CN113718520A - Preparation method and application of nanoparticle functionalized artificial spider silk - Google Patents
Preparation method and application of nanoparticle functionalized artificial spider silk Download PDFInfo
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- CN113718520A CN113718520A CN202110901855.1A CN202110901855A CN113718520A CN 113718520 A CN113718520 A CN 113718520A CN 202110901855 A CN202110901855 A CN 202110901855A CN 113718520 A CN113718520 A CN 113718520A
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- 229920001872 Spider silk Polymers 0.000 title claims abstract description 99
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 79
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 35
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
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- 239000000243 solution Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012460 protein solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002211 L-ascorbic acid Substances 0.000 claims description 8
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
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- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 230000006750 UV protection Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 241000588724 Escherichia coli Species 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 238000002166 wet spinning Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011781 sodium selenite Substances 0.000 claims description 3
- 229960001471 sodium selenite Drugs 0.000 claims description 3
- 235000015921 sodium selenite Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000001042 affinity chromatography Methods 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 claims description 2
- 238000000578 dry spinning Methods 0.000 claims description 2
- 238000010041 electrostatic spinning Methods 0.000 claims description 2
- 238000010353 genetic engineering Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
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- 239000002152 aqueous-organic solution Substances 0.000 claims 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000010931 gold Substances 0.000 description 11
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
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- 238000004220 aggregation Methods 0.000 description 1
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Images
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
A preparation method and application of nanoparticle functionalized artificial spider silk, which takes nascent artificial spider silk as a template and prepares nanoparticles in situ through chemical reaction to realize nanometer functionalization of spider silk, specifically comprises the following steps: soaking the recombinant spider silk protein nascent fiber in an ion solution, and pre-combining ions and protein molecular chains in the nascent fiber to form a nanoparticle nucleation site; and soaking the artificial spider silk by adopting a composite ion solution, and synthesizing nano particles which are uniformly dispersed and have uniform particle sizes in situ in the artificial spider silk. The preparation method is simple and convenient, the produced composite fiber contains nano-particles with smaller particle size and uniform dispersion, and the mechanical property of the fiber can be further improved through nano-functionalization, so that the toughness of the fiber exceeds that of a natural spider dragline; meanwhile, through multiple times of washing and drying, the functional properties of the composite fiber are hardly influenced, and different types of nano-particles can be prepared inside the fiber, so that the requirements of people on fiber materials in different scenes are met.
Description
Technical Field
The invention relates to a technology in the field of polymer biomaterials, in particular to a preparation method and application of nanoparticle functionalized artificial spider silk.
Background
Spider silks have the characteristics of high strength and good toughness, so the spider silks are highly concerned by researchers, however, the functions of the artificial spider silks obtained at present are single, and therefore, the spider silks are important means for expanding the application of the artificial spider silks. The nano-particles have unique functional properties due to small particle size. And thus is widely used in the preparation of functionalized materials. The existing spider silk nanometer functionalization methods mainly comprise two methods, one method is to add functionalized nanometer particles into a spider silk protein solution and then spin; the other is to perform functionalization directly on the surface coating of the spun fiber. However, both of these methods have problems that are difficult to solve by themselves. The protein spinning solution and the nano-particles are pre-mixed and then spun, and the problems that the nano-particles are not easy to mix and uniformly disperse in the high-concentration spinning solution, the particle size distribution of the added nano-particles is difficult to control, the content of the added nano-particles is limited, and the functionalization effect is weak and difficult to further promote exist. When the fiber is subjected to nano-functionalization by directly soaking a dispersion solution containing nano-particles, the nano-particles are difficult to enter the fiber, so that the nano-particles are distributed on the surface of the fiber in a large amount and large aggregates are easy to form, and the nano-particles in the treated fiber are difficult to exert the unique functional properties. In addition, the nano-coating prepared by the method is easy to be damaged by the environment, so that the function of the composite fiber is reduced. In summary, the major problems of the existing spider silk nano-functionalization are that the nano-material is difficult to enter the inside of the fiber and is difficult to be uniformly dispersed in the fiber with a small size, so that the composite fiber has weak functional properties and is not durable, thereby being limited in practical application.
