CN105646902A - Preparation method of iron-chitosan metal supermolecular gel - Google Patents
Preparation method of iron-chitosan metal supermolecular gel Download PDFInfo
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- CN105646902A CN105646902A CN201610202316.8A CN201610202316A CN105646902A CN 105646902 A CN105646902 A CN 105646902A CN 201610202316 A CN201610202316 A CN 201610202316A CN 105646902 A CN105646902 A CN 105646902A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/26—Iron; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
Abstract
The invention relates to a preparation method of iron-chitosan metal supermolecular gel and belongs to the field of biological functional material preparation. The method includes: preparing a chitosan solution; adding a ferric nitrate solution into the chitosan solution, mixing to form a stable iron-chitosan coordination compound, adding a NaOH solution under severe oscillation, and standing for 24 hours to allow coordination effect of the metal supermolecules to be brought into full play so as to obtain the stable and uniform iron-chitosan metal supermolecular gel. The iron-chitosan metal supermolecular gel prepared by the method has a self-healing function, is excellent in pH responsiveness and capable of sustainably releasing iron-chitosan coordination compounds, and can be hopefully used as an iron supplement agent to increase the effect of the iron supplement agent.
Description
Technical field
The invention belongs to Biofunctional materials preparation field, the preparation method relating to a kind of ferrum-chitosan-metal supermolecular gel, particularly relate to a kind of preparation method utilizing iron ion and metal-supermolecular mechanism formation ferrum-chitosan gel rubber of chitosan.
Background technology
Metal-supramolecular chemistry is based on a kind of non-covalent interaction of metal ligand, and it is prevalent in nature biotechnology body and sets up the molecular structure of complexity and participate in the self assembly of many natural materials. The non-covalent bond effect of the dynamic reversible of this uniqueness gives the structural complexity that metal supermolecular material is excellent, advanced functional and extension on molecule and inorganic level integrated application. Chitosan, as a big constituent of organic polysaccharide, has the biocompatibility of excellence, biological degradability, antibacterial activity and haemostatic properties, is a kind of natural biocompatible polymer material, and has been widely recognized and apply. Grandson et al. reports, transition metal ions is Ag such as+��Cu2+��Co2+��Ni2+��Zn2+��Cd2+��Pd2+Have been demonstrated to form hydrogel (MoldableSupramolecularHydrogelsCross-LinkedbyUltrafastCo mplexationofMetalIonsandBiopolymers (the plastic supramolecular hydrogel of multiple stimulation response is prepared in metal ion and the ultrafast complexation of biomacromolecule) with chitosan by metal supermolecular effect, Angew.Chem.Int.Ed.Engl.2015,54,7944.). The external influence factor such as pH and metal ion is had response not seen before by this metal supermolecular material; But, grandson et al. this strategy provided is for the Fe of the core as hemoglobin3+It is infeasible.
This Metal-coordinated supramolecules being made up of chitosan-ferrum has application prospect well, it is possible to substituting other polysaccharide chalybeates and be used as clinical iron supplement medicine, the metal supermolecular structure therefore preparing such chitosan-ferrum seems very necessary. It is likely due to the solubility product constant (K of hydrated ferric oxide.SP) cause that iron ion begins to when relatively low pH form precipitation, thus upsetting metal-supermolecule coordination, cause that this chitosan-ferrum supramolecular materials cannot be formed. K according to hydrated ferric oxide.SPIron ion is start precipitation at pH=1.87, pH value needed for ferrum-chitosan-metal supermolecular mechanism, thus under the experimental program that grandson et al. provides, always produce floccule and imperfect in other metal supermolecular effects similar under the hydrogel that produces.
