CN106380609A - Antibacterial carboxymethyl chitosan hydrogel and preparation method thereof - Google Patents
Antibacterial carboxymethyl chitosan hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN106380609A CN106380609A CN201610835824.XA CN201610835824A CN106380609A CN 106380609 A CN106380609 A CN 106380609A CN 201610835824 A CN201610835824 A CN 201610835824A CN 106380609 A CN106380609 A CN 106380609A
- Authority
- CN
- China
- Prior art keywords
- carboxymethyl chitosan
- antibacterial
- preparation
- hydrogel
- aqueous 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention discloses a preparation method of antibacterial carboxymethyl chitosan hydrogel. The preparation method of the antibacterial carboxymethyl chitosan hydrogel is characterized by comprising the following steps of (1) preparing carboxymethyl chitosan; (2) combining the carboxymethyl chitosan with transition metal ions through ion complexation reaction to prepare the antibacterial carboxymethyl chitosan hydrogel. The method has the advantages that the system is simple; the reaction is fast; the gel plasticity is high, and the like. Meanwhile, the carboxymethyl chitosan in a system and the transition metal ions have good sterilization effect, so that the goal of duplex sterilization is achieved. The antibacterial carboxymethyl chitosan hydrogel is different from conventional micromolecular antibacterial agents; the more broad-spectrum antibacterial activity is realized.
Description
Technical field
The present invention relates to a kind of carboxymethyl chitosan anti-bacterial hydrogel of complexed transition metal ion and its quickly preparation
Method, belongs to bio-medical gel technique field.
Background technology
Traditional anti-biotic material mainly passes through to introduce various small molecule antibacterial (as resisted in material body or its surface
Raw element, antibacterial etc.) obtaining anti-microbial property.But because these small molecule antibacterial generally have specificity and easily induce again
Bacterial resistance occurred.Therefore, what development had that broad spectrum of activity anti-biotic material seems particularly is important.Anti-bacterial hydrogel is because it is excellent
Good performance, is widely used in biomedical materials field.Wherein, the hydrogel that chemical crosslink reaction is obtained, oversubscription are compared
Nonbonding effect (as hydrogen bond, ionic interaction etc.) that sub- hydrogel can be passed through by the component of low-molecular-weight between molecule obtains
?.So that the preparation process of hydrogel becomes easier to and directly.
Chitin is a kind of polysaccharide mainly obtaining from Crustacean shell, it after deacetylated process, just
Another kind of relatively common cationic polysaccharide shitosan can be obtained.Shitosan is because its good biocompatibility, biology
Degradation property and anti-microbial property and the biomedicine field that is widely used.But because shitosan is insoluble in water so that its reality
Border application is limited by very large.And carboxymethyl chitosan is as a kind of important derivatives of shitosan, because it has greatly
The carboxyl of amount and hydroxyl are more easy to water-soluble chitosan derivatives so that carboxymethyl chitosan becomes a kind of.
It is compared to shitosan, the carboxymethyl chitosan using more preferable water solublity, biocompatibility and degradation property comes
Prepare supramolecular hydrogel and there is bigger advantage.Meanwhile, carboxymethyl chitosan is as a kind of important derivatives of shitosan, it
Anti-microbial property be also highly important property.There are some researches show carboxymethyl chitosan with respect to shitosan anti-microbial property
Improve.Simultaneously as containing substantial amounts of hydroxyl and amino in the molecule of Chitosan-phospholipid complex, easily it is cross-linked to form with absorption
The network structure of ability.Chitosan-phospholipid complex is made to become the important raw and processed materials preparing biologic medical purposes hydrogel.Mesh
Before, the hydrogel material prepared by carboxymethyl chitosan has been widely used in medicine delivery, organizational project and wound dressing
In biologic medical field.
It is to obtain the polymer-modified important method with more premium properties that metallic atom or ion are introduced polymer.
Similarly, there is research to attempt metal ion is incorporated in the network structure of polymer, obtain the more preferable oversubscription of combination property
Sub- hydrogel.In addition, some metal ions have some special performances, such as the broad-spectrum sterilization characteristic of silver ion.By its with
Polymer combination obtains composite and more can meet the needs on biologic medical.
Content of the invention
It is an object of the invention to provide the side of a kind of new antibacterial carboxymethyl chitosan hydrogel and its quick preparation
Method.
