CN104027300B - A kind of antibacterial chitosan gel rubber agent and preparation method thereof - Google Patents
A kind of antibacterial chitosan gel rubber agent and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of antibacterial chitosan gel rubber agent and preparation method thereof, this preparation method comprise prepare chitosan-containing complex liquid, prepare fibroin alcoholic solution, prepare carrageenan solutions, prepare quaternary phosphonium compound solution with prepare the steps such as gel.Antibacterial chitosan gel rubber agent of the present invention with polymer chitosan and low molecular chitosan complex for main matrix, repair adjuvant etc. combine composite with the use of Trimethoprim, gellant, histiocyte, avoid using other composition such as chemicals, bio-pharmaceutical, improve the safety of gel, also reduce costs and reduce the zest to patient simultaneously, promoting that patient gets well.The prepared antibacterial ability of antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, bacillus pyocyaneus etc. all reaches more than 99%, demonstrates good bacteriostasis.
Description
[technical field]
The invention belongs to medical drugs technical field.More specifically, the present invention relates to a kind of antibacterial chitosan gel rubber agent, also relate to the preparation method of described antibacterial chitosan gel rubber agent.
[background technology]
The superior function that macromolecule hydrogel material itself has, as swelling character, viscoelasticity behavior and suitable mechanical strength etc., it is made to cause numerous researcher great interest and concern, corresponding preparation and developmental research are maked rapid progress, are achieved great success, its application has penetrated into the every field such as health care, biological medicine, daily-use chemical industry, food, environmental protection, and is also expanding to more wide application.Particularly good biocompatibility makes again it have an optimistic view of in the application prospect of biomedical aspect, as can be used as tissue filling agent, medicinal slow release agent, the embedding of enzyme, protein electrophorese, contact lenses, artificial blood plasma, artificial skin, tissue engineering bracket material etc., and continually develop along with the hydrogel of excellent performance, biomedical technology level is improved greatly.Much research is verified, chitosan is as the unique alkaline polysaccharide of occurring in nature, there is obvious bactericidal action, in acid condition, the amino in high deacetylized chitosan molecule, with positive charge, can adsorb the antibacterial with negative charge, the life state of interference cell, make cell membrane deformation fracture, inclusions is oozed out, and causes bacterolysis and dead.Research also finds, high molecular weight chitosan has excellent gel characteristic, by the special electrostatic force of group in chitosan molecule chain, hydrophobe effect and hydrogen bond action, compound can be produced with some gellant, formation can keep the colloidal materials of large quantity of moisture, has very strong moisture absorption, performance of keeping humidity, can also provide enough viscosity simultaneously, the place such as mucosa, skin can be affixed on and not come off, pessimal stimulation and anaphylaxis etc. can not be produced to human body skin.Therefore, there is much research to concentrate at present and develop various chitosan gel rubber and applying biological engineering in medicine.
At present, some patents of invention or application for a patent for invention relate to employing chitosan and prepare gel, such as CN101278896B discloses a kind of chitosan nano silver gel agent and application thereof, and it is prepared by nanometer silver, chitosan base polymer, carbomer, Polycarbophil, cellulose, polyvinyl alcohol, Polyethylene Glycol, polyamide, clay, collagen protein, pectin, sulphuric acid, acetic acid, formic acid etc.CN103316033A discloses a kind of gel and uses thereof, and it is prepared by chitosan base polymer, hyalomitome acid, newborn acid, gel-type vehicle, wetting agent, diluent etc.CN102397474A discloses a kind of Sanguis Draxonis oral gel for the treatment of stress gastric ulcer, and it is prepared by Sanguis Draxonis extract, carbomer, chitosan, sodium carboxymethyl cellulose, diethanolamine etc.CN103520232A discloses a kind of preparation method of gel, and it is prepared by Fructus cnidii extract clathrate, Clindamycin Hydrochloride clathrate, hydroxypropyl cellulose, water, glycerol, chitosan, ethyl hydroxybenzoate alcoholic solution, aqueous sodium persulfate solution etc.In addition, CN102657602 discloses 3,5-hydroxyl-4-isopropyl toluylene chitosan gel rubber agent and preparation method thereof; CN102626524A discloses chitosan gynaecologic antibacterial gel and preparation method thereof; CN101757071A discloses a kind of Irreversible vagina antibiosis gel preparation and preparation method thereof etc.
There is following technological deficiency in these prior aries: though 1, most gel take chitosan as host matrix, but all other medicines of load, comprising chemicals, bio-pharmaceutical, Chinese herbal medicine or nanometer silver etc., the object adopting chitosan to make gel preparations mainly makes medicine play slow releasing function; 2, general use synthetic material carbomer etc. are as the main material forming gel; 3, do not use other can produce the natural activity biological material of damaged tissue and cytothesis effect, effectiveness and the safety of product are restricted.Therefore, research and development are a kind of makes simple, safety, environmental protection, and the Novel pure chitosan gel rubber agent with tissue repair function is significant for clinical treatment.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of antibacterial chitosan gel rubber agent.
