CN102140760A - Method for preparing fibroin modified nano zinc oxide biocompatible material - Google Patents
Method for preparing fibroin modified nano zinc oxide biocompatible material Download PDFInfo
- Publication number
- CN102140760A CN102140760A CN 201110086296 CN201110086296A CN102140760A CN 102140760 A CN102140760 A CN 102140760A CN 201110086296 CN201110086296 CN 201110086296 CN 201110086296 A CN201110086296 A CN 201110086296A CN 102140760 A CN102140760 A CN 102140760A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- fibroin
- solution
- biocompatible material
- preparation
- 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
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Cosmetics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Artificial Filaments (AREA)
Abstract
一种纳米材料技术领域的蚕丝蛋白修饰纳米氧化锌生物相容材料的制备方法，将脱胶蚕丝纤维经锌盐浸渍液的浸渍处理，得到含有氧化锌纳米颗粒的固态复合纤维，经CaCl2溶液的溶解和离心分离得到蚕丝蛋白修饰纳米氧化锌生物相容材料。本发明选用来源广泛、生物相容性好的天然桑蚕原丝纤维作为基体材料，工艺简单，技术成本低廉，制得的纳米氧化锌/蚕丝蛋白复合材料的生物相容性较好，并且氧化锌纳米颗粒团聚较少，特别适合应用于生物医用材料和生命科学研究领域。A method for preparing silk protein-modified nano-zinc oxide biocompatible materials in the technical field of nano-materials. The degummed silk fiber is impregnated with a zinc salt impregnating solution to obtain a solid composite fiber containing zinc oxide nanoparticles, which is treated with a CaCl solution. Dissolving and centrifuging to obtain the silk protein modified nano-zinc oxide biocompatible material. The present invention selects the natural mulberry silkworm protosilk fiber with wide sources and good biocompatibility as the base material, the process is simple, the technology cost is low, and the biocompatibility of the prepared nano-zinc oxide/silk protein composite material is good, and it is oxidized Zinc nanoparticles are less agglomerated and are especially suitable for application in the fields of biomedical materials and life science research.
Description
Technical field
What the present invention relates to is a kind of method of technical field of nano material, specifically is a kind of preparation method of fibroin decorated nanometer zinc oxide biocompatible material.
Background technology
Zinc oxide is a kind of semi-conducting material nontoxic, with low cost, and it is widely used among the personal care product.When the Zinc oxide particles yardstick is reduced to Nano grade, it will embody bulk effect that conventional nano material has, quantum size effect, macro quanta tunnel effect, surface-interfacial effect etc.Moreover, nano zine oxide also has the characteristic of antibiotic property and photic visible emitting, makes it be expected to be applied to bio-medical material and life science field, has been subjected to extensive concern in recent years.Yet, because nano zine oxide has higher specific surface area, very easily reunite and instability, be difficult to direct application, therefore often need in actual applications synthetic nano zine oxide is modified to obtain inorganic-organic composite material.There are some drawbacks in the synthetic preparation were established of modifying again of this elder generation, as the synthesis technique complexity, and the cost height, recombination process may cause decreased performance, and the organic decoration component is unfavorable for biocompatibility of product or the like.Therefore need the preparation method of simple and easy, an economic nano zine oxide biocompatible material of exploitation badly.
Find through retrieval prior art, Chinese patent application numbers 200810034036.6, name is called " a kind of Zinc oxide-polyalcohol nucleocapsid type luminous nano-particle and preparation method thereof ", the characteristics of this technology are to adopt the sol-gel chemical reaction to prepare zinc oxide nano-particle, adopt radical polymerization to prepare shell again, obtain to be applied to the Zinc oxide-polyalcohol nucleocapsid type luminous nano-particle of cell fluorescence mark through separating to purify again.Though this technology is successfully prepared the nano zine oxide that can be applicable to the life science field, but the step of preparation process of this technology is more, and the polymer-modified component of using is unfavorable for product long-term existence in vivo, has limited applying of this technology.
