CN103468002A - Preparation method of silk fibroin/metal nanoparticle composite system - Google Patents
Preparation method of silk fibroin/metal nanoparticle composite system Download PDFInfo
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Abstract
The invention provides a preparation method of a silk fibroin/metal nanoparticle composite system, belonging to the technical field of nanocomposite materials and preparation methods thereof. The preparation method comprises the steps of fully mixing metal nanoparticles with silk fibroin in a weight ratio of (1:9)-(9:1) so that silk fibroin is non-covalently adsorbed on the surfaces of the metal nanoparticles, thus obtaining the silk fibroin/metal nanoparticle composite system. The metal nanoparticles in the composite system prepared by the preparation method can not aggregate under the conditions that the pH value is 2-11 and the salinity is 0-1000mM, thus improving the stability and biocompatibility of the metal nanoparticles in the physiological environment. The silk fibroin/metal nanoparticle composite system provided by the invention is simple to prepare, is low in cost, has good stability and biocompatibility and has wide application prospects in the biomedical fields of drug sustained release, gene transmission, tissue engineering and the like.
Description
Technical field
The invention belongs to the preparing technical field of nano composite material, be specifically related to the preparation method of a kind of silk fibroin and inorganic metal Nanocomposites system.
Background technology
Metal nanoparticle, owing to having a series of excellent properties, as magnetic property, electrical properties, optical property etc., has obtained application more and more widely in fields such as biology, chemistry, medical science as nano material.At biomedical sector, comprise the nanoparticle that the fields such as medicament slow release, gene delivery, bio-molecular diagnostics and detection, biosensor are used, most all requirements can be in physiological environment stable dispersion under wider pH scope and higher salt concn environment for example, and biocompatibility is also the prerequisite of nanoparticle application in addition.Yet directly synthetic metal nanoparticle has very high specific surface energy usually in the aqueous solution, at acidic conditions, higher salt ionic concentration and all easily assemble under the time of putting of living forever.Just lost once assemble the special performance that this system has, thereby limited its application.
For improving metal nanoparticle stability and biocompatibility, people have carried out a series of trials.Molecule is as polyoxyethylene glycol (PEG) etc. preferably at nanoparticle surface modified biocompatibility for the method exchanged by sulfydryl, but because the Au-S key lacks permanent stability, and this modification needs polystep reaction, and synthetic complicated, cost is also higher.Adopt small molecules often modified under stability deficiency, especially acidic conditions and high salt ionic concentration condition or easily assemble golden nanometer particle.The investigator is also arranged at nanoparticle surface coated silica thin layer, obtaining metal nanoparticle is the composite nanoparticle that core silicon-dioxide is shell, gives the aqueous stability that nanoparticle is good.Polymkeric substance is also good stablizer in addition, and the polymkeric substance of the numerous species all template that is used as of success prepares metal nanoparticle.For example, patent CN 20110208707.8 has reported the preparation method of a kind of single polymer molecule nano particle and metal nanoparticle mixture.Patent CN 201110080358.6 has reported a kind of polystyrene/(noble metal nano particles@polyaniline) composite particles and preparation method thereof.Yet the biocompatibility of silicon-dioxide and these polymkeric substance is general, good growth that can not sustenticular cell.How to obtain the metallic nanoparticle subsystem that preparation is simple, have good physiological environment stability and biocompatibility, to metal nanoparticle, widespread use in the bio-medical field has great significance.
Silk fibroin is the natural polymer scleroproein extracted from silk, content accounts for 70% ~ 80% of silk, there is good biocompatibility, biological degradability, and can obtain different forms by different treatment, as fiber, solution, hydrogel, film, support etc.The technology of extracting at present silk fibroin is ripe, and silk fibroin is having potential application widely aspect organizational project, useful for drug delivery, biosensor.Zygomite fibroin and metal nanoparticle advantage separately, prepare silk fibroin with good biocompatibility and physiological environment stability/metal nanoparticle compound system by simple mode, yet there are no report.
Summary of the invention
The purpose of this invention is to provide a kind of simple, as can significantly to improve metal nanoparticle physiological environment stability and biocompatibility silk fibroin/metal nanoparticle compound system and preparation method thereof for preparing.
