CN102690297A - Chitooligosaccharide quaternary ammonium salt and its synthesis method - Google Patents
Chitooligosaccharide quaternary ammonium salt and its synthesis method Download PDFInfo
- Publication number
- CN102690297A CN102690297A CN2011100689523A CN201110068952A CN102690297A CN 102690297 A CN102690297 A CN 102690297A CN 2011100689523 A CN2011100689523 A CN 2011100689523A CN 201110068952 A CN201110068952 A CN 201110068952A CN 102690297 A CN102690297 A CN 102690297A
- Authority
- CN
- China
- Prior art keywords
- oligochitosan
- quaternary ammonium
- ammonium salt
- chitooligosaccharide
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides a chitooligosaccharide quaternary ammonium salt with a structural formula as formula (1). The preparation method of the chitooligosaccharide quaternary ammonium salt comprises the following steps of: taking a mixture of dimethyl sulfate and water as a solvent and dimethyl sulfate as a methylation reagent; during preparation, adding chitooligosaccharide into the solvent to prepare a chitooligosaccharide solution, then adding NaOH and NaCl into the solution, and conducting magnetic stirring for reaction at room temperature; precipitating the reaction solution with acetone, carrying out pumping filtration, filter cake washing, and drying, thus obtaining the chitooligosaccharide quaternary ammonium salt. The chitooligosaccharide quaternary ammonium salt of the invention has the quaternary ammonium group grafted to the chitooligosaccharide, and has strengthened bacteriostatic activity as well as its own advantages, thus boasting broad application prospects. The method of the invention adopts dimethyl sulfate as the methylation reagent which is characterized by inexpensiveness and low toxicity, and has the advantages of mild reaction condition, no need for other reaction solvent, high reaction efficiency, and simple reaction process, thus being conducive to mass production.
Description
Technical field
The present invention relates to a kind of pesticide material; Particularly a kind of oligochitosan quaternary ammonium salt the invention still further relates to the compound method of this oligochitosan quaternary ammonium salt.
Background technology
Oligochitosan is that chitosan is degraded into through enzyme process or chemical method, by 2 glucides of forming to 10 GS unit, has good water-solubility and unique physiologically active and function; Not only can produce resistance of wide spectrum by inducing plant, suppress the growth of several diseases pathogenic microorganism, can be after it is used by the microbiological deterioration in the soil; Edatope is not impacted; It can also improve the output of farm crop, improves crop quality, improves food nutrition and economic worth.
The agricultural chemicals initiative is a hi-tech, and is with high investment, high risk engineering, and developing a new varieties of pesticides at present in the world probably needs the 5-8 year, and hundred million dollars of expensive 1-2 screen the compound about 100,000.And along with the requirement of environmental problem, these numerals also will increase, the developing new product variety of having the ability at present have only An Wante, Bayer, Meng Shan all wait international large-scale agricultural chemicals company.How researching and developing the novel pesticide of China, is the severe problem that under situation about being gradually improved along with accession to WTO and intellectual property protection, faces.
Practical situation and research direction to international sterilant market; And the active situation of each series bactericidal agent, according to our technology and strength, row's theories such as thought that the employing substructure connects or biology are carried out derivatize to existing group with germicidal action and are modified; Develop the biological pesticide that has better fungicidal activity and degrade more easily; Be one with clearly defined objective, it is laborsaving to save money, and has the initiative approach of good prospect.Oligochitosan plays an increasingly important role in agriculture prodn as a kind of novel green agricultural chemicals.