Disclosure of Invention
Aiming at the defects that the fiber obtained by the prior art is single in function, does not have various functional properties such as photo-thermal conversion, fluorescence, antibiosis and/or ultraviolet resistance and cannot meet the industrial requirement in toughness, the invention provides a preparation method and application of a nanoparticle functionalized artificial spider silk, the preparation method is simple and convenient, the produced composite fiber contains nanoparticles with smaller particle size and uniform dispersion, and the mechanical property of the fiber can be further improved through nano functionalization, so that the toughness of the fiber exceeds that of the natural spider dragline silk; meanwhile, the functional properties of the composite fiber are hardly affected after a plurality of times of washing and drying. In addition, different types of nano-particles can be prepared in the fiber by adopting the method, so that the requirements of people on fiber materials in different scenes are met.
The invention is realized by the following technical scheme:
the invention relates to a preparation method of nanoparticle functionalized artificial spider silk, which takes nascent artificial spider silk as a template and prepares nanoparticles in situ through chemical reaction to realize nano-functionalization of the spider silk, and specifically comprises the following steps: soaking the recombinant spider silk protein nascent fiber in an ion solution, and pre-combining ions and protein molecular chains in the nascent fiber to form a nanoparticle nucleation site; and soaking the artificial spider silk by adopting a composite ion solution, and synthesizing nano particles which are uniformly dispersed and have uniform particle sizes in situ in the artificial spider silk.
The primary artificial spider silk refers to: and (3) solidifying the protein by utilizing a genetic engineering spider silk protein solution in an electrostatic spinning, wet spinning or dry spinning mode to obtain the fiber.
The in-situ preparation of the nano-particles refers to: the process of generating nanoparticles by soaking the fibers in two or more reactant solutions step by step to cause a chemical reaction to occur inside the artificial spider silk.
The invention relates to a nano-particle functionalized artificial spider silk prepared by the method, which contains nano-particles with uniform distribution and uniform particle size in the interior, the size of the nano-particles is less than 50nm, and the functionalized fibers respectively have the functional properties of photo-thermal conversion, fluorescence, antibiosis and/or ultraviolet resistance and the like and have excellent mechanical properties.
The compound ion solution comprises: an aqueous solution containing metal ions at a concentration of 0.3 to 10mM for forming sites for nanoparticle nucleation, and an aqueous or organic solution of sodium salt, or an aqueous or organic solution of L-ascorbic acid, or an aqueous or organic solution of thiourea at a concentration of 0.3 to 30mM for chemical reaction and nanoparticle synthesis inside the fiber.
The soaking is as follows: soaking in water solution containing metal ions at room temperature for 2-24h to allow the ions to enter the fiber and interact with protein to form the nucleation sites of the nanoparticles, and then placing in sodium salt water solution or organic solution at 25-100 ℃, or L-ascorbic acid water solution or organic solution, or thiourea water solution or organic solution for 2-24h to allow chemical reaction between different ions to synthesize the nanoparticles in the fiber.
The chemical reaction comprises at least one of the following:
copper chloride, copper sulfate, cobalt chloride, cadmium chloride, zinc sulfate and sodium plumbate are respectively precipitated and reacted with sodium sulfide or thiourea or sodium sulfite;
reacting cadmium chloride and sodium selenite with sodium borohydride;
thirdly, reacting cadmium chloride and sodium tellurite with sodium borohydride;
reacting ferric chloride and ferrous chloride with sodium hydroxide;
reacting chloroauric acid with sodium citrate;
sixthly, reacting silver nitrate with L-ascorbic acid.
The solution containing metal ions includes but is not limited to: copper chloride, copper sulfate, cobalt chloride, cadmium chloride, ferric chloride, ferrous chloride, chloroauric acid, zinc sulfate, silver nitrate, sodium plumbate, or combinations thereof.
The sodium salt aqueous solution includes but is not limited to: sodium sulfide, sodium hydroxide, sodium citrate, sodium borohydride, sodium sulfite, sodium selenite and sodium tellurite.
The organic solution of the L-ascorbic acid or the thiourea is as follows: l-ascorbic acid or thiourea is dissolved in ethanol or methanol.
The chemical reaction is preferably carried out by taking out the fiber after completion of the reaction and drying the fiber at room temperature.
The invention relates to application of the nanoparticle functionalized artificial spider silk, which is used in the fields of textiles, biomedicine and the like, in particular to functional properties of photothermal conversion, fluorescence, antibiosis, ultraviolet resistance and the like.