The know-why of the present invention
By the use of carboxymethyl chitosan as the polymer moieties preparing hydrogel, under the conditions of suitable pH, and as friendship
There is ion complexation reaction in the transition metal ionss of connection agent part, can extremely be quickly obtained antibacterial carboxymethyl chitosan water-setting
Glue.
For realizing above-mentioned purpose, the technical solution used in the present invention is:
(1) preparation of carboxymethyl chitosan
Shitosan is added stirring a period of time in the sodium hydrate aqueous solution of 20% (weight ratio), be subsequently gradually added chlorine
Acetic acid, continuous stirring reaction 2h under conditions of 40 DEG C.After reaction terminates, with 10% (volume ratio) acetic acid aqueous solution by mixed liquor
PH is adjusted to neutrality, and adds 70% (volume ratio) methanol aqueous solution.Subsequently filter, and fully washed with absolute methanol, finally will
The product obtaining is placed in 55 DEG C of vacuum drying oven 8h is dried and obtains final product carboxymethyl chitosan.
(2) preparation of supramolecular hydrogel
Carboxymethyl chitosan is added in the acetic acid aqueous solution of 1% (volume ratio), makes the carboxymethyl of 1-2% (weight ratio)
Shitosan mixed solution.Add sodium hydrate aqueous solution toward in carboxymethyl chitosan mixed solution again, and sway uniformly.Obtain new
Carboxymethyl chitosan mixed solution, subsequently toward its add transition-containing metal ion solution, just can extremely be quickly obtained network
Close the antibacterial carboxymethyl chitosan hydrogel having transition metal ionss.
The invention has the beneficial effects as follows:
(1) present invention reacts, by ion complexation, the method to prepare antibacterial carboxymethyl chitosan hydrogel, has system
Simply, it is swift in response and the advantages of gel plasticity is high.
(2) present invention preparation antibacterial carboxymethyl chitosan hydrogel gold-coloured staphylococci and escherichia coli are had good
Good inhibition.
(3) carboxymethyl chitosan that Inventive polymers part adopts all is had with the transition metal ionss of cross-linker moiety
Good bactericidal effect, it is achieved thereby that effect of double sterilization.Meanwhile, compare traditional small molecule antibacterial, the present invention carries
Supply a kind of construction method prepared and there is more broad spectrum of activity antimicrobial composite material.
Brief description
The antibacterial carboxylic first of zinc ion, copper ion and three kinds of transition metal ionss complexations of silver ion that Fig. 1 is prepared for the present invention
The design sketch of base aquagel;
Fig. 2 is antibacterial carboxymethyl chitosan hydrogel of the present invention to colibacillary inhibition;
Fig. 3 is the inhibition to gold-coloured staphylococci for the antibacterial carboxymethyl chitosan hydrogel of the present invention.
Specific embodiment
For a better understanding of the present invention, it is further elucidated with present disclosure with reference to embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1:
5g shitosan is added to stirring a period of time in 20% (weight ratio) sodium hydrate aqueous solution.Subsequently it is gradually added
15g monoxone, continuous stirring reaction 2h under conditions of 40 DEG C.After the completion of reaction, with 10% (volume ratio) acetic acid aqueous solution
PH of mixed is adjusted to neutrality, and adds 70% (volume ratio) methanol solution.Subsequently filter, and fully washed with absolute methanol.
The vacuum drying oven finally product obtaining being placed in 55 DEG C is dried 8h and obtains carboxymethyl chitosan.
The carboxymethyl chitosan being obtained is weighed in the acetic acid solution that 2g is added to 1% (volume ratio), obtains carboxymethyl shell
The mixed solution of polysaccharide.Take 600 μ L carboxymethyl chitosan mixed solutions and sodium hydrate aqueous solution (0.1mol/L~0.5mol/
L) mutually mix, obtain new carboxymethyl chitosan mixed solution solution.Subsequently, by zinc nitrate solution (0.1mol/L~0.5mol/
L) it is added thereto, just very can quickly obtain the antibacterial carboxymethyl chitosan hydrogel of complexation zinc ion.Equally, it is separately added into phase
Just complexation respectively can be obtained with the copper chloride solution of concentration, silver nitrate solution has the antibacterial carboxymethyl chitosan of copper ion, silver ion
Sucrose solution gel.