Utilize characteristics such as chitosan hydrolyzate Preparation of Chitosan oligochitosan has the specificity height, yield is high, cost is low, quality good, low in the pollution of the environment, but the enzyme activity of Remazol Brilliant Violet carboxymethyl chitin hydrolase then is the key problem in technology of oligochitosan preparation.At present both at home and abroad the research of Remazol Brilliant Violet carboxymethyl chitin hydrolase report document is more, and main research contents is in researchs such as the screening of enzyme, separation and purification, gene clone, enzymolysis chitosans, but the ubiquity enzyme activity is low, the problem that can not satisfy the suitability for industrialized production needs.This seminar is engaged in Remazol Brilliant Violet carboxymethyl chitin hydrolase/chitinase and studies for many years, from marine microorganism, screens highly active product chitosan bacterial strain, and the enzymatic production vigor reaches 1280u/ml, reaches Production by Enzymes oligochitosan requirement of massive production.
The research of chitosan quaternary ammonium salt, bibliographical information is more.The chitosan quaternary ammonium salt that modification obtains not only has the character of typical quaternary ammonium salt; Like antibacterial bacteriostatic property and moisture absorbability and moisture retentivity; And kept performances such as the original good film-forming properties of chitosan, flocculence, biocompatibility and biological degradation, make it potential using value arranged in functional high molecule material, Treatment of Industrial Water, textiles processing and other fields.In addition, because the quaternary ammonium group in the chitosan quaternary ammonium salt is connected on the linear polymeric skeleton, this makes it can be used as the load etc. that carrier is used for medicine, auxiliary agent, biomaterial again, has widened its range of application.
The research of oligochitosan quaternary ammonium salt rarely has report.It is 115% that substitution value has been studied in (2003) such as Ji Young Kim, concentration be 0.1% quaternized oligochitosan to the streptococcus mutant body (
Streptococcus Mutans)The inhibition activity experiment, find that the inhibition activity of oligochitosan in 24h is lower than 20% under this condition, and the inhibition activity of quaternized oligochitosan in 24h surpassed 85%, the quaternized bacteriostatic activity that improves oligochitosan greatly.Yao Qian etc. (2009) are with the synthetic oligochitosan quaternary ammonium salt of epoxypropyl trimethylammonium chloride ammonium.But its oligochitosan molecular weight is about 5,000, and oligochitosan molecular-weight average of the present invention is 1000.Above-mentioned two kinds of quaternizing agents that the preparation method adopted all are the epoxypropyl trimethylammonium chloride ammoniums, and epoxypropyl open loop, quaternary ammonium group of grafting on amino are adopted in its reaction; Temperature of reaction is at 70 ~ 80 ℃; Under the high temperature, easy oxidation of oligochitosan and fracture are not suitable for scale preparation.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to prior art, provide a kind of new, preparation is simple, the oligochitosan quaternary ammonium salt of good antimicrobial effect.
Another technical problem to be solved by this invention provides the more compound method of the oligochitosan quaternary ammonium salt of advantages of simple, workable, product good antimicrobial effect of a kind of method.
Technical problem to be solved by this invention is to realize through following technical scheme.The present invention is a kind of oligochitosan quaternary ammonium salt, is characterized in: its structural formula is suc as formula shown in (1),
Formula (1)
Wherein the numerical value of n is 0 ~ 15.
In the oligochitosan quaternary ammonium salt of the present invention; The amino of oligochitosan raw material part saccharide residue becomes quaternary ammonium salt structure through methylation reaction; Modular construction after it replaces is suc as formula shown in (1), and wherein the trimethylammonium response location is for replacing at random, might not be at two ends or the centre saccharide residue.
Technical problem to be solved by this invention can also further realize through following technical scheme.The invention also discloses a kind of preparation method of as the described oligochitosan quaternary ammonium salt of above technical scheme; Be characterized in; Its step is following: the mixture with methyl-sulfate and water is a solvent, and the volume ratio of methyl-sulfate and water is 4 ~ 8:1 in the solvent, makes methylating reagent with methyl-sulfate; During preparation oligochitosan added and process oligochitosan solution in the solvent, the mass and size specific concentration of oligochitosan solution is 4 ~ 10%, in solution, adds 0.5 ~ 4 times NaOH and NaCl of oligochitosan quality then respectively, reacts under the magnetic agitation, room temperature 6 ~ 18 hours; Reaction solution is used its 3 ~ 5 times of volume acetone precipitations, suction filtration, and filter cake washing, drying gets the oligochitosan quaternary ammonium salt.
