CN101008642B - Preparation method of nanometer semiconductor biocompatible materials - Google Patents
Preparation method of nanometer semiconductor biocompatible materials Download PDFInfo
- Publication number
- CN101008642B CN101008642B CN2007100368028A CN200710036802A CN101008642B CN 101008642 B CN101008642 B CN 101008642B CN 2007100368028 A CN2007100368028 A CN 2007100368028A CN 200710036802 A CN200710036802 A CN 200710036802A CN 101008642 B CN101008642 B CN 101008642B
- Authority
- CN
- China
- Prior art keywords
- sodium
- solution
- semiconductor
- silk fiber
- deionized water
- 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.)
- Expired - Fee Related
Links
Landscapes
- Peptides Or Proteins (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a preparation method of a nanometer semiconductor biocompatible material, which selects the silk fiber with wide source and good biocompatibility as the decoration material of the nanometer semiconductor, by means of degumming, dissolving and dialyzing the silk fiber and combining with dipping optimization technique, thereby obtaining the nanometer semiconductor biocompatible material decorated by the silk protein. The preparation method comprises the following steps: firstly degumming, pre-processing the silkworm protofilament to activate the amino acid on the surface of the fiber; secondly dipping in the metal salt solution and the sulfide solution in turn to perform optimization treatment, namely in-situ synthesizing the nanometer semiconductor particles with stable load on the silk fibre; then resolving through CaCl2 resolution and further dialyzing, thereby obtaining the nanometer metal sulfide semiconductor biocompatible material decorated by the silk protein. The invention has the advantages of simple process and low cost; the prepared nanocomposite has good biocompatibility, and has important application value in the fields of immunoanalysis, gene analysis, in vivo fluorescent imaging, clinic diagnosis, pharmaceutical screening, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer semiconductor biocompatible materials, specifically be by silk fiber is come unstuck, dissolving and dialysis treatment and obtain the nanometer semiconductor biocompatible materials that fibroin is modified in conjunction with the dipping optimisation technique, belong to new material technology field.
Background technology
Nano semiconductor material has many properties different with body phase material, as fluorescence, nonlinear optics, chemical activity, photoelectrocatalysis, opto-electronic conversion etc., many potential using values are arranged in national defence, electronics, chemical industry, nuclear technology, metallurgy, aviation, medicine, field such as false proof.Yet nano particle has higher specific surface area, the active easily oxidation in surface, very easily reunite and instability, and the defect luminescence that causes of surface imperfection has limited the performance of Nano semiconductor excellent fluorescence again, the inorganic nano material surfaces for biocompatibility is poor in addition, causes Nano semiconductor to be difficult to directly be used.In order to address these problems, must modify to obtain to have the nano composite material of actual application value its surface according to specific needs.
Nano semiconductor particles is modified the following certain methods of common employing: inorganics pack, surfactant pack, organic molecule pack, organic solvent pack, the auxiliary synthetic method of biomacromolecule.Wherein, the inorganics pack is the semi-conductive surface imperfection of decorated nanometer well, passivated surface is with the stabilized nanoscale semiconductor particle, and raising fluorescence quantum yield, yet it is synthetic to carry out in organic solvent often, and product water dissolubility and biocompatibility are poor, and Nano semiconductor particles is applied to biological field, also need its surface to be modified to improve water-soluble and biocompatibility, preparation process is quite complicated again.As seen, Nano semiconductor particles is applied to biological field, investigates above several method with biocompatibility, then the auxiliary synthetic method of biomacromolecule has maximum advantage.The auxiliary synthetic method of biomacromolecule is directly to adopt the synthetic and decorated nanometer semiconductor particle (or claiming fluorescence quantum) of biomacromolecule, constitute nanometer semiconductor biocompatible materials, at immunoassay, genetic analysis, the living body fluorescent imaging, clinical diagnosis, fields such as drug screening are with a wide range of applications.