Another object of the present invention is to provide the preparation method of described antibacterial chitosan gel rubber agent.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of preparation method of antibacterial chitosan gel rubber agent.
The step of this antibacterial chitosan gel rubber agent preparation method is as follows:
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously with distilled water, toward wherein adding molecular weight 60 × 10
4the high molecular weight chitosan of Da, deacetylation 85-95% and molecular weight are lower than 1 × 10
3the low-molecular weight chitoglycan of Da, deacetylation 98-100%, stirring and dissolving, adds polyoxyethylene Pilus Caprae seu Ovis alcohol ether again, stirs, obtain a kind of complex liquid of chitosan-containing after homogenize;
B, prepare fibroin alcoholic solution
Fibroin is added in ethanol water, stirring and dissolving, obtains a kind of fibroin alcoholic solution;
C, preparation carrageenan solutions
Distilled water is heated to temperature 90 ~ 100 DEG C, then adds carrageenan, stirring and dissolving, obtain a kind of carrageenan solutions;
D, prepare quaternary phosphonium compound solution
Pi-allyl triphenylphosphinebromide mixes according to weight ratio 1:1.8 ~ 2.2 with pi-allyl three amyl group phosphonium chloride, obtains a kind of mixture; Then described mixture is added in distilled water, after dissolving, adds sucrose fatty acid ester again, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
A preferred embodiment of the invention, in step, the weight ratio of glacial acetic acid and distilled water is 0.8 ~ 1.2:16 ~ 22.
According to another kind of preferred implementation of the present invention, in step, the weight ratio of described high molecular weight chitosan and described low-molecular weight chitoglycan is 1.8 ~ 2.2:2.6 ~ 3.4.
According to another kind of preferred implementation of the present invention, in step D, the weight ratio of polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount is 1:4.8 ~ 5.2.
According to another kind of preferred implementation of the present invention, in stepb, the weight ratio of fibroin and ethanol water is 0.3 ~ 0.8:1.6 ~ 2.4.
According to another kind of preferred implementation of the present invention, in stepb, the concentration of described ethanol water is by volume 80 ~ 95%.
According to another kind of preferred implementation of the present invention, in step C, the weight ratio of distilled water and carrageenan is 25 ~ 35:0.5 ~ 1.8.
According to another kind of preferred implementation of the present invention, in step D, the weight ratio of pi-allyl triphenylphosphinebromide and pi-allyl three amyl group phosphonium chloride mixture and distilled water is 0.1 ~ 0.5:8 ~ 12.
According to another kind of preferred implementation of the present invention, in step D, the weight ratio of pi-allyl triphenylphosphinebromide and pi-allyl three amyl group phosphonium chloride mixture and sucrose fatty acid ester is 0.1 ~ 0.5:0.8 ~ 1.2.
The invention still further relates to the antibacterial chitosan gel rubber agent adopting described preparation method to obtain.The antibacterial ability of described antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, Candida albicans or bacillus pyocyaneus reaches more than 99%.
In more detail the present invention will be described below.
The present invention relates to a kind of preparation method of antibacterial chitosan gel rubber agent.
The step of this antibacterial chitosan gel rubber agent preparation method is as follows:
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously with distilled water, toward wherein adding molecular weight 60 × 10
4the high molecular weight chitosan of Da, deacetylation 85-95% and molecular weight are lower than 1 × 10
3the low-molecular weight chitoglycan of Da, deacetylation 98-100%, stirring and dissolving, adds polyoxyethylene Pilus Caprae seu Ovis alcohol ether again, stirs, obtain a kind of complex liquid of chitosan-containing after homogenize;
In this step, the weight ratio of glacial acetic acid and distilled water is 0.8 ~ 1.2:16 ~ 22, and preferably, the weight ratio of glacial acetic acid and distilled water is 1.0:18 ~ 20.
The chemical constitution of chitosan (β-(1 → 4)-2-amino-2-deoxy-D-Glucose) is band cationic macromolecule alkalescence polysaccharide polymer, is nature uniquely positively charged, cation edible fiber; It has the physicochemical properties such as stable physical property, good dissolubility, hydrophilic hygroscopicity, biological degradability, biocompatibility and film property, caking property, breathability.
In the present invention, by high molecular weight chitosan and low-molecular weight chitoglycan with the use of object be to utilize the good gelling property of high molecular weight chitosan and the good antibacterial properties of low-molecular weight chitoglycan.
