CN107262734B - Synthesis in water Au@Cu2-xThe method of the super nanoparticle of E - Google Patents
Synthesis in water Au@Cu2-xThe method of the super nanoparticle of E Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 239000007864 aqueous solution Substances 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 43
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001509 sodium citrate Substances 0.000 claims abstract description 32
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 32
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 31
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 29
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 29
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 23
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 22
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229940069328 povidone Drugs 0.000 claims abstract description 14
- 239000010931 gold Substances 0.000 claims description 85
- 239000002253 acid Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 12
- RVXJIYJPQXRIEM-UHFFFAOYSA-N 1-$l^{1}-selanyl-n,n-dimethylmethanimidamide Chemical compound CN(C)C([Se])=N RVXJIYJPQXRIEM-UHFFFAOYSA-N 0.000 claims description 10
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- MPOKJOWFCMDRKP-UHFFFAOYSA-N gold;hydrate Chemical compound O.[Au] MPOKJOWFCMDRKP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 claims 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 235000019263 trisodium citrate Nutrition 0.000 description 20
- -1 polyethylene Polymers 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013170 computed tomography imaging Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007626 photothermal therapy Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of synthesis in water Au@Cu2‑xThe method of the super nanoparticle of E, which comprises heated after mixing aqueous solution of chloraurate and the first trisodium citrate, obtain mixture M 1, aqueous povidone solution is added in Xiang Suoshu mixture M 1, Au nano-particle solution is made；Au nano-particle solution obtained in step (1), the second trisodium citrate and mantoquita are mixed, mixture M 2 is made, mixture M 2 is adjusted to pH after thioacetamide and hydroxylamine hydrochloride is added into mixture M 2, to heat and Au@Cu being made after 9.2-9.42‑xThe super nanoparticle of S；This method is easy to operate, synthesis condition requires lower and has universality.
Description
Technical field
The present invention relates to the synthesis fields of super nanoparticle, and in particular, to a kind of synthesis in water Au@Cu2-xE is super
The method of nanoparticle.
Background technique
Au@Cu2-xThe super nanoparticle of S and Au@Cu2-xThe super nanoparticle of Se because its near-infrared have it is stronger absorption and
High photo and thermal stability and Au have outstanding X ray attenuation ability, are widely used in biological living, photoacoustic imaging, CT imaging
And in vivo tumor photo-thermal therapy.Currently, being directed to the Au@Cu of above-mentioned core-shell structure2-xThere are two types of the preparation method of S is general, one
Kind is that oil is combined to method, this makes him have poor biocompatibility；Another is that Au@CdS is obtained by synthesis in water,
Then Au@CuS is obtained by cation exchange, but due to the limitation of thermodynamical equilibrium, Cd ion can not be replaced completely, and
Permutizer condition is harsh, while Cd is toxic, is unfavorable for applying in biological living.
Therefore it provides a kind of synthesis in water Au@Cu that is easy to operate, having universality2-xThe method of the super nanoparticle of E
The problem of being urgent need to resolve of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of synthesis in water Au@Cu2-xThe method of the super nanoparticle of E, this method operation letter
Single, synthesis condition requires lower and has universality.
To achieve the goals above, the present invention provides a kind of synthesis in water Au@Cu2-xThe method of the super nanoparticle of E,
The described method includes:
(1) it is heated after mixing aqueous solution of chloraurate and the first trisodium citrate, obtains mixture M 1, Xiang Suoshu mixture
Aqueous povidone solution is added in M1, Au nano-particle solution is made；
(2) Au nano-particle solution obtained in step (1), the second trisodium citrate and mantoquita are mixed, mixing is made
Mixture M 2 is adjusted to pH after thioacetamide and hydroxylamine hydrochloride is added into mixture M 2, to add after 9.2-9.4 by object M2
The obtained Au@Cu of heat2-xThe super nanoparticle of S；Alternatively,
The described method includes:
(A) it is heated after mixing aqueous solution of chloraurate and the first trisodium citrate, obtains mixture M 3；To the mixture
Polystyrolsulfon acid aqueous solution is added in M3, Au nano-particle solution is made；
(B) Au nano-particle solution obtained in step (A), the second trisodium citrate and mantoquita are mixed, mixing is made
Mixture M 4 is adjusted to pH as N, N- dimethyl selenourea and hydroxylamine hydrochloride are added into mixture M 4 after 9.2-9.4 by object M4
Afterwards, Au@Cu is made after heating2-xThe super nanoparticle of Se；Wherein,
E is S or Se.