The preparation method of silk fibroin of the present invention/metal nanoparticle compound system is characterized in that in this compound system that metal nanoparticle is under 2 ~ 11 conditions and salt concn is clustering phenomena can not occur under 0-1000 mM condition at pH, comprises and is prepared as follows step:
1) prepare silk fibroin water solution
To remove pupa and shell lamellar silkworm silk cocoon or raw silk is inserted in the aqueous sodium carbonate of 0.5-2wt%, the weightmeasurement ratio of silk cocoon or raw silk and aqueous sodium carbonate is 50:1 ~ 150:1, boil 0.5 ~ 3 hour to remove surperficial silk gum, with deionized water wash three times, obtain the degumed silk cellulose fiber after drying, adopt calcium chloride-ethanol-water Ternary System or 9 ~ 9.5 mol L that mol ratio is 1:2:8
-1lithium bromide water solution as solvent system, dissolve the degumed silk cellulose fiber, the weightmeasurement ratio of degumed silk cellulose fiber and solvent system is 10: 1, solvent temperature is 40 ~ 80 ℃, and dissolution time is 1 ~ 3 h, obtains fibroin fiber solution, after fibroin fiber solution for vacuum suction filtration is removed to impurity, the dialysis tubing that the molecular weight cut-off of packing into is 8000-14000 dialysis continuously obtains pure silk fibroin water solution to remove salt ion in three days, and regulating silk fibroin water solution concentration is 0.01 ~ 10wt %;
2) prepare silk fibroin/metal nanoparticle compound system
Metal nanoparticle is scattered in water, be mixed with the metal nanoparticle aqueous solution of 0.01 ~ 1.0 wt%, the ratio that is 1:9 ~ 9:1 in the weight ratio of metal nanoparticle and silk fibroin adds silk fibroin water solution, stir lower fully mixing 0.5～12 hour, make that silk fibroin is non-covalent to be adsorbed on surfaces of metal nanoparticles, obtain silk fibroin/golden nanometer particle compound system.
The preparation method of above-mentioned silk fibroin/metal nanoparticle compound system, it is characterized in that a kind of or any two kinds of hud typed metal nanoparticles of the binary prepared in gold and silver, platinum and metallic palladium element in nanoparticle that described metal nanoparticle is gold and silver, platinum and palladium or take Z 250 as core, hud typed metal nanoparticle prepared for shell by any one in gold and silver, platinum and metallic palladium element, its metal nanoparticle particle diameter is 5 ~ 100 nanometers.
The preparation method of above-mentioned silk fibroin/metal nanoparticle compound system, is characterized in that described salt is sodium-chlor, Repone K, SODIUMNITRATE, saltpetre, sodium perchlorate or potassium perchlorate.
The beneficial effect that the present invention compared with prior art has is:
1, silk fibroin is a kind of natural polymer scleroproein, has good biocompatibility, the extractive technique maturation, and cost is low, pollution-free;
2, silk fibroin/metal nanoparticle compound system has satisfactory stability under physiological environment, and clustering phenomena can not occur under wider pH scope especially acidic conditions and under high salt concentration;
3. silk fibroin is applied widely, can obtain compound system by simple preparation process with the various metals nanoparticle, metal nanoparticle comprises a kind of or any two kinds of hud typed metal nanoparticles of the binary prepared in gold and silver, platinum and metallic palladium element in the nanoparticle of gold and silver, platinum and palladium or take Z 250 as core, hud typed metal nanoparticle prepared for shell by any one in gold and silver, platinum and metallic palladium element.
The accompanying drawing explanation
Fig. 1 is the golden nanometer particle of Trisodium Citrate reduction and the uv-visible absorption spectroscopy of silk fibroin/golden nanometer particle compound system;
Fig. 2 is the transmission electron microscope photo of silk fibroin/golden nanometer particle compound system;
Fig. 3 is the silk fibroin/uv-visible absorption spectroscopy of golden nanometer particle compound system under condition of different pH;
Fig. 4 is the uv-visible absorption spectra of silk fibroin/golden nanometer particle compound system under different sodium chloride concentration conditions.