Chinese patent application numbers 200910067985.9, name is called " method for preparing nano zinc oxide composite powder with natural polysaccharide ", the characteristics of this technology are to utilize the glucoside structure of natural polysaccharide to control granularity in the zinc oxide generative process, and prevent that the nano zine oxide that generates from big reunion taking place, and obtains nano zine oxide/starch composite granule or nano zine oxide/sodium carboxymethylcellulose composite granule.Though this technology is successfully prepared the nano zine oxide/natural polymer composite granule with biological medicine application prospect, yet, the nano zine oxide that generates in solution is very easily reunited, the effect that prevents big reunion is also only played in the adding of natural polysaccharide, thereby applying of this technology is subjected to certain restriction.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of preparation method of fibroin decorated nanometer zinc oxide biocompatible material is provided, the former silk fiber of natural silkworm of selecting wide material sources, good biocompatibility for use is as matrix material, technology is simple, technical costs is cheap, the biocompatibility of the nano zine oxide that makes/fibroin composite is better, and the Zinc oxide nanoparticle reunion is less, is particularly suitable for being applied to bio-medical material and life science field.
The present invention is achieved by the following technical solutions, the present invention is with the impregnation process of boiled silk fiber through the zinc salt maceration extract, obtain containing the solid-state composite fibre of Zinc oxide nanoparticle, obtain fibroin decorated nanometer zinc oxide biocompatible material through the dissolving and the centrifugation of CaCl2 solution.
The base material of described boiled silk fiber is the former silk fiber of natural silkworm, prepare in the following manner: place pH to carry out the hydro-thermal processing of coming unstuck the silkworm precursor smaller or equal to 7 sodium-salt aqueous solution, take out the back and preserve, obtain the boiled silk fiber with abundant rinsing of deionized water and vacuumize.
The consumption of described silkworm precursor is the corresponding 40mL sodium salt solution of 0.1g, and treatment temperature is 100～120 ℃, and the processing time is 0.5～2 hour.
The mass percent of sodium salt is 0.5～1.5% in the described sodium-salt aqueous solution.
Described sodium salt is NaOH (NaOH), sodium carbonate (Na
2CO
3), sodium bicarbonate (NaHCO
3), sodium acetate (NaAc), sodium nitrate (NaNO
3), sodium sulphate (Na
2SO
4), a kind of or combination in sodium chloride (NaCl) or the sodium bromide (NaBr).
Described impregnation process is meant: with the 70 ℃ of immersion 15～30min in the DMF of zinc acetate solution of boiled silk fiber elder generation, takes out and uses N, and the abundant rinsing of dinethylformamide, and then render to zinc acetate and H
2110～130 ℃ are soaked 10min in the DMF solution of O, take out and use N, and the abundant rinsing of dinethylformamide and deionized water is after vacuumize promptly gets the solid-state composite fibre that contains Zinc oxide nanoparticle.
Zinc ion concentration is 0.04mol/L in the DMF solution of described zinc acetate;
Described zinc acetate and H
2Zinc ion concentration is 0.04～0.08mol/L in the DMF solution of O, Zn
2+With H
2The concentration ratio of O is can obtain homodisperse Zinc oxide nanoparticle at 0.08～0.1 o'clock.
Described solid-state composite fibre and CaCl
2The ratio of solution is 0.4g: 25～30mL, and solution temperature is 45～60 ℃, and dissolution time is 1.5～5 hours.
Described CaCl
2Solution is meant: mol ratio is 1: 8: 2 CaCl
2: H
2O: C
2H
5The mixed solution of OH.
The fibroin decorated nanometer zinc oxide biocompatible material that the present invention obtains by method for preparing, its average grain diameter is 10～15nm, narrow diameter distribution, on silk fiber homodisperse nano zine oxide, can finally obtain the nano zine oxide that fibroin is modified through further processing.
