CN105801878A - Preparation method of silk fibroin-based nano MOFs (metal-organic frameworks) - Google Patents
Preparation method of silk fibroin-based nano MOFs (metal-organic frameworks) Download PDFInfo
- Publication number
- CN105801878A CN105801878A CN201610217963.6A CN201610217963A CN105801878A CN 105801878 A CN105801878 A CN 105801878A CN 201610217963 A CN201610217963 A CN 201610217963A CN 105801878 A CN105801878 A CN 105801878A
- Authority
- CN
- China
- Prior art keywords
- preparation
- silk fibroin
- acid
- rare earth
- fibroin albumen
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Peptides Or Proteins (AREA)
- Cosmetics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of nanomaterials and relates to a preparation method of silk fibroin-based nano MOF (metal-organic framework) materials. The MOFs in different nano shapes can be prepared through adjustment of the ratio of rare-earth ions to silk fibroin macromolecules. The preparation method of the silk fibroin-based nano MOF materials comprises steps as follows: silk fibers are degummed and then dissolved and dialyzed in a ternary solution prepared from calcium chloride, ethanol and water, a silk fibroin solution with certain concentration is prepared, under normal temperature or hydrothermal reaction conditions, the silk fibroin solution is induced by different amounts of the rare-earth ions or mixtures of the rare-earth ions and micromolecular polycarboxylic acid, and protein macromolecule-based MOFs adopting different nano structures are synthesized under the molecular self-assembly action. The preparation method is simple and easy to implement, raw materials are easy to obtain, and the silk fibroin-based MOF materials in various nano shapes can be prepared.
Description
Technical field
The invention belongs to technical field of nano material, the preparation method relating to a kind of fibroin albumen base nanometer MOFs material.
Background technology
Metal organic frame (MOFs) material is a kind of novel Inorganic-Organic Hybrid Material, and especially rare earth MOFs has more performance advantage in the field such as optical, electrical, magnetic, catalysis, absorption, energy storage than traditional inorganic and organic material.MOFs material has abundant loose structure and open site, it is possible to easily it is carried out functionalized modification.MOFs materials synthesis is also more convenient, under room temperature and hydrothermal condition, be easy to get bulk-shaped monocrystal body MOFs, but its application in vivo of the bigger size limitation of block materials, it is therefore desirable to and a preparation nanometer MOFs material could realize the detection in cell and biological living and diagnostic function.The research of nanometer MOFs material especially rare earth MOFs, also in the starting stage, rationally selects organic ligand, improves preparation method and size control technique, and make its research being applied in biomedicine field need to be deeply developed.
Fibroin albumen is topmost ingredient in silkworm silk, compared with the macromolecule that other is natural, and fibroin albumen good biocompatibility, biodegradable, it is possible to processed in aqueous, there is various active functional group, such as-OH ,-COOH ,-NH2Deng, it is easy to functionalized modification.Along with going deep into that its physicochemical property is studied, both at home and abroad to the application of fibroin albumen just from traditional field of textiles to biological medicine, the field such as cosmetics, food expands.In conjunction with the advantage of MOFs Yu fibroin albumen macromole, developing its actual application value needs researcher to carry out substantial amounts of work.Ge etc. (GeJ., LeiJD., ZRN..Protein-inorganichybridnanoflowers.Naturenanotechno logy, 2012,7: 428 432) adopt Cu2+Ion and bovine serum albumin macromole assembled inorganic-organic polymer hybrid nano-material, this nano material is due to high specific surface area and the fixation to enzyme, activity and the stability of enzyme can be strengthened, illustrate that adopting protein macromolecule to assemble MOFs material as organic ligand is an extraordinary thinking, but article induces bovine serum albumin only with transition metal ions, is not directed to the field of the rare earth ion interaction with fibroin albumen macromole and possible application.
Summary of the invention
The preparation method that the technical problem to be solved in the present invention is to provide a kind of fibroin albumen base nanometer MOFs.Preparation method simplicity is quick, pollution-free, adopt fibroin protein macromole as organic ligand assemble nanometer MOFs material, there is good biocompatibility and safety, it is possible to be applied to the fluorescence temperature in biomedicine, pH and the field such as little molecular detection and medicament slow release.
Realization the technical scheme is that first by silk fiber sericin removal, again with calcium chloride, the ternary solution of second alcohol and water dissolves and dialyses, prepare certain density silk fibroin protein solution, under room temperature or hydrothermal reaction condition, adopt different amounts of rare earth ion or rare earth ion and little molecule polycarboxylic mixture that silk fibroin protein solution is induced, by the protein macromolecule base MOFs of the different nanostructured of molecular self-assembling effect synthesis.