Embodiment
The present invention is by silk fibroin water solution and metal nanoparticle aqueous solution, makes that silk fibroin is non-covalent to be adsorbed on surfaces of metal nanoparticles, obtains silk fibroin/metal nanoparticle compound system.Silk fibroin can prepare compound system with the various metals nanoparticle, comprise a kind of or any two kinds of hud typed metal nanoparticles of the binary prepared in gold and silver, platinum and metallic palladium element in the nanoparticle of gold and silver, platinum and palladium or take Z 250 as core, hud typed metal nanoparticle prepared for shell by any one in gold and silver, platinum and metallic palladium element.Compound system has improved stability and the biocompatibility of metal nanoparticle in condition of different pH and high salt ionic concentration environment.Following embodiment is to further illustrate of the present invention, rather than limits the scope of the invention.
Embodiment 1:
(1) prepare silk fibroin water solution:
20 g are removed to pupa and shell the Na that lamellar silkworm silk cocoon is inserted 2 L 0.5wt%
2cO
3in the aqueous solution, boil 0.5 hour to remove surperficial silk gum, use deionized water wash three times, obtain the degumed silk cellulose fiber after drying.Adopt calcium chloride-alcohol-water (mol ratio 1:2:8) ternary system to dissolve the degumed silk cellulose fiber, the weightmeasurement ratio of degumed silk cellulose fiber and ternary solvent system is 10: 1,60 ℃ of solvent temperatures, and dissolution time is 3 h, obtains fibroin fiber solution.The solution for vacuum suction filtration is removed to impurity, and the dialysis tubing that the molecular weight cut-off of then packing into is 8000-14000 dialysis continuously obtains pure silk fibroin water solution to remove salt ion in three days.Regulating silk fibroin protein solution concentration is 0.01wt%.
(2) prepare metal nanoparticle:
In 250 mL single port flasks, add the HAuCl of 100 mL 1 mM
4solution, after ebuillition of heated, the disposable sodium citrate solution that adds 9.34 mL 38.8 mM, react 10 minutes, removes oil bath and continue reaction 15 minutes, obtains the stable solution of gold nanoparticles of Trisodium Citrate.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain golden nanometer particle.
Transmission electron microscope results shows: the golden nanometer particle median size obtained is about 13 nm.
(3) prepare silk fibroin/metal nanoparticle compound system:
Golden nanometer particle is scattered in water, is mixed with the golden nanometer particle aqueous solution of 0.1 wt%.The ratio that is 9:1 in the weight ratio of golden nanometer particle and silk fibroin adds silk fibroin water solution, stirs fully to mix 0.5 hour down, makes that silk fibroin is non-covalent to be adsorbed on nanoparticle surface, obtains silk fibroin/golden nanometer particle compound system.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/golden nanometer particle compound system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated:
Use NaH
2pO
4with Na
2hPO
4the phosphate buffered saline buffer that compound concentration is 20 mM, the HCl by adding 0.1M or the NaOH of 0.1M regulate pH.
Be 1:1 according to volume ratio, the silk fibroin of above-mentioned preparation/golden nanometer particle compound system is mixed from the phosphate buffered saline buffer (20 mM) of different pH (2-11), after standing 10 minutes, test uv-visible absorption spectroscopy.
The uv-visible absorption spectroscopy result shows: clustering phenomena does not occur in silk fibroin/golden nanometer particle compound system in pH is the 2-11 scope, has satisfactory stability.
Different salt concn stability inferiors are estimated:
According to volume ratio, be 1:1, by the silk fibroin of above-mentioned preparation/golden nanometer particle compound system from containing different sodium chloride concentrations (0 mM, 100 mM, 150 mM, 200 mM, 500 mM, 1000 mM, 2000 mM) phosphate buffered saline buffer (pH 7.4,20 mM) mixes, and after standing 10 minutes, tests uv-visible absorption spectroscopy.
The uv-visible absorption spectroscopy result shows: clustering phenomena does not under high salt concn occur in silk fibroin/golden nanometer particle compound system, has satisfactory stability.