Technical effects
The invention integrally solves the problems that the nano material is difficult to enter the inside of the fiber and is difficult to be uniformly dispersed in the fiber in a small size, so that the composite fiber has weak functional property and is not durable. The invention provides a site for chemical reaction through the pre-combination of ions and protein molecular chains, so that nanoparticles can be generated in situ in the fiber. Meanwhile, the hierarchical structure of the fiber limits the further growth and aggregation of the nanoparticles, so that the nanoparticles can be uniformly distributed in the fiber in a smaller size, and stronger functional properties and mechanical properties are provided for the functionalized composite fiber. Compared with the existing functionalization mode of directly soaking artificial spider silk in a dispersion solution containing nano particles or adding nano particles into a spinning solution and then spinning, the functionalization mode of the invention is simple, convenient and efficient, the nano particles prepared in the fiber have small and uniform particle size, and the composite fiber has various functional properties of stronger photothermal conversion, fluorescence, antibiosis and/or ultraviolet resistance. Since the nanoparticles are contained inside the fiber, the fiber has strong durability properties. Meanwhile, more beta-folded crystal structures in the fibers are induced by nano functionalization, so that the mechanical property of the composite fibers is remarkably improved, and the toughness of the composite fibers exceeds that of natural spider dragline wires.
Drawings
FIG. 1 is a schematic diagram of a condensed phase solution of recombinant spider silk protein after dialysis as a spinning solution;
FIG. 2 is a schematic diagram of the appearance of CuS nanoparticles in a CuS nanoparticle functionalized artificial spider silk;
FIG. 3 is a schematic diagram of the mechanical properties of CuS nanoparticle functionalized artificial spider silk;
FIG. 4 is a schematic diagram comparing the temperature rise of CuS nanoparticle functionalized artificial spider silk and nascent spider silk under the irradiation of a sunlight simulator;
FIG. 5 is a schematic diagram showing temperature rise of CuS nanoparticle functionalized artificial spider silk after five times of water washing and drying under irradiation of a 980nm laser emitter;
FIG. 6 is a schematic diagram of the mechanical properties of CdS nanoparticle functionalized artificial spider silk;
FIG. 7 is a comparison of fluorescence spectra of CdS nanoparticle functionalized artificial spider silk and nascent spider silk;
FIG. 8 is a schematic diagram of the morphology of Au nanoparticles in an Au nanoparticle functionalized artificial spider silk;
FIG. 9 is a schematic diagram of the mechanical properties of Au nanoparticle functionalized artificial spider silk;
FIG. 10 is a comparison of UV transmission for Au nanoparticle functionalized artificial spider silk and nascent spider silk;
fig. 11 is a comparison of the inhibition of escherichia coli and staphylococcus aureus by Au nanoparticle functionalized artificial spider silk and nascent spider silk.
Detailed Description
Example 1
The embodiment relates to a preparation method of copper sulfide nanoparticle functionalized artificial spider silk, which comprises the following specific steps:
1) soaking the recombinant spider silk protein nascent fiber in water for 2 minutes, then beginning to elongate, soften and increase the freedom degree of molecular chains, and stretching the fiber in water to 6 times of the original length.
The recombinant spider silk protein nascent fiber is obtained by wet spinning of a high-concentration spinning solution of the recombinant spider silk protein, and specifically comprises the following steps: sucking the high-concentration spinning solution of the recombinant spider silk protein into an injector, extruding the spinning solution into a coagulating bath of 90% ethanol (pH5.0) by using a micro-fluid chip through an injection pump, and dehydrating and solidifying the recombinant spider silk protein into nascent fiber.
The high-concentration spinning solution of the recombinant spider silk protein, namely a condensed phase of the recombinant spider silk protein, is prepared by dialyzing a recombinant spider silk protein solution in a buffer solution containing 0.02M sodium chloride (pH7.4) for 12 hours.
During dialysis, the recombinant protein solution undergoes liquid-liquid phase separation into a dilute phase and a condensed phase (as shown in FIG. 1).
The recombinant spider silk protein solution is prepared by the following steps:
step i) mixing the recombinant escherichia coli wet thallus expressing the recombinant spider silk protein in a ratio of 1: 10 in a weight ratio in a resuspension buffer containing 300mM sodium chloride, and stirred at 4 ℃ for 1 hour to obtain a mixed solution A.
And step ii) performing wall breaking treatment on the mixed solution A by using a high-pressure homogenizer, centrifuging, and collecting supernatant to obtain a solution B.
