CN103724618A - Preparation method for light sensitivity gamma-polyglutamic acid grafted copolymer micelle - Google Patents
Preparation method for light sensitivity gamma-polyglutamic acid grafted copolymer micelle Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920001577 copolymer Polymers 0.000 title claims abstract description 6
- 239000000693 micelle Substances 0.000 title abstract description 7
- 229920002643 polyglutamic acid Polymers 0.000 title abstract 4
- 206010034960 Photophobia Diseases 0.000 title abstract 3
- 208000013469 light sensitivity Diseases 0.000 title abstract 3
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 claims description 50
- 230000036211 photosensitivity Effects 0.000 claims description 50
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 41
- 229920000578 graft copolymer Polymers 0.000 claims description 41
- 238000000502 dialysis Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- GLNDAGDHSLMOKX-UHFFFAOYSA-N coumarin 120 Chemical compound C1=C(N)C=CC2=C1OC(=O)C=C2C GLNDAGDHSLMOKX-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 7
- 150000007942 carboxylates Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 4
- 229940059260 amidate Drugs 0.000 claims description 3
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 claims 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000001338 self-assembly Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 5
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- 239000002245 particle Substances 0.000 abstract description 5
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- 229920002521 macromolecule Polymers 0.000 abstract description 2
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 abstract 1
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 abstract 1
- 238000007112 amidation reaction Methods 0.000 abstract 1
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- 229960000956 coumarin Drugs 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 208000001132 Osteoporosis Diseases 0.000 description 2
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- 210000000748 cardiovascular system Anatomy 0.000 description 2
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- 208000017983 photosensitivity disease Diseases 0.000 description 2
- 231100000434 photosensitization Toxicity 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- 102000004169 proteins and genes Human genes 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- WHUUTDBJXJRKMK-GSVOUGTGSA-N D-glutamic acid Chemical compound OC(=O)[C@H](N)CCC(O)=O WHUUTDBJXJRKMK-GSVOUGTGSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- PMOWTIHVNWZYFI-WAYWQWQTSA-N cis-2-coumaric acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1O PMOWTIHVNWZYFI-WAYWQWQTSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- PMOWTIHVNWZYFI-UHFFFAOYSA-N o-Coumaric acid Natural products OC(=O)C=CC1=CC=CC=C1O PMOWTIHVNWZYFI-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Abstract
The invention provides a preparation method for a light sensitivity gamma-polyglutamic acid grafted copolymer micelle, and belongs to the technical field of high polymer materials and natural macromolecules. The method comprises the following steps: introducing cumarin primitives on side chains of gamma-polyglutamic acid through amidation reaction to endow the gamma-polyglutamic acid with amphipathicity and light sensitivity to some extent; adopting a solvent exchanging method to realize self-assembly so as to form the micelle. The prepared micelle has excellent biocompatibility and biodegradability, can be applied to the field of biological coatings, particle emulsifiers, biological active molecule load releasing and the like, and has an excellent application prospect in the field of biomaterials accordingly.
Description
A kind of preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer micella
Technical field
The present invention relates to a kind of preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer micella, on gamma-polyglutamic acid-side chain, introduce photosensitive tonka bean camphor primitive, by the self-assembly of exchange of solvent method, obtain micella, belong to functional polymer technology and natural macromolecular technical field.
Technical background
Gamma-polyglutamic acid-is that a class is the synthetic superpolymer with good biocompatibility and biodegradability of microorganism by Bacillus, is by L
-the alpha-amino group of L-glutamic acid and/or D-Glu and γ-carboxyl are combined by amido linkage a kind of biomacromolecule forming.Gamma-polyglutamic acid-is as a kind of biomacromolecule, has good biological degradability, biocompatibility, strong water-retentivity, to human body toxicological harmless etc.These characteristics have determined the extensive use of gamma-polyglutamic acid-in fields such as agricultural, food, medicine, environmental protection, cosmetic industry, tobacco, leather manufacture industry and plant seed protections, are a kind of natural macromolecular materials that exploitation is worth that has.Therefore the research of gamma-polyglutamic acid-and derivative thereof has caused concern both domestic and external in recent years.Amphiphilic gamma-polyglutamic acid-multipolymer can be micella by external stimulus self-assembly, and gamma-polyglutamic acid-copolymer micelle has the performances such as good biological degradability, biocompatibility and toxic effects can be applied to the technical field of biological material such as the load of medicine and protein.Akashi etc. are at Na
2cO
3in the aqueous solution take water-soluble carbodiimide as catalyzer, L-Phe ethyl ester as modify primitive gamma-polyglutamic acid-is carried out to graft reaction, the nanoparticle of self-assembly is successfully applied to protein and drug loading.