Embodiment 2:
(1) prepare silk fibroin water solution:
20 g raw silks are inserted to the Na of 1 L 1 wt%
2cO
3in the aqueous solution, boil 1 hour to remove surperficial silk gum, use deionized water wash three times, obtain the degumed silk cellulose fiber after drying.Adopt the LiBr aqueous solution of 9 M to dissolve the fibroin fiber come unstuck, the weightmeasurement ratio of fibroin fiber and the LiBr aqueous solution is 10:1,40 ℃ of solvent temperatures, and dissolution time 2h, obtain fibroin fiber solution.Fibroin fiber solution for vacuum suction filtration is removed to impurity, dialyse continuously three days in the dialysis tubing that the molecular weight cut-off of then packing into is 8000-14000 to remove salt ion, obtain pure silk fibroin water solution.Regulating silk fibroin protein solution concentration is 0.05 wt%.
(2) prepare the aqueous solution of metal nanoparticle:
In 250 mL single port flasks, add 100 mL water, add 0.05 mmol AgNO
3with 0.05 mmol Trisodium Citrate.The sodium borohydride aqueous solution that adds 6 mL 10 mM under agitation condition, continue to stir half hour to obtain the stable silver nano-particle solution of Trisodium Citrate.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain Nano silver grain.
Transmission electron microscope results shows: the Nano silver grain median size obtained is about 5 nm.
(3) prepare silk fibroin/metal nanoparticle compound system:
Nano silver grain is scattered in water, is mixed with the Nano silver grain aqueous solution of 0.05 wt%.The ratio that is 8:2 in the weight ratio of Nano silver grain and silk fibroin adds silk fibroin water solution, stirs fully to mix 1 hour down, and silk fibroin is adsorbed on nanoparticle surface, obtains the compound system of silk fibroin/Nano silver grain.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/Nano silver grain compound system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated: with embodiment 1;
Uv-visible absorption spectroscopy shows: clustering phenomena does not occur in silk fibroin/Nano silver grain compound system in pH is the 2-11 scope, has satisfactory stability.
Different salt concn stability inferiors are estimated: except used salt is Repone K, with embodiment 1;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not under high salt concn occur in silk fibroin/Nano silver grain compound system, has satisfactory stability.
Embodiment 3:
(1) prepare silk fibroin water solution:
50 g are removed to pupa and shell the Na that lamellar silkworm silk cocoon is inserted 3 L 0.5wt%
2cO
3in the aqueous solution, boil 2 hours to remove surperficial silk gum, use deionized water wash three times, obtain the degumed silk cellulose fiber after drying.Adopt calcium chloride-alcohol-water (mol ratio 1:2:8) ternary system to dissolve the fibroin fiber come unstuck, the weightmeasurement ratio of fibroin fiber and ternary solvent system is 10: 1,80 ℃ of solvent temperatures, and dissolution time is 1 h, obtains fibroin fiber solution.The solution for vacuum suction filtration is removed to impurity, and the dialysis tubing that the molecular weight cut-off of then packing into is 8000-14000 dialysis continuously obtains pure silk fibroin water solution to remove salt ion in three days.
Regulating silk fibroin protein solution concentration is 0.15 wt%.
(2) prepare the aqueous solution of metal nanoparticle:
In 250 mL single port flasks, add the H of 100 mL 1 mM
2ptCl
6solution, after ebuillition of heated, the disposable sodium citrate solution that adds 9.34 mL 38.8 mM, react 10 minutes, removes oil bath and continue reaction 15 minutes, obtains the stable nano platinum particle solution of Trisodium Citrate.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain nano platinum particle.
Transmission electron microscope results shows: the nano platinum particle median size obtained is about 16 nm.
(3) prepare silk fibroin/metal nanoparticle compound system:
Nano platinum particle is scattered in water, is mixed with the nano platinum particle aqueous solution of 0.01 wt%.The ratio that is 7:3 in the weight ratio of nano platinum particle and silk fibroin adds silk fibroin water solution, stirs fully to mix 2 hours down, and silk fibroin is adsorbed on nanoparticle surface, obtains the compound system of silk fibroin/nano platinum particle.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/nano platinum particle compound system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated: with embodiment 1;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not occur in silk fibroin/nano platinum particle compound system in pH is the 2-11 scope, has satisfactory stability.
Different salt concn stability inferiors are estimated: except used salt is SODIUMNITRATE, with embodiment 1;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not under high salt concn occur in silk fibroin/nano platinum particle compound system, has satisfactory stability.