At this, the present invention proposes a breakthrough ferrum-chitosan supermolecular gel and prepares the scheme of bottleneck, it is intended to pass through Fe3+The flocculent deposit of generation in metal-supermolecular mechanism process is avoided with the pre-complexation of chitosan in situ.Causing Fe3+Start before by simply changing Fe with chitosan supramolecular chemistry3+, the addition sequence of chitosan and sodium hydroxide, it is allowed to this metal-supramolecular chemistry effectively carries out. The amino Partial protons of chitosan molecule chain is made to strengthen its water solublity to prepare chitosan solution by acetate dissolution method, then with the chelate of the blended formation ferrum of ferric ion solutions and chitosan. Can spontaneously avoid under the precondition of its sequestering properties owing to pH raises the precipitation caused, and the metal supermolecular coordination ability repaired between metal ion and chitosan forms supermolecular gel in a more effective manner. Subsequently, after adding NaOH deprotonation, Fe3+Can with adjacent group such as-NH2,-OH, the coordination chelating further such as-NH-C=O forms the polyalcohol hydrogel of crosslinking. This deprotonation process acts preferentially on chitosan molecule chain, and along with iron ion with the coordination closing on group thus formed pass through supramolecular complex. Such as document AMagneticStudyofanFe-ChitosanComplexandItsRelevancetoOth erBiomolecules (magnetic of ferrum-chitosan coordination compound and the Study on Similarity with other biological macromole thereof), Biomacromolecules, 2000,1, described in 413-417, iron ion can carry out with five or hexa-coordinate mode with closing on group. This metal supermolecular hydrogel has a self-healing performance, and pH has the response of excellence can realize the sustainability to ferrum-chitosan complex discharge.
Summary of the invention
For Shortcomings in prior art, the preparation method that the invention provides a kind of ferrum-chitosan gel rubber, particular by Fe3+With chitosan by the pre-complexation of original position thus avoiding the generation hydroxide preparation method to form chitosan-ferrum supramolecular hydrogel in metal-supermolecular mechanism process. Chitosan prepared by the present invention-molten iron gel has self-healing performance and pH response, it is possible to the slow release iron ion when stomach pH, and is expected to improve the action effect of iron supplementary.
The present invention realizes above-mentioned technical purpose by techniques below means:
The preparation method of a kind of ferrum-chitosan gel rubber, described method is based on metal-supermolecular mechanism, comprises the steps:
S1. the preparation of chitosan solution:
Dissolve the chitosan in and acetum is formed stable homogeneous and has the chitosan solution of certain viscosity;
The mass concentration of the wherein said chitosan solution obtained is 1%-4%; The mass concentration of described acetum is 1%.
S2. the preparation of ferrum-chitosan gel rubber:
Ferrum-chitosan the coordination compound stable with the blended formation of chitosan solution in advance by iron nitrate aqueous solution, NaOH solution is added subsequently under acutely concussion, stand 24 hours, allow its metal supermolecular coordination fully act on obtaining the ferrum-chitosan supermolecular gel of stable uniform; Adding NaOH solution deprotonation, hydroxide ion has precedence over hydrion reaction, thus avoiding iron ion to generate precipitation when this pH, destroys the metal-supermolecular mechanism between iron ion and chitosan; It is noted here that: must shake rapidly and acutely to ensure that hydroxide ion fully mixes rapidly with chitosan molecule when adding NaOH solution.
Wherein, described iron nitrate aqueous solution concentration is 0.5��0.9mol/L;
The concentration of described sodium hydroxide (NaOH) solution is 0.4��0.8mol/L.
The volume ratio of described iron nitrate aqueous solution and chitosan solution is 1:8;
The addition of NaOH solution and the volume ratio of chitosan solution are 1-3:8.
The program is intended to cause Fe3+Start before by simply changing Fe with chitosan supramolecular chemistry3+, the addition sequence of chitosan and sodium hydroxide, it is allowed to this metal-supramolecular chemistry effectively carries out. It is said that in general, cause that the amine groups of Partial protons strengthens the solubility chitosan solution with preparation of chitosan molecule by acetate dissolution method, the coordination between chitosan and metal ion is utilized to promote the formation of ferrum-Chitosan Chelate. Under the precondition of its sequestering properties, Fe can be spontaneously avoided in the formation of this chelate3+Precipitation, and effectively facilitate the metal supermolecular effect between iron ion and chitosan molecule chain. Subsequently, after adding NaOH deprotonation, Fe3+Can with adjacent group such as-NH2,-OH, the coordination chelating further such as-NH-C=O forms the polyalcohol hydrogel of crosslinking.