Find by literature search, a lot of reports around preparation biocompatibility nano-functional material have been arranged, as Chinese patent 200610018657.6, name is called " a kind of stable water soluble chitin derivatives fluorescent quantal-points and preparation method thereof ", the technical characterstic of this patent is with the chitosan derivatives to be template, form nano microcrystalline in its position, molecule grid Central Plains growth, particle diameter is between 2～6nm.Its preparation method is that chitosan derivatives is dissolved in the distilled water, under the stirring at room condition, add metal salt solution and form complex compound, continuing to add under the high-speed stirred sulfur family precursor solution formation Nano semiconductor crystallite is quantum dot again, through reflux, dialysis, obtain size homogeneous, quantum dot solution that fluorescence efficiency is high.Yet in course of reaction, need to use nitrogen protection, limited it and applied.And for example United States Patent (USP) 7,129,058, name is called " Method ofproduction of a nanoparticle of a compound semiconductor in a cavity of protein ", the technical characterstic of this patent is to utilize the specified protein molecule (as apoferritin, Dps albumen, CCMV albumen, or TMV albumen etc.) inwall is electronegative hole, presoma with Cd or Zn, the presoma of S or Se mixes with above-mentioned protein solution, synthetic quantum dot particle in the hole, synthetic quantum dot size depends on the size in specified protein molecule hole, and the continuous adjustability of size is restricted.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of nanometer semiconductor biocompatible materials is provided, technology is simple relatively, technical costs is cheap, and the Nano semiconductor compound substance good biocompatibility that makes is at immunoassay, genetic analysis, the living body fluorescent imaging, clinical diagnosis, fields such as drug screening are with a wide range of applications.
For realizing this purpose, the present invention selects wide material sources for use, the silk fiber of good biocompatibility is as the decorative material of Nano semiconductor, by silk fiber is come unstuck, dissolving and dialysis treatment and in conjunction with the dipping optimisation technique, obtain the nanometer semiconductor biocompatible materials that fibroin is modified.At first the silkworm precursor is come unstuck pre-service with the amino acid on activation fiber surface, then in metal salt solution and sulfide solution, flood the i.e. Nano semiconductor particles of original position synthesizing stable load on silk fiber of optimization process successively, pass through CaCl again
2The dissolving of solution and further through dialysis treatment promptly obtains the nano metal sulphide semiconductor biocompatible materials that fibroin is modified.
Method concrete steps of the present invention are as follows:
1, selects biomaterial silkworm precursor, be placed on and carry out the hydro-thermal processing of coming unstuck in alkalescence or the neutral sodium-salt aqueous solution, the silk consumption is 0.1g silkworm precursor correspondence 35～45mL sodium-salt aqueous solution, treatment temperature is 100～120 ℃, processing time is 0.5～2 hour, take out then with the abundant rinsing of deionized water to remove the sodium salt on surface, preserve through vacuum drying again, obtain the boiled silk fiber.The mass percent of sodium salt is 0.5～1.5% in the described sodium-salt aqueous solution.
2, adopt dipping to optimize technology original position on silk fiber and generate Nano semiconductor particles.Being about to the boiled silk fiber soaked 3～5 days in concentration is the metal salt solution of 0.1～1mol/L earlier, taking-up is with the abundant rinsing of deionized water, and then render in the sulphur source solution that concentration is 0.1～0.4mol/L and soaked 1～48 hour, taking-up is with the abundant rinsing of deionized water, again through vacuum drying, the silk fiber of Nano semiconductor particles that obtained load.
3, the load that step 2 is obtained the silk fiber of Nano semiconductor particles place CaCl
2Handle the silk consumption has been 0.4g load silk correspondence 25～30mL CaCl of Nano semiconductor particles in the solution
2Solution, treatment temperature are 45～60 ℃, and the processing time is 1.5～5 hours.Obtain the uniform yellow liquid of clarification.
4, the uniform yellow liquid of clarification that step 3 is obtained places 6000～8000 regenerated cellulose film bag filters, with deionized water dialysis 2～3 days, changes deionized water every day one time.Finally obtain clarifying uniform weak yellow liquid, be prepared nanometer semiconductor biocompatible materials.
Sodium salt described in the step 1 of the present invention refers to NaOH (NaOH), sodium carbonate (Na especially
2CO
3), sodium bicarbonate (NaHCO
3), sodium acetate (NaAc), sodium nitrate (NaNO
3), sodium sulphate (Na
2SO
4), sodium chloride (NaCl), sodium bromide (NaBr), get wherein one or more.
Sodium-salt aqueous solution concentration described in the step 1 of the present invention and pH value and hydrothermal treatment consists condition etc. are determined according to needs of production, to guarantee that silk is come unstuck and activates the corresponding amino acid in silk fiber surface is purpose.
