CN102140760B - Method for preparing fibroin modified nano zinc oxide biocompatible material - Google Patents
Method for preparing fibroin modified nano zinc oxide biocompatible material Download PDFInfo
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- CN102140760B CN102140760B CN 201110086296 CN201110086296A CN102140760B CN 102140760 B CN102140760 B CN 102140760B CN 201110086296 CN201110086296 CN 201110086296 CN 201110086296 A CN201110086296 A CN 201110086296A CN 102140760 B CN102140760 B CN 102140760B
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Abstract
The invention relates to a method for preparing a fibroin modified nano zinc oxide biocompatible material in the technical field of nanomaterials. The method comprises the following steps of: impregnating degummed silk fibers by using zinc salt impregnation liquid to obtain solid composite fibers containing zinc oxide nanoparticles; and dissolving in CaCl2 solution, and performing centrifugal separation to obtain the fibroin modified nano zinc oxide biocompatible material. Natural silkworm precursor fibers which are wide in source and high in biocompatibility are taken as a base material, the process is simple, technical cost is low, the prepared nano zinc oxide/fibroin composite material has high biocompatibility and is particularly suitable for the fields of biomedical materials and life science research, and a small number of zinc oxide nanoparticles are agglomerated.
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 received 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 modify to obtain inorganic-organic composite material in actual applications synthetic nano zine oxide.There are some drawbacks in the synthetic preparation were established of modifying again of this elder generation, and complicated like synthesis technique, cost is high, and recombination process possibly 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.
Retrieval through to prior art is found; One Chinese patent application numbers 200810034036.6; Name is called " a kind of Zinc oxide-polyalcohol nucleocapsid type luminous nano-particle and preparation method thereof "; These technological characteristics 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 step of preparation process that should 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.
One Chinese patent application numbers 200910067985.9; Name is called " method for preparing nano zinc oxide composite powder with natural polysaccharide "; These technological characteristics are to utilize the glucoside structure of natural polysaccharide to control the granularity in the zinc oxide generative process; And prevent that the nano zine oxide that generates from people's 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 in solution, generates 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 receives certain restriction.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of preparation method of fibroin decorated nanometer zinc oxide biocompatible material is provided, and the former silk fiber of natural silkworm of selecting wide material sources, good biocompatibility for use is as matrix material, and 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 realizes that through following technical scheme the present invention obtains containing the solid-state composite fibre of Zinc oxide nanoparticle, through CaCl with the impregnation process of boiled silk fiber through the zinc salt maceration extract
2The dissolving of solution and centrifugation obtain fibroin decorated nanometer zinc oxide biocompatible material.
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 more than 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 acid carbonate (NaHCO
3), sodium acetate (NaAc), sodium nitrate (NaNO
3), sodium sulphate (Na
2SO
3), 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 molar concentration rate 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 the CaCl of l:8:2
2: H
2O:C
2H
5The mixed solution of OH.
The fibroin decorated nanometer zinc oxide biocompatible material that the present invention obtains through 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 be evenly distributed, it is less to reunite; And under UV-irradiation, can launch orange-yellow fluorescence, be particularly suitable for 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
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
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 ℃, and the processing time is 1 hour, takes 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 impregnated in the CaCl of 25mL
2, in the solution, soaked 2 hours at 60 ℃, obtain the suspension of fibroin decorated nanometer zinc oxide.Suspension is carried out centrifugal treating, isolate nano zine oxide/fibroin deposition, 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 ℃, and the processing time is 1.5 hours, takes 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 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 deposition, 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 ℃, and the processing time is 1.5 hours, takes 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 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 deposition, 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 (9)
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 CaC1
2The dissolving of solution and centrifugation obtain fibroin decorated nanometer zinc oxide biocompatible material;
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 N-dimethyl methyl acid amide and deionized water is after vacuumize promptly gets the solid-state composite fibre that contains Zinc oxide nanoparticle.
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 more than 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 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 molar concentration rate of O is can obtain homodisperse Zinc oxide nanoparticle at 0.08～0.1 o'clock.
7. 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.
8. according to the preparation method of claim 1 or 7 described fibroin decorated nanometer zinc oxide biocompatible materials, it is characterized in that described CaCl
2Solution is meant: mol ratio is the CaCl of 1:8:2
2: H
2O:C
2H
5The mixed solution of OH.
9. a fibroin decorated nanometer zinc oxide biocompatible material is characterized in that, prepares according to the arbitrary said method of claim 1-8, and its average grain diameter is 10～15nm.
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| 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 |
| 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 |
| CN106990088B (en) * | 2017-06-08 | 2019-09-27 | 厦门大学 | A kind of photon crystal humidity sensor and preparation method thereof |
| 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 fibroin regulation |
| CN110721318B (en) * | 2019-11-20 | 2023-06-13 | 温州医科大学 | Disulfiram nanoparticle and preparation method and application thereof |
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| 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 |
| CN101008642B (en) * | 2007-01-25 | 2011-04-13 | 上海交通大学 | Preparation method of nanometer semiconductor biocompatible materials |
| BRPI0909430A2 (en) * | 2008-03-10 | 2015-12-08 | Tata Chemicals Ltd | process for preparing zinc oxide nanoparticles |
| CN101446036B (en) * | 2008-12-26 | 2011-03-16 | 苏州大学 | Method for adhering sericin and nanometer material on real silk fabric |
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