A kind of preparation method of fibroin albumen base nanometer MOFs, its preparation method comprises the following steps:
First silkworm silk is carried out degumming process, under 70 ~ 80 ° of C, 1g fibroin is dissolved in the 400mL calcium chloride water containing ethanol, natural cooling after solution clarification, remove impurity by filtered through gauze, filtrate loads bag filter put in deionized water and dialyse, dialyse 3 days, change 3 water every day, obtain the silk fibroin protein solution that concentration is 2.5g/L, load in reagent bottle, be stored in refrigerator cold-storage standby；Under room temperature or hydrothermal reaction condition, adopt different amounts of rare earth ion or rare earth ion and little molecule polycarboxylic mixture that silk fibroin protein solution is induced, by molecular self-assembling effect synthesis of solid microgranule, filter and take out, repeatedly rinse with deionized water, room temperature is dried, and prepares the fibroin albumen base MOFs material of different nanostructured
The described calcium chloride water containing ethanol, its mol ratio is CaCl2:EtOH:H2O=1:2:8,
Described rare earth ion is Eu3+、Tb3+、Pr3+、Nd3+、La3+In the mixture of a kind of or any two kinds of rare earth ions, the mol ratio of double; two rare earth ions is 1:1 ~ 100,
Described rare earth ion and the polycarboxylic mass ratio of little molecule are 1:1 ~ 10,
Described little molecule polycarboxylic acid is: benzoic acid, oxalic acid, fumaric acid, citric acid, pyridinedicarboxylic acid, to the one in benzene dicarboxylic acid, trimesic acid, Pyromellitic Acid or ethylene-dimalonic acid
The mass ratio of described rare earth ion and silk fibroin protein solution is 1:30 ~ 300,
Described hydro-thermal reaction is with deionized water for medium, and reaction temperature is 50 ~ 100 ° of C, and the response time is 12 ~ 48h,
The temperature-fall period of described hydro-thermal reaction, it is necessary to temperature programmed control, rate of temperature fall is 0.5 ~ 5 ° of C per hour.
Owing to adopting above technical scheme, the fibroin albumen base nanometer MOFs obtained by preparation method of the present invention has the advantage that
(1) by regulating and controlling the amount of rare earth ion, the ratio of double; two rare earth ions or the polycarboxylic kind of little molecule, the multidimensional nanotopography regulation and control of MOFs material are very easily realized.
(2) fibroin albumen base nanometer MOFs material has good biocompatibility and safety, it is possible to be applied to the fluorescence temperature in biomedicine, pH and the field such as little molecular detection and medicament slow release.
(3) preparation method of the present invention is simple, easy, and raw material is easy to get, it is possible to prepare the fibroin albumen macromole base MOFs material of multiple nanotopography.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of Fig. 1, Fig. 2, Fig. 3, Fig. 4 and Fig. 5 respectively fibroin albumen base nanometer MOFs material prepared by embodiment 1,2,3,4,5, by regulating and controlling the amount of rare earth ion or different little molecule polycarboxylic acids, it is possible to form the MOFs of different nanotopography.
Detailed description of the invention
With specific embodiment, technical scheme is described below, but protection scope of the present invention is not limited to this:
0.1g silkworm silk is carried out degumming process by embodiment 1, adopts the calcium chloride water 40mL(CaCl containing ethanol2:EtOH:H2O=1:2:8, reaction temperature is 70 ~ 80 ° of C) it is dissolved to clarification, cooling, filtered through gauze removes impurity, filtrate loads bag filter and puts in deionized water and dialyse, dialyse 3 days, change 3 water every day, obtain the silk fibroin protein solution that concentration is 2.5g/L, under normal temperature condition, slowly add 200 μ LEu to it3+, molecular self-assembling reacts 2 days, and solution is muddy, has solid particle to generate, and filters and takes out, repeatedly rinses with deionized water, and room temperature is dried, and prepares the fibroin albumen base MOFs material of nanostructured shown in Fig. 1 in accompanying drawing.
0.1g silkworm silk is carried out degumming process by embodiment 2, adopts the calcium chloride water 40mL(CaCl containing ethanol2:EtOH:H2O=1:2:8, reaction temperature is 70 ~ 80 ° of C) it is dissolved to clarification, cooling, filtered through gauze removes impurity, filtrate loads bag filter and puts in deionized water and dialyse, dialyse 3 days, change 3 water every day, obtain the silk fibroin protein solution that concentration is 2.5g/L, under normal temperature condition, slowly add 400 μ LEu to it3+, molecular self-assembling reacts 2 days, and solution is muddy, has solid particle to generate, and filters and takes out, repeatedly rinses with deionized water, and room temperature is dried, and prepares the fibroin albumen base MOFs material of nanostructured shown in Fig. 2 in accompanying drawing.