Embodiment 4:
(1) prepare silk fibroin water solution:
10 g raw silks are inserted to the Na of 1 L 2 wt%
2cO
3in the aqueous solution, boil 0.5 hour to remove surperficial silk gum, use deionized water wash three times, obtain the degumed silk cellulose fiber after drying.Adopt the LiBr aqueous solution of 9.5 M to dissolve the fibroin fiber come unstuck, the weightmeasurement ratio of fibroin fiber and the LiBr aqueous solution is 10:1,40 ℃ of solvent temperatures, and dissolution time 2h, obtain fibroin fiber solution.The solution for vacuum suction filtration is removed to impurity, dialyse continuously three days in the dialysis tubing that the molecular weight cut-off of then packing into is 8000-14000 to remove salt ion, obtain pure silk fibroin water solution.Regulating silk fibroin protein solution concentration is 0.2 wt%.
(2) prepare the aqueous solution of metal nanoparticle:
The H of 1 mL 50 mM
2pdCl
4-tetraethylene-glycol solution, 1 mL 50 mM polyvinylpyrrolidones-tetraethylene-glycol solution, 1 mL 75 mM cetyl trimethylammonium bromides-tetraethylene-glycol solution joins in the round-bottomed flask of 50 ml, and then add 7.0 ml tetraethylene-glycols, making the reaction solution cumulative volume is 10.0 ml.After mixing, insert 170 ℃ of oil bath isothermal reaction 2.5 h, solution is transformed into dark brown black by scarlet, obtains Technique of Nano Pd colloidal solution.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain Pd nano particle.
Transmission electron microscope results shows: the Pd nano particle median size obtained is about 56 nm.
(3) prepare silk fibroin/metal nanoparticle compound system;
Pd nano particle is scattered in water, is mixed with the Pd nano particle aqueous solution of 1 wt%.The ratio that is 6:4 in the weight ratio of Pd nano particle and silk fibroin adds silk fibroin water solution, stirs fully to mix 5 hours down, and silk fibroin is adsorbed on nanoparticle surface, obtains silk fibroin/Pd nano particle compound system.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/Pd nano particle compound system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated: with embodiment 1;
Uv-visible absorption spectroscopy shows: clustering phenomena does not occur in silk fibroin/Pd nano particle compound system in pH is the 2-11 scope, has satisfactory stability.
Different salt concn stability inferiors are estimated: except used salt is saltpetre, with embodiment 1;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not under high salt concn occur in silk fibroin/Pd nano particle compound system, has satisfactory stability.
Embodiment 5:
(1) prepare silk fibroin water solution:
Preparation process is with embodiment 1, and regulating silk fibroin protein solution concentration is 1 wt%.
(2) prepare the aqueous solution of metal nanoparticle:
HAuCl by 100 mL 1 mM
4solution is heated to boiling, and then the disposable sodium citrate solution that adds 9.34 mL 38.8 mM, react 10 minutes, removes oil bath and continues reaction 15 minutes, the golden nanometer particle that the acquisition particle diameter is 13 nm.
The 10 mL solution of gold nanoparticles of utilizing aforesaid method to make are diluted to 100 mL ebuillition of heated, and property adds the sodium citrate solution of 1 mL 38.8 mM again, then adds in three batches the AgNO of 5 mL 10 mM
3solution, prepare core-shell type Au-Ag nano-particle solution.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain core-shell type Au-Ag nanoparticle.
Transmission electron microscope results shows: the core-shell type Au-Ag nanoparticle median size obtained is about 30 nm.
(3) prepare silk fibroin/metal nanoparticle compound system;
Core-shell type Au-Ag nanoparticle is scattered in water, is mixed with the nanoparticle aqueous solution of 0.05 wt%.The ratio that is 1:1 in the weight ratio of nanoparticle and silk fibroin adds silk fibroin water solution, stirs fully to mix 6 hours down, and silk fibroin is adsorbed on nanoparticle surface, obtains silk fibroin/core-shell type Au-Ag Nanocomposites system.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/core-shell type Au-Ag Nanocomposites system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated: with embodiment 1;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not occur, has satisfactory stability in silk fibroin/core-shell type Au-Ag Nanocomposites system in pH is the 2-11 scope.
