CN103467330A - Preparation method of copper-tyrosine coordination polymer one-dimensional micro-nano crystal - Google Patents
Preparation method of copper-tyrosine coordination polymer one-dimensional micro-nano crystal Download PDFInfo
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Abstract
The invention relates to a preparation method of copper-tyrosine coordination polymer one-dimensional micro-nano crystal. The method comprises the steps of dispersing tyrosine and copper salt into solvent water or a mixed solvent of water and ethyl alcohol, not adding a surface active agent or adding right amount of surface active agent, and directly or dropwise adding alkali liquor into the mixture to adjust the potential of hydrogen (pH) value to be less than or equal to 12 to obtain a reaction mixture; after that, carrying out ultrasonic treatment or intense agitation on the reaction mixture; carrying out centrifugal separation on the obtained blue precipitate; sequentially washing the precipitate by distilled water and ethyl alcohol, and drying the product to obtain blue powder which is the copper-tyrosine coordination polymer one-dimensional micro-nano crystal. The obtained product is pure [Cu (tyr) 2]n and is a one-dimensional rod or band; furthermore, the method can regulate and control the size of the product within a large range along with the different preparation conditions, wherein the width range is 80nm-4mu m, and the length range is 1-10mu m. The preparation method of the copper-tyrosine coordination polymer one-dimensional micro-nano crystal is simple to operate, easy in obtain of raw materials, mild in conditions, simple, convenient and fast.
Description
Technical field
The present invention relates to a kind of preparation method of micro-nano-scale ligand polymer, be specifically related to the preparation method of a kind of copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance.
Background technology
Ligand polymer is a class by coordinate bond by metal ion or bunch hybrid inorganic-organic materials be formed by connecting with organic ligand, because its stability, multifunctionality, Modulatory character etc. are widely used in a lot of aspects such as catalysis, atmosphere storage and separation, optical material, magneticsubstance (referring to (a) SR Batten, SM Neville, DR Turner, Coordination Polymers:Design, Analysis and Application, 2008. (b) Chemical Society Reviews, 38 (2009) .).Property due to micro Nano material, the ligand polymer of micro-nano-scale is causing that increasing concern and research are (referring to (a) J Della Rocca recently, WB Lin, Nanoscale Metal-Organic Frameworks:Magnetic Resonance Imaging Contrast Agents and Beyond, European Journal of Inorganic Chemistry, (2010) 3725-34. (b) RC Huxford, J Della Rocca, WB Lin, Metal-organic frameworks as potential drug carriers, Current Opinion in Chemical Biology, 14 (2010) 262-8. (c) J Della Rocca, DM Liu, WB Lin, Nanoscale Metal-Organic Frameworks for Biomedical Imaging and Drug Delivery, Accounts of Chemical Research, 44 (2011) 957-68.).
Copper in copper-tyrosine ligand polymer is typical transition metal, can be used as the active centre of various procedures, amino acid ligand provides again potential biocompatibility and chirality (referring to (a) SC Sahoo, T Kundu, R Banerjee, Helical Water Chain Mediated Proton Conductivity in Homochiral Metal-Organic Frameworks with Unprecedented Zeolitic unh-Topology, Journal of the American Chemical Society, 133 (2011) 17950-8. (b) R Chen, CY Gao, YP Wu, H Wang, HJ Zhou, YP Liu, et al., Facile synthesis of functional bismuth-amino acid coordination polymer nano-structures, Chem Commun, 47 (2011) 8136-8. (c) C Li, K Deng, ZY Tang, L Jiang, Twisted Metal-Amino Acid Nanobelts:Chirality Transcription from Molecules to Frameworks, Journal of the American Chemical Society, 132 (2010) 8202-9. (d) I Imaz, M Rubio-Martinez, WJ Saletra, DB Amabilino, D Maspoch, Amino Acid Based Metal-Organic Nanofibers, Journal of the American Chemical Society, 131 (2009) 18222-3.), therefore copper-tyrosine ligand polymer is the functional materials with splendid application prospect.Though the report of the existing relevant crystalline structure of this material (referring to: (a) A Wojciechowska, M Daszkiewicz, A Bienko, Polymeric Zn (II) and Cu (II) complexes with exobidentate bridging L-tyrosine:Synthesis, structural and spectroscopic properties, Polyhedron, 28 (2009) 1481-9. (b) JB Weng, MC Hong, Q Shi, R Cao, ASC Chan, Chiral supramolecular assemblies derived from the insertion of a segmental ligand into a copper-tyrosine framework, European Journal of Inorganic Chemistry, (2002) 2553-6.), but there is no so far any report about its micro-nano brilliant preparation.