In this step, the weight ratio of described high molecular weight chitosan and described low-molecular weight chitoglycan is 1.8 ~ 2.2:2.6 ~ 3.4.If the amount of high molecular weight chitosan too low or too high time, then the gelling properties of this gel can be made to be affected.Similarly, if the amount of low-molecular weight chitoglycan too low or too high time, then the anti-microbial property of gel can be made to be affected.Therefore, the weight ratio of described high molecular weight chitosan and described low-molecular weight chitoglycan is 1.8 ~ 2.2:2.6 ~ 3.4 is rational, preferably 2.0:2.8 ~ 3.2.
The high molecular weight chitosan that the present invention uses and low-molecular weight chitoglycan are product solds in the market, the high molecular weight chitosan such as sold with trade name food pharmaceutical grade chitosan by Jinan Haidebei Marine Organism Engineering Co., Ltd., the low-molecular weight chitoglycan that hundred taste bio tech ltd, effluent north sell with trade name chitosan.
Described polyoxyethylene Pilus Caprae seu Ovis alcohol ether (ethoxylatedlanolinalcohol) is made up by additive reaction of lanolin alcohol and oxirane.In the present invention, the effect of polyoxyethylene Pilus Caprae seu Ovis alcohol ether is to improve solubilising and the infiltration compatible role improved skin.
In this step, the weight ratio of described polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount (amount of described high molecular weight chitosan and the amount sum of described low-molecular weight chitoglycan) is 1:4.8 ~ 5.2.According to the present invention, if chitosan total amount is less than 4,8, then the formation effect of gel and antibacterial action can be made to decline; If chitosan total amount is greater than 5.2, then gel can be made to decline to the moistening of skin and osmosis effect; Therefore, chitosan total amount is 4.8 ~ 5.2 is appropriate, preferably 1:5.0.
The polyoxyethylene Pilus Caprae seu Ovis alcohol ether that the present invention uses is product sold in the market, such as by standing grain major company of Britain with trade name polyoxyethylene Pilus Caprae seu Ovis alcohol ether product sold.
B, prepare fibroin alcoholic solution
Fibroin is added in ethanol water, stirring and dissolving, obtains a kind of fibroin alcoholic solution.
Fibroin is the natural polymer fibrin extracted from silkworm silk, its content is 70% ~ 80% of silkworm silk amount, it contains 18 seed amino acids, and wherein the amount of glycine (gly), alanine (ala) and serine (ser) is more than 80% of described total amino acid content.
In this step, the weight ratio of fibroin and ethanol water is 0.3 ~ 0.8:1.6 ~ 2.4.The concentration of described ethanol water is by volume 80 ~ 95%.
According to the present invention, the amount of fibroin and ethanol water is less than or is all worthless higher than this scope, because fibroin amount height then makes dissolving not exclusively and solution viscosity is higher, measure low, do not reach the nursing to skin and repairing effect that fibroin plays.Preferably, the weight ratio of fibroin and ethanol water is 0.4 ~ 0.6:1.8 ~ 2.2.
The fibroin that the present invention uses is product sold in the market, such as by Suzhou Bao Sili fibroin fiber Science and Technology Ltd. with trade name fibroin fiber product sold.
C, preparation carrageenan solutions
Distilled water is heated to temperature 90 ~ 100 DEG C, then adds carrageenan, stirring and dissolving, obtain a kind of carrageenan solutions.
Carrageenan (kappa-Carrageenan) is the hydrophilic colloid extract from the red algae zostera marina such as Eucheuma muricatum (Gmel.) Web.Van Bos., polysaccharide sulfuric ester calcium, potassium, sodium, ammonium salt that it is made up of galactose and Anhydrogalactose..The carrageenan that the present invention uses is product sold in the market, such as by Beilun In Ningbo Ya Xu Chemical Co., Ltd. with trade name carrageenan product sold.
In this step, the weight ratio of distilled water and carrageenan is 25 ~ 35:0.5 ~ 1.8.
D, prepare quaternary phosphonium compound solution
Pi-allyl triphenylphosphinebromide mixes according to weight ratio 1:1.8 ~ 2.2 with pi-allyl three amyl group phosphonium chloride, obtains a kind of mixture; Then described mixture is added in distilled water, after dissolving, adds sucrose fatty acid ester again, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
In this step, the effect of pi-allyl triphenylphosphinebromide (Allyltriphenylphosphoniumbromide) is by the effect with three phenyl, improves the gelling properties of gel, improves the anti-microbial property of chitosan.
The effect of pi-allyl three amyl group phosphonium chloride (Allyltriamylphosphoniumchloride) is the effect by being with straight chained alkyl (amyl group) quaternary phosphonium compound, produce cooperative effect with band phenyl quaternary phosphonium compound, greatly promote the gelling property of gel and the anti-microbial property of chitosan.
The effect of sucrose fatty acid ester (SucroseFattyAcidEsters) plays emulsifying and Stabilization as a kind of non-ionic surface active agent, meanwhile, also can promote antibacterial effect further.
The pi-allyl triphenylphosphinebromide that the present invention uses is product sold in the market, such as, according to pi-allyl triphenylphosphinebromide product prepared by Ji'nan University's CN102020675B patented technology.