The present invention utilizes the biomimesis synthetic technology, the complex process of nano zine oxide technology of preparing existence in the past, the bottleneck problems such as difficult control and the difficult improvement of biocompatibility of reuniting have been solved effectively, the scheme that is proposed is simple and easy to do, not only utilize the building-up process of natural silk fiber control nano zine oxide, also utilize natural silk albumen to improve the biocompatibility of product.The nano zine oxide that the present invention makes/fibroin composite good stability, biocompatibility is good, the size of nano particle and being evenly distributed, and it is less to reunite, and under UV-irradiation, can launch orange-yellow fluorescence, be particularly suitable as biological labled material.Consider the extensive use of natural silk in medical field, this composite is of great immediate significance in fields such as bio-medical material and life sciences and potential using value.
The specific embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Select biomaterial silkworm precursor 0.1g, be placed on the 40mL mass percent concentration and be and carry out the hydro-thermal processing of coming unstuck in 0.5% the aqueous sodium carbonate, treatment temperature is 110 ℃, processing time is 1 hour, take out the sodium salt of removing the surface with the abundant rinsing of deionized water then, preserve through vacuumize, obtain the boiled silk fiber.The boiled silk fiber is immersed in the DMF solution of the 0.04mol/L zinc acetate for preparing, soak 15min, take out with the abundant rinsing of DMF, and then render to zinc acetate (0.04mol/L) and the H for preparing at 70 ℃
2In the DMF solution of O (0.44mol/L), soak 10min, take out with DMF and the abundant rinsing of deionized water at 110 ℃.Vacuumize promptly gets nano zine oxide/silk fibre composites, 0.4g nano zine oxide/silk fiber be impregnated in the CaCl of 25mL
2In the solution, soaked 2 hours, obtain the suspension of fibroin decorated nanometer zinc oxide at 60 ℃.Suspension is carried out centrifugal treating, isolate nano zine oxide/fibroin precipitation, use CaCl successively
2Solution and deionized water washing obtain fibroin decorated nanometer zinc oxide biocompatible material.Wherein the average grain diameter of nano zine oxide is 13nm, evenly disperses the orange-yellow fluorescence of emission under the irradiation of ultraviolet light, the defect luminescence of corresponding nano zine oxide.
Embodiment 2
Select biomaterial silkworm precursor 0.5g, be placed on the 200mL mass percent concentration and be and carry out the hydro-thermal processing of coming unstuck in 0.5% the sodium hydrate aqueous solution, treatment temperature is 110 ℃, processing time is 1.5 hours, take out then with the abundant rinsing of deionized water to remove the sodium salt on surface, preserve through vacuumize, obtain the boiled silk fiber.The boiled silk fiber is immersed in the DMF solution of the 0.04mol/L zinc acetate for preparing, soak 20min, take out with the abundant rinsing of DMF, and then render to zinc acetate (0.08mol/L) and the H for preparing at 70 ℃
2In the DMF solution of O (0.88mol/L), soak 10min, take out with DMF and the abundant rinsing of deionized water at 120 ℃.Vacuumize promptly gets nano zine oxide/silk fibre composites, 0.4g nano zine oxide/silk fiber be impregnated in the CaCl of 30mL
2In the solution, soaked 4 hours, obtain the suspension of fibroin decorated nanometer zinc oxide at 50 ℃.Suspension is carried out centrifugal treating, isolate nano zine oxide/fibroin precipitation, use CaCl successively
2Solution and deionized water washing obtain fibroin decorated nanometer zinc oxide biocompatible material.Wherein the average grain diameter of nano zine oxide is 13nm, evenly disperses the orange-yellow fluorescence of emission under the irradiation of ultraviolet light, the defect luminescence of corresponding nano zine oxide.