Tonka bean camphor is the lactone of coumarinic acid, has aromatic odour, is distributed widely in higher plant.Coumarin kind compound has physiologically active and many-sided clinical application widely, and biological activity is mainly manifested in antivirus action, anti-microbial effect, antitumor action, antioxygenation, function of resisting osteoporosis, the effect to cardiovascular systems and photosensitization etc.Coumarin kind compound is widely used in the aspects such as functional light responsive material such as perfume industry, medicine industry, pesticide industry, photoresponse polymer micelle, nanogel/microgel in recent years.
This patent has been invented a kind of preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer micella, the tonka bean camphor of photosensitivity is grafted on gamma-polyglutamic acid-side chain, the graft copolymer obtaining self-assembly in selective solvent methyl-sulphoxide/aqueous systems forms micella, this micella has good biocompatibility, biological degradability and photosensitivity, can be applicable to the fields such as biological coating, particle emulsifying agent and bioactive molecules load release.
Summary of the invention
The object of this invention is to provide a kind of preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer micella, the micella pattern that obtains is regular, size distribution homogeneous, can absorb the UV-light of certain wavelength, has photosensitivity and pH responsiveness.
Another object of the present invention is also that the photosensitivity gamma-polyglutamic acid-graft copolymer micella obtaining has good biocompatibility, and this micella can be used for the fields such as biological coating, particle emulsifying agent and bioactive molecules load release.
Its mentality of designing is: (1) carries out chemically modified with 7-amino-4-methylcoumarin to H type gamma-polyglutamic acid-, at H type gamma-polyglutamic acid-side chain, introduce the photosensitive tonka bean camphor primitive of hydrophobicity, give gamma-polyglutamic acid-certain amphiphilic and photosensitivity; (2) self-assembly in selective solvent methyl-sulphoxide/water of photosensitive amphiphilic gamma-polyglutamic acid-graft copolymer forms micella, micella has certain photosensitivity and pH responsiveness, intends for fields such as biological coating, particle emulsifying agent and bioactive molecules load releases.
Technical scheme of the present invention is:
A preparation method for photosensitivity gamma-polyglutamic acid-graft copolymer, is characterized in that the reaction equation of preparation process is:
Wherein, n is the polymerization degree, and m is grafting, and H type gamma-polyglutamic acid-molecular-weight average is 200～500kDa.
The preparation of photosensitivity gamma-polyglutamic acid-graft copolymer is that H type gamma-polyglutamic acid-is dissolved in methyl-sulphoxide, adds successively 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, I-hydroxybenzotriazole and 7-amino-4-methylcoumarin to carry out amidate action.Reaction finishes, reaction solution is precipitated with dehydrated alcohol, centrifugation goes out solid, solid proceeds in dialysis tubing and removes residual 7-amino-4-methylcoumarin and solvent methyl-sulphoxide with deionized water dialysis after dissolving with methyl-sulphoxide, and lyophilize can obtain photosensitivity gamma-polyglutamic acid-graft copolymer (gamma-polyglutamic acid--g-7-amino-4-methylcoumarin).
The preparation of photosensitivity gamma-polyglutamic acid-graft copolymer micella is that gamma-polyglutamic acid--g-7-amino-4-methylcoumarin is dissolved in methyl-sulphoxide, dropwise be added to the water, after be transferred to dialyse in dialysis tubing and obtain photosensitivity gamma-polyglutamic acid-graft copolymer (gamma-polyglutamic acid--g-7-amino-4-methylcoumarin) micellar aqueous solution except desolventizing methyl-sulphoxide.
The preparation method of described photosensitivity gamma-polyglutamic acid-graft copolymer, the ratio that it is characterized in that reacting the amount of substance of carboxylate group and 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride in H type gamma-polyglutamic acid-structural unit is 6:1～1:6; In H type gamma-polyglutamic acid-structural unit, carboxylate group is 6:1～1:6 with the ratio of the amount of substance of I-hydroxybenzotriazole; In H type gamma-polyglutamic acid-structural unit, carboxylate group is 6:1～1:6 with the ratio of 7-amino-4-methylcoumarin amount of substance.