Oligochitosan itself has antibacterial character, and soluble in water, good biocompatibility, no cytotoxicity.Oligochitosan quaternary ammonium salt of the present invention is with quaternary ammonium salt group, is grafted on the oligochitosan, and its bacteriostatic activity has obtained reinforcement, and has the advantage of oligochitosan self, and it has a extensive future.
The inventive method adopts alkylated reaction, and it is quaternized that C2 is gone up amino, reacts under the room temperature.The methyl-sulfate that reaction is adopted is as methylating reagent, low price, low toxicity; Reaction conditions is gentle, does not need other reaction solvents, and reaction efficiency is very high, at room temperature reacts just to obtain the higher quaternized products of quaternized degree about 6 h, and reaction process is handled simple, helps scale operation.
Description of drawings
Fig. 1 is oligochitosan quaternary ammonium salt IR spectroscopy figure.
Fig. 2 is former reality of oligochitosan and oligochitosan quaternary ammonium salt H
1-NMR analyzes collection of illustrative plates.
Embodiment
Following with reference to accompanying drawing, further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not constitute restriction to its right.
Embodiment 1.A kind of oligochitosan quaternary ammonium salt, its structural formula is suc as formula shown in (1),
Formula (1)
Wherein the numerical value of n is 0 ~ 15.
Embodiment 2.A kind of preparation method like embodiment 1 described oligochitosan quaternary ammonium salt, its step is following: the mixture with methyl-sulfate and water is a solvent, and the volume ratio of methyl-sulfate and water is 4:1 in the solvent, makes methylating reagent with methyl-sulfate; During preparation oligochitosan added and process oligochitosan solution in the solvent, the mass and size specific concentration of oligochitosan solution is 4%, in solution, adds 0.5 times NaOH and NaCl of oligochitosan quality then respectively, magnetic agitation, and reaction is 6 hours under the room temperature; Reaction solution is used its 3 times of volume acetone precipitations, suction filtration, and filter cake washing, drying gets the oligochitosan quaternary ammonium salt.
Embodiment 3.A kind of preparation method like embodiment 1 described oligochitosan quaternary ammonium salt, its step is following: the mixture with methyl-sulfate and water is a solvent, and the volume ratio of methyl-sulfate and water is 8:1 in the solvent, makes methylating reagent with methyl-sulfate; During preparation oligochitosan added and process oligochitosan solution in the solvent, the mass and size specific concentration of oligochitosan solution is 10%, in solution, adds 4 times NaOH and NaCl of oligochitosan quality then respectively, magnetic agitation, and reaction is 18 hours under the room temperature; Reaction solution is used its 5 times of volume acetone precipitations, suction filtration, and filter cake washing, drying gets the oligochitosan quaternary ammonium salt.
Embodiment 4.A kind of preparation method like embodiment 1 described oligochitosan quaternary ammonium salt, its step is following: the mixture with methyl-sulfate and water is a solvent, and the volume ratio of methyl-sulfate and water is 6:1 in the solvent, makes methylating reagent with methyl-sulfate; During preparation oligochitosan added and process oligochitosan solution in the solvent, the mass and size specific concentration of oligochitosan solution is 7%, in solution, adds 2 times NaOH and NaCl of oligochitosan quality then respectively, magnetic agitation, and reaction is 12 hours under the room temperature; Reaction solution is used its 4 times of volume acetone precipitations, suction filtration, and filter cake washing, drying gets the oligochitosan quaternary ammonium salt.
Oligochitosan target level of product quality described in following examples 5-8 is referring to table 1, and its product is available from the great marine life Science and Technology Ltd. in Qingdao, and lot number is 20101224S.
