CN103224574A - Chitosan phosphorylation modification method - Google Patents
Chitosan phosphorylation modification method Download PDFInfo
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- CN103224574A CN103224574A CN2013101222175A CN201310122217A CN103224574A CN 103224574 A CN103224574 A CN 103224574A CN 2013101222175 A CN2013101222175 A CN 2013101222175A CN 201310122217 A CN201310122217 A CN 201310122217A CN 103224574 A CN103224574 A CN 103224574A
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Abstract
The present invention relates to a chitosan phosphorylation modification method, which comprises the following steps: 1) a reaction, wherein under a condition of a temperature of 0-5 DEG C, 1 g of chitosan is dissolved into 7 ml of methyl sulfonic acid, 0.5-3.5 g of phosphorus pentoxide is added, and a continuous mechanical stirring reaction is performed for 2-3 h in the protection of nitrogen gas; and 2) separation, wherein ether is added to the reaction system obtained from the step 1) to carry out precipitation, centrifugation is performed, acetone and methanol are sequentially adopted to wash the precipitate, deionized water is adopted to dissolve the precipitate, the turbid solution is sequentially subjected to dialysis and vacuum concentration, and the concentrated solution is subjected to freeze-drying to obtain the product. The chitosan phosphorylation modification method has the following advantages that: 1, the method has characteristics of simpleness, easy operation, high yield, and environmental protection, and is suitable for industrial production in reactions; 2, the obtained product has a high substitution degree, and the phosphate has strong chelating ability; and 3, the obtained product can be widely used in agriculture, textile, medicine, food, cosmetics, environmental protection and other fields.
Description
Technical field
The invention belongs to biological chemical field, be specifically related to a kind of method of chitosan being carried out phosphorylation modification.
Background technology
Chitin also claims chitin, chemistry (1,4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-callose by name, and molecular weight reaches millions of.The structure of chitin and cellulosic fairly similar.Be the C of each residue
2The amino that last hydroxyl is acetylation replaces.Chitin is because intramolecularly and intermolecular hydrogen bond action are insoluble in usual vehicle, and this has limited further applying of chitin to a great extent.Water-soluble in order to increase it, usually chitin deacetylase is prepared chitosan.Chitosan could dissolve under acidic conditions, has limited its range of application.
It is to improve its fundamental property, enlarge one of means of its Application Areas that chitosan is carried out chemically modified.Chitosan after the modification, physico-chemical property has had variation, helps organism after solvability strengthens and absorbs, the Physiology and biochemistry activity that performance makes new advances.Phosphorus is the important element composition of human body, has important role in numerous vital movements.At present, also do not find not phosphorated life entity in the vital process.Why phosphorus be the important element in the vital process, is because the catalyzed reaction of most enzymes is all regulated and control with phosphorylation and dephosphorylation.The required basic storage element ATP of organism has participated in almost each reaction in the life chemistry process, and metabolic processes often is that intermediate carries out with the phosphorous derivant.Glycogen and starch produce Cori ester by phosphorolysis and enter the glycolysis approach.Connect by phosphodiester bond between the nucleosides of biological intravital hereditary material DNA and RNA.The research of at present relevant chitosan phosphorous derivant is less, but its potential Application Areas relates to many aspects, as metal-chelating, biological medicine, pharmaceutical carrier, sclerotin repair tissue engineering materials, fungistat and fuel cell etc.
Summary of the invention
Technical problem to be solved by this invention be propose at above-mentioned prior art a kind of simple to operate, productive rate is high, environmental pollution is little, the method for widely used chitosan phosphorylation modification.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the method for chitosan phosphorylation modification is characterized in that including following steps:
1) reaction: under 0-5 ℃ condition, 1 gram chitosan is dissolved in 7 milliliters of methylsulphonic acids, adds 0.5-3.5 gram Vanadium Pentoxide in FLAKES then, continues mechanical stirring reaction 2-3 hour under nitrogen protection;
2) separate: to step 1) gained reaction system add ether sedimentation, centrifugal after, more successively with acetone and methanol wash precipitation; Use the deionized water dissolution precipitation then; Turbid liquid dialysis final vacuum concentrates, and the concentrated solution lyophilize gets product.
Press such scheme, by increasing Vanadium Pentoxide in FLAKES to improve the substitution value of final product in reaction system, wherein, Vanadium Pentoxide in FLAKES increase quality is 0.2-0.8 a times of chitosan in the step 1) reaction process.
Press such scheme, step 2) to adopt the molecular weight cut-off of dialysis tubing be 3500-8000 to dialysis procedure.
Reaction equation involved in the present invention:
Substitution reaction can take place in No. 2 carbon amino, No. 3 carbon hydroxyls and No. 6 carbon hydroxyls in theory.In real reaction, No. 6 the carbon hydroxyl is positioned at outside the sugar ring sterically hindered minimum, the easiest generation substitution reaction of the hydroxyl on it.Above-mentioned reaction equation is substituted by example with hydroxyl on No. 6 carbon the mode of chitosan phosphorylation reaction is illustrated.