Beneficial effects of the present invention:
(1) method that the present invention adopts utilizes metal-supermolecular mechanism successfully to prepare complete ferrum-chitosan supermolecular gel first, compared with traditional method, preparation process is simple and avoids the glutaraldehyde using biological murder by poisoning as cross-linking agent so that ferrum-chitosan supermolecular gel has application prospect better;
(2) method that the present invention adopts can be prevented effectively from iron ion and produce precipitation at low ph conditions, is conducive to carrying out in order of metal-supermolecular mechanism between iron ion and chitosan molecule, and copper ion etc. is equally possible by this method;
(3) ferrum of the present invention-chitosan supermolecular gel has self-healing performance, can effectively expand its application;
(4) ferrum of the present invention-chitosan supermolecular gel has pH response, it is possible to dissociate formation ferrum-chitosan coordination compound in acid condition;
(5) ferrum of the present invention-chitosan supermolecular gel can when gastric acid sustainability Iron Release-chitosan complex, perhaps can as a kind of excellent iron supplementary, have excellence biologic applications prospect.
Accompanying drawing explanation
Fig. 1 is the macrograph of ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel, wherein, A be scalpel cutting before macrograph; B is the macrograph after being cut by scalpel.
Fig. 2 is flow chart prepared by ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel; Wherein A, B, C, D respectively chitosan (A), the chitosan (B) after dissolving, and the chitosan (C) after iron ion chelating, and the schematic diagram of the ferrum ultimately formed-chitosan supermolecular gel (D).
Fig. 3 is the XRD figure of ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel (CS-Fegel), chitosan (CS) and ferrum-chitosan complex (CS-Fe).
The Raman that Fig. 4 is ferrum-chitosan supermolecular gel (c) described in the embodiment of the present invention 1, chitosan (a) and ferrum-chitosan complex (b) schemes.
The FTIR that Fig. 5 is ferrum-chitosan supermolecular gel (c) described in the embodiment of the present invention 1, chitosan (a) and ferrum-chitosan complex (b) schemes.
Fig. 6 is cutting drawing and the self-healing performance table view thereof of ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel.
Fig. 7 is ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel design sketch of slow release ferrum-chitosan complex when simulating gastric acid.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Ferrum described in technique scheme-chitosan supermolecular gel self-healing performance and pH response embodiment particularly as follows:
(1) self-healing
Take a block ferrum-chitosan supermolecular gel and be positioned on culture dish, this supermolecular gel cut into two pieces and against putting together from centre with scalpel subsequently, after 24h, observe its self-healing performance (being again fused into a piece with two clotting glue to be preferred).
(2) pH response behavioral study:
The bag filter that ferrum-chitosan supermolecular gel molecular cut off is 3000 is installed in the buffer solution being placed in different pH value, shoot photo every 2h, observe its Behavioral change under condition of different pH.
Embodiment 1:
1, the preparation of ferrum-chitosan supermolecular gel:
(1) preparation of chitosan solution:
1g acetic acid is added water and is settled to 100mL, be dissolved in above-mentioned solution by 1g chitosan subsequently to be sufficiently stirred for and stand overnight stand-by.
(2) preparation of ferrum-chitosan supermolecular gel:
Fully mix to ensure that iron ion and the abundant coordination of chitosan molecule form coordination compound under acutely concussion by the iron nitrate aqueous solution of 100 �� L0.5M and 800 �� L chitosan solutions, under acutely concussion, be rapidly added the sodium hydroxide solution of 100 �� L0.4M subsequently to realize the deprotonation to chitosan molecule and to cause the metal between iron ion and chitosan molecule-supermolecular mechanism formation ferrum-chitosan supermolecular gel. Put this ferrum-chitosan supermolecular gel after 24h until ambient temperatare to be successfully formed.
Fig. 1 is the macrograph of ferrum of the present invention-chitosan supermolecular gel, and as seen from the figure, the ferrum of preparation-chitosan supermolecular gel is rust, and embodies good gel characteristic.