Embodiment 3
Select biomaterial silkworm precursor 0.1g, be placed on the 40mL mass percent concentration and be and carry out the hydro-thermal processing of coming unstuck in 1% the aqueous sodium carbonate, treatment temperature is 100 ℃, processing time is 1.5 hours, take out then with the abundant rinsing of deionized water to remove the sodium salt on surface, preserve through vacuumize, obtain the boiled silk fiber.The boiled silk fiber is immersed in the DMF solution of the 0.04mol/L zinc acetate for preparing, soak 15min, take out with the abundant rinsing of DMF, and then render to zinc acetate (0.08mol/L) and the H for preparing at 70 ℃
2In the DMF solution of O (0.53mol/L), soak 10min, take out with DMF and the abundant rinsing of deionized water at 110 ℃.Vacuumize promptly gets nano zine oxide/silk fibre composites, 0.4g nano zine oxide/silk fiber be impregnated in the CaCl of 25mL
2In the solution, soaked 2 hours, obtain the suspension of fibroin decorated nanometer zinc oxide at 60 ℃.Suspension is carried out centrifugal treating, isolate nano zine oxide/fibroin precipitation, use CaCl successively
2Solution and deionized water washing obtain fibroin decorated nanometer zinc oxide biocompatible material.Wherein the agglomeration of nano zine oxide is comparatively serious, the nano particle aggregate about a lot of 200nm occurs.
Claims (10)
1. the preparation method of a fibroin decorated nanometer zinc oxide biocompatible material is characterized in that, with the impregnation process of boiled silk fiber through the zinc salt maceration extract, obtains containing the solid-state composite fibre of Zinc oxide nanoparticle, through CaCl
2The dissolving of solution and centrifugation obtain fibroin decorated nanometer zinc oxide biocompatible material.
2. the preparation method of fibroin decorated nanometer zinc oxide biocompatible material according to claim 1 is characterized in that, the base material of described boiled silk fiber is the former silk fiber of natural silkworm.
3. the preparation method of fibroin decorated nanometer zinc oxide biocompatible material according to claim 1 and 2, it is characterized in that, described boiled silk fiber prepares in the following manner: place pH to carry out the hydro-thermal processing of coming unstuck smaller or equal to 7 sodium-salt aqueous solution the silkworm precursor, take out the back and preserve, obtain the boiled silk fiber with abundant rinsing of deionized water and vacuumize.
4. the preparation method of fibroin decorated nanometer zinc oxide biocompatible material according to claim 3, it is characterized in that, the consumption of described silkworm precursor is the corresponding 40mL sodium salt solution of 0.1g, and treatment temperature is 100～120 ℃, and the processing time is 0.5～2 hour..
5. the preparation method of fibroin decorated nanometer zinc oxide biocompatible material according to claim 3 is characterized in that the mass percent of sodium salt is 0.5～1.5% in the described sodium-salt aqueous solution.
6. the preparation method of fibroin decorated nanometer zinc oxide biocompatible material according to claim 1, it is characterized in that, described impregnation process is meant: with the 70 ℃ of immersion 15～30min in the DMF of zinc acetate solution of boiled silk fiber elder generation, take out and use N, the abundant rinsing of dinethylformamide, and then render to zinc acetate and H
2110～130 ℃ are soaked 10min in the DMF solution of O, take out and use N, and the abundant rinsing of dinethylformamide and deionized water is after vacuumize promptly gets the solid-state composite fibre that contains Zinc oxide nanoparticle.
7. the preparation method of fibroin decorated nanometer zinc oxide biocompatible material according to claim 6 is characterized in that zinc ion concentration is 0.04mol/L in the DMF solution of described zinc acetate; Described zinc acetate and H
2Zinc ion concentration is 0.04～0.08mol/L in the DMF solution of O, Zn
2+With H
2The concentration ratio of O is can obtain homodisperse Zinc oxide nanoparticle at 0.08～0.1 o'clock.
8. the preparation method of fibroin decorated nanometer zinc oxide biocompatible material according to claim 1 is characterized in that, described solid-state composite fibre and CaCl
2The ratio of solution is 0.4g: 25～30mL, and solution temperature is 45～60 ℃, and dissolution time is 1.5～5 hours.