Through the above technical solutions, the present invention by will aqueous solution of chloraurate and the first trisodium citrate mix after heat,
Mixture M 1 is obtained, aqueous povidone solution is added in Xiang Suoshu mixture M 1, Au nano-particle solution is made；It will step
Suddenly Au nano-particle solution, the second trisodium citrate and mantoquita mixing obtained in (1), is made mixture M 2, by mixture M 2
PH is adjusted to after thioacetamide and hydroxylamine hydrochloride is added into mixture M 2, to heat and Au@Cu being made after 9.2-9.42-xS is super
Grade nanoparticle；Aqueous povidone solution, N, the replacement of N- dimethyl selenourea are replaced using polystyrolsulfon acid aqueous solution
Au@Cu is finally made in thioacetamide2-xThe super nanoparticle of Se.The preparation method is easy to operate, synthesis condition requirement is lower
And have universality, Au@Cu obtained2-xThe super nanoparticle of S and Au@Cu2-xHave in the super nanoparticle of Se without containing toxic
Evil substance, can be applied to biological living field.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the extinction spectra figure of Au nanoparticle PVP before and after the processing；
Fig. 2 is the dynamic light scattering diagram of Au nanoparticle PVP before and after the processing；
Fig. 3 is Au nanoparticle PVP Zeta electric potential figure before and after the processing；
Fig. 4 is Au@Cu2-xExtinction spectra figure of the super nanoparticle of S under different-grain diameter；
Fig. 5 is Au@Cu2-xTransmission electron microscope picture of the super nanoparticle of S under different-grain diameter；
Fig. 6 is the Au@Cu that partial size is 13.5nm2-xThe Au@Cu that the super nanoparticle of S and partial size are 13.5nm2-xSe is super
The high resolution electron microscopy figure of nanoparticle；
Fig. 7 is the Au@Cu that partial size is 13.5nm2-xThe Zeta electric potential figure of the super nanoparticle of S；
Fig. 8 is the Au@Cu that partial size is 13.5nm2-xThe infrared figure of the super nanoparticle of S.
Appended drawing reference
After 2-Au nanoparticle is modified with PVP before 1-Au nanoparticle is modified with PVP
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of synthesis in water Au@Cu2-xThe method of the super nanoparticle of E, which comprises (1) will
It is heated after aqueous solution of chloraurate and the mixing of the first trisodium citrate, obtains mixture M 1, poly- second is added in Xiang Suoshu mixture M 1
Au nano-particle solution is made in alkene pyrrolidone aqueous solution；(2) by Au nano-particle solution obtained in step (1), the second lemon
Lemon acid trisodium and mantoquita mixing, are made mixture M 2, and mixture M 2 is adjusted to pH to add after 9.2-9.4 into mixture M 2
After entering thioacetamide and hydroxylamine hydrochloride, heats and Au@Cu is made2-xThe super nanoparticle of S；Or, which comprises (A) will
It is heated after aqueous solution of chloraurate and the mixing of the first trisodium citrate, obtains mixture M 3；Polyphenyl is added into the mixture M 3
Au nano-particle solution is made in vinyl sulfonic acid aqueous solution；(B) by Au nano-particle solution obtained in step (A), the second lemon
Sour trisodium and mantoquita mixing, are made mixture M 4, and mixture M 4 is adjusted to pH to be added after 9.2-9.4 into mixture M 4
After N, N- dimethyl selenourea and hydroxylamine hydrochloride, Au Cu is made after heating2-xThe super nanoparticle of Se；Wherein, E is S or Se.Here
X > 0.The preparation method is easy to operate, synthesis condition requires lower and has universality, Au@Cu obtained2-xThe super nanometer of S
Particle and Au@Cu2-xPoisonous and harmful substance is not contained in the super nanoparticle of Se, can be applied to biological living field.