The flow chart that in Fig. 2 prepared by ferrum described in embodiment 1-chitosan supermolecular gel, as can be seen from the figure this programme is mainly through changing Loading sequence to avoid the generation of precipitation of hydroxide.
Fig. 3 is the XRD figure of the XRD figure of ferrum of the present invention-chitosan supermolecular gel and pure chitosan and ferrum-chitosan complex, as can be seen from the figure, after iron ion and chitosan form coordination compound, the characteristic peak of chitosan disappears, and the substitute is at about the 25 �� broad peaks produced. Further, formed after supermolecular gel, at 29.52 ��, 32.08 ��, 39.20 ��, 42.78 �� and 48.07 �� of positions occur in that new characteristic peak, it was demonstrated that after supermolecular mechanism, its crystalline structure changes further.
Raman figure and the Raman of pure chitosan and ferrum-chitosan complex that Fig. 4 is ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel scheme, relative to pure chitosan, after iron ion and chitosan form coordination compound there is significant skew in its Raman characteristic peak, it was demonstrated that the successful coordination of iron ion and chitosan.
Fig. 5 is that the FTIR figure of ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel and the FTIR of pure chitosan and ferrum-chitosan complex schemes. It can be seen that the characteristic absorption peak of chitosan molecule lays respectively at �� (CH) at2923cm-1,��(CO)at1089cm-1and1670cm-1. At 1525cm-1The amino stretching vibration peak at place and 1385cm-1The hydroxyl characteristic peak at place and 1156,1089 and 1027cm-1Carbonyl characteristic absorption peak all there is a degree of reduction and skew, it was demonstrated that iron ion and the coordination of these groups, demonstrate chemical action composition and the metal-supermolecular mechanism of ferrum-chitosan supermolecular gel.
2, self-healing and pH response behavioral study
(1) block ferrum-chitosan supermolecular gel is positioned on culture dish, this supermolecular gel cut into two pieces and against putting together from centre with scalpel subsequently, change supermolecular gel self-healing after 24h to complete, observe its self-healing performance (being again fused into a piece with two clotting glue to be preferred).
Result shows: this ferrum-chitosan supermolecular gel has excellent self-healing performance, is greatly expanded the application performance of metal-supramolecular hydrogel.
(2) bag filter that ferrum-chitosan supermolecular gel molecular cut off is 3000 is installed in the buffer solution being placed in different pH value (2.2,4,6,7.4), shoot photo at regular intervals, observe its Behavioral change under condition of different pH.
Result shows: this ferrum-chitosan supermolecular gel progressively dissociates when simulating gastric acid pH, slow release ferrum-chitosan complex; And occur swelling under weak neutrallty condition but not dissociate.
Fig. 6 is A, B, C is cutting drawing and the self-healing performance table view thereof of ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel, by figure A it can be seen that the ferrum-chitosan supermolecular gel of preparation is successfully cut into two pieces and is stacked upon. By scheming B it can be seen that two clotting glue are fused into one piece after 24h. Further, from figure C it can be seen that namely use tweezers to pick up, two clotting glue still connect together securely, it was demonstrated that its excellent integrity and self-healing.
Fig. 7 is the macrograph after ferrum described in the embodiment of the present invention 1-chitosan supermolecular gel dissociates under condition of different pH. Test result indicate that, ferrum-chitosan supermolecular gel is stable in physiological conditions, and first swelling when simulating gastric acid pH, then slow releasing forms its ferrum-chitosan complex, and this feature is particularly important for the action effect improving iron supplementary.
Embodiment 2:
1, the preparation of ferrum-chitosan supermolecular gel:
(1) preparation of chitosan solution:
1g acetic acid is added water and is settled to 100mL, be dissolved in above-mentioned solution by 2g chitosan subsequently to be sufficiently stirred for and stand overnight stand-by.