Different salt concn stability inferiors are estimated: except used salt is sodium perchlorate, with embodiment 1;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not under high salt concn occur, has satisfactory stability in silk fibroin/core-shell type Au-Ag Nanocomposites system.
Embodiment 6:
(1) prepare silk fibroin water solution:
Preparation process is with embodiment 2, and regulating silk fibroin protein solution concentration is 2 wt%.
(2) prepare the aqueous solution of metal nanoparticle:
In 250 mL single port flasks, add 100 mL water, add 0.05 mmol AgNO
3with 0.05 mmol Trisodium Citrate.The sodium borohydride aqueous solution that adds 6 mL 10 mM under agitation condition, continue to stir half hour to obtain the Nano silver grain that particle diameter is 16 nm.
10 mL 1 mM K
2ptCl
6first reflux 1 h of solution, then the 20 mL silver nano-particle solution that add aforesaid method to make and the sodium citrate solution of 0.8 mL 38.8 mM mix, reheat 1 h that refluxes, solution becomes reddish-brown, prepares core-shell type Ag-Pt nano-particle solution.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain core-shell type Ag-Pt nanoparticle.
Transmission electron microscope results shows: the core-shell type Ag-Pt nanoparticle median size obtained is about 32 nm.
(3) prepare the metal nanoparticle compound system that silk fibroin is modified:
Core-shell type Ag-Pt nanoparticle is scattered in water, is mixed with the nanoparticle aqueous solution of 0.2 wt%.The ratio that is 4:6 in the weight ratio of nanoparticle and silk fibroin adds silk fibroin water solution, stirs fully to mix 3 hours down, and silk fibroin is adsorbed on surfaces of metal nanoparticles, obtains silk fibroin/core-shell type Ag-Pt Nanocomposites system.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/core-shell type Ag-Pt Nanocomposites system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated: with embodiment 1;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not occur, has satisfactory stability in silk fibroin/core-shell type Ag-Pt Nanocomposites system in pH is the 2-11 scope.
Different salt concn stability inferiors are estimated: except used salt is potassium perchlorate, with embodiment 1;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not under high salt concn occur in silk fibroin core-shell type Ag-Pt Nanocomposites system, has satisfactory stability.
Embodiment 7:
(1) prepare silk fibroin water solution:
Preparation process is with embodiment 3, and regulating silk fibroin protein solution concentration is 4 wt%.
(2) prepare the aqueous solution of metal nanoparticle:
At first add 150 mL ultrapure waters in the three-necked bottle of 250 mL, and lead to nitrogen deoxygenation 15 min under 50 ℃, prepare oxygen-free water.Pour 30 ~ 40 mL oxygen-free waters into from three-necked bottle to a small beaker, dissolve 4.3246 g FeCl
36H
2o and 1.5909 g FeCl
24H
2the blended solid of O adds 12.5 mL ammoniacal liquor in three-necked bottle.Under logical nitrogen protection condition by Fe
3+with Fe
2+mixing solutions pour into rapidly in three-necked bottle, solution becomes rapidly black.After continuing reaction 30 min, under magnet is auxiliary, clear liquid is poured out, and, with the oxygen-free water washing precipitation prepared in advance five times, obtained Fe
3o
4nanoparticle.
By Fe obtained above
3o
4nanoparticle is ultrasonic to be scattered in 100 mL deaerated water.Add 1.2 mL oleic acid in system, reaction 3 h under 70 ℃.Under magnet is auxiliary, clear liquid is poured out, with ethanol, washed precipitation five times, obtain the Fe of oleic acid modified
3o
4nanoparticle.Fe by the oleic acid modified of the above-mentioned preparation of 0.3 g
3o
4nanoparticle dissolution forms stable colloidal solution in 1.5 ml hexanaphthenes, then adds 30mL 5mg mL
-1tween 20 solution, ultrasonic 10 min form miniemulsions.The miniemulsion obtained is transferred in the three-necked bottle of 100 mL, logical nitrogen, at 60 ℃ of lower solvent flashing 6 h, obtains the Fe that tween 20 is modified
3o
4aggregate.