The preparation method of described photosensitivity gamma-polyglutamic acid-graft copolymer, it is characterized in that adopting ethanol is precipitation agent, reaction solution volume and ethanol volume ratio are 1:3～1:8.
The preparation of described photosensitivity gamma-polyglutamic acid-graft copolymer micella is to adopt exchange of solvent method: gamma-polyglutamic acid--g-7-amino-4-methylcoumarin is dissolved in methyl-sulphoxide, dropwise be added to the water, after be transferred in dialysis tubing and dialyse, except desolventizing methyl-sulphoxide, can obtain photosensitivity gamma-polyglutamic acid-graft copolymer (gamma-polyglutamic acid--g-7-amino-4-methylcoumarin) micellar aqueous solution.
The preparation method of described photosensitivity gamma-polyglutamic acid-graft copolymer micella, it is characterized in that photosensitivity gamma-polyglutamic acid--g-7-amino-4-methylcoumarin to be dissolved in and in methyl-sulphoxide, to form 0.1～15.0mg/mL copolymer solution, dropwise be added to the water, after be transferred in dialysis tubing and dialyse, except desolventizing methyl-sulphoxide, obtain photosensitivity gamma-polyglutamic acid-graft copolymer micellar aqueous solution.
The preparation method of described photosensitivity gamma-polyglutamic acid-graft copolymer micella, it is characterized in that the dimethyl sulfoxide solution of photosensitivity gamma-polyglutamic acid--g-7-amino-4-methylcoumarin, dropwise join in the water of 0.5～15 times of volume, after be transferred in dialysis tubing and dialyse, except desolventizing methyl-sulphoxide, obtain photosensitivity gamma-polyglutamic acid-graft copolymer (gamma-polyglutamic acid--g-7-amino-4-methylcoumarin) micellar aqueous solution.
Photosensitivity gamma-polyglutamic acid--g-7-amino-4-methylcoumarin copolymer micelle that the preparation method of described photosensitivity gamma-polyglutamic acid-graft copolymer micella obtains is regular spherical, and in the aqueous solution, median size is 600nm.
Major advantage of the present invention is:
(1) the present invention prepares gamma-polyglutamic acid-as raw material take microorganism polymerization, safety non-toxic, and the biocompatibility that tool is good and biological degradability, have advantages of that synthetic macromolecule is incomparable; Raw material is easy to get, recyclable regenerative, meets the viewpoint of Sustainable development, has good economic worth and application prospect.
(2) tonka bean camphor is another important source material.Coumarin kind compound has physiologically active and many-sided clinical application widely, and biological activity is mainly manifested in antivirus action, anti-microbial effect, antitumor action, antioxygenation, function of resisting osteoporosis, the effect to cardiovascular systems and photosensitization etc.
(3) in dimethylsulfoxide solvent, 7-amino-4-methylcoumarin and gamma-polyglutamic acid-carry out amidate action and obtain graft product, tonka bean camphor primitive can form hydrophobic microcell, thereby give gamma-polyglutamic acid-certain amphiphilic micella that is self-assembled into, micella has photosensitivity, can be used for the fields such as biological coating, particle emulsifying agent and bioactive molecules load release.
Accompanying drawing explanation
Fig. 1 gamma-polyglutamic acid-and gamma-polyglutamic acid--g-7-amino-4-methylcoumarin
1h NMR spectrogram;
The size distribution of Fig. 2 gamma-polyglutamic acid--g-7-amino-4-methylcoumarin micella and γ EM figure;
The UV spectrum of Fig. 3 gamma-polyglutamic acid--g-7-amino-4-methylcoumarin micella under the different UV-irradiation time;
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited thereto.