The present invention will provide a kind of method for preparing copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance first.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of method for preparing copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, it is characterized in that: tyrosine and mantoquita are scattered in the mixed solvent of aqueous solvent or water and ethanol, do not add or add proper amount of surfactant, directly or after dripping alkali lye adjusting pH value≤12 obtain reaction mixture; Subsequently reaction mixture is carried out to supersound process or stirring; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is described copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance.
In above-mentioned method, the mixed solvent of described water and ethanol, wherein the volume fraction of water is 20 ~ 100%.
In above-mentioned method, described tyrosine is TYR, DL-tyrosine or D-Tyrosine.
In above-mentioned method, described mantoquita is cupric chloride, cupric nitrate, copper sulfate or neutralized verdigris.
Preferably, in above-mentioned method, the mass volume ratio of the mixed solvent of described tyrosine and water or water and ethanol is 0.03 ~ 0.6 gram: 20 milliliters; The mol ratio of tyrosine and mantoquita is 1:0.3 ~ 2.
Preferably,
In above-mentioned method, described tensio-active agent is preferably polyvinylpyrrolidone, polyoxyethylene glycol or tween etc., and in the mixed solvent of water or water and ethanol, consumption is 0 ~ 5 gram/100 milliliter;
In above-mentioned method, described alkali is sodium hydroxide or potassium hydroxide;
In above-mentioned method, the pH value of described reaction mixture is 5 ~ 10.
In above-mentioned method, described reaction conditions is supersound process or high degree of agitation, until reaction mixture generates blue precipitation.
The prepared copper of method of the present invention-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, through XRD determining, result shows that it is pure copper-tyrosine ligand polymer [Cu (tyr)
2]
nthe position at all peaks all with the crystallographic data of foundation bibliographical information (referring to A Wojciechowska, M Daszkiewicz, A Bienko, Polymeric Zn (II) and Cu (II) complexes with exobidentate bridging L-tyrosine:Synthesis, structural and spectroscopic properties, Polyhedron, 28 (2009) 1481-9.) matching and powdery diffractometry spectrum be complementary, do not find the dephasign peak.By the TEM photo, observe micro-nano rod or band that product of the present invention is one dimension, and, along with the difference of preparation condition, can in very large range regulate and control the product size: width is from about 80nm to about 4 μ m; Length is from about 1 μ m to about 10 μ m.
Normally, the membership that adds of tensio-active agent reduces the product size significantly, and pH value purity and the yield effect to product is larger.Simultaneously, supersound process (especially large power supersonic, as the cell pulverization machine) greatly fast reaction speed, reduce the reaction times and reduce the product size.
The method for preparing copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance of the present invention is simple to operate, raw material is easy to get, mild condition, easy fast.Products therefrom is highly purified copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, and the product size can in very large range be regulated and controled.
Below in conjunction with specific embodiment, describe the present invention.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
The accompanying drawing explanation
The XRD spectra that Fig. 1 (a) is the prepared copper of method of the present invention-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance; (b) be that crystallographic data according to bibliographical information is (referring to A Wojciechowska, M Daszkiewicz, A Bienko, Polymeric Zn (II) and Cu (II) complexes with exobidentate bridging L-tyrosine:Synthesis, structural and spectroscopic properties, Polyhedron, 28 (2009) 1481-9.) matching and XRD spectra.
