CN102766267B - Preparation method of chitosan hydrogel containing magnetic nanoparticle - Google Patents
Preparation method of chitosan hydrogel containing magnetic nanoparticle Download PDFInfo
- Publication number
- CN102766267B CN102766267B CN201210255353.7A CN201210255353A CN102766267B CN 102766267 B CN102766267 B CN 102766267B CN 201210255353 A CN201210255353 A CN 201210255353A CN 102766267 B CN102766267 B CN 102766267B
- Authority
- CN
- China
- Prior art keywords
- particle
- chitosan
- magnetic nanoparticle
- containing magnetic
- hydrogel containing
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a preparation method of chitosan hydrogel containing magnetic nanoparticle, which comprises the following steps of: (1) dissolving the chitosan powder in 0.5%-5% of acetic acid solution, mechanically stirring until clarification; taking 5-10ml of the mixture obtained in the step (1), adding 200ul-1000ul of magnetic nanoparticle dispersion with the iron content of 1.2g/ml-1.4g/ml, then adding 200ul-1000ul of crosslinking agent, reacting at room temperature for 2h-36h, and conducting Schiff reaction to produce the chitosan hydrogel containing magnetic nanoparticle. The magnetic nanoparticle is polyacrylic acid coated iron oxide nanoparticle. The crosslinking agent is glutaraldehyde or a mixture of polyethylene glycol and formaldehyde. The chitosan hydrogel containing magnetic nanoparticle is brown, transparent and has no significant precipitation and reunion internal, can be used as an auxiliary pressure material for masks used in the burn treatment, so as to enable the mask better fit the face of people and further strengthen the effect of pressure treatment.
Description
Technical field
The present invention relates to the gel technology of preparing of chitosan and derivative thereof, and the technology of preparing that contains the chitosan of magnetic nano-particle and the plural gel of derivative thereof.
Background technology
Chitosan (chitosan) is that the chitin (chitin) extensively being existed by nature obtains through deacetylation, and chemical name is Chitosan (1-4)-2-amino-B-D glucose, and molecular formula is as follows:
It is tasteless, odorless, nontoxicity.In chitosan macromole, there are active hydroxyl and amino; they have stronger chemical reaction ability; under given conditions; the chemical reactions such as chitosan can be hydrolyzed, alkylation, acylations, carboxymethylation, sulfonation, nitrated, halogenation, oxidation, reduction, condensation and complexing; can generate the various chitosan derivatives with different performance, and there is good water-retentivity and chemical stability.By the anti-microbial activity of research chitosan and derivative thereof, oxidation-resistance, ionogen adsorptive power, is applied to the fields such as life and medical science.Especially at medical field, chitosan and derivative thereof are widely used as microcosmic medical material, as being used as medicament sustained-release matrix, hemostatic agent, base mateiral of artificial tissue and organ etc.
Glutaraldehyde (GA), molecular formula is
on monomer whose, with 2 aldehyde radicals, act on thin base, hydroxyl, carboxyl and the amino of tropina, can make it alkylation, cause that protein coagulating causes bacterium death to play the killing action to microorganism.Therefore, glutaraldehyde, as high effect disinfectants, is widely used in sterilizing and sterilization, has the feature of wide spectrum, efficient, low toxicity.Although it has certain pungency to organism, under working concentration, pungency is little, corrodibility is low, can think safety and low toxicity.Also be the good linking agent of chemical crosslink reaction.But, little to metal protection, be subject to the features such as organic substance influence is little, good stability.
Polyoxyethylene glycol has another name called polymkeric substance, the polyoxyethylene (PEO-LS) of α-hydrogen-ω-hydroxyl (oxygen-1,2-second two bases).Molecular-weight average in the general name of approximately 200 at least 6000 ethylene glycol superpolymer.Along with the difference of molecular-weight average, character is also variant.No color or smell thick liquid is to waxy solid.Water-soluble, ethanol and many other organic solvents.Steam forces down.To thermally-stabilised.Inoperative with many chemical, be not hydrolyzed, never degenerate.Nontoxic, to eyes and skin without obvious stimulation.
Formaldehyde is a kind of colourless, has the gas of intense stimulus type smell.Soluble in water, alcohol and ether.Formaldehyde is gaseous state at normal temperatures, conventionally with aqueous solution form, occurs.Soluble in water and ethanol, 35～40% formalin is called formalin.Formaldehyde is a kind of important organic raw material, is mainly used in plastics industry, synthon, leather industry, medicine, dyestuff etc.