Embodiment 1: the preparation of photosensitivity gamma-polyglutamic acid-graft copolymer
The H type gamma-polyglutamic acid-of 5mmol is dissolved in 40mL methyl-sulphoxide, stirring and dissolving, add successively 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride of 1mmol, the I-hydroxybenzotriazole of 2mmol, 7-amino-4-methylcoumarin of 2mmol, continues stirring reaction 24h.Reaction finishes, dehydrated alcohol precipitation by reaction solution with 8 times of volumes, the centrifugal 15min of 5000rpm, isolate solid, solid proceeds in dialysis tubing and removes residual 7-amino-4-methylcoumarin and solvent methyl-sulphoxide with deionized water dialysis after dissolving with methyl-sulphoxide, and lyophilize can obtain gamma-polyglutamic acid--g-7-amino-4-methylcoumarin multipolymer.
Embodiment 2: the preparation of photosensitivity gamma-polyglutamic acid-graft copolymer
The H type gamma-polyglutamic acid-of 2mmol is dissolved in 40mL methyl-sulphoxide, stirring and dissolving, add successively 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride of 2mmol, the I-hydroxybenzotriazole of 2mmol, 7-amino-4-methylcoumarin of 4mmol, continues stirring reaction 24h.Reaction finishes, dehydrated alcohol precipitation by reaction solution with 5 times of volumes, the centrifugal 15min of 5000rpm, isolate solid, solid proceeds in dialysis tubing and removes residual 7-amino-4-methylcoumarin and solvent methyl-sulphoxide with deionized water dialysis after dissolving with methyl-sulphoxide, and lyophilize can obtain gamma-polyglutamic acid--g-7-amino-4-methylcoumarin multipolymer.
Embodiment 3: the preparation of photosensitivity gamma-polyglutamic acid-graft copolymer
The H type gamma-polyglutamic acid-of 0.5mmol is dissolved in 40mL methyl-sulphoxide, stirring and dissolving, add successively 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride of 1mmol, the I-hydroxybenzotriazole of 1mmol, 7-amino-4-methylcoumarin of 1mmol, continues stirring reaction 24h.Reaction finishes, dehydrated alcohol precipitation by reaction solution with 3 times of volumes, the centrifugal 15min of 5000rpm, isolate solid, solid proceeds in dialysis tubing and removes residual 7-amino-4-methylcoumarin and solvent methyl-sulphoxide with deionized water dialysis after dissolving with methyl-sulphoxide, and lyophilize can obtain gamma-polyglutamic acid--g-7-amino-4-methylcoumarin multipolymer.
Embodiment 4: the preparation of photosensitivity gamma-polyglutamic acid-graft copolymer micella
Gamma-polyglutamic acid--g-7-amino-4-methylcoumarin is dissolved in to the solution that forms 10mg/mL in methyl-sulphoxide, dropwise join in 10 times of volumes of deionized water, being transferred to dialyses in dialysis tubing obtains photosensitive gamma-polyglutamic acid--g-7-amino-4-methylcoumarin micella except desolventizing methyl-sulphoxide.
Embodiment 5: the preparation of photosensitivity gamma-polyglutamic acid-graft copolymer micella
Gamma-polyglutamic acid--g-7-amino-4-methylcoumarin is dissolved in to the solution that forms 5mg/mL in methyl-sulphoxide, dropwise join in 8 times of volumes of deionized water, being transferred to dialyses in dialysis tubing obtains photosensitive gamma-polyglutamic acid--g-7-amino-4-methylcoumarin micella except desolventizing methyl-sulphoxide.Embodiment 6: the preparation of photosensitivity gamma-polyglutamic acid-graft copolymer micella
Gamma-polyglutamic acid--g-7-amino-4-methylcoumarin is dissolved in to the solution that forms 0.5mg/mL in methyl-sulphoxide, dropwise join in 5 times of volumes of deionized water, being transferred to dialyses in dialysis tubing obtains photosensitive gamma-polyglutamic acid--g-7-amino-4-methylcoumarin micella except desolventizing methyl-sulphoxide.
Claims (5)
1. a preparation method for photosensitivity gamma-polyglutamic acid-graft copolymer micella, is characterized in that step is:
(1) preparation of photosensitivity gamma-polyglutamic acid-graft copolymer
H type gamma-polyglutamic acid-is dissolved in L methyl-sulphoxide, adds successively 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, I-hydroxybenzotriazole and 7-amino-4-methylcoumarin to carry out amidate action.Reaction finishes, reaction solution is precipitated with dehydrated alcohol, centrifugation goes out solid, solid proceeds in dialysis tubing and removes residual 7-amino-4-methylcoumarin and solvent methyl-sulphoxide with deionized water dialysis after dissolving with methyl-sulphoxide, and lyophilize can obtain photosensitivity gamma-polyglutamic acid-graft copolymer (gamma-polyglutamic acid--g-7-amino-4-methylcoumarin).