The metal salt solution of choosing described in the step 2 of the present invention is caddy (CdCl
2) solution; Sulphur source solution is sodium sulphide (Na
2S) solution.
CaCl described in the step 3 of the present invention
2Solution refers to that especially mol ratio is the CaCl of 1:8:2
2: H
2O:C
2H
5The OH mixed solution.
Described in the step 3 of the present invention at CaCl
2Processing time in the solution in the light of actual conditions decides, and is purpose to obtain the uniform yellow liquid of clarification.
Dialysis time described in the step 4 of the present invention is in the light of actual conditions decided, to remove the CaCl in the solution
2Be purpose.
The present invention has substantive distinguishing features and marked improvement.The present invention is by the amino acid of pre-service with activation silk fiber surface that the silkworm precursor is come unstuck; Then in metal salt solution and sulfide solution, flood optimization process successively, i.e. the Nano semiconductor particles of original position synthesizing stable load on silk fiber; Pass through CaCl again
2The dissolving of solution and further through dialysis treatment promptly obtains the nano metal sulphide semiconductor biocompatible materials that fibroin is modified.The nanometer semiconductor biocompatible materials institutional framework that the present invention makes is even, biocompatibility is good, good stability, and the size of nano particle can be controlled by regulating impregnation technology.This preparation method is simple and easy to do, low cost of manufacture and environmental protection, bottleneck problems such as the difficult adjusting of preparing technique process complexity, cost height and particle size in the past, biocompatibility difference have been solved effectively, for preparation biocompatibility nano-functional material provides the technological guidance.The nanometer semiconductor biocompatible materials of the present invention's preparation will be at immunoassay, genetic analysis, and the living body fluorescent imaging, clinical diagnosis, fields such as drug screening are with a wide range of applications.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described.Following examples do not constitute limitation of the invention.
Embodiment 1
Select biomaterial silkworm precursor 0.6g, be placed on the 240mL 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 1.5 hours, take out the sodium salt of removing the surface with the abundant rinsing of deionized water then, preserve through vacuum drying, obtain the boiled silk fiber.The boiled silk fiber is immersed in the cadmium chloride solution of the 0.1mol/L prepare and soaked 120 hours, taking-up is with the abundant rinsing of deionized water, and then render in the sodium sulphide maceration extract of the 0.2mol/L for preparing and soaked 48 hours, taking-up is with the abundant rinsing of deionized water, again through vacuum drying, the silk fiber of Nano semiconductor particles that obtained load.This load of weighing 0.4g the silk fiber of Nano semiconductor particles, put it into the CaCl that the 25mL mol ratio is 1:8:2
2: H
2O:C
2H
5In the OH mixed solution,, obtain the uniform yellow liquid of clarification 45 ℃ of insulations 5 hours.Again this liquid is placed 6000～8000 regenerated cellulose film bag filters,, change deionized water every day one time with deionized water dialysis 3 days.Finally obtain clarifying uniform weak yellow liquid, i.e. nanometer semiconductor biocompatible materials.
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 100 ℃, processing time is 1 hour, take out then with the abundant rinsing of deionized water to remove the sodium salt on surface, preserve through vacuum drying, obtain the boiled silk fiber.The boiled silk fiber is immersed in the cadmium chloride solution of the 0.1mol/L prepare and soaked 100 hours, taking-up is with the abundant rinsing of deionized water, and then render in the sodium sulphide maceration extract of the 0.1mol/L for preparing and soaked 12 hours, taking-up is with the abundant rinsing of deionized water, again through vacuum drying, the silk fiber of Nano semiconductor particles that obtained load.This load of weighing 0.2g the silk fiber of Nano semiconductor particles, put it into the CaCl that the 13mL mol ratio is 1:8:2
2: H
2O:C
2H
5In the OH mixed solution,, obtain the uniform yellow liquid of clarification 60 ℃ of insulations 2 hours.Again this yellow liquid is placed 6000～8000 regenerated cellulose film bag filters,, change deionized water every day one time with deionized water dialysis 2 days.Finally obtain clarifying uniform weak yellow liquid, i.e. nanometer semiconductor biocompatible materials.