Magnetic nano-particle is that nanoparticle is by number atom or molecular former subgroup or molecular group seldom, the size of its particle is between 1-100nm, the feature that nanoparticle is different from body construction is: nanoparticle has shell structure, because the upper layer of particle accounts for significant proportion, and surface atom is both without long-range order, again without the noncrystalline layer of short-range order, can think that the virtual condition of particle surface layer more approaches gaseous state, and in the heart portion of particle, there is the atom that the complete crystallization cycle arranges, but its structure is slightly different from body sample, the structure of this specific type of nanoparticle has caused it to have the effect of four aspects: surface effects, volume effect, quantum size effect and macro quanta tunnel effect, and produce thus many special propertys: unusual mechanics, electricity, magnetics, calorifics, optics and chemically reactive etc.Because magnetic nano-particle has its special paramagnetic characteristic, thereby have broad application prospects at aspects such as giant magnetoresistance, magnetic liquid and magnetic recording, soft magnetism, permanent magnetism, magnetic cooling, giant magnetoimpedance material and magnetic-optic devices, magnetic detectors.
Hydrogel is to take water as dispersion medium, containing the crosslink polymer network structure of hydrophilic radical and hydrophobic group.As the high water-keeping material of a kind of high water suction, hydrogel is widely used in the facial mask in multiple fields makeup, defervescence plaster used, pain easing plaster, and the preservation agent in foodstuffs industry, thickening material, pharmaceutical carrier in medical treatment etc.
In burn treatment, patient's shaping and postoperative rehabilitation problem are the keys in therapeutic process.In the process of rehabilitation and scar treatment, be widely used stretch fabric and plastic mask, with pressure therapy, treat.Because people's shape of face looks are complicated, height differs, even if take pressure therapy can not obtain desirable result.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of chitosan derivatives hydrogel containing magnetic nano-particle.
Another object of the present invention is to provide a kind of preparation method of the chitosan derivatives hydrogel containing magnetic nano-particle.
To achieve these goals, technical scheme provided by the invention is as follows:
A preparation method who contains the aquagel of magnetic nano-particle, comprises the following steps:
(1), chitosan powder is dissolved in the acetic acid solution of 0.5%-5%, mechanical stirring until clarification be mixed with 0.002%-1%(and be 0.002-1g chitosan and be dissolved in the chitosan solution that 100m l acetum forms) chitosan solution, standby.
(2), get the mixed solution 5-10mL of step (1), adding iron level is 1.2g/ml-1.4g/ml magnetic nano-particle dispersion liquid 200 μ L-1500 μ L;
(3), add linking agent 200uL-1000uL, under room temperature, react 2h-36h, there is schiff reaction, generate the aquagel containing magnetic nano-particle;
Described magnetic nano-particle is the coated ferriferrous oxide nano-particle of polyacrylic acid, and median size is 10nm-20nm;
Described linking agent is the glutaraldehyde of 1wt%-25wt% or the mixed solution of polyoxyethylene glycol 0.05g-0.6g and formaldehyde (36wt%-40wt% stoste).Molecular weight polyethylene glycol Mw is respectively 10K and 20K.
Principle explanation: the amino that contains positively charged on the molecular chain of chitosan, and a large amount of electronegative carboxyls are contained on the coated ferriferrous oxide nano-particle surface of polyacrylic acid, there is electrostatic adhesion in both, then add linking agent glutaraldehyde and chitosan and schiff reaction occurs, the crosslinked hydrogel that contains nanoparticle that directly obtains; Or first add formaldehyde and chitosan generation schiff reaction, form two keys of C=N, and then add polyoxyethylene glycol and gained Schiff's base generation addition reaction, obtain the aquagel containing nanoparticle, be brown, transparent, inner without obvious sediment and reunion.
Chitosan can directly react and make hydrogel with the mixed solution of polyoxyethylene glycol with linking agent glutaraldehyde or formaldehyde, but owing to adopting acetic acid to make solvent, product is with certain yellow, and character is similar to silica gel, and degree of crosslinking is larger, and its shearing modulus is higher, but frangible.
Accompanying drawing explanation
The Electronic Speculum figure of the aquagel containing magnetic nano-particle that Fig. 1 embodiment 1 obtains.Chitosan gel rubber after freeze-drying is vesicular.
The Electronic Speculum figure of the aquagel containing magnetic nano-particle that Fig. 2 embodiment 3 obtains.Under the scale of 100 μ m, observe equally, compare with embodiment 1, along with the increase of glutaraldehyde usage quantity, degree of crosslinking increases, and the freeze-drying structure porosity of chitosan gel rubber increases.
Embodiment
The coated ferriferrous oxide nano-particle of polyacrylic acid is purchased from Beijing Deco Dao Jin Science and Technology Ltd. (median size is 10nm-20nm); Chitosan purchased from traditional Chinese medicines group (1, deacetylation is 80%-95%, molecular weight 590K-600K; 2, deacetylation >95%, molecular weight 280K-310K).