In a preferred embodiment of the invention, in order to be made, form is regular, is uniformly dispersed and homogeneous grain diameter
Au@Cu2-xThe super nanoparticle of S and Au@Cu2-xThe super nanoparticle of Se, in step (1) and step (2), relative to 2.5 ×
10-5Gold chloride in the aqueous solution of chloraurate of mol, the dosage of the water in the aqueous solution of chloraurate are 95-110mL, institute
The dosage for stating the first trisodium citrate is 8.7 × 10-5-8.8×10-5Mol, it is poly- in the aqueous povidone solution
The dosage of vinylpyrrolidone is 0.15-0.25g, and the dosage of the water in the aqueous povidone solution is 8-12mL,
The dosage of second trisodium citrate is 1.8 × 10-5-2.2×10-5Mol, the dosage of the mantoquita are 8.8 × 10-6-9.2
×10-6Mol, the dosage of the thioacetamide are 2.8 × 10-6-1.8×10-5Mol, the dosage 2.8 of the hydroxylamine hydrochloride ×
10-5-1.6×10-4mol；
In step (A) and step (B), relative to 2.5 × 10-5Gold chloride in the aqueous solution of chloraurate of mol, it is described
The dosage of water in aqueous solution of chloraurate is 95-110mL, and the dosage of first trisodium citrate is 8.7 × 10-5-8.8×
10-5Mol, the dosage of the polyvinylpyrrolidone in the polystyrolsulfon acid aqueous solution are 0.15-0.25g, the polyethylene
The dosage of water in pyrrolidone solution is 8-12mL, and the dosage of second trisodium citrate is 1.8 × 10-5-2.2×
10-5Mol, the dosage of the mantoquita are 8.8 × 10-6-9.2×10-6The dosage of mol, the N, N- dimethyl selenourea be 2.8 ×
10-6-1.8×10-5Mol, the dosage 2.8 × 10 of the hydroxylamine hydrochloride-5mol-1.6×10-4mol。
In a preferred embodiment of the invention, in order to enable gold chloride can be decomposed adequately, so that mixing
Object M1 can preferably be reacted with aqueous povidone solution and polystyrolsulfon acid aqueous solution respectively, wherein step (1)
In step (A), the aqueous solution of chloraurate the preparation method comprises the following steps: by gold chloride and water under conditions of magnetic agitation, heating
It boils, aqueous solution of chloraurate is made；
The method that Au nano-particle solution is made in step (1) specifically includes: being added into the aqueous solution of chloraurate boiled
After first trisodium citrate, continues to heat 28-32min, mixture M 1 is obtained, after the mixture M 1 is cooled to 20-25 DEG C
Aqueous povidone solution is added thereto, Au nano-particle solution is made；
The method that Au nano-particle solution is made in step (A) specifically includes: being added into the aqueous solution of chloraurate boiled
After first trisodium citrate, continues to heat 28-32min, mixture M 1 is obtained, after the mixture M 1 is cooled to 20-25 DEG C
Polystyrolsulfon acid aqueous solution is added thereto, Au nano-particle solution is made.
In a preferred embodiment of the invention, the weight average molecular weight of the polyvinylpyrrolidone is 30000-
50000；The weight average molecular weight of the polystyrolsulfon acid is 60000-80000, it is preferred that the weight of polyvinylpyrrolidone here
Average molecular weight is 40000, and the weight average molecular weight of polystyrolsulfon acid is 70000.
In a preferred embodiment of the invention, in order to enable Au@Cu2-xThe super nanoparticle of S and Au@Cu2- xThe super nanoparticle of Se can be formed preferably, and in step (2), the mixture M 2 adjusts pH's method particularly includes: utilizes
The mixture M 2 is adjusted pH to 9.2-9.4 by the sodium hydroxide of 0.4-0.6mol/L；
In step (B), the mixture M 2 adjusts pH's method particularly includes: utilizes the sodium hydroxide of 0.4-0.6mol/L
The mixture M 2 is adjusted into pH to 9.2-9.4.
In a preferred embodiment of the invention, in order to enable Au@Cu2-xThe super nanoparticle of S and Au@Cu2- xThe super nanoparticle of Se can be formed preferably, be passed through nitrogen during the preparation process and protected, anyway raw material is in reaction process
In be oxidized, the mixture M 2 is passed through nitrogen after adjusting pH, and the thioacetyl is added under conditions of magnetic agitation later
Amine and the hydroxylamine hydrochloride；
In step (B), the mixture M 2 is passed through nitrogen after adjusting pH, later under conditions of magnetic agitation described in addition
Thioacetamide and the hydroxylamine hydrochloride.
In a preferred embodiment of the invention, in order to enable can preferably be reacted between raw material, step (2)
The method for all using oil bath heating with the heating in step (B), and the temperature heated is 65-75 DEG C, further, the oil bath
The return time of heating is 10-14h.
In a preferred embodiment of the invention, in order to preferably provide Cu ion source, in step (1)
The mantoquita be one of cupric sulfate pentahydrate, copper nitrate and copper chloride or a variety of；
The mantoquita in step (B) is one of cupric sulfate pentahydrate, copper nitrate and copper chloride or a variety of.
In a preferred embodiment of the invention, in order to remove the super nanoparticle of Au@Cu2-xS obtained and
Au@Cu2-xImpurity in the super nanoparticle of Se, by the Au@Cu obtained2-xThe super nanoparticle of S and the Au@Cu2- xThe super nanoparticle of Se carries out centrifugal purification, and the time of the centrifugal purification is 25-35min.
The present invention will be described in detail by way of examples below.Polyvinylpyrrolidone used below is divided equally again
Son amount is 40000, and the weight average molecular weight of polystyrolsulfon acid is 70000.