The TEM photo that Fig. 2 a ~ Fig. 2 h is the prepared copper of method of the present invention-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance.
Embodiment
Below by specific embodiment, technical solutions according to the invention are further described in detail, but are necessary to point out that following examples, only for the description to summary of the invention, do not form limiting the scope of the invention.
The preparation of embodiment 1. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
0.36 gram TYR, 0.20 gram neutralized verdigris are scattered in 20 ml waters, and the pH value is about 5; High degree of agitation 3 hours; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 89%.The powder X-ray RD result of product (seeing accompanying drawing 1) shows that it is pure copper-tyrosine ligand polymer [Cu (tyr)
2]
nthe position at all peaks all with the crystallographic data of foundation bibliographical information (referring to A Wojciechowska, M Daszkiewicz, A Bienko, Polymeric Zn (II) and Cu (II) complexes with exobidentate bridging L-tyrosine:Synthesis, structural and spectroscopic properties, Polyhedron, 28 (2009) 1481-9.) matching and powdery diffractometry spectrum be complementary, do not find the dephasign peak.By TEM photo (seeing accompanying drawing 2a), observing this product is wide approximately 2 μ m, the one-dimensional rod-like structure of length (8 ~ 9) μ m.
The preparation of embodiment 2. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
0.36 gram TYR, 0.20 gram neutralized verdigris are scattered in 20 ml waters, and the pH value is about 5; By ultrasonic cell disrupte machine supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 92%.The powder X-ray RD result of product and the result of embodiment 1 match.By TEM photo (seeing accompanying drawing 2b), observing this product is wide approximately (1 ~ 2) μ m, the one-dimensional rod-like structure of length (5 ~ 7) μ m.
The preparation of embodiment 3. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the NaOH aqueous solution carefully is added dropwise in the mixture of 0.36 gram TYR, 0.25 gram neutralized verdigris and 20 ml waters, regulate pH value to 9; Subsequently mixture is used to ultrasonic cell disrupte machine supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 83%.The powder X-ray RD result of product and the result of embodiment 1 match.By TEM photo (seeing accompanying drawing 2c), observing this product is wide approximately (0.5 ~ 1) μ m, the one-dimensional rod-like structure of length (2 ~ 3) μ m.
The preparation of embodiment 4. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the NaOH aqueous solution carefully is added dropwise in the mixture of 0.36 gram TYR, 0.25 gram neutralized verdigris and 20 ml waters, regulate pH value to 10; Subsequently by mixture high degree of agitation 3 hours; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 80%.The powder X-ray RD result of product and the result of embodiment 1 match.By TEM photo (seeing accompanying drawing 2d), observing this product is wide approximately (0.8 ~ 1) μ m, the one-dimensional rod-like structure of length (5 ~ 6) μ m.
The preparation of embodiment 5. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the KOH aqueous solution carefully is added dropwise in the mixture of 0.36 gram TYR, 0.25 gram neutralized verdigris and 20 ml waters, regulate pH value to 9; Subsequently by mixture supersound process 30 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 85%.The powder X-ray RD result of product and the result of embodiment 1 match.By TEM photo (seeing accompanying drawing 2e), observe the stub that this product is (2 ~ 4) μ m size.
The preparation of embodiment 6. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the KOH aqueous solution carefully is added dropwise in the mixture of 0.36 gram TYR, 0.25 gram neutralized verdigris, 0.11 gram polyvinylpyrrolidone and 20 ml waters, regulate pH value to 9; Subsequently by mixture supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 82%.The powder X-ray RD result of product and the result of embodiment 1 match.By TEM photo (seeing accompanying drawing 2f), observing this product is wide approximately 500 nm, the one-dimensional rod-like structure of length (2 ~ 5) μ m.
The preparation of embodiment 7. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the NaOH aqueous solution carefully is added dropwise in the mixture of 0.36 gram TYR, 0.25 gram neutralized verdigris, 0.22 gram polyvinylpyrrolidone and 20 ml waters, regulate pH value to 10; Subsequently by mixture supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 84%.The powder X-ray RD result of product and the result of embodiment 1 match.By TEM photo (seeing accompanying drawing 2g), observing this product is wide approximately 200 nm, the one-dimensional rod-like structure of length (1 ~ 3) μ m.