Fig. 2, Fig. 3 are the antibacterial experiment that the antibacterial carboxymethyl chitosan hydrogel prepared is carried out, respectively with escherichia coli, gold
Color staphylococcuses are experimental subject.Wherein CMCh-Zn, CMCh-Cu, CMCh-Ag and CMCh represent respectively complexation have zinc ion,
Copper ion, the carboxymethyl chitosan hydrogel of silver ion and pure carboxymethyl chitosan hydrogel, had in the complexation of preparation
Cross and around the carboxymethyl chitosan hydrogel of metal ion, all occur in that obvious inhibition zone.
Claims (4)
1. a kind of antibacterial carboxymethyl chitosan hydrogel is it is characterised in that preparation method is carried out according to the following steps:
The preparation of (a) carboxymethyl chitosan
Shitosan is added stirring a period of time in the sodium hydrate aqueous solution of 20% (weight ratio), be subsequently gradually added chloroethene
Acid, continuous stirring reaction 2h under conditions of 40 DEG C.After reaction terminates, with 10% (volume ratio) acetic acid aqueous solution by pH of mixed
It is adjusted to neutrality, and add 70% (volume ratio) methanol aqueous solution.Subsequently filter, and fully washed with absolute methanol, finally incite somebody to action
To product be placed in 55 DEG C of vacuum drying oven 8h be dried and obtain final product carboxymethyl chitosan.
The preparation of (b) supramolecular hydrogel
Carboxymethyl chitosan is added in the acetic acid aqueous solution of 1% (volume ratio), makes the carboxymethyl chitosan of 1-2% (weight ratio)
Sugared mixed solution.The sodium hydrate aqueous solution of 0.1mol/L~0.5mol/L is added again toward in carboxymethyl chitosan mixed solution,
And sway uniformly.Obtain new carboxymethyl chitosan mixed solution, subsequently add containing of 0.1mol/L~0.5mol/L toward it
Cross the solution of metal ion, just can extremely be quickly obtained complexation has the antibacterial carboxymethyl chitosan water-setting of transition metal ionss
Glue.
2. according to claim 1 antibacterial carboxymethyl chitosan hydrogel preparation method it is characterised in that:Described carboxymethyl
The molecular weight of shitosan is 1~50,000.
3. according to claim 1 antibacterial carboxymethyl chitosan hydrogel preparation method it is characterised in that:Described transition gold
Genus ion is zinc ion, copper ion and silver ion etc..
4. according to claim 1 antibacterial carboxymethyl chitosan hydrogel preparation method it is characterised in that:Gel process ten
Divide quick, gel time is very short.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610835824.XA CN106380609A (en) | 2016-09-19 | 2016-09-19 | Antibacterial carboxymethyl chitosan hydrogel and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610835824.XA CN106380609A (en) | 2016-09-19 | 2016-09-19 | Antibacterial carboxymethyl chitosan hydrogel and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106380609A true CN106380609A (en) | 2017-02-08 |
Family
ID=57935897
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610835824.XA Pending CN106380609A (en) | 2016-09-19 | 2016-09-19 | Antibacterial carboxymethyl chitosan hydrogel and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106380609A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108384069A (en) * | 2018-03-09 | 2018-08-10 | 广东工业大学 | A kind of metal coordination supramolecule hydrogel and preparation method thereof |
CN108926574A (en) * | 2018-09-20 | 2018-12-04 | 天津科技大学 | A kind of hydridization anti-bacterial hydrogel and preparation method thereof |
CN111743856A (en) * | 2020-06-09 | 2020-10-09 | 华南农业大学 | Triptolide ophthalmic material and preparation method and application thereof |
CN112480434A (en) * | 2020-11-30 | 2021-03-12 | 西安交通大学 | Copper ion antibacterial hydrogel and preparation method and application thereof |
CN114409928A (en) * | 2022-02-07 | 2022-04-29 | 南京易亨制药有限公司 | High-elasticity-modulus polymer hydrogel and preparation method and application thereof |
CN116671516A (en) * | 2023-08-04 | 2023-09-01 | 云南熙乐科技有限公司 | Preparation method of aqueous self-degradation antibacterial spray |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103908693A (en) * | 2014-04-15 | 2014-07-09 | 山东颐诺生物科技有限公司 | Bionic alginate composite antimicrobial dressing and preparation method thereof |
CN105288704A (en) * | 2015-10-19 | 2016-02-03 | 武汉理工大学 | Polyamide-amine dendrimer modified chitosan wound repair hydrogel as well as preparation method and application thereof |
-
2016