9. according to the preparation method of claim 1 or 8 described fibroin decorated nanometer zinc oxide biocompatible materials, it is characterized in that described CaCl
2Solution is meant: mol ratio is 1: 8: 2 CaCl
2: H
2O: C
2H
5The mixed solution of OH.
10. a fibroin decorated nanometer zinc oxide biocompatible material is characterized in that, prepares according to the described method of above-mentioned arbitrary claim, and its average grain diameter is 10～15nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110086296 CN102140760B (en) | 2011-04-07 | 2011-04-07 | Method for preparing fibroin modified nano zinc oxide biocompatible material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110086296 CN102140760B (en) | 2011-04-07 | 2011-04-07 | Method for preparing fibroin modified nano zinc oxide biocompatible material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102140760A true CN102140760A (en) | 2011-08-03 |
| CN102140760B CN102140760B (en) | 2012-12-12 |
Family
ID=44408539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110086296 Expired - Fee Related CN102140760B (en) | 2011-04-07 | 2011-04-07 | Method for preparing fibroin modified nano zinc oxide biocompatible material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102140760B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572507A (en) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for antibiosis ultraviolet prevention silk fibroin nanofiber membrane |
| CN103898735A (en) * | 2014-04-11 | 2014-07-02 | 西南大学 | Preparation method and product of zinc oxide nanorod matrix modified silk |
| CN106990088A (en) * | 2017-06-08 | 2017-07-28 | 厦门大学 | A kind of photon crystal humidity sensor and preparation method thereof |
| CN108318546A (en) * | 2018-04-27 | 2018-07-24 | 杭州电子科技大学 | Regulate and control the NO of multi-element metal oxide composite material based on silk-fibroin2The preparation method of gas sensor |
| CN110721318A (en) * | 2019-11-20 | 2020-01-24 | 温州医科大学 | Disulfiram nano-particles and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927969A (en) * | 1973-09-24 | 1975-12-23 | Us Agriculture | Insectproofing wool with zinc acetate |
| JPH0351365A (en) * | 1989-07-18 | 1991-03-05 | Nippon Keori Kk | Deodorizing fiber and production thereof |
| CN1865501A (en) * | 2006-06-22 | 2006-11-22 | 上海交通大学 | Process for preparing nano noble metal reinforced silk fiber-base composite materials |
| CN101008642A (en) * | 2007-01-25 | 2007-08-01 | 上海交通大学 | Preparation method of nanometer semiconductor biocompatible materials |
| CN101446036A (en) * | 2008-12-26 | 2009-06-03 | 苏州大学 | Method for adhering sericin and nanometer material on real silk fabric |
| CN101965315A (en) * | 2008-03-10 | 2011-02-02 | 塔塔化学有限公司 | Process for the preparation of nano zinc oxide particles |
-
2011
- 2011-04-07 CN CN 201110086296 patent/CN102140760B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927969A (en) * | 1973-09-24 | 1975-12-23 | Us Agriculture | Insectproofing wool with zinc acetate |
| JPH0351365A (en) * | 1989-07-18 | 1991-03-05 | Nippon Keori Kk | Deodorizing fiber and production thereof |
| CN1865501A (en) * | 2006-06-22 | 2006-11-22 | 上海交通大学 | Process for preparing nano noble metal reinforced silk fiber-base composite materials |
| CN101008642A (en) * | 2007-01-25 | 2007-08-01 | 上海交通大学 | Preparation method of nanometer semiconductor biocompatible materials |
| CN101965315A (en) * | 2008-03-10 | 2011-02-02 | 塔塔化学有限公司 | Process for the preparation of nano zinc oxide particles |
| CN101446036A (en) * | 2008-12-26 | 2009-06-03 | 苏州大学 | Method for adhering sericin and nanometer material on real silk fabric |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572507A (en) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for antibiosis ultraviolet prevention silk fibroin nanofiber membrane |
| CN103898735A (en) * | 2014-04-11 | 2014-07-02 | 西南大学 | Preparation method and product of zinc oxide nanorod matrix modified silk |