The preparation of embodiment 8. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the KOH aqueous solution carefully is added dropwise in the mixture of 0.36 gram TYR, 0.25 gram neutralized verdigris, 0.44 gram polyvinylpyrrolidone and 20 ml waters, regulate pH value to 10; Subsequently by mixture supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 80%.The powder X-ray RD result of product and the result of embodiment 1 match.By TEM photo (seeing accompanying drawing 2h), observing this product is wide approximately (100 ~ 200) nm, monodimension nano stick or the zonal structure of length (1 ~ 2) μ m.
The preparation of embodiment 9. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
0.36 gram TYR, 0.20 gram neutralized verdigris are scattered in the mixture (wherein the volume fraction of water is 20%) of 20 ml waters and ethanol, use ultrasonic cell disrupte machine supersound process 20 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 76%.The XRD of product and TEM result are all similar with embodiment 1 ~ 8, and this product is wide approximately (2 ~ 3) μ m, the one-dimensional rod-like structure of length (6 ~ 7) μ m.
The preparation of embodiment 10. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
0.36 gram D-Tyrosine, 0.25 gram neutralized verdigris are scattered in the mixture (wherein the volume fraction of water is 70%) of 20 ml waters and ethanol, use ultrasonic cell disrupte machine supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 81%.The XRD of product and TEM result are all similar with embodiment 1 ~ 8, and this product is wide approximately 2 μ m, the one-dimensional rod-like structure of length (5 ~ 6) μ m.
The preparation of embodiment 11. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the NaOH aqueous solution carefully is added dropwise in the mixture (wherein the volume fraction of water is 90%) of 0.36 gram DL-tyrosine, 0.20 gram neutralized verdigris and 20 ml waters and ethanol, regulate pH value to 10; By ultrasonic cell disrupte machine supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 79%.The XRD of product and TEM result are all similar with embodiment 1 ~ 8, and this product is wide approximately 2 μ m, the one-dimensional rod-like structure of length (4 ~ 6) μ m.
The preparation of embodiment 12. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
0.36 gram TYR, 0.19 gram cupric chloride are scattered in 20 ml waters, and the pH value is about 5; By ultrasonic cell disrupte machine supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 82%.The XRD of product and TEM result are all similar with embodiment 1 ~ 8, and this product is wide approximately (1 ~ 2) μ m, the one-dimensional rod-like structure of length (5 ~ 7) μ m.
The preparation of embodiment 13. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the KOH aqueous solution carefully is added dropwise in the mixture of 0.36 gram TYR, 0.24 gram cupric nitrate and 20 ml waters, regulate pH value to 10; Subsequently by mixture high degree of agitation 3 hours; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 78%.The XRD of product and TEM result are all similar with embodiment 1 ~ 8, and this product is wide approximately 800 nm, the one-dimensional rod-like structure of length (4 ~ 6) μ m.
The preparation of embodiment 14. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the NaOH aqueous solution carefully is added dropwise in the mixture of 0.36 gram TYR, 0.26 gram copper sulfate, 0.15 gram polyvinylpyrrolidone and 20 ml waters, regulate pH value to 10; Subsequently by mixture supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 83%.The XRD of product and TEM result are all similar with embodiment 1 ~ 8, and this product is wide approximately (300 ~ 400) nm, the one-dimensional rod-like structure of length (2 ~ 3) μ m.
The preparation of embodiment 15. bronze medals-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance
Under high degree of agitation, the KOH aqueous solution carefully is added dropwise in the mixture of 0.18 gram TYR, 0.10 gram neutralized verdigris, 0.10 gram polyvinylpyrrolidone and 20 ml waters, regulate pH value to 9; Subsequently by mixture supersound process 10 minutes; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, productive rate 71%.The XRD of product and TEM result are all similar with embodiment 1 ~ 8, and this product is wide about 400nm, the one-dimensional rod-like structure of length (2 ~ 3) μ m.