(2) preparation of photosensitivity gamma-polyglutamic acid-graft copolymer micella
The preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer micella adopts exchange of solvent method: gamma-polyglutamic acid--g-7-amino-4-methylcoumarin is dissolved in methyl-sulphoxide, dropwise be added to the water, after be transferred to and in dialysis tubing, dialyse except desolventizing methyl-sulphoxide, can obtain photosensitivity gamma-polyglutamic acid-graft copolymer (gamma-polyglutamic acid--g-7-amino-4-methylcoumarin) micellar aqueous solution.
2. the preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer according to claim 1, is characterized in that in step 1 that the ratio of the amount of substance of carboxylate group and 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride in H type gamma-polyglutamic acid-structural unit is 6:1～1:6; In H type gamma-polyglutamic acid-structural unit, carboxylate group is 6:1～1:6 with the ratio of the amount of substance of I-hydroxybenzotriazole; In H type gamma-polyglutamic acid-structural unit, carboxylate group is 6:1～1:6 with the ratio of 7-amino-4-methylcoumarin amount of substance.
3. the preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer according to claim 1, its characterization step is that in 1, to adopt ethanol be precipitation agent, reaction solution volume and ethanol volume ratio are 1:3～1:8.
4. the preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer micella according to claim 1, it is characterized in that photosensitivity photosensitivity gamma-polyglutamic acid-graft copolymer to be dissolved in and in methyl-sulphoxide, to form 0.1～15.0mg/mL copolymer solution, dropwise be added to the water, after be transferred to dialyse in dialysis tubing and obtain photosensitivity gamma-polyglutamic acid-graft copolymer micellar aqueous solution except desolventizing methyl-sulphoxide.
5. the preparation method of photosensitivity gamma-polyglutamic acid-graft copolymer micella according to claim 1, it is characterized in that the dimethyl sulfoxide solution of photosensitivity gamma-polyglutamic acid--g-7-amino-4-methylcoumarin, dropwise join in the water of 0.5～15 times of volume, after be transferred in dialysis tubing and dialyse, except desolventizing methyl-sulphoxide obtains photosensitivity gamma-polyglutamic acid-graft copolymer (gamma-polyglutamic acid--g-7-amino-4-methylcoumarin) micellar aqueous solution.
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| CN109485845A (en) * | 2018-09-13 | 2019-03-19 | 天津大学 | A kind of preparation method of hydrophobically modified polyglutamic acid and its trehalose is promoted to be loaded into the application of cell |
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| CN104195618A (en) * | 2014-07-31 | 2014-12-10 | 江南大学 | Electro-deposition preparation method of magnesium-based biological nano coating material |
| CN106178116A (en) * | 2016-07-20 | 2016-12-07 | 江南大学 | A kind of preparation method of photosensitive n-trimethyl chitosan chloride antimicrobial coating |
| CN107569716A (en) * | 2017-04-26 | 2018-01-12 | 温州医科大学附属口腔医院 | A kind of preparation method of titanium implant surface pH response medicine controlled releasing coatings |
| CN107569716B (en) * | 2017-04-26 | 2020-10-20 | 温州医科大学附属口腔医院 | Preparation method of pH-responsive drug controlled-release coating on surface of titanium implant |
| CN109485845A (en) * | 2018-09-13 | 2019-03-19 | 天津大学 | A kind of preparation method of hydrophobically modified polyglutamic acid and its trehalose is promoted to be loaded into the application of cell |
| CN109485845B (en) * | 2018-09-13 | 2021-04-20 | 天津大学 | Preparation method of hydrophobically modified polyglutamic acid and application of hydrophobically modified polyglutamic acid in promoting loading of trehalose into cells |
| CN110215411A (en) * | 2019-06-03 | 2019-09-10 | 江南大学 | A kind of composite nanoparticle and preparation method thereof that wide spectrum is sun-proof |
| CN110215411B (en) * | 2019-06-03 | 2022-06-10 | 江南大学 | Broad-spectrum sunscreen composite nanoparticle and preparation method thereof |
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| CN103724618B (en) | 2016-10-26 |
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