Compared with prior art, the present invention has following advantage:
1, the inventive method is simple to operation, productive rate is high, environmental friendliness, is applicable to suitability for industrialized production in reaction, and methylsulphonic acid is not only the good solvent of chitosan, also is the effective catalyst of this phosphorylation reaction;
2, products therefrom substitution value height.The modification group phosphate radical has certain surge capability, makes product keep dissolved state in very wide pH value scope, and phosphate radical also has very strong sequestering power simultaneously;
3, adopting the inventive method to prepare can directly water-soluble phosphonized chitosan dry powder, and products therefrom can be widely used in fields such as agricultural, weaving, medicine, food, makeup, environment protection.
Description of drawings
Fig. 1 is the infrared spectra comparison diagram of chitosan and embodiment 1 gained phosphonized chitosan, and wherein Fig. 1 (a) is the infrared spectrogram of chitosan, and Fig. 1 (b) is the infrared spectrogram of embodiment 1 gained phosphonized chitosan.
Embodiment
Below in conjunction with embodiment the present invention is described in further details, but this explanation can not be construed as limiting the invention.
Embodiment 1:
2g chitosan and 14ml methylsulphonic acid are mixed, add 6 gram Vanadium Pentoxide in FLAKESs then, under protection of nitrogen gas, 2 ℃ of down lasting mechanical stirring reactions 2 hours; Add 70ml ether sedimentation, centrifugal to the gained reaction system.Again successively with 42ml acetone, 42ml methanol wash precipitation.Then with 50ml deionized water dissolving precipitation.Turbid liquid is that 6000 dialysis tubings dialysis final vacuum concentrates through molecular weight cut-off, and the concentrated solution lyophilize gets product.
Fig. 1 is the infrared spectra comparison diagram of chitosan and embodiment 1 gained phosphonized chitosan, and wherein Fig. 1 (a) is the infrared spectrogram of chitosan, and Fig. 1 (b) is the infrared spectrogram of embodiment 1 gained phosphonized chitosan.For chitosan, 3500-3400cm
-1It is the stretching vibration absorption band of hydroxyl OH; 2878cm
-1Be that the sugar ring is gone up methyne CH
2The symmetrical stretching vibration absorption band; 1600cm
-1Be amino of chitosan NH
2The in-plane bending vibration absorption band.After the chitosan phosphorylation, at 524cm
-1Tangible absorption band occurs, this is the feature flexural vibration absorption band of P-O key.1600cm
-1The strong amino absorption band at place disappears.1660cm
-1And 1560cm
-1The place is the absorption band of phosphamidon, proves that phosphate group and No. 2 carbon amino have formed the phosphamidon key.The Infrared spectroscopy of chitosan and phosphonized chitosan shows that phosphate group closes with the glucosamine loops of chitosan, and phosphate group both can be gone up hydroxy esterification with glucosamine sugar ring, also can with amino phosphinylidyne amination.
The mensuration of phosphonized chitosan substitution value is to adopt the phosphorus molybdenum blue spectrophotometric method to measure the phosphorus content of product, is converted into the substitution value of phosphonized chitosan: use sulfuric acid-nitrate mixture digestion to destroy organic substance, and phosphate transfection is turned to orthophosphoric acid salt.Under acidic conditions, the ammonium phosphomolybdate that orthophosphoric acid salt and ammonium molybdate reaction generate forms " molybdenum blue " by the reductive agent effect, with the light absorption value of spectrophotometric determination blueness at the 825nm wavelength.Read corresponding phosphorus content from typical curve.The substitution value of phosphate radical (Degree of substitution DS) is defined as the number of contained phosphate radical in each glucosamine unit, and calculation formula is as follows:
The substitution value of DS in the formula---sample
The deacetylation of DD---sample (degree of deacetylation)
P---the percentage composition of phosphorus in the sample
203-42DD---deacetylation is the unitary molecular weight of glucosamine in the sample of DD
31---the molecular weight of phosphorus atom
80---a phosphate group replaces the increasing amount of back molecular weight
After tested, the substitution value of gained phosphonized chitosan is 0.92.
Dentine to people's tooth carries out surperficial demineralization processing, immerses in the phosphonized chitosan solution again, and dry back is at the outer one deck phosphonized chitosan that covers of dentine.Phosphonized chitosan can induce mineral substance calcium phosphate to be deposited on Dentinal surface, and effect is better than fluorochemical, and phosphonized chitosan induces the deposition ratio of calcium ion to fluoridize object height 7.3%.
Embodiment 2:
3g chitosan and 21ml methylsulphonic acid are mixed, add 8 gram Vanadium Pentoxide in FLAKESs then, under protection of nitrogen gas, lasting mechanical stirring under 4 ℃ slowly increases Vanadium Pentoxide in FLAKES 2g again, reacts 3 hours; Add 100ml ether sedimentation, centrifugal to the gained reaction system.Use 60ml acetone, 60ml methanol wash more successively.Then with 80ml deionized water dissolving precipitation.Turbid liquid is that 3500 dialysis tubings dialysis final vacuum concentrates through molecular weight cut-off, and the concentrated solution lyophilize gets product.