Embodiment 1
A kind of preparation method of the aquagel containing magnetic nano-particle:
(1), 0.29g chitosan powder is dissolved in the acetic acid solution of 30mL 1%, after mechanical stirring 3h, to clarification, standing 3h removes bubble afterwards.And filter;
(2), in the resulting mixed solution of step (1), add 500 μ L containing Fe
3o
4the dispersion liquid of nanoparticle (median size is 10nm-14nm) (iron level is 1.285mg/mL), then shake 1h;
(3), the resulting mixed solution of step (2) is placed in to 40 ℃ of water-baths, dropwise drips wherein 1% glutaraldehyde solution totally 500 μ L, and impose mechanical stirring or concussion 3h, can obtain brown transparent aquagel.
Embodiment 2
Difference from Example 1 is the deacetylation >95% of the chitosan powder that uses in step 1.
Embodiment 3
Difference from Example 1 is that step 3 drips 25% glutaraldehyde solution totally 200 μ L, and imposes machinery concussion 10min, can obtain the transparent aquagel of brownish black.
Adopt the aquagel of the embodiment of the present invention 3 preparations as the aux. pressure material in burn treatment mask, according to the requirement of rehabilitation, generally scar place is at least needed to keep 18mm mercury column, it is the stress of 2400Pa, the chitosan gel rubber that embodiment 3 obtains glutaraldehyde cross-linking provides material as stress, the pressure that can load more than 2500Pa, if further improve degree of crosslinking, load still can continue to rise.Can make the mask people's face of more fitting, play the effect of further reinforcement pressure therapy.Adding of magnetic nano-particle, can play the effect of strengthening gel mechanical property, simultaneously also can the initiation of outside magnetic field under, there is local segregation, play the effect of controlled local enhancement.Finally, according to the pressurized deformed state of hydrogel, feed back the manufacture in facial mould.
Embodiment 4
Difference from Example 1 is that step 2 adds 1000 μ L containing Fe
3o
4magnetic nano-particle; Obtain the transparent aquagel of brownish black.
Embodiment 5
Difference from Example 1 is that step 2 adds 1500L to add containing Fe
3o
4the aqueous solution of magnetic nano-particle, the transparent aquagel of acquisition brownish black, now compares and embodiment 3, brown darker, but without reuniting or precipitation.
Embodiment 6
Difference from Example 4 is, in step 3, adding molecular-weight average is polyoxyethylene glycol (PEG) 0.2g of 10k, machinery concussion 1h is above to nothing precipitation, then adds the formaldehyde reference liquid (36wt%-40wt%) of 0.3mL, can obtain brown, transparent chitosan composite aquogel.
Embodiment 7
Difference from Example 6 is in step 3, adds the polyoxyethylene glycol M of 0.4g
n=20K, the transparent aquagel of acquisition brownish black.
Embodiment material that 8-10 adopts is as shown in table 1:
Table 1
Claims (1)
1. contain a preparation method for the aquagel of magnetic nano-particle, comprise the following steps:
(1), chitosan powder is dissolved in the acetic acid solution of 0.5%-5%, mechanical stirring until clarification;
?(2), get the mixed solution 5-10mL of step (1), adding iron level is 1.2g/ml-1.4g/ml magnetic nano-particle dispersion liquid 200 μ L-1500 μ L; Magnetic nano-particle is the coated ferriferrous oxide nano-particle of polyacrylic acid
(3), add linking agent 200 μ L-1000 μ L, under room temperature, react 2h-36h, schiff reaction occurs, generate the aquagel containing magnetic nano-particle, the glutaraldehyde that linking agent is 1wt%-25wt% or linking agent are the mixed solution of polyoxyethylene glycol 0.05g-0.6g and formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210255353.7A CN102766267B (en) | 2012-07-23 | 2012-07-23 | Preparation method of chitosan hydrogel containing magnetic nanoparticle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210255353.7A CN102766267B (en) | 2012-07-23 | 2012-07-23 | Preparation method of chitosan hydrogel containing magnetic nanoparticle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102766267A CN102766267A (en) | 2012-11-07 |
| CN102766267B true CN102766267B (en) | 2014-03-05 |
Family
ID=47093870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210255353.7A Expired - Fee Related CN102766267B (en) | 2012-07-23 | 2012-07-23 | Preparation method of chitosan hydrogel containing magnetic nanoparticle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102766267B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646902B (en) * | 2016-04-01 | 2018-11-09 | 江苏大学 | A kind of preparation method of iron-chitosan-metal supermolecular gel |
| CN108060158A (en) * | 2018-02-10 | 2018-05-22 | 成都理工大学 | A kind of chitosan magnetic carries the preparation method of denitrifying bacteria bead |
| CN108992702A (en) * | 2018-06-26 | 2018-12-14 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of porous nano oxide modifying chitosan medical aerogel dressing |