Get the Fe that the above-mentioned tween 20 prepared of 1.5 mg is modified
3o
4aggregate again is dispersed in 1 mL 0.1 mg mL under ultrasonication
-1tween 20 solution in, to the HAuCl that adds 2.5 mL 18.5 mM in system
4solution, place 30 min under room temperature.The xitix that adds 2 mL 350 mM in the most backward system, in 1 min, the color of solution becomes bluish voilet by yellow.Prepare core-shell type Fe
3o
4/ Au nano-particle solution.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain core-shell type Fe
3o
4/ Au nanoparticle.
Transmission electron microscope results shows: the core-shell type Fe obtained
3o
4/ Au nanoparticle median size is about 95 nm.
(3) prepare the metal nanoparticle compound system that silk fibroin is modified:
By core-shell type Fe
3o
4/ Au nanoparticle is scattered in water, is mixed with the nanoparticle aqueous solution of 0.8 wt%.The ratio that is 3:7 in the weight ratio of nanoparticle and silk fibroin adds silk fibroin water solution, stirs fully to mix 10 hours down, and silk fibroin is adsorbed on nanoparticle surface, obtains silk fibroin/core-shell type Fe
3o
4/ Au Nanocomposites system.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/core-shell type Fe
3o
4/ Au Nanocomposites system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated: with embodiment 1;
The uv-visible absorption spectroscopy result shows, silk fibroin/core-shell type Fe
3o
4clustering phenomena does not occur in/Au Nanocomposites system in pH is the 2-11 scope, has satisfactory stability.
Different salt concn stability inferiors are estimated: with embodiment 3;
The uv-visible absorption spectroscopy result shows: silk fibroin/core-shell type Fe
3o
4clustering phenomena does not under high salt concn occur in/Au Nanocomposites system, has satisfactory stability.
Embodiment 8:
(1) prepare silk fibroin water solution:
Preparation process is with embodiment 4, and regulating silk fibroin protein solution concentration is 8 wt%.
(2) prepare the aqueous solution of metal nanoparticle:
Prepare the Fe that tween 20 is modified
3o
4the aggregate process is with embodiment 7.1.5 the Fe that the tween 20 that mg prepares is modified
3o
4aggregate again is dispersed in 1 mL 0.1 mg mL under ultrasonication
-1tween 20 solution in, add 2.5mL 18.8 mM AgNO in system
3solution, at room temperature place 30 min, then in system, adds 2mL 12 mM xitix, and the color of solution is very soon by the light yellow canescence that becomes.Prepared core-shell type Fe
3o
4/ Ag nano-particle solution.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain core-shell type Fe
3o
4/ Ag nanoparticle.
Transmission electron microscope results shows: the core-shell type Fe obtained
3o
4/ Ag nanoparticle median size is about 100 nm
(3) prepare the metal nanoparticle compound system that silk fibroin is modified:
By core-shell type Fe
3o
4/ Ag nanoparticle is scattered in water, is mixed with the nanoparticle aqueous solution of 1 wt%.The ratio that is 1:9 in the weight ratio of nanoparticle and silk fibroin adds silk fibroin water solution, stirs fully to mix 12 hours down, and silk fibroin is adsorbed on nanoparticle surface, obtains silk fibroin/core-shell type Fe
3o
4/ Ag Nanocomposites system.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/core-shell type Fe
3o
4/ Ag Nanocomposites system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated: with embodiment 1;
The uv-visible absorption spectroscopy result shows: silk fibroin/core-shell type Fe
3o
4clustering phenomena does not occur in/Ag Nanocomposites system in pH is the 2-11 scope, has satisfactory stability.
Different salt concn stability inferiors are estimated: with embodiment 4;
The uv-visible absorption spectroscopy result shows: silk fibroin/core-shell type Fe
3o
4clustering phenomena does not under high salt concn occur in/Ag Nanocomposites system, has satisfactory stability.
Embodiment 9:
(1) prepare silk fibroin water solution:
Preparation process is with embodiment 1, and regulating silk fibroin protein solution concentration is 10 wt%.