Claims (9)
1. a method for preparing copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance, it is characterized in that: tyrosine and mantoquita are scattered in the mixed solvent of water or water and ethanol, do not add or add proper amount of surfactant, directly or after dripping alkali lye adjusting pH value≤12 obtain reaction mixture; Subsequently reaction mixture is carried out to supersound process or stirring; By the blue precipitation and centrifugal separation of gained, with distilled water and ethanol, wash successively, then dry, the gained blue powder is described copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance.
2. method according to claim 1, it is characterized in that: the mass volume ratio of the mixed solvent of described tyrosine and water or water and ethanol is 0.03 ~ 0.6 gram: 20 milliliters; The mol ratio of tyrosine and mantoquita is 1:0.3 ~ 2.
3. method according to claim 1, it is characterized in that: the mixed solvent of described water and ethanol, wherein the volume fraction of water is 20 ~ 100%.
4. method according to claim 1, it is characterized in that: described tyrosine is TYR, DL-tyrosine or D-Tyrosine.
5. method according to claim 1, it is characterized in that: described mantoquita is cupric chloride, cupric nitrate, copper sulfate or neutralized verdigris.
6. method according to claim 1, it is characterized in that: described tensio-active agent is polyvinylpyrrolidone, polyoxyethylene glycol or tween, in the mixed solvent of water or water and ethanol, consumption is 0 ~ 5 gram/100 milliliter.
7. method according to claim 1, it is characterized in that: described alkali is sodium hydroxide or potassium hydroxide.
8. method according to claim 1, it is characterized in that: the pH value of described reaction mixture is 5 ~ 10.
9. method according to claim 1, it is characterized in that: described copper-tyrosine ligand polymer one-dimensional micro-nanometer crystalline substance is micro-nano rod or the band of one dimension, width 80nm ~ 4 μ m; Length 1 μ m ~ 10 μ m.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311576A (en) * | 2014-09-11 | 2015-01-28 | 南京师范大学 | Preparation method of copper-tyrosine-bipyridine coordination polymer micro nanocrystal |
| CN106279715A (en) * | 2016-08-30 | 2017-01-04 | 武汉大学 | A kind of copper peptide Porous coordination polymer and its preparation method and application |
| CN109745566A (en) * | 2019-02-21 | 2019-05-14 | 温州生物材料与工程研究所 | The method of metal organic coordination polymer wrapping biological macromolecular based on histidine small peptide |
| CN109771390A (en) * | 2019-02-21 | 2019-05-21 | 温州生物材料与工程研究所 | A kind of histidine small peptide-metal coordinating polymer nano particle preparation method of pH response |
| CN112430193A (en) * | 2020-11-30 | 2021-03-02 | 长沙兴嘉生物工程股份有限公司 | Preparation method and application of copper tyrosine |
-
2013
- 2013-09-17 CN CN2013104223767A patent/CN103467330A/en active Pending
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| 徐烽超: "纳米铜—氨基酸配位聚合物的制备、表征及电传感性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311576A (en) * | 2014-09-11 | 2015-01-28 | 南京师范大学 | Preparation method of copper-tyrosine-bipyridine coordination polymer micro nanocrystal |
| CN106279715A (en) * | 2016-08-30 | 2017-01-04 | 武汉大学 | A kind of copper peptide Porous coordination polymer and its preparation method and application |
| CN109745566A (en) * | 2019-02-21 | 2019-05-14 | 温州生物材料与工程研究所 | The method of metal organic coordination polymer wrapping biological macromolecular based on histidine small peptide |
| CN109771390A (en) * | 2019-02-21 | 2019-05-21 | 温州生物材料与工程研究所 | A kind of histidine small peptide-metal coordinating polymer nano particle preparation method of pH response |
| CN112430193A (en) * | 2020-11-30 | 2021-03-02 | 长沙兴嘉生物工程股份有限公司 | Preparation method and application of copper tyrosine |
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Application publication date: 20131225 |