Embodiment 3
Select biomaterial silkworm precursor 1g, be placed on the 400mL mass percent concentration and be and carry out the hydro-thermal processing of coming unstuck in 1% the aqueous sodium carbonate, treatment temperature is 120 ℃, processing time is 2 hours, take out then with the abundant rinsing of deionized water to remove the sodium salt on surface, preserve through vacuum drying, obtain the boiled silk fiber.The boiled silk fiber is immersed in the cadmium chloride solution of the 0.5mol/L prepare and soaked 120 hours, taking-up is with the abundant rinsing of deionized water, and then render in the sodium sulphide maceration extract of the 0.1mol/L for preparing and soaked 1 hour, taking-up is with the abundant rinsing of deionized water, again through vacuum drying, the silk fiber of Nano semiconductor particles that obtained load.This load of weighing 0.6g the silk fiber of Nano semiconductor particles, put it into the CaCl that the 38mL mol ratio is 1:8:2
2: H
2O:C
2H
5In the OH mixed solution,, obtain the uniform yellow liquid of clarification 60 ℃ of insulations 5 hours.Again this yellow liquid is placed 6000～8000 regenerated cellulose film bag filters,, change deionized water every day one time with deionized water dialysis 3 days.Finally obtain clarifying uniform weak yellow liquid, i.e. nanometer semiconductor biocompatible materials.
Claims (3)
1. the preparation method of a nanometer semiconductor biocompatible materials is characterized in that comprising following concrete steps:
1) selects biomaterial silkworm precursor, be placed on and carry out the hydro-thermal processing of coming unstuck in alkalescence or the neutral sodium-salt aqueous solution, the silk consumption is 0.1g silkworm precursor correspondence 35～45mL sodium-salt aqueous solution, treatment temperature is 100～120 ℃, processing time is 0.5～2 hour, take out then with the abundant rinsing of deionized water to remove the sodium salt on surface, preserve, obtain the boiled silk fiber through vacuum drying; The mass percent of sodium salt is 0.5～1.5% in the described sodium-salt aqueous solution;
2) the boiled silk fiber was soaked 3～5 days in concentration is the metal salt solution of 0.1～1mol/L earlier, take out with the abundant rinsing of deionized water; And then render in the sulphur source solution that concentration is 0.1～0.4mol/L and soaked 1～48 hour, take out with the abundant rinsing of deionized water, again through vacuum drying, the silk fiber of Nano semiconductor particles that obtained load; Described metal salt solution is a cadmium chloride solution; Described sulphur source solution is sodium sulfide solution;
3) with load the silk fiber of Nano semiconductor particles place CaCl
2Handle the silk consumption has been 0.4g load silk fiber correspondence 25～30mL CaCl of Nano semiconductor particles in the solution
2Solution, treatment temperature are 45～60 ℃, and the processing time is 1.5～5 hours, obtain the uniform yellow liquid of clarification;
4) the uniform yellow liquid of the clarification that will obtain places 6000～8000 regenerated cellulose film bag filters, with deionized water dialysis 2～3 days, changes deionized water every day one time, obtains clarifying uniform weak yellow liquid and is nanometer semiconductor biocompatible materials.
2. according to the preparation method of the nanometer semiconductor biocompatible materials of claim 1, it is characterized in that 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), sodium chloride (NaCl), sodium bromide (NaBr), get wherein one or more.