(2) preparation of ferrum-chitosan supermolecular gel:
Fully mix to ensure that iron ion and the abundant coordination of chitosan molecule form coordination compound under acutely concussion by the iron nitrate aqueous solution of 100 �� L0.7M and 800 �� L chitosan solutions, under acutely concussion, be rapidly added the sodium hydroxide solution of 200 �� L0.6M subsequently to realize the deprotonation to chitosan molecule and to cause the metal between iron ion and chitosan molecule-supermolecular mechanism formation ferrum-chitosan supermolecular gel. Put this ferrum-chitosan supermolecular gel after 24h until ambient temperatare to be successfully formed.
2, self-healing and pH response behavioral study
(1) block ferrum-chitosan supermolecular gel is positioned on culture dish, this supermolecular gel cut into two pieces and against putting together from centre with scalpel subsequently, after 24h, observe its self-healing performance (being again fused into a piece with two clotting glue to be preferred).
Result shows: this ferrum-chitosan supermolecular gel has excellent self-healing performance, is greatly expanded the application performance of metal-supramolecular hydrogel.
(2) bag filter that ferrum-chitosan supermolecular gel molecular cut off is 3000 is installed in the buffer solution being placed in different pH value, shoot photo at regular intervals, observe its Behavioral change under condition of different pH.
Result shows: this ferrum-chitosan supermolecular gel progressively dissociates when simulating gastric acid pH, slow release ferrum-chitosan complex. And occur swelling under weak neutrallty condition but not dissociate.
Embodiment 3:
1, the preparation of ferrum-chitosan supermolecular gel:
(1) preparation of chitosan solution:
1g acetic acid is added water and is settled to 100mL, be dissolved in above-mentioned solution by 4g chitosan subsequently to be sufficiently stirred for and stand overnight stand-by.
(2) preparation of ferrum-chitosan supermolecular gel:
Fully mix to ensure that iron ion and the abundant coordination of chitosan molecule form coordination compound under acutely concussion by the iron nitrate aqueous solution of 100 �� L0.9M and 800 �� L chitosan solutions, under acutely concussion, be rapidly added the sodium hydroxide solution of 300 �� L0.8M subsequently to realize the deprotonation to chitosan molecule and to cause the metal between iron ion and chitosan molecule-supermolecular mechanism formation ferrum-chitosan supermolecular gel.Put this ferrum-chitosan supermolecular gel after 24h until ambient temperatare to be successfully formed.
2, self-healing and pH response behavioral study
(1) block ferrum-chitosan supermolecular gel is positioned on culture dish, this supermolecular gel cut into two pieces and against putting together from centre with scalpel subsequently, after 24h, observe its self-healing performance (being again fused into a piece with two clotting glue to be preferred).
Result shows: this ferrum-chitosan supermolecular gel has excellent self-healing performance, is greatly expanded the application performance of metal-supramolecular hydrogel.
(2) bag filter that ferrum-chitosan supermolecular gel molecular cut off is 3000 is installed in the buffer solution being placed in different pH value, shoot photo at regular intervals, observe its Behavioral change under condition of different pH.
Result shows: this ferrum-chitosan supermolecular gel progressively dissociates when simulating gastric acid pH, slow release ferrum-chitosan complex. And occur swelling under weak neutrallty condition but not dissociate.
Claims (9)
1. ferrum-chitosan supermolecular gel, it is characterised in that described ferrum-chitosan supermolecular gel utilizes the metal between iron ion and chitosan molecule-supermolecular mechanism to form polymer network, has self-healing performance and pH response.
2. the preparation method of a kind of ferrum-chitosan supermolecular gel as claimed in claim 1, it is characterised in that comprise the steps:
S1. the preparation of chitosan solution:
Dissolve the chitosan in and acetum is formed stable homogeneous and has the chitosan solution of certain viscosity;
S2. the preparation of ferrum-chitosan gel rubber:
By ferrum-chitosan coordination compound stable to iron nitrate aqueous solution and the blended formation of chitosan solution, under acutely concussion, add NaOH solution subsequently, stand 24 hours, it is thus achieved that the ferrum of stable uniform-chitosan supermolecular gel.