The pi-allyl three amyl group phosphonium chloride that the present invention uses is product sold in the market, such as by Shanghai Di Bai chemicals Technology Co., Ltd. with trade name pi-allyl three amyl group phosphonium chloride ionic liquid product sold.
The sucrose fatty acid ester that the present invention uses is product sold in the market, such as by Hangzhou Jin Helai food additive company limited with trade name sucrose ester product sold.
In the present invention, the weight ratio of pi-allyl triphenylphosphinebromide and pi-allyl three amyl group phosphonium chloride mixture and distilled water is 0.1 ~ 0.5:8 ~ 12.
When the amount of distilled water is 8 ~ 12, if the amount of described mixture is less than 0.1, then make the Synergistic antimicrobial effect of itself and chitosan influenced; If the amount of described mixture is greater than 0.5, then the gelling hardness of gel is undesirable; Therefore, the amount of described mixture is 0.1 ~ 0.5 is suitable, and preferably, the weight ratio of pi-allyl triphenylphosphinebromide and pi-allyl three amyl group phosphonium chloride mixture and distilled water is 0.2 ~ 0.4:9 ~ 11.
In this step, the weight ratio of pi-allyl triphenylphosphinebromide and pi-allyl three amyl group phosphonium chloride mixture and sucrose fatty acid ester (SucroseFattyAcidEsters) is 0.1 ~ 0.5:0.8 ~ 1.2.
When the amount of described mixture is 0.1 ~ 0.5, if the amount of sucrose fatty acid ester is less than 0.8, then emulsifying and Stabilization bad; If the amount of sucrose fatty acid ester is greater than 1.2, then unfavorable to gelling properties; Therefore, the amount of sucrose fatty acid ester is 0.8 ~ 1.2 is suitable, and preferably, the weight ratio of pi-allyl triphenylphosphinebromide and pi-allyl three amyl group phosphonium chloride mixture and sucrose fatty acid ester is 0.2 ~ 0.4:0.9 ~ 1.1.
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again this mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
Antibacterial chitosan gel rubber agent of the present invention detects through the antibacterial detection method of national standard (GB/T16886) and analyzes, the prepared antibacterial ability of antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, bacillus pyocyaneus etc. all reaches more than 99%, demonstrates good bacteriostasis.
The present invention is for main matrix with polymer chitosan and low molecular chitosan complex, repair adjuvant etc. combine composite with the use of Trimethoprim, gellant, histiocyte, avoid using other chemicals, bio-pharmaceutical and Chinese herbal medicine and the composition such as nanometer silver, carbomer, improve the safety of gel, also reduce costs and reduce the zest to patient simultaneously, promoting that patient gets well.
The chitosan anti-bacteria gel adopting the present invention to prepare can be applied to treatment bacterial skin infections, men and women's pruritus vulvae, vaginitis, vitamin B1 deficiency, decubital ulcer, skin chronicity ulcer etc.
Chitosan anti-bacteria gel of the present invention can adopt the conventional method known by the technical staff in the art to apply.
[beneficial effect]
The present invention compared with prior art has following beneficial effect:
1, chitosan anti-bacteria gel main body of the present invention is natural product chitosan, and do not use other chemistry synthesized or bio-pharmaceutical, Chinese herbal medicine etc., not easily produce drug resistance, biological safety is high;
2, with molecular weight 60 × 10
4the high molecular weight chitosan of Da, as gelled matrix, with the use of natural seaweed extracts such as carrageenans, obtains good gelatinization results, avoids using the synthetic chemistry materials such as carbomer, further increases safety and the environmental benefit of product;
3, adopt molecular weight lower than the high deacetylized chitosan of 1000Da low-molecular-weight as antibacterial main body, with the use of quaternary phosphonium compound as synergist, obtain good antibacterial effect, avoid using other medicines;
4, employ the natural activity biological material that fibroin and sucrose-fatty ester complexes etc. have damaged tissue and cytothesis effect, can promote that patient gets well function early;
5, chitosan anti-bacteria gel of the present invention has efficient collaborative anti-harmful microorganism effect, to antibacterial, virus, fungus, all there is obvious killing effect, staphylococcus aureus, hemolytic chain bacterium, bacillus pyocyaneus, Candida albicans and the clinical bacteria such as escherichia coli and other harmful fungoid are all had to the kill efficiency of more than 99%.
[detailed description of the invention]
The present invention can be understood better by following embodiment.
Embodiment 1: the preparation of chitosan anti-bacteria gel
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously according to weight ratio 0.9:22 with distilled water, according to the weight ratio 1.8:2.6 of high molecular weight chitosan and low-molecular weight chitoglycan, in its glacial acetic acid aqueous solution, add the molecular weight 60 × 10 sold with trade name food pharmaceutical grade chitosan by Jinan Haidebei Marine Organism Engineering Co., Ltd.