0.1g silkworm silk is carried out degumming process by embodiment 3, adopts the calcium chloride water 40mL(CaCl containing ethanol2:EtOH:H2O=1:2:8, reaction temperature is 70 ~ 80 ° of C) it is dissolved to clarification, cooling, filtered through gauze removes impurity, filtrate loads bag filter and puts in deionized water and dialyse, dialyse 3 days, change 3 water every day, obtain the silk fibroin protein solution that concentration is 2.5g/L, under normal temperature condition, slowly add 600 μ LEu to it3+, molecular self-assembling reacts 2 days, and solution is muddy, has solid particle to generate, and filters and takes out, repeatedly rinses with deionized water, and room temperature is dried, and prepares the fibroin albumen base MOFs material of nanostructured as illustrated in figure 3 of the drawings.
0.1g silkworm silk is carried out degumming process by embodiment 4, adopts the calcium chloride water 40mL(CaCl containing ethanol2:EtOH:H2O=1:2:8, reaction temperature is 70 ~ 80 ° of C) it is dissolved to clarification, cooling, filtered through gauze removes impurity, filtrate loads bag filter and puts in deionized water and dialyse, dialyse 3 days, change 3 water every day, obtain the silk fibroin protein solution that concentration is 2.5g/L, under normal temperature condition, slowly add 1000 μ LEu to it3+, molecular self-assembling reacts 2 days, and solution is muddy, has solid particle to generate, and filters and takes out, repeatedly rinses with deionized water, and room temperature is dried, and prepares the fibroin albumen base MOFs material of nanostructured shown in Fig. 4 in accompanying drawing.
0.1g silkworm silk is carried out degumming process by embodiment 5, adopts the calcium chloride water 40mL(CaCl containing ethanol2:EtOH:H2O=1:2:8, reaction temperature is 70 ~ 80 ° of C) it is dissolved to clarification, cooling, filtered through gauze removes impurity, filtrate loads bag filter and puts in deionized water and dialyse, dialyse 3 days, change 3 water every day, obtain the silk fibroin protein solution that concentration is 2.5g/L, be placed in water heating kettle, add 200 μ LEu to it3+With 0.2g dipicolinic acid, after reacting 24h under 80 ° of C, when temperature programmed control, it is down to room temperature with per hour 2 ° of C, solution there is solid particle generate, filter and take out, repeatedly rinse with deionized water, room temperature is dried, and prepares the fibroin albumen base MOFs material of nanostructured as illustrated in figure 5 of the drawings.
Claims (8)
1. the preparation method of a fibroin albumen base nanometer MOFs, its preparation method includes procedure below: first silkworm silk is carried out degumming process, under 70 ~ 80 ° of C, 1g fibroin is dissolved in the 400mL calcium chloride water containing ethanol, natural cooling after solution clarification, remove impurity by filtered through gauze, filtrate is loaded bag filter and puts in deionized water and dialyse, dialyse 3 days, change 3 water every day, obtain the silk fibroin protein solution that concentration is 2.5g/L, load in reagent bottle, be stored in refrigerator cold-storage standby；Under room temperature or hydrothermal reaction condition, adopt different amounts of rare earth ion or rare earth ion and the polycarboxylic mixture of little molecule and silk fibroin protein solution induced reaction, by molecular self-assembling effect synthesis of solid microgranule, filter and take out, repeatedly rinse with deionized water, room temperature is dried, and prepares the fibroin albumen base MOFs material of different nanostructured.
2. the preparation method of a kind of fibroin albumen base nanometer MOFs according to claim 1, it is characterised in that: the described calcium chloride water containing ethanol, its mol ratio is CaCl2:EtOH:H2O=1:2:8。
3. the preparation method of a kind of fibroin albumen base nanometer MOFs according to claim 1, it is characterised in that: described rare earth ion is Eu3+、Tb3+、Pr3+、Nd3+、La3+In the mixture of a kind of or any two kinds of rare earth ions, the mol ratio of double; two rare earth ions is 1:1 ~ 100.
4. the preparation method of a kind of fibroin albumen base nanometer MOFs according to claim 1, it is characterised in that: described rare earth ion and the polycarboxylic mass ratio of little molecule are 1:1 ~ 10.