And step iii) separating and purifying the solution B by nickel column affinity chromatography, eluting the hybrid protein by using a buffer solution containing 70mM imidazole (pH8.0), and eluting the target protein by using a buffer solution containing 250mM imidazole (pH8.0) to obtain the recombinant spider silk protein solution.
2) The fiber after stretching treatment in water is put into 0.3-8mM copper chloride solution and soaked for 12h at room temperature.
3) Then the treated fiber is placed in a mixed solution of 0.9-24mM sodium sulfide and 90% ethanol and treated for 6h at 60 ℃. And (4) taking out the fiber after the treatment is finished, and drying the fiber at room temperature overnight to obtain the copper sulfide nanoparticle functionalized artificial spider silk.
Compared with the prior art of directly preparing copper sulfide nano particles in a spinning solution and then spinning, the toughness of the functionalized artificial spider silk prepared by the copper sulfide nano particles prepared by the embodiment is remarkably improved and can reach 164.5MJm on average-3(as shown in fig. 3). The temperature can rise by 20 c after 200s of simulated solar irradiation, which is twice as high as the nascent fiber (as shown in fig. 4).
Example 2
The embodiment relates to a preparation method of cadmium sulfide quantum dot functionalized artificial spider silk, which comprises the following specific steps:
1) soaking the recombinant spider silk protein nascent fiber in water for 2 minutes, then beginning to elongate, soften and increase the freedom degree of molecular chains, and stretching the fiber in water to 6 times of the original length.
2) The fiber stretched in water is placed in a 1mM cadmium chloride solution and soaked for 12 hours at room temperature.
3) The treated fibers were then placed in 3mM sodium sulfide solution and treated for 6h at room temperature. And (4) taking out the fiber after the treatment is finished, and drying the fiber at room temperature overnight to obtain the cadmium sulfide quantum dot functionalized artificial spider silk.
Compared with the existing method for functionalizing the spider silk by directly soaking the quantum dot dispersion solution, the intensity of the cadmium sulfide quantum dot functionalized artificial spider silk prepared by the embodiment is remarkably improved, can reach 373MPa on average (as shown in figure 5), and can generate an emission peak with a wavelength of 430nm (as shown in figure 6) under the excitation of ultraviolet light with a wavelength of 380 nm.
Example 3
The embodiment relates to a preparation method of gold nanoparticle functionalized artificial spider silk, which comprises the following specific steps:
1) soaking the recombinant spider silk protein nascent fiber in water for 2 minutes, then beginning to elongate, soften and increase the freedom degree of molecular chains, and stretching the fiber in water to 6 times of the original length.
2) The fiber stretched in water was immersed in a 0.8mM chloroauric acid solution at room temperature for 12 hours.
3) The treated fibers were then placed in 8mM sodium citrate solution and treated at 75 ℃ for 6 h. And (4) taking out the fiber after the treatment is finished, and drying the fiber at room temperature overnight to obtain the gold nanoparticle functionalized artificial spider silk.
Compared with the existing method for synthesizing nanoparticles on the regenerated fiber in situ by using redox reaction, the gold nanoparticles synthesized by the embodiment have uniform particle size (as shown in fig. 7) and are uniformly distributed in the fiber. The strength of the obtained gold nanoparticle functionalized artificial spider silk is remarkably improved and can reach 220MPa (as shown in figure 8) on average. Meanwhile, compared with the primary fiber, the transmittance of the gold nanoparticle functionalized artificial spider silk to ultraviolet rays is reduced by 10-20% (as shown in figure 9), and the gold nanoparticle functionalized artificial spider silk can treat staphylococcus aureus (G)+) And Escherichia coli (G-) has 60-75% of inhibitory effect (as shown in figure 10), so it has strong anti-ultraviolet and antibacterial effects.
The foregoing embodiments may be modified in many different ways by those skilled in the art without departing from the spirit and scope of the invention, which is defined by the appended claims and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A preparation method of nanoparticle functionalized artificial spider silk is characterized in that nascent artificial spider silk is used as a template, nanoparticles are prepared in situ through chemical reaction to realize nanometer functionalization of the spider silk, and specifically the method comprises the following steps: soaking the recombinant spider silk protein nascent fiber in an ion solution, and pre-combining ions and protein molecular chains in the nascent fiber to form a nanoparticle nucleation site; and soaking the artificial spider silk by adopting a composite ion solution, and synthesizing nano particles which are uniformly dispersed and have uniform particle sizes in situ in the artificial spider silk.