3. according to the preparation method of the nanometer semiconductor biocompatible materials of claim 1, it is characterized in that described CaCl
2Solution is that mol ratio is 1: 8: 2 CaCl
2: H
2O: C
2H
5The OH mixed solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100368028A CN101008642B (en) | 2007-01-25 | 2007-01-25 | Preparation method of nanometer semiconductor biocompatible materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100368028A CN101008642B (en) | 2007-01-25 | 2007-01-25 | Preparation method of nanometer semiconductor biocompatible materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101008642A CN101008642A (en) | 2007-08-01 |
| CN101008642B true CN101008642B (en) | 2011-04-13 |
Family
ID=38697174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100368028A Expired - Fee Related CN101008642B (en) | 2007-01-25 | 2007-01-25 | Preparation method of nanometer semiconductor biocompatible materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101008642B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140760B (en) * | 2011-04-07 | 2012-12-12 | 上海交通大学 | Method for preparing fibroin modified nano zinc oxide biocompatible material |
| CN103468002A (en) * | 2013-09-03 | 2013-12-25 | 太原理工大学 | Preparation method of silk fibroin/metal nanoparticle composite system |
| CN106551433A (en) * | 2015-09-28 | 2017-04-05 | 宜兴市艺蝶针织有限公司 | A kind of silkworm silk stocking and its production technology |
| CN106480538B (en) * | 2016-09-21 | 2019-07-02 | 上海咏姿时装有限公司 | A kind of quantum dot/regenerated silk fiber and preparation method thereof based on electrostatic spinning |
| CN107687088A (en) * | 2017-09-04 | 2018-02-13 | 西南大学 | Conductive silk fabric is prepared with zinc chloride/formic acid solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528655A (en) * | 2003-10-09 | 2004-09-15 | 同济大学 | Method for preparing one-dimensional nano material using vivi-bean sprouts as template |
| CN1715190A (en) * | 2005-06-20 | 2006-01-04 | 同济大学 | With verdant is the method for template and reactor one-step synthesis IIB family sulfide semiconductor nano material |
| CN1831080A (en) * | 2006-03-29 | 2006-09-13 | 武汉大学 | Stable, water soluble chitin derivatives fluorescent quantal-points and prepn. method therefor |
-
2007
- 2007-01-25 CN CN2007100368028A patent/CN101008642B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528655A (en) * | 2003-10-09 | 2004-09-15 | 同济大学 | Method for preparing one-dimensional nano material using vivi-bean sprouts as template |
| CN1715190A (en) * | 2005-06-20 | 2006-01-04 | 同济大学 | With verdant is the method for template and reactor one-step synthesis IIB family sulfide semiconductor nano material |
| CN1831080A (en) * | 2006-03-29 | 2006-09-13 | 武汉大学 | Stable, water soluble chitin derivatives fluorescent quantal-points and prepn. method therefor |
Non-Patent Citations (1)
| Title |
|---|
| Qun Dong，Huilan Su，Di Zhang.In Situ Depositing Silver Nanoclusters on Silk Fibroin Fibers Supports by a Novel Biotemplate Redox Technique at Room Temperature.《J.Phys.Chem.B》.2005,第109卷(第37期),17429-17434. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101008642A (en) | 2007-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Microsphere organization of nanorods directed by PEG linear polymer | |
| CN101008642B (en) | Preparation method of nanometer semiconductor biocompatible materials | |
| Devi et al. | Eggshell membrane: a natural biotemplate to synthesize fluorescent gold nanoparticles | |
| CN103361885B (en) | A kind of preparation method of antibacterial fibroin fiber film | |
| CN103193273B (en) | Preparation method of extra-long manganese dioxide nanowires | |
| CN101044848A (en) | Nanometer silver antibiotic powder fixed by silk fibroin and preparation method thereof | |
| Lü et al. | Wool keratin-stabilized silver nanoparticles | |
| CN105801878B (en) | A kind of fibroin albumen base nanometer MOFs preparation method | |
| CN101302032A (en) | Preparation of cupric oxide nano-material | |
| CN101073830B (en) | Gelatin-silver nano-material production method | |
| CN102849774A (en) | Method for preparing nanometer cerium oxide by hydrothermal method | |
| CN101323977A (en) | Preparation of big length to diameter ratio aluminum oxide nanowire | |
| KR20100073892A (en) | Agarose or gellan as morphology-directing agents for the preparation of selenium nanowires | |
| CN109079153A (en) | A kind of supramolecular hydrogel preparation method of silver-containing nanoparticles | |
| CN107032982A (en) | A kind of preparation method of oxalic acid cobalt nanowire | |
| CN1305773C (en) | Preparation for zinc oxide nanometer material | |
| CN1865501A (en) | Process for preparing nano noble metal reinforced silk fiber-base composite materials | |
| CN107324377B (en) | A kind of zinc metastannate/stannic oxide concave surface cubic materials and preparation method thereof | |
| CN103588244B (en) | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis | |
| Biswas et al. | Facile synthesis of luminescent TiO2 nanorods using an anionic surfactant: Their photosensitization and photocatalytic efficiency | |
| Seth et al. | Green synthesis of hierarchically structured metal and metal oxide nanomaterials | |
| CN1974413B (en) | Process of preparing nanometer hexagonal oxide sheet | |
| CN102234128A (en) | Process for preparing nano copper hydroxide by homogeneous precipitation | |
| CN101885505A (en) | Method for preparing calcium fluoride hollow nanospheres | |
| Semenova et al. | Hierarchic nanostructuring by self–reduction of silver (I) oxide complexes |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110413 Termination date: 20140125 |