5. the preparation method of a kind of fibroin albumen base nanometer MOFs according to claim 1, it is characterised in that: described little molecule polycarboxylic acid is: benzoic acid, oxalic acid, fumaric acid, citric acid, pyridinedicarboxylic acid, to the one in benzene dicarboxylic acid, trimesic acid, Pyromellitic Acid or ethylene-dimalonic acid.
6. the preparation method of a kind of fibroin albumen base nanometer MOFs according to claim 1, it is characterised in that: the mass ratio of described rare earth ion and silk fibroin protein solution is 1:30 ~ 300.
7. the preparation method of a kind of fibroin albumen base nanometer MOFs according to claim 1, it is characterised in that: described hydro-thermal reaction is with deionized water for medium, and reaction temperature is 50 ~ 100 ° of C, and the response time is 12 ~ 48h.
8. the preparation method of a kind of fibroin albumen base nanometer MOFs according to claim 1, it is characterised in that: the temperature-fall period of described hydro-thermal reaction, it is necessary to temperature programmed control, rate of temperature fall is 0.5 ~ 5 ° of C per hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610217963.6A CN105801878B (en) | 2016-04-11 | 2016-04-11 | A kind of fibroin albumen base nanometer MOFs preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610217963.6A CN105801878B (en) | 2016-04-11 | 2016-04-11 | A kind of fibroin albumen base nanometer MOFs preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801878A true CN105801878A (en) | 2016-07-27 |
| CN105801878B CN105801878B (en) | 2017-12-29 |
Family
ID=56459676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610217963.6A Expired - Fee Related CN105801878B (en) | 2016-04-11 | 2016-04-11 | A kind of fibroin albumen base nanometer MOFs preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801878B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107184564A (en) * | 2017-05-17 | 2017-09-22 | 浙江大学 | A kind of method of the nuclear shell structure nano microballoons of synthesis fibroin albumen@ZIF 8 |
| CN110498930A (en) * | 2019-09-17 | 2019-11-26 | 江西省吉安市水文局(江西省吉安市水资源监测中心) | A kind of preparation method and applications of Lanthanide Coordination Polymers nano material |
| CN111394999A (en) * | 2020-01-19 | 2020-07-10 | 浙江大学 | Construction method of composite environment-friendly material based on flat wire |
| CN112210890A (en) * | 2020-09-23 | 2021-01-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of iron-based metal organic framework material fiber, product and application thereof |
| CN113384533A (en) * | 2021-06-15 | 2021-09-14 | 西南大学 | Preparation of tirapazamine-loaded silk fibroin ferriporphyrin nano material |
| CN113944053A (en) * | 2021-11-19 | 2022-01-18 | 廊坊师范学院 | Preparation method of MOFs material with detection application in extreme environment |
| CN114106815A (en) * | 2021-12-06 | 2022-03-01 | 廊坊师范学院 | Preparation method of rare earth MOFs protein fiber composite fluorescent sensing material |
| CN114292522A (en) * | 2021-11-30 | 2022-04-08 | 上海工程技术大学 | Preparation method and application of composite film based on fibroin and two-dimensional metal organic framework material and friction nano generator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120237697A1 (en) * | 2011-05-29 | 2012-09-20 | Dr. Amir Reza Abbasi | METHOD FOR SURFACE COATING CuBTC METAL-ORGANIC FRAMEWORK NANOSTRUCTURES ON NATURAL FIBERS |
| CN104987731A (en) * | 2015-07-03 | 2015-10-21 | 苏州大学 | One-dimension nanochain-typed Fe3O4/silk protein compound and preparation method thereof |
-
2016
- 2016-04-11 CN CN201610217963.6A patent/CN105801878B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120237697A1 (en) * | 2011-05-29 | 2012-09-20 | Dr. Amir Reza Abbasi | METHOD FOR SURFACE COATING CuBTC METAL-ORGANIC FRAMEWORK NANOSTRUCTURES ON NATURAL FIBERS |
| CN104987731A (en) * | 2015-07-03 | 2015-10-21 | 苏州大学 | One-dimension nanochain-typed Fe3O4/silk protein compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 艾仕云等: ""纳米银/丝素复合材料的制备及其光谱性质研究"", 《光谱学与光谱分析》 * |
| 韩龙龙等: ""稀土对丝素膜结构及溶解性的作用研究"", 《丝绸》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107184564A (en) * | 2017-05-17 | 2017-09-22 | 浙江大学 | A kind of method of the nuclear shell structure nano microballoons of synthesis fibroin albumen@ZIF 8 |
| CN107184564B (en) * | 2017-05-17 | 2020-06-16 | 浙江大学 | Method for synthesizing silk fibroin @ ZIF-8 core-shell structure nano microspheres |