2. The method for preparing nanoparticle-functionalized artificial spider silk according to claim 1, wherein the nascent artificial spider silk is: and (3) solidifying the protein by utilizing a genetic engineering spider silk protein solution in an electrostatic spinning, wet spinning or dry spinning mode to obtain the fiber.
3. The method for preparing nanoparticle-functionalized artificial spider silk according to claim 1, wherein the in-situ preparation of nanoparticles is: the process of generating nanoparticles by soaking the fibers in two or more reactant solutions step by step to cause a chemical reaction to occur inside the artificial spider silk.
4. The method for preparing nanoparticle-functionalized artificial spider silk according to claim 1 or 2, wherein the recombinant spider silk protein primary fiber is obtained by wet spinning of a high-concentration spinning solution of a recombinant spider silk protein, and specifically comprises: absorbing the high-concentration spinning solution of the recombinant spider silk protein into an injector, extruding the high-concentration spinning solution into an ethanol coagulating bath through a microfluid chip by using an injection pump, and dehydrating and solidifying the recombinant spider silk protein into nascent fiber.
5. The method for preparing nanoparticle-functionalized artificial spider silk according to claim 4, wherein the high-concentration spinning solution of recombinant spider silk protein, i.e. the condensed phase of recombinant spider silk protein, is obtained by dialyzing a solution of recombinant spider silk protein in a buffer solution containing sodium chloride.
6. The method for preparing nanoparticle-functionalized artificial spider silks according to claim 5, wherein the recombinant spider silk protein solution is prepared by:
step i) mixing the recombinant escherichia coli wet thallus expressing the recombinant spider silk protein in a ratio of 1: 10 in a weight ratio in a resuspension buffer containing 300mM sodium chloride, and stirring for 1h at 4 ℃ to obtain a mixed solution A;
step ii) performing wall breaking treatment on the mixed solution A by using a high-pressure homogenizer, centrifuging, and collecting supernatant to obtain a solution B;
and step iii) separating and purifying the solution B by nickel column affinity chromatography, eluting the hybrid protein by using a buffer solution containing 70mM imidazole, and eluting the target protein by using a buffer solution containing 250mM imidazole to obtain the recombinant spider silk protein solution.
7. The method of preparing nanoparticle-functionalized artificial spider silk according to claim 1, wherein the composite ion solution comprises: an aqueous solution containing metal ions at a concentration of 0.3 to 10mM for forming sites for nanoparticle nucleation, and an aqueous or organic solution of sodium salt, or an aqueous or organic solution of L-ascorbic acid, or an aqueous or organic solution of thiourea at a concentration of 0.3 to 30mM for chemical reaction and nanoparticle synthesis inside the fiber.
8. The method for preparing nanoparticle-functionalized artificial spider silk according to claim 1 or 7, wherein the soaking is: soaking in aqueous solution containing metal ions at room temperature for 2-24h to allow the ions to enter the fiber and interact with protein to form the nucleation sites of the nanoparticles, and then placing in sodium salt aqueous solution or organic solution at 25-100 ℃, or L-ascorbic acid aqueous solution or organic solution, or thiourea aqueous solution or organic solution for 2-24h to allow chemical reaction between different ions to synthesize the nanoparticles inside the fiber;
the chemical reaction comprises at least one of the following:
copper chloride, copper sulfate, cobalt chloride, cadmium chloride, zinc sulfate and sodium plumbate are respectively precipitated and reacted with sodium sulfide or thiourea or sodium sulfite;
reacting cadmium chloride and sodium selenite with sodium borohydride;
thirdly, reacting cadmium chloride and sodium tellurite with sodium borohydride;
reacting ferric chloride and ferrous chloride with sodium hydroxide;
reacting chloroauric acid with sodium citrate;
sixthly, reacting silver nitrate with L-ascorbic acid.
9. A nanoparticle functionalized artificial spider silk prepared by the method of any one of claims 1-8 is characterized in that the inside of the artificial spider silk contains uniformly distributed nanoparticles with uniform particle size, the size of the nanoparticles is less than 50nm, and the artificial spider silk has photothermal conversion, fluorescence, antibacterial and/or ultraviolet resistance functions.
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