Table 1
| Number-average molecular weight | ＜2000 |
| Deacetylation (%) | 91.5 |
| PH value (1% aqueous solution) | 5.3 |
| Weight loss on drying (%) | 6.5 |
| Ignition residue (%) | 0.35 |
MALDI-TOF-MS method determining molecular weight distribution collection of illustrative plates.In the collection of illustrative plates, the mensuration nuclear-cytoplasmic ratio is: 375.2,536.2,697.3,858.4,1019.5,1180.6.Analyze oligochitosan distribution of polymerization degree scope: 2-7 sugar by this.The relative content of wherein various polymerization degree oligochitosans is estimated as follows: chitobiose 4.25% ﹑ chitotriose 27.83% ﹑ shell tetrose 30.90% ﹑ shell pentasaccharides 25.94% ﹑ shell six sugared 9.91% ﹑ shells, seven sugar 1.18%.
Embodiment 5.Oligochitosan quaternary ammonium salt compound method and bacteriostatic experiment one.
Take by weighing 1.2gNaOH, 0.88gNaCl is dissolved in the 4ml deionized water, adds the 16ml methyl-sulfate, stirs; Take by weighing the 1g oligochitosan, be dissolved in above-mentioned solution, react 6h under the magnetic agitation, room temperature; Use acetone precipitation, suction filtration; Acetone, washing with alcohol; Secondary filtration, freeze-drying gets the oligochitosan quaternary ammonium salt.
Get present embodiment products therefrom oligochitosan quaternary ammonium salt, use IR spectroscopy, the result is referring to Fig. 1.
Among Fig. 1: curve 1 is the raw material peak, and curve 2 is the product peak.
3400cm
-1About broad peak be O-H, the overlapping peaks of N-H stretching vibration.2900cm
-1, 2800cm
-1Bimodal, be CH3, the CH2 stretching vibration peak.1600cm
-1About the peak be N-H flexural vibration peaks.1380cm
-1About the peak be-CH3 scissoring vibration peak.1034cm
-1~ 1250cm
-1The peak be C-N flexural vibration peaks.
In the raw material, 1520cm-1 has the peak, is N-H in-plane bending vibration peak, and in product, this peak disappears, at 1480cm
-1The peak occurs, prove the appearance of N methyl.3400cm
-1About the peak die down and 1600cm by force
-1About the peak die down, also prove the disappearance of N-H.1380cm
-1, it is more sharp-pointed more by force that the product peak becomes, and proves the adding of methyl.620cm in the product
-1Sharp-pointed strong peak appears in the place, proves band Cl
-Quaternary ammonium salt.
Get present embodiment products therefrom oligochitosan quaternary ammonium salt, study its growth inhibition ratio several kinds of agricultural chemicals pathogenic bacterium.Oligochitosan is done the positive control experiment.Suppress percentage referring to table 2.In the table 2: A: Monilinia fructicola B: Valsa mali C: cotton-wilt fusarium D: the corn smut bacterium.
Table 2
Embodiment 6.Oligochitosan quaternary ammonium salt compound method experiment two.
Take by weighing 0.6g NaOH, 0.88g NaCl is dissolved in the 4ml deionized water, adds the 16ml methyl-sulfate, stirs; Take by weighing the 1g oligochitosan, be dissolved in above-mentioned solution, react 6h under the magnetic agitation, room temperature; Use acetone precipitation, suction filtration; Acetone, washing with alcohol; Secondary filtration, freeze-drying gets the oligochitosan quaternary ammonium salt.
Get present embodiment products therefrom oligochitosan quaternary ammonium salt, H
1-NMR atlas analysis, the result is referring to Fig. 2.Among Fig. 2,1 is oligochitosan raw material collection of illustrative plates, and 2 is present embodiment synthetic product collection of illustrative plates.