4the molecular weight 800Da that the northern hundred taste bio tech ltd of the high molecular weight chitosan of Da, deacetylation 88%, effluent sell with trade name chitosan, the low-molecular weight chitoglycan of deacetylation 100%, stirring and dissolving, add according to the weight ratio 1:4.8 of polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount the polyoxyethylene Pilus Caprae seu Ovis alcohol ether sold with trade name polyoxyethylene Pilus Caprae seu Ovis alcohol ether by standing grain major company of Britain again after homogenize, stir, obtain a kind of complex liquid of chitosan-containing;
B, prepare fibroin alcoholic solution
According to fibroin and concentration by volume 80% the weight ratio 0.3:1.8 of ethanol water, to be added in described ethanol water with the fibroin that trade name fibroin fiber is sold by Suzhou Bao Sili fibroin fiber Science and Technology Ltd., stirring and dissolving, obtains a kind of fibroin alcoholic solution;
C, preparation carrageenan solutions
Distilled water is heated to temperature 90 DEG C, then in its distilled water, adds the carrageenan sold with trade name carrageenan by Beilun In Ningbo Ya Xu Chemical Co., Ltd., stirring and dissolving according to the weight ratio 25:1.0 of distilled water and carrageenan, obtain a kind of carrageenan solutions;
D, prepare quaternary phosphonium compound solution
Mixed according to weight ratio 1:1.8 with the pi-allyl three amyl group phosphonium chloride sold with trade name pi-allyl three amyl group phosphonium chloride ionic liquid by Shanghai Di Bai chemicals Technology Co., Ltd. by the pi-allyl triphenylphosphinebromide product prepared according to Ji'nan University's CN102020675B patented technology, obtain a kind of mixture; Then according to the weight ratio 0.1:11 of described mixture and distilled water, described mixture is added in distilled water, the sucrose fatty acid ester sold with trade name sucrose ester by Hangzhou Jin Helai food additive company limited is added again after dissolving, wherein said mixture and the weight ratio of sucrose fatty acid ester are 0.1:1.1, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again this mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
Determine according to the national standard antibacterial detection method detection analysis that this description describes, the antibacterial ability of antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, bacillus pyocyaneus prepared by the present embodiment all reaches 99.3%.
Embodiment 2: the preparation of chitosan anti-bacteria gel
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously according to weight ratio 0.8:16 with distilled water, according to the weight ratio 2.0:3.4 of high molecular weight chitosan and low-molecular weight chitoglycan, in its glacial acetic acid aqueous solution, add the molecular weight 60 × 10 sold with trade name food pharmaceutical grade chitosan by Jinan Haidebei Marine Organism Engineering Co., Ltd.
4the molecular weight 900Da that the northern hundred taste bio tech ltd of the high molecular weight chitosan of Da, deacetylation 85%, effluent sell with trade name chitosan, the low-molecular weight chitoglycan of deacetylation 98%, stirring and dissolving, add according to the weight ratio 1:5.2 of polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount the polyoxyethylene Pilus Caprae seu Ovis alcohol ether sold with trade name polyoxyethylene Pilus Caprae seu Ovis alcohol ether by standing grain major company of Britain again after homogenize, stir, obtain a kind of complex liquid of chitosan-containing;
B, prepare fibroin alcoholic solution
According to fibroin and concentration by volume 85% the weight ratio 0.4:2.3 of ethanol water, to be added in described ethanol water with the fibroin that trade name fibroin fiber is sold by Suzhou Bao Sili fibroin fiber Science and Technology Ltd., stirring and dissolving, obtains a kind of fibroin alcoholic solution;
C, preparation carrageenan solutions
Distilled water is heated to temperature 92 DEG C, then in its distilled water, adds the carrageenan sold with trade name carrageenan by Beilun In Ningbo Ya Xu Chemical Co., Ltd., stirring and dissolving according to the weight ratio 30:0.5 of distilled water and carrageenan, obtain a kind of carrageenan solutions;
D, prepare quaternary phosphonium compound solution
Mixed according to weight ratio 1:2.0 with the pi-allyl three amyl group phosphonium chloride sold with trade name pi-allyl three amyl group phosphonium chloride ionic liquid by Shanghai Di Bai chemicals Technology Co., Ltd. by the pi-allyl triphenylphosphinebromide product prepared according to Ji'nan University's CN102020675B patented technology, obtain a kind of mixture; Then according to the weight ratio 0.5:8 of described mixture and distilled water, described mixture is added in distilled water, the sucrose fatty acid ester sold with trade name sucrose ester by Hangzhou Jin Helai food additive company limited is added again after dissolving, wherein said mixture and the weight ratio of sucrose fatty acid ester are 0.2:0.8, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again this mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
Determine according to the national standard antibacterial detection method detection analysis that this description describes, the antibacterial ability of antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, bacillus pyocyaneus prepared by the present embodiment all reaches 99.6%.
