complex dissolves fully, mass ratio by cyclodextrin double-core copper complex and epoxidation cellulose fibre is 1: 0.8～1.5 adding epoxidation cellulose fibres, and the concussion reaction is 2 hours in 45～60 ℃ of water-baths; Stop concussion, add an amount of distilled water, washing, filtration are till eluate is neutrality;
E) collect the fiber that obtains through above-mentioned processing,, obtain fiber with chiral Recognition function 40～50 ℃ of oven dry.
2. the preparation method of chiral recognition functional fiber according to claim 1 is characterized in that described cyclodextrin is alpha-cyclodextrin or beta-schardinger dextrin-.
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| CN2008101204797A CN101363191B (en) | 2008-09-08 | 2008-09-08 | Method for preparing chiral recognition functional fiber |
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| CN2008101204797A CN101363191B (en) | 2008-09-08 | 2008-09-08 | Method for preparing chiral recognition functional fiber |
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| CN101363191B true CN101363191B (en) | 2011-02-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101798352B (en) * | 2010-01-05 | 2011-12-21 | 湖南中烟工业有限责任公司 | Modified cellulose with tar and harm reducing function, paper filter tip and preparation method thereof |
| CN104297316B (en) * | 2014-10-24 | 2016-11-02 | 常州大学 | A kind of chiral sensor based on beta-schardinger dextrin-and preparation method thereof |
| WO2018113384A1 (en) * | 2016-12-19 | 2018-06-28 | 山东大学 | One-step method for synthesizing cyclodextrin-modified transition metal oxide material |
| CN108384030B (en) * | 2018-04-02 | 2020-09-08 | 常州大学 | Preparation method of environment-friendly high-molecular microcrystal |
| CN109307682A (en) * | 2018-11-21 | 2019-02-05 | 常州大学 | A method of phenylalanine enantiomer is identified based on binary self assembly |
| CN110952218A (en) * | 2019-11-28 | 2020-04-03 | 江阴龙阳纺织有限公司 | Preparation method of nano-enhanced far infrared thermal fabric |
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