In the raw material collection of illustrative plates, the peak at 4.5＜δ＜5 places is the C1 peak.3.4 the peak at＜δ＜4.0 places is C3, C4, C5, C6 peak.The peak at δ ≈ 3.2 places is the C2 peak.The peak at δ ≈ 2.1 places is the peak of methyl on the ethanoyl.
In the synthetic product collection of illustrative plates, several groups strong peaks appear in 3.0＜δ＜3.4 places.δ ≈ 3.3 is O-CH
3The peak, δ ≈ 3.2 is N-(CH
3)
3The peak.δ ≈ 3.0 is N-(CH
3)
2The peak.Peak, δ ≈ 3.2 place is very strong, proves that quaternization degree is very high.
Embodiment 7.Oligochitosan quaternary ammonium salt compound method and bacteriostatic experiment three.
Take by weighing 1.2gNaOH, 0.88gNaCl is dissolved in the 4ml deionized water, adds the 16ml methyl-sulfate, stirs; Take by weighing the 1g oligochitosan, be dissolved in above-mentioned solution, react 12h under the magnetic agitation, room temperature; Use acetone precipitation, suction filtration; Acetone, washing with alcohol; Secondary filtration, freeze-drying gets the oligochitosan quaternary ammonium salt.
Get present embodiment products therefrom oligochitosan quaternary ammonium salt, study its influence to Phytophthora capsici mycelial growth amount in the Erwin nutrient solution, oligochitosan is done positive control.The result sees table 3:
Table 3 oligochitosan and oligochitosan quaternary ammonium salt are to the influence of Phytophthora capsici mycelial growth amount in the Erwin nutrient solution
Experiment shows that the oligochitosan quaternary ammonium salt suppresses stronger than oligochitosan to the production of Phytophthora capsici mycelia.
Embodiment 8.Oligochitosan quaternary ammonium salt compound method and bacteriostatic experiment four.
Take by weighing 6gNaOH, 4.4gNaCl is dissolved in the 10ml deionized water, adds the 40ml methyl-sulfate, stirs; Take by weighing the 5g oligochitosan, be dissolved in above-mentioned solution, react 18h under the magnetic agitation, room temperature; Use acetone precipitation, suction filtration; Acetone, washing with alcohol; Secondary filtration, freeze-drying gets the oligochitosan quaternary ammonium salt.
Get present embodiment gained oligochitosan quaternary ammonium salt product, do it aureus with inhibition is tested, as positive control, the result sees table 4 with oligochitosan:
The size of the antibacterial ring of table 4 streptococcus aureus
In the experiment, chitosan quaternary ammonium salt group transparent circle proves that obviously greater than the oligochitosan group oligochitosan quaternary ammonium salt is more obvious to the staphylococcic inhibition of Jin Hansi.The excellent oligochitosan of the fungistatic effect of chitosan quaternary ammonium salt.
Claims (2)
1. oligochitosan quaternary ammonium salt is characterized in that: its structural formula is suc as formula shown in (1),
Formula (1)
Wherein the numerical value of n is 0 ~ 15.