| CN110498930A (en) * | 2019-09-17 | 2019-11-26 | 江西省吉安市水文局(江西省吉安市水资源监测中心) | A kind of preparation method and applications of Lanthanide Coordination Polymers nano material |
| CN111394999A (en) * | 2020-01-19 | 2020-07-10 | 浙江大学 | Construction method of composite environment-friendly material based on flat wire |
| CN112210890A (en) * | 2020-09-23 | 2021-01-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of iron-based metal organic framework material fiber, product and application thereof |
| CN113384533A (en) * | 2021-06-15 | 2021-09-14 | 西南大学 | Preparation of tirapazamine-loaded silk fibroin ferriporphyrin nano material |
| CN113384533B (en) * | 2021-06-15 | 2022-02-22 | 西南大学 | Preparation of tirapazamine-loaded silk fibroin ferriporphyrin nano material |
| CN113944053A (en) * | 2021-11-19 | 2022-01-18 | 廊坊师范学院 | Preparation method of MOFs material with detection application in extreme environment |
| CN113944053B (en) * | 2021-11-19 | 2024-03-01 | 廊坊师范学院 | Preparation method of MOFs material with detection application in extreme environment |
| CN114292522A (en) * | 2021-11-30 | 2022-04-08 | 上海工程技术大学 | Preparation method and application of composite film based on fibroin and two-dimensional metal organic framework material and friction nano generator |
| CN114292522B (en) * | 2021-11-30 | 2022-11-04 | 上海工程技术大学 | Preparation method and application of composite film based on fibroin and two-dimensional metal organic framework material and friction nano generator |
| CN114106815A (en) * | 2021-12-06 | 2022-03-01 | 廊坊师范学院 | Preparation method of rare earth MOFs protein fiber composite fluorescent sensing material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801878B (en) | 2017-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105801878A (en) | Preparation method of silk fibroin-based nano MOFs (metal-organic frameworks) | |
| CN102120044B (en) | Chitosan and carbon nanometer tube compound surgical dressing and preparation method thereof | |
| CN101891962B (en) | Preparation method of silk fibroin porous three-dimensional material | |
| WO2018072679A1 (en) | Biomimetic biomineralized artificial bone repair material and preparation method therefor and use thereof | |
| CN110330004B (en) | Method for regulating morphology of hydroxyapatite micro-nano material by using phosphorus source | |
| CN101897994B (en) | Biological composite scaffold for repairing bone defect and preparation method thereof | |
| CN102516777B (en) | Aqueous solution of silk fibroin and preparation method for aqueous solution | |
| CN103361885A (en) | Preparation method of antibacterial silk fibroin fibrous membrane | |
| CN100388970C (en) | Method for preparing polylactic porous microball | |
| CN105297289B (en) | A kind of fibroin albumen energy-saving and temperature-regulating fiber membrane preparation method | |
| JP6029078B2 (en) | Method for producing fibroin powder from silk products or silk filaments | |
| CN107537063B (en) | A kind of complex stephanoporate bracket of carbon nanotubes and preparation method thereof | |
| CN107089677A (en) | Preparation method of zinc oxide nanoparticles based on silk fibroin biological template regulation | |
| CN103834050A (en) | Method for preparing gelatin/nano-silver/chitosan derivative composite film | |
| CN107693845A (en) | The bilayer that ectonexine loads HAp and VEGF respectively imitates periosteum material | |
| CN101723341A (en) | Preparation method of hydroxylapatite nano fibers or nano wires | |
| CN103225175B (en) | Method for preparing polyvinyl alcohol nano fibrous membrane containing nano silver and amino acid | |
| CN103007354A (en) | Enhanced calcium phosphate bone repair material and preparation method thereof | |
| CN112921659A (en) | Method for preparing medical wound dressing by micro-fluidic air-jet spinning method | |
| CN108137843A (en) | Porous formed body | |
| CN103656756B (en) | Nano-hydroxyapatite/silk fibroin composite membrane material and preparation method thereof | |
| CN101327341A (en) | Method for preparing nano-scale fibroin-hydroxylapatite mineralized complex fiber | |
| CN101601871B (en) | Bionic bone repair material of mineralized electro-spinning gelatin superfine fibers and preparation method thereof | |
| CN101008642B (en) | Preparation method of nanometer semiconductor biocompatible materials | |
| CN108479650A (en) | A kind of osmanthus flower fragrance-fibroin albumen microcapsules and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171229 Termination date: 20190411 |