After tested, gained phosphonized chitosan substitution value is 1.27.
Claims (3)
1. the method for chitosan phosphorylation modification is characterized in that including following steps:
1) reaction: under 0-5 ℃ condition, 1 gram chitosan is dissolved in 7 milliliters of methylsulphonic acids, adds 0.5-3.5 gram Vanadium Pentoxide in FLAKES then, continues mechanical stirring reaction 2-3 hour under nitrogen protection;
2) separate: to step 1) gained reaction system add ether sedimentation, centrifugal after, more successively with acetone and methanol wash precipitation; Use the deionized water dissolution precipitation then; Turbid liquid dialysis final vacuum concentrates, and the concentrated solution lyophilize gets product.
2. according to the method for the described chitosan phosphorylation modification of claim 1, it is characterized in that: pass through in reaction system, to increase Vanadium Pentoxide in FLAKES in the step 1) reaction process to improve the substitution value of final product, wherein, Vanadium Pentoxide in FLAKES increase quality be chitosan 0.2-0.8 doubly.
3. according to the method for claim 1 or 2 described chitosan phosphorylation modifications, it is characterized in that: step 2) to adopt the molecular weight cut-off of dialysis tubing be 3500-8000 to dialysis procedure.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103515613A (en) * | 2013-10-02 | 2014-01-15 | 中国地质大学（武汉） | Additive for lithium-sulfur batteries and anode material containing same |
| CN103682255A (en) * | 2013-12-25 | 2014-03-26 | 中国地质大学（武汉） | Preparation method of positive plate of lithium sulphur secondary battery |
| CN105990580A (en) * | 2015-02-12 | 2016-10-05 | 深圳市比克电池有限公司 | Negative electrode material, and negative plate of lithium ion battery and preparation method thereof |
| CN106188343A (en) * | 2016-07-27 | 2016-12-07 | 华南理工大学 | A kind of biodegradable halogen-free flame retardants and preparation method thereof |
| CN110203902A (en) * | 2019-05-09 | 2019-09-06 | 中国地质大学（武汉） | A kind of nitrogen-high-densit micro-pore carbon material of oxygen-phosphor codoping and its preparation method and application |
| CN113185622A (en) * | 2021-04-29 | 2021-07-30 | 华南理工大学 | High-phosphorus-content chitosan derivative, preparation method thereof and application thereof in loading of nano zero-valent iron |
| CN114983863A (en) * | 2022-07-06 | 2022-09-02 | 青岛海之林生物科技开发有限公司 | Modified alginate composition for skin repair and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103515613A (en) * | 2013-10-02 | 2014-01-15 | 中国地质大学（武汉） | Additive for lithium-sulfur batteries and anode material containing same |
| CN103515613B (en) * | 2013-10-02 | 2017-06-30 | 中国地质大学（武汉） | A kind of lithium-sulfur cell additive, the positive electrode containing the additive |
| CN103682255A (en) * | 2013-12-25 | 2014-03-26 | 中国地质大学（武汉） | Preparation method of positive plate of lithium sulphur secondary battery |
| CN103682255B (en) * | 2013-12-25 | 2016-07-13 | 中国地质大学（武汉） | A kind of preparation method of the positive plate of lithium-sulfur rechargeable battery |
| CN105990580A (en) * | 2015-02-12 | 2016-10-05 | 深圳市比克电池有限公司 | Negative electrode material, and negative plate of lithium ion battery and preparation method thereof |
| CN106188343A (en) * | 2016-07-27 | 2016-12-07 | 华南理工大学 | A kind of biodegradable halogen-free flame retardants and preparation method thereof |
| CN110203902A (en) * | 2019-05-09 | 2019-09-06 | 中国地质大学（武汉） | A kind of nitrogen-high-densit micro-pore carbon material of oxygen-phosphor codoping and its preparation method and application |
| CN110203902B (en) * | 2019-05-09 | 2021-06-04 | 中国地质大学（武汉） | Nitrogen-oxygen-phosphorus co-doped high-density microporous carbon material and preparation method and application thereof |
| CN113185622A (en) * | 2021-04-29 | 2021-07-30 | 华南理工大学 | High-phosphorus-content chitosan derivative, preparation method thereof and application thereof in loading of nano zero-valent iron |
| CN113185622B (en) * | 2021-04-29 | 2022-05-24 | 华南理工大学 | High-phosphorus-content chitosan derivative, preparation method thereof and application thereof in loading of nano zero-valent iron |
| CN114983863A (en) * | 2022-07-06 | 2022-09-02 | 青岛海之林生物科技开发有限公司 | Modified alginate composition for skin repair and application thereof |
| CN114983863B (en) * | 2022-07-06 | 2023-09-15 | 青岛海之林生物科技开发有限公司 | Modified alginate composition for skin repair and application thereof |
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Application publication date: 20130731 |