2. the preparation method of an oligochitosan quaternary ammonium salt as claimed in claim 1; It is characterized in that; Its step is following: the mixture with methyl-sulfate and water is a solvent, and the volume ratio of methyl-sulfate and water is 4 ~ 8:1 in the solvent, makes methylating reagent with methyl-sulfate; During preparation oligochitosan added and process oligochitosan solution in the solvent, the mass and size specific concentration of oligochitosan solution is 4 ~ 10%, in solution, adds 0.5 ~ 4 times NaOH and NaCl of oligochitosan quality then respectively, reacts under the magnetic agitation, room temperature 6 ~ 18 hours; Reaction solution is used its 3 ~ 5 times of volume acetone precipitations, suction filtration, and filter cake washing, drying gets the oligochitosan quaternary ammonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100689523A CN102690297A (en) | 2011-03-22 | 2011-03-22 | Chitooligosaccharide quaternary ammonium salt and its synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100689523A CN102690297A (en) | 2011-03-22 | 2011-03-22 | Chitooligosaccharide quaternary ammonium salt and its synthesis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102690297A true CN102690297A (en) | 2012-09-26 |
Family
ID=46856049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100689523A Pending CN102690297A (en) | 2011-03-22 | 2011-03-22 | Chitooligosaccharide quaternary ammonium salt and its synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102690297A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086670A (en) * | 2014-05-22 | 2014-10-08 | 中国科学院烟台海岸带研究所 | Chitosan quaternary ammonium salt containing triazole, and preparation method and application thereof |
| WO2016154533A1 (en) * | 2015-03-25 | 2016-09-29 | President And Fellows Of Harvard College | Synthesis of desosamines |
| CN107312110A (en) * | 2017-07-06 | 2017-11-03 | 山东师范大学 | A kind of N thiosemicarbazides O quaternary ammonium salts chitosan oligosaccharide and preparation method and application |
| US9982005B2 (en) | 2013-04-04 | 2018-05-29 | President And Fellows Of Harvard College | Macrolides and methods of their preparation and use |
| CN108530560A (en) * | 2018-03-23 | 2018-09-14 | 克灵美（天津）生物科技有限公司 | Selective broad spectrum antimicrobial polysaccharide and its application |
| US10633407B2 (en) | 2014-10-08 | 2020-04-28 | President And Fellows Of Harvard College | 14-membered ketolides and methods of their preparation and use |
| US10640528B2 (en) | 2015-03-25 | 2020-05-05 | President And Fellows Of Havard College | Macrolides with modified desosamine sugars and uses thereof |
| CN114208928A (en) * | 2021-12-22 | 2022-03-22 | 昆山真金食品有限公司 | Flavored syrup and preparation method thereof |
-
2011
- 2011-03-22 CN CN2011100689523A patent/CN102690297A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11634449B2 (en) | 2013-04-04 | 2023-04-25 | President And Fellows Of Harvard College | Macrolides and methods of their preparation and use |
| US10913764B2 (en) | 2013-04-04 | 2021-02-09 | President And Fellows Of Harvard College | Macrolides and methods of their preparation and use |
| US9982005B2 (en) | 2013-04-04 | 2018-05-29 | President And Fellows Of Harvard College | Macrolides and methods of their preparation and use |
| CN104086670A (en) * | 2014-05-22 | 2014-10-08 | 中国科学院烟台海岸带研究所 | Chitosan quaternary ammonium salt containing triazole, and preparation method and application thereof |
| CN104086670B (en) * | 2014-05-22 | 2016-09-07 | 中国科学院烟台海岸带研究所 | A kind of chitosan quaternary ammonium salt containing triazole and preparation thereof and application |
| US11466046B2 (en) | 2014-10-08 | 2022-10-11 | President And Fellows Of Harvard College | 14-membered ketolides and methods of their preparation and use |
| US10633407B2 (en) | 2014-10-08 | 2020-04-28 | President And Fellows Of Harvard College | 14-membered ketolides and methods of their preparation and use |
| US10544182B2 (en) | 2015-03-25 | 2020-01-28 | Presidents and Fellow of Harvard College | Synthesis of desosamines |
| JP2018510878A (en) * | 2015-03-25 | 2018-04-19 | プレジデント アンド フェローズ オブ ハーバード カレッジ | Synthesis of desosamine |