Embodiment 3: the preparation of chitosan anti-bacteria gel
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously according to weight ratio 1.2:18 with distilled water, according to the weight ratio 2.2:3.2 of high molecular weight chitosan and low-molecular weight chitoglycan, in its glacial acetic acid aqueous solution, add the molecular weight 60 × 10 sold with trade name food pharmaceutical grade chitosan by Jinan Haidebei Marine Organism Engineering Co., Ltd.
4the molecular weight 960Da that the northern hundred taste bio tech ltd of the high molecular weight chitosan of Da, deacetylation 92%, effluent sell with trade name chitosan, the low-molecular weight chitoglycan of deacetylation 100%, stirring and dissolving, add according to the weight ratio 1:5.0 of polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount the polyoxyethylene Pilus Caprae seu Ovis alcohol ether sold with trade name polyoxyethylene Pilus Caprae seu Ovis alcohol ether by standing grain major company of Britain again after homogenize, stir, obtain a kind of complex liquid of chitosan-containing;
B, prepare fibroin alcoholic solution
According to fibroin and concentration by volume 90% the weight ratio 0.6:1.6 of ethanol water, to be added in described ethanol water with the fibroin that trade name fibroin fiber is sold by Suzhou Bao Sili fibroin fiber Science and Technology Ltd., stirring and dissolving, obtains a kind of fibroin alcoholic solution;
C, preparation carrageenan solutions
Distilled water is heated to temperature 100 DEG C, then in its distilled water, adds the carrageenan sold with trade name carrageenan by Beilun In Ningbo Ya Xu Chemical Co., Ltd., stirring and dissolving according to the weight ratio 35:1.8 of distilled water and carrageenan, obtain a kind of carrageenan solutions;
D, prepare quaternary phosphonium compound solution
Mixed according to weight ratio 1:2.2 with the pi-allyl three amyl group phosphonium chloride sold with trade name pi-allyl three amyl group phosphonium chloride ionic liquid by Shanghai Di Bai chemicals Technology Co., Ltd. by the pi-allyl triphenylphosphinebromide product prepared according to Ji'nan University's CN102020675B patented technology, obtain a kind of mixture; Then according to the weight ratio 0.4:10 of described mixture and distilled water, described mixture is added in distilled water, the sucrose fatty acid ester sold with trade name sucrose ester by Hangzhou Jin Helai food additive company limited is added again after dissolving, wherein said mixture and the weight ratio of sucrose fatty acid ester are 0.5:1.0, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again this mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
Determine according to the national standard antibacterial detection method detection analysis that this description describes, the antibacterial ability of antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, bacillus pyocyaneus prepared by the present embodiment all reaches 99.2%.
Embodiment 4: the preparation of chitosan anti-bacteria gel
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously according to weight ratio 1.0:20 with distilled water, according to the weight ratio 1.9:3.0 of high molecular weight chitosan and low-molecular weight chitoglycan, in its glacial acetic acid aqueous solution, add the molecular weight 60 × 10 sold with trade name food pharmaceutical grade chitosan by Jinan Haidebei Marine Organism Engineering Co., Ltd.
4the molecular weight 845Da that the northern hundred taste bio tech ltd of the high molecular weight chitosan of Da, deacetylation 95%, effluent sell with trade name chitosan, the low-molecular weight chitoglycan of deacetylation 98%, stirring and dissolving, add according to the weight ratio 1:4.9 of polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount the polyoxyethylene Pilus Caprae seu Ovis alcohol ether sold with trade name polyoxyethylene Pilus Caprae seu Ovis alcohol ether by standing grain major company of Britain again after homogenize, stir, obtain a kind of complex liquid of chitosan-containing;
B, prepare fibroin alcoholic solution
According to fibroin and concentration by volume 95% the weight ratio 0.8:2.4 of ethanol water, to be added in described ethanol water with the fibroin that trade name fibroin fiber is sold by Suzhou Bao Sili fibroin fiber Science and Technology Ltd., stirring and dissolving, obtains a kind of fibroin alcoholic solution;
C, preparation carrageenan solutions
Distilled water is heated to temperature 96 DEG C, then in its distilled water, adds the carrageenan sold with trade name carrageenan by Beilun In Ningbo Ya Xu Chemical Co., Ltd., stirring and dissolving according to the weight ratio 30:1.4 of distilled water and carrageenan, obtain a kind of carrageenan solutions;
D, prepare quaternary phosphonium compound solution
Mixed according to weight ratio 1:2.0 with the pi-allyl three amyl group phosphonium chloride sold with trade name pi-allyl three amyl group phosphonium chloride ionic liquid by Shanghai Di Bai chemicals Technology Co., Ltd. by the pi-allyl triphenylphosphinebromide product prepared according to Ji'nan University's CN102020675B patented technology, obtain a kind of mixture; Then according to the weight ratio 0.2:12 of described mixture and distilled water, described mixture is added in distilled water, the sucrose fatty acid ester sold with trade name sucrose ester by Hangzhou Jin Helai food additive company limited is added again after dissolving, wherein said mixture and the weight ratio of sucrose fatty acid ester are 0.4:1.2, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again this mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
Determine according to the national standard antibacterial detection method detection analysis that this description describes, the antibacterial ability of antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, bacillus pyocyaneus prepared by the present embodiment all reaches 99.6%.