3. the preparation method of a kind of ferrum-chitosan supermolecular gel according to claim 2, it is characterised in that the mass concentration of the chitosan solution obtained described in step S1 is 1%-4%; The mass concentration of described acetum is 1%.
4. the preparation method of a kind of ferrum-chitosan supermolecular gel according to Claims 2 or 3, it is characterised in that the concentration of aqueous solution of the ferric nitrate described in step S2 is 0.5��0.9mol/L.
5. the preparation method of a kind of ferrum-chitosan supermolecular gel according to Claims 2 or 3, it is characterised in that the concentration of sodium hydroxide (NaOH) solution described in step S2 is 0.4��0.8mol/L.
6. the preparation method of a kind of ferrum-chitosan supermolecular gel according to Claims 2 or 3, it is characterised in that the volume ratio of iron nitrate aqueous solution described in step S2 and chitosan solution is 1:8.
7. the preparation method of a kind of ferrum-chitosan supermolecular gel according to Claims 2 or 3, it is characterised in that the addition of NaOH solution described in step S2 and the volume ratio of chitosan solution are 1-3:8.
8. the application of ferrum-chitosan supermolecular gel as claimed in claim 1, it is characterised in that described application be described ferrum-chitosan supermolecular gel can when stomach pH slow release iron ion.
9. ferrum-chitosan supermolecular gel application in preparing iron supplement medicine or food as claimed in claim 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105949364A (en) * | 2016-07-22 | 2016-09-21 | 合肥工业大学 | Novel photo-irradiation induced self-repairing precious metal nano composite hydrogel and preparation method thereof |
| CN107200799A (en) * | 2017-04-28 | 2017-09-26 | 东南大学 | Metallic ion coordination natural polymer/polyacrylic acid selfreparing gel process for preparing |
| 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 |
| CN108452370A (en) * | 2018-05-04 | 2018-08-28 | 中南大学 | A kind of compound supramolecular hydrogel and preparation method thereof |
| CN108636452A (en) * | 2018-05-16 | 2018-10-12 | 华侨大学 | A kind of preparation method and applications of chitosan loaded Zero-valent Iron pellet catalyst |
| WO2020018120A1 (en) * | 2018-07-20 | 2020-01-23 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Conformable neural interface device with hydrogel adhesion and methods of using the same |
| CN114249844A (en) * | 2021-10-13 | 2022-03-29 | 重庆朋辉化工产品有限公司 | Polysaccharide iron with controllable molecular weight and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105949364A (en) * | 2016-07-22 | 2016-09-21 | 合肥工业大学 | Novel photo-irradiation induced self-repairing precious metal nano composite hydrogel and preparation method thereof |
| CN107200799A (en) * | 2017-04-28 | 2017-09-26 | 东南大学 | Metallic ion coordination natural polymer/polyacrylic acid selfreparing gel process for preparing |
| CN107200799B (en) * | 2017-04-28 | 2019-08-20 | 东南大学 | Metallic ion coordination natural polymer/polyacrylic acid selfreparing gel process for preparing |
| 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 |
| CN108452370A (en) * | 2018-05-04 | 2018-08-28 | 中南大学 | A kind of compound supramolecular hydrogel and preparation method thereof |
| CN108452370B (en) * | 2018-05-04 | 2020-09-11 | 中南大学 | Composite supermolecule hydrogel and preparation method thereof |
| CN108636452A (en) * | 2018-05-16 | 2018-10-12 | 华侨大学 | A kind of preparation method and applications of chitosan loaded Zero-valent Iron pellet catalyst |
| CN108636452B (en) * | 2018-05-16 | 2021-04-30 | 华侨大学 | Preparation method and application of chitosan-loaded zero-valent iron pellet catalyst |
| WO2020018120A1 (en) * | 2018-07-20 | 2020-01-23 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Conformable neural interface device with hydrogel adhesion and methods of using the same |
| CN114249844A (en) * | 2021-10-13 | 2022-03-29 | 重庆朋辉化工产品有限公司 | Polysaccharide iron with controllable molecular weight and preparation method thereof |
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| CN105646902B (en) | 2018-11-09 |
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