| CN103898735B (en) * | 2014-04-11 | 2015-09-02 | 西南大学 | Zinc oxide nano rod matrix modifies preparation method of silk and products thereof |
| CN106990088A (en) * | 2017-06-08 | 2017-07-28 | 厦门大学 | A kind of photon crystal humidity sensor and preparation method thereof |
| CN108318546A (en) * | 2018-04-27 | 2018-07-24 | 杭州电子科技大学 | Regulate and control the NO of multi-element metal oxide composite material based on silk-fibroin2The preparation method of gas sensor |
| CN108318546B (en) * | 2018-04-27 | 2021-05-11 | 杭州电子科技大学 | Preparation method of NO2 gas sensor based on silk protein regulation |
| CN110721318A (en) * | 2019-11-20 | 2020-01-24 | 温州医科大学 | Disulfiram nano-particles and preparation method and application thereof |
| CN110721318B (en) * | 2019-11-20 | 2023-06-13 | 温州医科大学 | Disulfiram nanoparticle and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102140760B (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102140760A (en) | Method for preparing fibroin modified nano zinc oxide biocompatible material | |
| CN104872082B (en) | A kind of nano zine oxide for preparing high-performance silk freshens food and educates silkworm method and its product | |
| CN106012677B (en) | Nano Silver composite hydroxylapatite overlong nanowire anti-bacteria paper | |
| CN104878468A (en) | Nano-titanium dioxide-feeding silkworm rearing method for preparing high-performance silk and product prepared by nano-titanium dioxide-feeding silkworm rearing method | |
| CN102491298A (en) | Preparation method for linear nanometre hydroxylapatite | |
| CN106592005A (en) | Nano-composite fiber material and preparation method thereof | |
| CN107620221A (en) | A kind of paper pulp fiber reduction and the method for loading nano silvery particle | |
| CN107089677A (en) | Preparation method of zinc oxide nanoparticles based on silk fibroin biological template regulation | |
| Figueiredo et al. | Bacterial Cellulose‐based nanocomposites: roadmap for innovative materials | |
| CN106835673A (en) | A kind of UV resistance zinc oxide silk composite fiber and preparation method thereof | |
| CN103319739A (en) | Preparation method of chitin nanofiber/polylactic acid composite film | |
| CN104294582A (en) | Preparation method of anti-ultraviolet finishing agent for silk fabric | |
| CN103498331A (en) | Nano TiO2/ZnO-doped composite hydrosol, and preparation method thereof and finishing method of textile | |
| CN102605459A (en) | Tourmaline/chitosan composite material and preparation method thereof | |
| CN104878467A (en) | Nano-aluminum oxide-feeding silkworm rearing method for preparing high-performance silk and product prepared by nano-aluminum oxide-feeding silkworm rearing method | |
| CN106216709A (en) | A kind of method preparing O carboxymethyl chitosan parcel nanometer silver | |
| CN1635033A (en) | Modified nano oxide, preparation method and use thereof | |
| Plumejeau et al. | Hybrid metal oxide@ biopolymer materials precursors of metal oxides and metal oxide-carbon composites | |
| CN106519307A (en) | Bacterial cellulose/fullerene composite material and preparation method thereof | |
| CN100460064C (en) | Preparation method of biomorphic three-dimensional network structure palladium-based nano-photocatalytic material | |
| CN104336069A (en) | Antibacterial and antifungal agent of Fe3+ doped multi-needle nano-ZnO and preparation method thereof | |
| CN106046423A (en) | Method for preparing nanometer ZnO/cellulose composite materials | |
| CN101008642B (en) | Preparation method of nanometer semiconductor biocompatible materials | |
| CN101475726B (en) | Polymethyl methacryate microsphere coating zinc oxide composite material and preparation thereof | |
| CN115058787A (en) | Preparation method of antibacterial and antiviral cool fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121212 Termination date: 20150407 |
|
| EXPY | Termination of patent right or utility model |