| US10640528B2 (en) | 2015-03-25 | 2020-05-05 | President And Fellows Of Havard College | Macrolides with modified desosamine sugars and uses thereof |
| CN107531737A (en) * | 2015-03-25 | 2018-01-02 | 哈佛大学的校长及成员们 | The synthesis of desosamine |
| US11008358B2 (en) | 2015-03-25 | 2021-05-18 | President And Fellows Of Harvard College | Synthesis of desosamines |
| US11535643B2 (en) | 2015-03-25 | 2022-12-27 | President And Fellows Of Harvard College | Macrolides with modified desosamine sugars and uses thereof |
| WO2016154533A1 (en) * | 2015-03-25 | 2016-09-29 | President And Fellows Of Harvard College | Synthesis of desosamines |
| CN107312110A (en) * | 2017-07-06 | 2017-11-03 | 山东师范大学 | A kind of N thiosemicarbazides O quaternary ammonium salts chitosan oligosaccharide and preparation method and application |
| CN108530560A (en) * | 2018-03-23 | 2018-09-14 | 克灵美（天津）生物科技有限公司 | Selective broad spectrum antimicrobial polysaccharide and its application |
| CN114208928A (en) * | 2021-12-22 | 2022-03-22 | 昆山真金食品有限公司 | Flavored syrup and preparation method thereof |
| CN114208928B (en) * | 2021-12-22 | 2023-10-03 | 昆山真金食品有限公司 | Flavored syrup and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102690297A (en) | Chitooligosaccharide quaternary ammonium salt and its synthesis method | |
| CN101033264B (en) | Chitosan biguanide hydrochloride, preparation method and use thereof | |
| CN102321195B (en) | Chitosan aminoethyl quaternary ammonium salt derivative and preparation method thereof | |
| Sajomsang et al. | Antibacterial activity of quaternary ammonium chitosan containing mono or disaccharide moieties: Preparation and characterization | |
| Dhillon et al. | Green synthesis approach: extraction of chitosan from fungus mycelia | |
| Eweis et al. | Antifungal efficacy of chitosan and its thiourea derivatives upon the growth of some sugar-beet pathogens | |
| Fan et al. | Synthesis, characterization, and antifungal evaluation of diethoxyphosphoryl polyaminoethyl chitosan derivatives | |
| Xie et al. | Synthesis and characterization of water-soluble chitosan derivate and its antibacterial activity | |
| Xiao et al. | Preparation and characterization of antimicrobial chitosan-N-arginine with different degrees of substitution | |
| Lim et al. | Synthesis and antimicrobial activity of a water-soluble chitosan derivative with a fiber-reactive group | |
| Rabea et al. | In vitro assessment of N-(benzyl) chitosan derivatives against some plant pathogenic bacteria and fungi | |
| Schmid et al. | Scleroglucan: biosynthesis, production and application of a versatile hydrocolloid | |
| CN101891904B (en) | Kelp oligosaccharide and preparation method and application thereof | |
| Huang et al. | Antibacterial activity evaluation of quaternary chitin against Escherichia coli and Staphylococcus aureus | |
| CN104672346B (en) | The preparation method of guanidine radicals chitosan quaternary amine | |
| Mi et al. | Enhanced antifungal and antioxidant activities of new chitosan derivatives modified with Schiff base bearing benzenoid/heterocyclic moieties | |
| Krishnaveni et al. | Extraction and characterization of chitin and chitosan from f. Solani cbnr bkrr, synthesis of their bionanocomposites and study of their productive application | |
| CN109517090A (en) | A kind of preparation method of the degree of polymerization and the controllable labyrinth chitosan oligosaccharide of deacetylation | |
| CN101698157A (en) | Anion-exchange agent prepared by using fermented straws, preparation method thereof and use thereof | |
| CN107043432A (en) | Amphoteric carboxymethyl chitosan guanidine salt derivative and preparation method thereof | |
| CN112480288A (en) | Ionized chitosan and preparation method and application thereof | |
| CN1944467A (en) | Chitosan guanidine salt derivative and its preparing method | |
| Zhu et al. | Preparation, characterization, and antifungal evaluation of a new type of aminourea chitooligosaccharide derivatives | |
| CN102558388B (en) | 6-amine-substituted-6-deoxidizing chitosan derivant and preparation method thereof | |
| CN107304234B (en) | Double-modified carboxymethyl chitosan derivative and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120926 |