Embodiment 5: the preparation of chitosan anti-bacteria gel
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously according to weight ratio 0.9:16 with distilled water, according to the weight ratio 2.2:3.0 of high molecular weight chitosan and low-molecular weight chitoglycan, in its glacial acetic acid aqueous solution, add the molecular weight 60 × 10 sold with trade name food pharmaceutical grade chitosan by Jinan Haidebei Marine Organism Engineering Co., Ltd.
4the molecular weight 900Da that the northern hundred taste bio tech ltd of the high molecular weight chitosan of Da, deacetylation 88%, effluent sell with trade name chitosan, the low-molecular weight chitoglycan of deacetylation 100%, stirring and dissolving, add according to the weight ratio 1:4.9 of polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount the polyoxyethylene Pilus Caprae seu Ovis alcohol ether sold with trade name polyoxyethylene Pilus Caprae seu Ovis alcohol ether by standing grain major company of Britain again after homogenize, stir, obtain a kind of complex liquid of chitosan-containing;
B, prepare fibroin alcoholic solution
According to fibroin and concentration by volume 80% the weight ratio 0.4:2.4 of ethanol water, to be added in described ethanol water with the fibroin that trade name fibroin fiber is sold by Suzhou Bao Sili fibroin fiber Science and Technology Ltd., stirring and dissolving, obtains a kind of fibroin alcoholic solution;
C, preparation carrageenan solutions
Distilled water is heated to temperature 92 DEG C, then in its distilled water, adds the carrageenan sold with trade name carrageenan by Beilun In Ningbo Ya Xu Chemical Co., Ltd., stirring and dissolving according to the weight ratio 35:1.4 of distilled water and carrageenan, obtain a kind of carrageenan solutions;
D, prepare quaternary phosphonium compound solution
Mixed according to weight ratio 1:1.8 with the pi-allyl three amyl group phosphonium chloride sold with trade name pi-allyl three amyl group phosphonium chloride ionic liquid by Shanghai Di Bai chemicals Technology Co., Ltd. by the pi-allyl triphenylphosphinebromide product prepared according to Ji'nan University's CN102020675B patented technology, obtain a kind of mixture; Then according to the weight ratio 0.5:10 of described mixture and distilled water, described mixture is added in distilled water, the sucrose fatty acid ester sold with trade name sucrose ester by Hangzhou Jin Helai food additive company limited is added again after dissolving, wherein said mixture and the weight ratio of sucrose fatty acid ester are 0.2:1.2, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again this mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
Determine according to the national standard antibacterial detection method detection analysis that this description describes, the antibacterial ability of antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, bacillus pyocyaneus prepared by the present embodiment all reaches 99.8%.
Embodiment 6: the preparation of chitosan anti-bacteria gel
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously according to weight ratio 1.2:20 with distilled water, according to the weight ratio 1.8:3.4 of high molecular weight chitosan and low-molecular weight chitoglycan, in its glacial acetic acid aqueous solution, add the molecular weight 60 × 10 sold with trade name food pharmaceutical grade chitosan by Jinan Haidebei Marine Organism Engineering Co., Ltd.
4the molecular weight 845Da that the northern hundred taste bio tech ltd of the high molecular weight chitosan of Da, deacetylation 92%, effluent sell with trade name chitosan, the low-molecular weight chitoglycan of deacetylation 100%, stirring and dissolving, add according to the weight ratio 1:4.8 of polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount the polyoxyethylene Pilus Caprae seu Ovis alcohol ether sold with trade name polyoxyethylene Pilus Caprae seu Ovis alcohol ether by standing grain major company of Britain again after homogenize, stir, obtain a kind of complex liquid of chitosan-containing;
B, prepare fibroin alcoholic solution
According to fibroin and concentration by volume 85% the weight ratio 0.6:1.6 of ethanol water, to be added in described ethanol water with the fibroin that trade name fibroin fiber is sold by Suzhou Bao Sili fibroin fiber Science and Technology Ltd., stirring and dissolving, obtains a kind of fibroin alcoholic solution;
C, preparation carrageenan solutions
Distilled water is heated to temperature 90 DEG C, then in its distilled water, adds the carrageenan sold with trade name carrageenan by Beilun In Ningbo Ya Xu Chemical Co., Ltd., stirring and dissolving according to the weight ratio 30:1.0 of distilled water and carrageenan, obtain a kind of carrageenan solutions;
D, prepare quaternary phosphonium compound solution
Mixed according to weight ratio 1:2.2 with the pi-allyl three amyl group phosphonium chloride sold with trade name pi-allyl three amyl group phosphonium chloride ionic liquid by Shanghai Di Bai chemicals Technology Co., Ltd. by the pi-allyl triphenylphosphinebromide product prepared according to Ji'nan University's CN102020675B patented technology, obtain a kind of mixture; Then according to the weight ratio 0.2:11 of described mixture and distilled water, described mixture is added in distilled water, the sucrose fatty acid ester sold with trade name sucrose ester by Hangzhou Jin Helai food additive company limited is added again after dissolving, wherein said mixture and the weight ratio of sucrose fatty acid ester are 0.2:1.0, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again this mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
Determine according to the national standard antibacterial detection method detection analysis that this description describes, the antibacterial ability of antibacterial chitosan gel rubber agent to staphylococcus aureus, escherichia coli, streptococcus, bacillus pyocyaneus prepared by the present embodiment all reaches 99.5%.
Claims (9)
1. a preparation method for antibacterial chitosan gel rubber agent, is characterized in that the step of this preparation method is as follows:
A, prepare the complex liquid of chitosan-containing
Glacial acetic acid is mixed homogeneously with distilled water, toward wherein adding molecular weight 60 × 10
4the high molecular weight chitosan of Da, deacetylation 85-95% and molecular weight are lower than 1 × 10
3the low-molecular weight chitoglycan of Da, deacetylation 98-100%, stirring and dissolving, adds polyoxyethylene Pilus Caprae seu Ovis alcohol ether again, stirs, obtain a kind of complex liquid of chitosan-containing after homogenize; The weight ratio of described high molecular weight chitosan and described low-molecular weight chitoglycan is 1.8 ~ 2.2:2.6 ~ 3.4;
B, prepare fibroin alcoholic solution
Fibroin is added in ethanol water, stirring and dissolving, obtains a kind of fibroin alcoholic solution;
C, preparation carrageenan solutions
Distilled water is heated to temperature 90 ~ 100 DEG C, then adds carrageenan, stirring and dissolving, obtain a kind of carrageenan solutions;
D, prepare quaternary phosphonium compound solution
Pi-allyl triphenylphosphinebromide mixes according to weight ratio 1:1.8 ~ 2.2 with pi-allyl three amyl group phosphonium chloride, obtains a kind of mixture; Then described mixture is added in distilled water, after dissolving, adds sucrose fatty acid ester again, stir, obtain a kind of containing sucrose fatty acid ester quaternary phosphonium compound solution;
E, prepare gel
The fibroin alcoholic solution that complex liquid and the step B of chitosan-containing steps A obtained obtain is mixed homogeneously, again mixed solution is added in the carrageenan solutions that step C obtains, stir, then add that step D obtains containing sucrose fatty acid ester quaternary phosphonium compound solution, add distilled water, mix homogeneously, obtains described antibacterial chitosan gel rubber agent.
2. preparation method according to claim 1, is characterized in that in step, and the weight ratio of glacial acetic acid and distilled water is 0.8 ~ 1.2:16 ~ 22.
3. preparation method according to claim 1, is characterized in that in step, and the weight ratio of polyoxyethylene Pilus Caprae seu Ovis alcohol ether and chitosan total amount is 1:4.8 ~ 5.2.
4. preparation method according to claim 1, is characterized in that in stepb, and the weight ratio of fibroin and ethanol water is 0.3 ~ 0.8:1.6 ~ 2.4.
5. preparation method according to claim 1, is characterized in that in stepb, and the concentration of described ethanol water is by volume 80 ~ 95%.
6. preparation method according to claim 1, is characterized in that in step C, and the weight ratio of distilled water and carrageenan is 25 ~ 35:0.5 ~ 1.8.
7. preparation method according to claim 1, is characterized in that in step D, and the weight ratio of pi-allyl triphenylphosphinebromide and pi-allyl three amyl group phosphonium chloride mixture and distilled water is 0.1 ~ 0.5:8 ~ 12.
8. preparation method according to claim 1, is characterized in that in step D, and the weight ratio of pi-allyl triphenylphosphinebromide and pi-allyl three amyl group phosphonium chloride mixture and sucrose fatty acid ester is 0.1 ~ 0.5:0.8 ~ 1.2.
9. the antibacterial chitosan gel rubber agent that obtains of preparation method according to claim 1, is characterized in that it reaches more than 99% to the antibacterial ability of staphylococcus aureus, escherichia coli, streptococcus, Candida albicans or bacillus pyocyaneus.
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| CN107715102A (en) * | 2017-10-19 | 2018-02-23 | 关亚玲 | A kind of preparation method of the thimerosal comprising fibroin |
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