| CN109895131B (en) * | 2019-03-27 | 2022-06-21 | 江苏大学 | Magnetic control software grabbing robot based on magnetic programming temperature-sensitive hydrogel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803275A (en) * | 2005-12-06 | 2006-07-19 | 青岛科技大学 | Novel silica gel loaded cross-linked chitosan adsorbent for heavy metal |
| CN101882496A (en) * | 2009-05-04 | 2010-11-10 | 杨琥 | Chitosan-polyacrylamide magnetic composite microsphere material, preparation method and application thereof |
| CN101892217A (en) * | 2010-06-02 | 2010-11-24 | 中国水产科学研究院黄海水产研究所 | Preparation method of magnetic chitosan compound microsphere immobilized marine alkaline proteinase |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050064045A1 (en) * | 2003-09-18 | 2005-03-24 | Sheng-Ping Zhong | Injectable therapeutic formulations |
-
2012
- 2012-07-23 CN CN201210255353.7A patent/CN102766267B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803275A (en) * | 2005-12-06 | 2006-07-19 | 青岛科技大学 | Novel silica gel loaded cross-linked chitosan adsorbent for heavy metal |
| CN101882496A (en) * | 2009-05-04 | 2010-11-10 | 杨琥 | Chitosan-polyacrylamide magnetic composite microsphere material, preparation method and application thereof |
| CN101892217A (en) * | 2010-06-02 | 2010-11-24 | 中国水产科学研究院黄海水产研究所 | Preparation method of magnetic chitosan compound microsphere immobilized marine alkaline proteinase |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102766267A (en) | 2012-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | Advances in hydrogels based on dynamic covalent bonding and prospects for its biomedical application | |
| Geng et al. | Recent advances in carboxymethyl chitosan-based materials for biomedical applications | |
| Qu et al. | Degradable conductive injectable hydrogels as novel antibacterial, anti-oxidant wound dressings for wound healing | |
| Anirudhan et al. | Fabrication of a bioadhesive transdermal device from chitosan and hyaluronic acid for the controlled release of lidocaine | |
| KR101557973B1 (en) | Polymer Nano Particle Containing UV Blocking Material and Method for Preparing the Same | |
| CN102766267B (en) | Preparation method of chitosan hydrogel containing magnetic nanoparticle | |
| PL191316B1 (en) | Therapeutic chemical compound and application thereof in production of a locally administered barrier preparation, an uv radiation absorbing preparation or an antiviral antimycotic or anti-inflammatory | |
| ES2361459A1 (en) | Chitosan gel for dermatological use, production method therefor and use of same | |
| CN108158995A (en) | A kind of gynaecology's anti-bacteria foaming agent containing chitosan and preparation method thereof | |
| CN110101653A (en) | A kind of nasal cavity situ-gel composition, Its Preparation Method And Use | |
| CN115444815B (en) | PH response type antibacterial slow-release gel and preparation method thereof | |
| CN103083472A (en) | Nano silver anti-inflammatory gel for treating gynecologic inflammation and preparation method thereof | |
| KR20150128481A (en) | Composition for application of skin comprising of extracellular matrix and thermo sensitive macromolecule | |
| CN106821963A (en) | A kind of method of utilization cellulose base temperature and the load of pH sensitive hydrogels and slow releasing pharmaceutical | |
| Aljabali et al. | Nanocelluloses as a novel vehicle for controlled drug delivery | |
| Jafari et al. | pH-sensitive biocompatible chitosan/sepiolite-based cross-linked citric acid magnetic nanocarrier for efficient sunitinib release | |
| Su et al. | A hydrogel dressing with tunable critical temperature and photothermal modulating melittin release for multiply antibacterial treatment | |
| Ali et al. | NIR-responsive carboxymethyl-cellulose hydrogels containing thioketal-linkages for on-demand drug delivery system | |
| Li et al. | A pH-Sensitive and mitochondria-modulating intelligent multilayered dressing system for a comprehensive therapeutic strategy of diabetic wounds | |
| Tamara Perchyonok et al. | Alternative chitosan based drug delivery system to fight oral mucositis: Synergy of conventional and bioactives towards the optimal solution | |
| KR20140080467A (en) | Polymer Nano Particle Containing UV Blocking Material and Method of Preparing the Same | |
| CN109662942A (en) | A kind of antibacterial temperature sensitive type gel preparation and preparation method thereof | |
| JPH0525863B2 (en) | ||
| CN113788878A (en) | Self-assembled short peptide, and application thereof in broad-spectrum vaccine and biomedicine | |
| Sosedova et al. | Synthesis of chalcogen-containing nanocomposites of selenium and tellurium with arabinogalactan and a study of their toxic and antimicrobial properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140305 Termination date: 20160723 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |