CN103304733B - A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel - Google Patents
A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel Download PDFInfo
- Publication number
- CN103304733B CN103304733B CN201310241674.6A CN201310241674A CN103304733B CN 103304733 B CN103304733 B CN 103304733B CN 201310241674 A CN201310241674 A CN 201310241674A CN 103304733 B CN103304733 B CN 103304733B
- Authority
- CN
- China
- Prior art keywords
- preparation
- polymer nano
- nano hydrogel
- responsive polymer
- degradable environment
- 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
Landscapes
- Medicinal Preparation (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to technical field of polymer materials, the preparation of a kind of degradable environment-responsive polymer nano hydrogel and application.The present invention is with N caprolactam as principal monomer, with N, N ' double (acryloyl) cystamine is cross-linking agent, and to introduce the hydrophilic monomers such as methacrylic acid, n-methylolacrylamide, polyethylene glycol monomethyl ethermethacrylic acid esters (Mw=2000) be comonomer, obtained the polymer nano hydrogel of degradable multiple environment-responsive by precipitation polymerization preparation method.Raw material of the present invention is easy to get, and preparation method is simple, with water as solvent, and environmental sound.The polymer nano hydrogel good dispersion prepared, size is homogeneous, has good stability and biocompatibility.By controlling consumption and the pH value of environment of methacrylic acid, N n-methylolacrylamide, polyethylene glycol monomethyl ethermethacrylic acid esters etc., the phase transition temperature of scalable polymer, thus can be applicable to the fixed point release of medicine, as the carrier of drug targeting release.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of environment correspondence for drug controlled release
The preparation method and application of poly-(N-caprolactam) nanogel.
Background technology
Polyalcohol hydrogel be can in water swelling but undissolved tridimensional network system, compared with hydrophobic polymer
Having lot of advantages, the size such as particle is controlled, good colloidal stability and biocompatibility.It addition, polymer water-setting
Glue can adsorb medicine or bioactive molecule, and the material fixed can be made to keep activity, therefore hydrogel for a long time
Have a wide range of applications in fields such as drug controlled release.
In recent years, environment sensitive nano-hydrogel causes as medicine controlled release carrier and pays close attention to widely, and it can sense
The change of external environment information (such as temperature, pH value, ionic strength, reduction potential, light etc.), and make the physicochemical properties of self
Change such that it is able to realize the control release of medicine.Wherein, temperature sensitivity nano-hydrogel has attracted vast research people
Member, because the temperature of cancerous tumours cell is usually above normal cell, temperature sensitive polymer can be achieved with at high temperature
Quickly release anti-cancer medicine, the function of slow Slow release under low temperature, thus efficiently reduce the infringement of agents on normal cells.
The most classical temperature sensitive polymer is NIPA, but limits owing to having certain cytotoxicity
It is as the application of pharmaceutical carrier.In recent years, another kind of temperature sensing polymer poly-(N-caprolactam), it is subject to
The concern of vast research worker.Its good biocompatibility, phase transition temperature is 30 ~ 32 oC, can be by adding other copolymerization list
Body regulates phase transition temperature, therefore can be used as pharmaceutical carrier, it is achieved the control release of medicine.
But, the nano-hydrogel based on poly-(N-caprolactam) of report mostly is nondegradable at present, because of
And the abundant release to medicine cannot be realized.The fall of polymer nano hydrogel can be realized by introducing functional cross-linking agent
Solve.It was discovered by researchers that the concentration of intracellular reducing substances glutathion is about 2-10 mM, much larger than extracellular (2-20 μ
M), this makes the reduction potential difference of intraor extracellular.Based on this point, we introduce a kind of crosslinking containing disulfide bond
Agent N, N '-bis-(acryloyl) cystamine, the polymer nano hydrogel formed by cross-linking agent with it is in cell reducing environment
The disulfide bond of middle inside is reduced into sulfydryl and ruptures, and makes whole polymer network untie the linear polymerization becoming little molecule
Thing, medicine is by fully, discharge rapidly then.
For degradable environment-responsive polymer nano hydrogel, the synthetic method major part of current document report
More complicated, step is many, and how to carry out in organic facies.(oneself is interior for N-vinyl to use aqueous deposited polymerization to prepare degradable poly
Amide) pertinent literature of nano-hydrogel is little, and this preparation method is simple and environmentally-friendly, efficiency is higher, and the particle,colloid prepared
Good stability, good biocompatibility, it is possible to discharge by the response of environment being realized the control of medicine, thus be a kind of preferable
Pharmaceutical carrier.
Summary of the invention
It is an object of the invention to propose a kind of degradable environment-responsive polymer nano hydrogel and preparation side thereof
Method and application.
The degradable environment-responsive polymer nano hydrogel that the present invention proposes, by using precipitation polymerization in aqueous phase
Prepare.Drawing of comonomer methacrylic acid, N hydroxymethyl acrylamide, polyethylene glycol monomethyl ethermethacrylic acid esters etc.
Enter the phase transition temperature being possible not only to change polymer, and make it have pH sensitivity；Equally, poly glycol monomethyl ether methyl
The introducing of acrylate also improves its biocompatibility while changing polymer phase transition temperature.It addition, preparing
Cheng Zhong, introduces the cross-linking agent containing disulfide bond dexterously, makes the polymer nano hydrogel prepared energy in reducing environment
Enough degradable such that it is able to realize the fixed point release of medicine.Its preparation process is as follows:
(1) with water as solvent, by 950 ~ 980mg N-caprolactam, 20 ~ 40 mg methacrylic acids or N-hydroxyl
Methacrylamide, 20 ~ 100 mg sodium lauryl sulphates and 10 ~ 100 mg sodium bicarbonate are dissolved in 100 mL water；
(2) by 20 ~ 200 mg cross-linking agent N, N '-bis-(acryloyl) cystamine is dissolved in 1 ~ 10 mL dimethyl sulfoxide, and turns
Move in the reaction system of step (1) gained；Under mechanical stirring, in nitrogen atmosphere, after reaction temperature is risen to 60 ~ 80 DEG C,
Rapidly join 10 ~ 100 mg potassium peroxydisulfates, after polyreaction 0.25-1 h, add 0 ~ 100 mg poly glycol monomethyl ether methyl-prop
Olefin(e) acid ester, stopped reaction after 4-8 h, nitrogen atmosphere is slowly cooled to room temperature；After reaction terminates, dialysis removes unreacted
Monomer, linear polymer and other impurity, i.e. can get degradable environment-responsive polymer nano hydrogel after lyophilizing.
The most unreacted monomer refers to N-caprolactam, methacrylic acid, N hydroxymethyl acrylamide and polyethyleneglycol first
Ether metacrylic acid ester；Linear polymer is the linear polymer that several monomer copolymerization is formed；Other impurity are dodecyl sulfur
Acid ammonium, sodium bicarbonate and potassium peroxydisulfate etc..
In the present invention, in step (2), mechanical agitation speed is 100 ~ 400 rpm.
In the present invention, Mw=2000 of polyethylene glycol monomethyl ethermethacrylic acid esters.
Utilize the degradable environment-responsive polymer nano hydrogel that preparation method of the present invention obtains as medicine control
The application of the carrier of release.
Raw material of the present invention is easy to get, and preparation method is simple, with water as solvent, and environmental sound.The polymer nano prepared
Rice hydrogel good dispersion, size is homogeneous, has good stability and biocompatibility.By controlling methacrylic acid or N-
N-methylolacrylamide, the phase in version of consumption scalable polymer nano hydrogel of polyethylene glycol monomethyl ethermethacrylic acid esters
Temperature, can be applicable to the fixed point release of medicine, as the carrier of drug targeting release.Due to the introducing containing disulfide bond crosslinking agent
Make polymer nano hydrogel have degradability in reducing environment, thus medicine can fully, discharge rapidly.
Have the multiple environment-responsives such as temperature, reduction, pH due to polymer nano hydrogel, the product that the inventive method obtains is at medicine
Thing controls release field and has great application prospect.
The method preparing degradable environment correspondence polymer nano hydrogel at present both at home and abroad mainly uses reverse microemulsion
Liquid polymerization and active free radical polymerization method, the substantial amounts of organic solvent of the many uses of these methods or surfactant, and step
Rapid many, operation complexity.Comparatively speaking, the invention have the characteristics that:
(1) polymerization uses precipitation polymerization, with water as solvent, harmless to human and environment, makes preparation method become simultaneously
Simple to operation；
(2) the polymer nano hydrogel size prepared by is homogeneous, and good stability has good biocompatibility；
(3) phase transition temperature of polymer nano hydrogel is controlled；
(4) introduce disulfide bond crosslinking agent cleverly, make the polymer nano hydrogel can be complete in cell reducing environment
Degraded, thus discharge medicine quickly, fully, improve the utilization rate of medicine.
Accompanying drawing explanation
Fig. 1, the transmission electron microscope photo (× 2W) of degradable environment-responsive polymer nano hydrogel, background phosphotungstic acid
Dyeing.
Fig. 2, the transmission electron microscope photo (× 5W) of degradable environment-responsive polymer nano hydrogel, background phosphotungstic acid
Dyeing.
Detailed description of the invention
The present invention is further illustrated below by embodiment.
Embodiment 1: by 980 mg N-caprolactams, 20 mg methacrylic acids, 20 mg lauryl sulphate acid
Sodium and 25 mg sodium bicarbonate are dissolved in 100 mL water.Cross-linking agent 40 mg N, N '-bis-(acryloyl) cystamine is dissolved to 2
In mL dimethyl sulfoxide, it is transferred in reaction system after fully dissolving.It is kept stirring for speed 200 rpm and nitrogen atmosphere, will be anti-
After answering temperature to rise to 60 ~ 80 DEG C, rapidly joining potassium peroxydisulfate 25 mg, polyreaction is initiated immediately.Stopped reaction after 6 h,
Room temperature it is slowly cooled in nitrogen atmosphere.After reaction terminates, remove unreacted monomer, linear polymer by the method for dialysis
Deng other impurity, i.e. can get (pH 7.4,0.15 M NaCl) phase transition temperature under physiological condition after lyophilizing is 37.6oC
Degradable environment-responsive polymer nano hydrogel.
Embodiment 2: by 970 mg N-caprolactams, 30 mg methacrylic acids, 20 mg lauryl sulphate acid
Sodium and 25 mg sodium bicarbonate are dissolved in 100 mL water.Cross-linking agent 40 mg N, N '-bis-(acryloyl) cystamine is dissolved to 2
In mL dimethyl sulfoxide, it is transferred in reaction system after fully dissolving.It is kept stirring for speed 200 rpm and nitrogen atmosphere, will be anti-
After answering temperature to rise to 60 ~ 80 DEG C, rapidly joining potassium peroxydisulfate 25 mg, polyreaction is initiated immediately.Stopped reaction after 6 h,
Room temperature it is slowly cooled in nitrogen atmosphere.After reaction terminates, remove unreacted monomer, linear polymer by the method for dialysis
Deng other impurity, i.e. can get (pH 7.4,0.15 M NaCl) phase transition temperature under physiological condition after lyophilizing is 40.0oC
Degradable environment-responsive polymer nano hydrogel.
Embodiment 3: by 960 mg N-caprolactams, 40 mg methacrylic acids, 20 mg lauryl sulphate acid
Sodium and 25 mg sodium bicarbonate are dissolved in 100 mL water.Cross-linking agent 40 mg N, N '-bis-(acryloyl) cystamine is dissolved to 2
In mL dimethyl sulfoxide, it is transferred in reaction system after fully dissolving.It is kept stirring for speed 200 rpm and nitrogen atmosphere, will be anti-
After answering temperature to rise to 60 ~ 80 DEG C, rapidly joining potassium peroxydisulfate 25 mg, polyreaction is initiated immediately.Stopped reaction after 6 h,
Room temperature it is slowly cooled in nitrogen atmosphere.After reaction terminates, remove unreacted monomer, linear polymer by the method for dialysis
Deng other impurity, i.e. can get (pH 7.4,0.15 M NaCl) phase transition temperature under physiological condition after lyophilizing is 44.2oC
Degradable environment-responsive polymer nano hydrogel.
Embodiment 4: by 970 mg N-caprolactams, 30 mg methacrylic acids, 20 mg lauryl sulphate acid
Sodium and 25 mg sodium bicarbonate are dissolved in 100 mL water.Cross-linking agent 40 mg N, N '-bis-(acryloyl) cystamine is dissolved to 2
In mL dimethyl sulfoxide, it is transferred in reaction system after fully dissolving.It is kept stirring for speed 200 rpm and nitrogen atmosphere, will be anti-
After answering temperature to rise to 60 ~ 80 DEG C, rapidly joining potassium peroxydisulfate 25 mg, polyreaction is initiated immediately.After half an hour, add 10
Mg polyethylene glycol monomethyl ethermethacrylic acid esters, stopped reaction after 6 h, nitrogen atmosphere is slowly cooled to room temperature.Reaction
After end, with other impurity such as the method unreacted monomer of removing of dialysis, linear polymers, after lyophilizing, i.e. can get physiology bar
Under part, (pH 7.4,0.15 M NaCl) phase transition temperature is 41.0oThe degradable environment-responsive polymer nanocomposite water-setting of C
Glue.
Embodiment 5: by 970 mg N-caprolactams, 30 mg methacrylic acids, 20 mg lauryl sulphate acid
Sodium and 25 mg sodium bicarbonate are dissolved in 100 mL water.Cross-linking agent 40 mg N, N '-bis-(acryloyl) cystamine is dissolved to 2
In mL dimethyl sulfoxide, it is transferred in reaction system after fully dissolving.It is kept stirring for speed 200 rpm and nitrogen atmosphere, will be anti-
After answering temperature to rise to 60 ~ 80 DEG C, rapidly joining potassium peroxydisulfate 25 mg, polyreaction is initiated immediately.After half an hour, add 30
Mg polyethylene glycol monomethyl ethermethacrylic acid esters, stopped reaction after 6 h, nitrogen atmosphere is slowly cooled to room temperature.Reaction
After end, with other impurity such as the method unreacted monomer of removing of dialysis, linear polymers, after lyophilizing, i.e. can get physiology bar
Under part, (pH 7.4,0.15 M NaCl) phase transition temperature is 43.2oThe degradable environment-responsive polymer nanocomposite water-setting of C
Glue.
Embodiment 6: by 970 mg N-caprolactams, 30 mg methacrylic acids, 20 mg lauryl sulphate acid
Sodium and 25 mg sodium bicarbonate are dissolved in 100 mL water.Cross-linking agent 40 mg N, N '-bis-(acryloyl) cystamine is dissolved to 2
In mL dimethyl sulfoxide, it is transferred in reaction system after fully dissolving.It is kept stirring for speed 200 rpm and nitrogen atmosphere, will be anti-
After answering temperature to rise to 60 ~ 80 DEG C, rapidly joining potassium peroxydisulfate 25 mg, polyreaction is initiated immediately.After half an hour, add 50
Mg polyethylene glycol monomethyl ethermethacrylic acid esters, stopped reaction after 6 h, nitrogen atmosphere is slowly cooled to room temperature.Reaction
After end, with other impurity such as the method unreacted monomer of removing of dialysis, linear polymers, after lyophilizing, i.e. can get physiology bar
Under part, (pH 7.4,0.15 M NaCl) phase transition temperature is 44.5oThe degradable environment-responsive polymer nanocomposite water-setting of C
Glue.
Embodiment 7: by 970 mg N-caprolactams, 30 mg methacrylic acids, 20 mg lauryl sulphate acid
Sodium and 25 mg sodium bicarbonate are dissolved in 100 mL water.Cross-linking agent 40 mg N, N '-bis-(acryloyl) cystamine is dissolved to 2
In mL dimethyl sulfoxide, it is transferred in reaction system after fully dissolving.It is kept stirring for speed 200 rpm and nitrogen atmosphere, will be anti-
After answering temperature to rise to 60 ~ 80 DEG C, rapidly joining potassium peroxydisulfate 25 mg, polyreaction is initiated immediately.After half an hour, add 100
Mg polyethylene glycol monomethyl ethermethacrylic acid esters, stopped reaction after 6 h, nitrogen atmosphere is slowly cooled to room temperature.Reaction
After end, with other impurity such as the method unreacted monomer of removing of dialysis, linear polymers, after lyophilizing, i.e. can get physiology bar
Under part, (pH 7.4,0.15 M NaCl) phase transition temperature is 47.5oThe degradable environment-responsive polymer nanocomposite water-setting of C
Glue.
Embodiment 8: preparation 1mg mL-1Amycin aqueous solution.Take a certain amount of Doxorubicin solution and containing polymer nanocomposite
The dispersion liquid mixing of hydrogel carrier, medicine is 0.3 with the mass ratio of carrier, stirring 12～24h under room temperature, and centrifugation is used
Deionized water is washed 3 times repeatedly, obtains the nano-hydrogel of medicine carrying.The supernatant collected is tested for uv absorption, draws medicine carrying
Rate is 14%, and envelop rate is 62%.
Claims (4)
1. the preparation method of a degradable environment-responsive polymer nano hydrogel, it is characterised in that specifically comprise the following steps that
(1) with water as solvent, by 950 ~ 980mg N-caprolactam, 20 ~ 40 mg methacrylic acids or N-methylol
Acrylamide, 20 ~ 100 mg sodium lauryl sulphates and 10 ~ 100 mg sodium bicarbonate are dissolved in 100 mL water；
(2) by 20 ~ 200 mg cross-linking agent N, N '-bis-(acryloyl) cystamine is dissolved in 1 ~ 10 mL dimethyl sulfoxide, and is transferred to
In the reaction system of step (1) gained；Under mechanical stirring, in nitrogen atmosphere, after reaction temperature is risen to 60 ~ 80 DEG C, quickly
Add 10 ~ 100 mg potassium peroxydisulfates, after polyreaction 0.25-1 h, add 0 ~ 100 mg poly glycol monomethyl ether methacrylic acid
Ester, stopped reaction after 4-8 h, nitrogen atmosphere is slowly cooled to room temperature；After reaction terminates, dialysis removes unreacted list
Body, linear polymer and other impurity, i.e. can get degradable environment-responsive polymer nano hydrogel after lyophilizing.
The preparation method of degradable environment-responsive polymer nano hydrogel the most according to claim 1, its feature exists
In step (2), mechanical agitation speed is 100 ~ 400 rpm.
The preparation method of degradable environment-responsive polymer nano hydrogel the most according to claim 1, its feature exists
Mw=2000 in polyethylene glycol monomethyl ethermethacrylic acid esters.
4. the degradable environment-responsive polymer nano hydrogel that a preparation method as claimed in claim 1 obtains is as medicine
Thing controls the application of the carrier of release.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310241674.6A CN103304733B (en) | 2013-06-19 | 2013-06-19 | A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310241674.6A CN103304733B (en) | 2013-06-19 | 2013-06-19 | A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103304733A CN103304733A (en) | 2013-09-18 |
| CN103304733B true CN103304733B (en) | 2016-09-28 |
Family
ID=49130484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310241674.6A Expired - Fee Related CN103304733B (en) | 2013-06-19 | 2013-06-19 | A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103304733B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061664B (en) * | 2015-09-15 | 2017-03-29 | 云南师范大学 | A kind of pH and temperature dual response polymer and its production and use |
| CN106810636B (en) * | 2016-12-29 | 2019-11-15 | 华中科技大学 | The nanogel and nanogel drug-loading system of tumor microenvironment intelligent response |
| CN106883340B (en) * | 2017-02-28 | 2019-08-06 | 北京科技大学 | A kind of preparation method and applications of triple responsive nano gels |
| CN108794684A (en) * | 2018-06-08 | 2018-11-13 | 上海大学 | Responsive to temperature type siRNA nanogel carriers and preparation method thereof |
| CN110358004A (en) * | 2019-07-08 | 2019-10-22 | 南京信息工程大学 | A kind of Intelligent Composite hydrogel of doped graphene and preparation method thereof |
| CN110407980B (en) * | 2019-08-14 | 2021-12-14 | 中国林业科学研究院林产化学工业研究所 | Preparation method of cellulose high-molecular surfactant-based pH and temperature dual-response type composite hydrogel |
| CN110354282B (en) * | 2019-08-23 | 2021-11-09 | 东华大学 | Manganese dioxide and adriamycin loaded nano hydrogel and preparation and application thereof |
| CN111184917B (en) * | 2020-02-27 | 2021-09-28 | 福州大学 | Temperature-sensitive collagen-based hydrogel loaded with bioactive polypeptide and preparation method thereof |
| CN113419580B (en) * | 2021-06-29 | 2022-06-24 | 武汉理工大学 | Intelligent temperature control device based on passive radiation cooling and solar heating and preparation method thereof |
| CN113745652B (en) * | 2021-08-17 | 2023-04-04 | 华中科技大学 | Polymer electrolyte based on disulfide bond exchange reaction, preparation and application thereof |
| CN113801267A (en) * | 2021-09-24 | 2021-12-17 | 长春工业大学 | Thermosensitive polymer nano-microsphere for profile control and flooding and preparation method thereof |
| CN114805681B (en) * | 2022-03-29 | 2023-04-21 | 中海石油(中国)有限公司 | Degradable methyl styrene copolymer powder, preparation method thereof and high-temperature plugging application |
| CN115894770A (en) * | 2022-11-28 | 2023-04-04 | 广东昊天服装实业有限公司 | Preparation method and application of nanogel composite dyeing antibacterial agent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995078A (en) * | 2006-12-21 | 2007-07-11 | 天津大学 | Redispersable pH-sensitive polymer hydrogel sub-micrometer grain containing acid and alkaline group, and its preparation method |
| CN101555306A (en) * | 2009-05-05 | 2009-10-14 | 苏州大学 | Method for synthesizing hydrogel |
| CN101856508A (en) * | 2010-05-21 | 2010-10-13 | 天津大学 | Novel aquagel tissue filling agent used for ophthalmonogy |
| CN101948556A (en) * | 2010-08-13 | 2011-01-19 | 太原理工大学 | Preparation method of pH-responsive microgel |
| CN102432774A (en) * | 2011-09-01 | 2012-05-02 | 中科院广州化学有限公司 | Biodegradable temperature response hydrogel and preparation method thereof |
| CN102911311A (en) * | 2012-11-06 | 2013-02-06 | 中国科学院长春应用化学研究所 | Copolymer hydrogel and preparation method thereof |
-
2013
- 2013-06-19 CN CN201310241674.6A patent/CN103304733B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995078A (en) * | 2006-12-21 | 2007-07-11 | 天津大学 | Redispersable pH-sensitive polymer hydrogel sub-micrometer grain containing acid and alkaline group, and its preparation method |
| CN101555306A (en) * | 2009-05-05 | 2009-10-14 | 苏州大学 | Method for synthesizing hydrogel |
| CN101856508A (en) * | 2010-05-21 | 2010-10-13 | 天津大学 | Novel aquagel tissue filling agent used for ophthalmonogy |
| CN101948556A (en) * | 2010-08-13 | 2011-01-19 | 太原理工大学 | Preparation method of pH-responsive microgel |
| CN102432774A (en) * | 2011-09-01 | 2012-05-02 | 中科院广州化学有限公司 | Biodegradable temperature response hydrogel and preparation method thereof |
| CN102911311A (en) * | 2012-11-06 | 2013-02-06 | 中国科学院长春应用化学研究所 | Copolymer hydrogel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 双重响应N-乙烯基己内酰胺、甲基丙烯酸共聚微凝胶的研究;程祥胜等;《青岛大学学报（工程技术版）》;20100331;第25卷(第1期);第61页，1.2微凝胶合成，2.1微凝胶的合成与结构表征 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103304733A (en) | 2013-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103304733B (en) | A kind of preparation method and application of degradable environment-responsive polymer nano hydrogel | |
| Liu et al. | Homogeneous and real super tough multi-bond network hydrogels created through a controllable metal ion permeation strategy | |
| CN103408683B (en) | The preparation method of the photothermal response hydrogel that a kind of physical/chemical is cross-linked | |
| CN100393760C (en) | Nanometer aquogel with both pH and temperature sensitivity and its prepn process | |
| CN100575376C (en) | A kind of magnetic temperature sensing nano-particle and synthetic method thereof with biocompatibility | |
| Fan et al. | Erythrocytes load of low molecular weight chitosan nanoparticles as a potential vascular drug delivery system | |
| CN104592702B (en) | Organic matter capable of self-healing/inorganic nano particle hybridization material and preparation method thereof | |
| Zhao et al. | Synthesis of surfactant-free hydroxypropyl methylcellulose nanogels for controlled release of insulin | |
| Deng et al. | Stimuli-responsive nanocellulose hydrogels: an overview | |
| CN104974305B (en) | The preparation method of tumor microenvironment sensitivity polysaccharide-based nano-particle | |
| CN103756020B (en) | A kind of preparation method with the nano-composite supramolecular hydrogel of photosensitivity | |
| Cui et al. | Near-infrared absorbing amphiphilic semiconducting polymers for photoacoustic imaging | |
| Fan et al. | Animal-derived natural products review: focus on novel modifications and applications | |
| Le et al. | Upper critical solution temperature polymeric drug carriers | |
| Fan et al. | Advances in synthesis and applications of self-healing hydrogels | |
| CN102161729A (en) | Preparation method of water-soluble polysaccharide/hydrophobic monomer formed nanoparticles | |
| CN102492250A (en) | Temperature-sensitive polymer/gold nanoparticle hybrid microspheres and preparation method thereof | |
| Ji et al. | Hybridization of graphene oxide into nanogels to acquire higher photothermal effects for therapeutic delivery | |
| CN103333295B (en) | Preparation method of thymopentin molecularly-imprinted magnetic microspheres | |
| CN102875978A (en) | Preparation method of gold nanoparticle/poly(3,4-dioxyethyl)thiophene (PEDOT) composite material | |
| CN102516562B (en) | Method for preparing gel by using magnetic hybrid microspheres as cross-link points | |
| Medeiros et al. | Biocompatible and multi-responsive poly (N-vinylcaprolactam)-based microgels: The role of acidic comonomers in the colloidal properties and phase transition as a function of temperature and pH | |
| CN101962463B (en) | Preparation method of hydrolysis-free biodegradable acrylic polymer nano hydrogel | |
| CN102718976B (en) | Preparation method of in-situ induced hyaluronic acid micelle | |
| CN108003266A (en) | A kind of quadruple stimuli responsive polyaminoacid nanogel and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160928 Termination date: 20190619 |