- 2016-09-19 CN CN201610835824.XA patent/CN106380609A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103908693A (en) * | 2014-04-15 | 2014-07-09 | 山东颐诺生物科技有限公司 | Bionic alginate composite antimicrobial dressing and preparation method thereof |
CN105288704A (en) * | 2015-10-19 | 2016-02-03 | 武汉理工大学 | Polyamide-amine dendrimer modified chitosan wound repair hydrogel as well as preparation method and application thereof |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108384069A (en) * | 2018-03-09 | 2018-08-10 | 广东工业大学 | A kind of metal coordination supramolecule hydrogel and preparation method thereof |
CN108926574A (en) * | 2018-09-20 | 2018-12-04 | 天津科技大学 | A kind of hydridization anti-bacterial hydrogel and preparation method thereof |
CN111743856A (en) * | 2020-06-09 | 2020-10-09 | 华南农业大学 | Triptolide ophthalmic material and preparation method and application thereof |
CN111743856B (en) * | 2020-06-09 | 2021-07-23 | 华南农业大学 | Triptolide ophthalmic material and preparation method and application thereof |
CN112480434A (en) * | 2020-11-30 | 2021-03-12 | 西安交通大学 | Copper ion antibacterial hydrogel and preparation method and application thereof |
CN114409928A (en) * | 2022-02-07 | 2022-04-29 | 南京易亨制药有限公司 | High-elasticity-modulus polymer hydrogel and preparation method and application thereof |
CN114409928B (en) * | 2022-02-07 | 2024-04-09 | 南京易亨制药有限公司 | Polymer hydrogel with high elastic modulus, preparation method and application thereof |
CN116671516A (en) * | 2023-08-04 | 2023-09-01 | 云南熙乐科技有限公司 | Preparation method of aqueous self-degradation antibacterial spray |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106380609A (en) | Antibacterial carboxymethyl chitosan hydrogel and preparation method thereof | |
Ruiz et al. | Chitosan, chitosan derivatives and their biomedical applications | |
EP3044353B1 (en) | Method of producing a swellable polymer fibre | |
CN101463144B (en) | Preparation method of hydroxypropyl chitosan / oxidized sodium alginate self-crosslinking antibacterial hydrogel material | |
CN105478792B (en) | A kind of environment-friendly preparation method thereof of modification of chitosan nano silver colloidal sol | |
CN102105524A (en) | Three-dimensional nanocomposite materials consisting of a polysaccharidic matrix and metallic nanoparticles, preparation and use thereof | |
CN101463145A (en) | Carboxymethyl chitosan / oxidized sodium alginate self-crosslinking antibacterial hydrogel material | |
CN106866998B (en) | A kind of chitosan quaternary ammonium salt/carboxymethyl cellulose superabsorbent hydrogel and its preparation method and application | |
CN110448722A (en) | A kind of injectable is containing the temperature sensitive composite antibacterial hydrogel material of tannic acid and its preparation and application | |
CN106146913A (en) | A kind of chitosan-based hydrogel and its preparation method and application | |
CN104546717A (en) | Highly-antibacterial chitosan film-forming agent and preparation method thereof | |
CN112426981A (en) | Metal ion crosslinked hydrogel and preparation method and application thereof | |
JP4321007B2 (en) | Polysaccharide complex and method for producing the same | |
CN110064070A (en) | Containing organic quaternary ammonium salt or with silane end organic quaternary ammonium salt anti-bacterial hydrogel and preparation method thereof | |
CN101927030A (en) | Preparation method of biological dressing containing nano silver, zinc and bismuth | |
JP4356289B2 (en) | Polysaccharide complex and method for producing the same | |
JP4846147B2 (en) | Method for producing material coated or impregnated with oxidized polysaccharide material | |
JP5024262B2 (en) | Material and biocompatible material coated or impregnated with oxidized polysaccharide material | |
US9499641B2 (en) | Alginate monomer structure with metal crystallite embedded, alginate salt structure with metal crystallite embedded and method of producing alginate hydrogel with metal crystallite incorporated | |
CN105010393A (en) | Preparation method of copper and zinc combination antiseptic | |
CN107163159B (en) | A kind of halogen-containing chitosan quaternary ammonium salt and its preparation method and application | |
CN101401586A (en) | Simple production method for nano-silver antiseptic solution | |
CN102599190B (en) | Preparation method of hemicelluloses-based antibacterial antioxidant | |
JP2004002586A (en) | Polysaccharide complex and method for producing the same | |
JP5110046B2 (en) | Polysaccharide complex and method for producing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170208 |