(2) prepare the aqueous solution of metal nanoparticle:
In 250 mL single port flasks, add 100 mL water, add 10 mg HAuCl after ebuillition of heated
4, 10 mg Trisodium Citrates, the lower reaction of boiling 10 minutes, remove oil bath and continue reaction 15 minutes, obtains the stable solution of gold nanoparticles of Trisodium Citrate.Under 15000 rev/mins of high speeds centrifugal 30 minutes, obtain golden nanometer particle.
Transmission electron microscope results shows, the nano-particles size obtained is about 50 nm.
(3) prepare the metal nanoparticle compound system that silk fibroin is modified:
Golden nanometer particle is scattered in water, is mixed with the golden nanometer particle aqueous solution of 0.5 wt%.The ratio that is 2:8 in the weight ratio of nanoparticle and silk fibroin adds silk fibroin water solution, stirs fully to mix 1 hour down, and silk fibroin is adsorbed on nanoparticle surface, obtains silk fibroin/golden nanometer particle compound system.
Uv-visible absorption spectroscopy and transmission electron microscope results show: silk fibroin/golden nanometer particle compound system is not assembled, favorable dispersity.
(4) estimation of stability:
Different pH condition stability inferiors are estimated: with embodiment 1;
The uv-visible absorption spectroscopy result shows, clustering phenomena does not occur silk fibroin/golden nanometer particle compound system in pH is the 2-11 scope, has satisfactory stability.
Different salt concn stability inferiors are estimated: with embodiment 5;
The uv-visible absorption spectroscopy result shows: clustering phenomena does not under high salt concn occur in silk fibroin/golden nanometer particle compound system, has satisfactory stability.
Claims (3)
1. the preparation method of silk fibroin/metal nanoparticle compound system is characterized in that in this compound system that metal nanoparticle is under 2 ~ 11 conditions and salt concn is clustering phenomena can not occur under 0-1000 mM condition at pH, comprises and is prepared as follows step:
1) prepare silk fibroin water solution
To remove pupa and shell lamellar silkworm silk cocoon or raw silk is inserted in the aqueous sodium carbonate of 0.5-2wt%, the weightmeasurement ratio of silk cocoon or raw silk and aqueous sodium carbonate is 50:1 ~ 150:1, boil 0.5 ~ 3 hour to remove surperficial silk gum, with deionized water wash three times, obtain the degumed silk cellulose fiber after drying, adopt calcium chloride-ethanol-water Ternary System or 9 ~ 9.5 mol L that mol ratio is 1:2:8
-1lithium bromide water solution as solvent system, dissolve the degumed silk cellulose fiber, the weightmeasurement ratio of degumed silk cellulose fiber and solvent system is 10: 1, solvent temperature is 40 ~ 80 ℃, and dissolution time is 1 ~ 3 h, obtains fibroin fiber solution, after fibroin fiber solution for vacuum suction filtration is removed to impurity, the dialysis tubing that the molecular weight cut-off of packing into is 8000-14000 dialysis continuously obtains pure silk fibroin water solution to remove salt ion in three days, and regulating silk fibroin water solution concentration is 0.01 ~ 10wt %;
2) prepare silk fibroin/metal nanoparticle compound system
Metal nanoparticle is scattered in water, be mixed with the metal nanoparticle aqueous solution of 0.01 ~ 1.0 wt%, the ratio that is 1:9 ~ 9:1 in the weight ratio of metal nanoparticle and silk fibroin adds silk fibroin water solution, stir lower fully mixing 0.5～12 hour, make that silk fibroin is non-covalent to be adsorbed on surfaces of metal nanoparticles, obtain silk fibroin/golden nanometer particle compound system.
2. the preparation method of silk fibroin according to claim 1/metal nanoparticle compound system, it is characterized in that a kind of or any two kinds of hud typed metal nanoparticles of the binary prepared in gold and silver, platinum and metallic palladium element in nanoparticle that described metal nanoparticle is gold and silver, platinum and palladium or take Z 250 as core, hud typed metal nanoparticle prepared for shell by any one in gold and silver, platinum and metallic palladium element, its metal nanoparticle particle diameter is 5 ~ 100 nanometers.
3. the preparation method of silk fibroin/metal nanoparticle compound system according to claim 1, is characterized in that described salt is sodium-chlor, Repone K, SODIUMNITRATE, saltpetre, sodium perchlorate or potassium perchlorate.
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