Embodiment 1
By 2.5 × 10-5Under conditions of magnetic agitation, heating is boiled for mol gold chloride and 99mL water, and it is water-soluble that gold chloride is made
8.75 × 10 are added into the aqueous solution of chloraurate boiled for liquid-5After the first trisodium citrate of mol, continues to heat 30min, obtain
Aqueous povidone solution is added (by the poly- second of 0.2g in mixture M 1 thereto after the mixture M 1 is cooled to 25 DEG C
Alkene pyrrolidone is dispersed in 10mL water and is made), Au nano-particle solution is made；By Au nano-particle solution, 2 × 10-5Mol
Two trisodium citrates and 9 × 10-6The mixing of mol cupric sulfate pentahydrate, is made mixture M 2, will be mixed using the sodium hydroxide of 0.5mol/L
Close object M2 be adjusted to pH be 9.3 after, be passed through 20min nitrogen, later under conditions of magnetic agitation be added 3 × 10-6Sulphur described in mol
For acetamide and 3 × 10-5Hydroxylamine hydrochloride described in mol, oil bath heating under the conditions of 70 DEG C, flow back 12h after carry out 30min centrifugation it is pure
Change, obtains Au@Cu2-xThe super nanoparticle A1 of S.
Embodiment 2
It is prepared according to the method for embodiment 1, unlike, the dosage of the thioacetamide is 6 × 10-6Mol,
The dosage of the hydroxylamine hydrochloride is 6 × 10-5Mol finally obtains Au@Cu2-xThe super nanoparticle A2 of S.
Embodiment 3
It is prepared according to the method for embodiment 1, unlike, the dosage of the thioacetamide is 1.2 × 10- 5Mol, the dosage of the hydroxylamine hydrochloride are 1.2 × 10-4Mol finally obtains Au@Cu2-xThe super nanoparticle A3 of S.
Embodiment 4
It is prepared according to the method for embodiment 1, unlike, the dosage of the thioacetamide is 1.5 × 10- 5Mol, the dosage of the hydroxylamine hydrochloride are 1.5 × 10-4Mol finally obtains Au@Cu2-xThe super nanoparticle A4 of S.
Embodiment 5
It is prepared according to the method for embodiment 1, unlike, relative to 2.5 × 10-5The gold chloride of mol is water-soluble
The dosage of gold chloride in liquid, the water in the aqueous solution of chloraurate is 110mL, and the dosage of first trisodium citrate is
8.8×10-5Mol, the dosage of the polyvinylpyrrolidone in the aqueous povidone solution are 0.25g, the poly- second
The dosage of water in alkene pyrrolidone aqueous solution is 12mL, and the dosage of second trisodium citrate is 2.2 × 10-5Mol, institute
The dosage for stating mantoquita is 9.2 × 10-6Mol, the dosage of the thioacetamide are 1.8 × 10-5Mol, the hydroxylamine hydrochloride
Dosage 1.6 × 10-4Mol finally obtains Au@Cu2-xThe super nanoparticle A5 of S.
Embodiment 6
It is prepared according to the method for embodiment 1, unlike, relative to 2.5 × 10-5The gold chloride of mol is water-soluble
Gold chloride in liquid, the dosage of the water in the aqueous solution of chloraurate are 95mL, and the dosage of first trisodium citrate is 8.7
×10-5Mol, the dosage of the polyvinylpyrrolidone in the aqueous povidone solution are 0.15g, the polyethylene pyrrole
The dosage of water in pyrrolidone aqueous solution is 8mL, and the dosage of second trisodium citrate is 1.8 × 10-5Mol, the mantoquita
Dosage be 8.8 × 10-6Mol, the dosage of the thioacetamide are 2.8 × 10-6Mol, the dosage of the hydroxylamine hydrochloride
2.8×10-5Mol finally obtains Au@Cu2-xThe super nanoparticle A6 of S.
Embodiment 7
It is prepared according to the method for embodiment 1, unlike, polyethylene pyrrole is replaced using polystyrolsulfon acid aqueous solution
Pyrrolidone aqueous solution, N, N- dimethyl selenourea replace thioacetamide, finally obtained Au Cu2-xThe super nanoparticle B1 of Se.
Embodiment 8
It is prepared according to the method for embodiment 2, unlike, polyethylene pyrrole is replaced using polystyrolsulfon acid aqueous solution
Pyrrolidone aqueous solution, N, N- dimethyl selenourea replace thioacetamide, finally obtained Au Cu2-xThe super nanoparticle B2 of Se.
Embodiment 9
It is prepared according to the method for embodiment 3, unlike, polyethylene pyrrole is replaced using polystyrolsulfon acid aqueous solution
Pyrrolidone aqueous solution, N, N- dimethyl selenourea replace thioacetamide, finally obtained Au Cu2-xThe super nanoparticle B3 of Se.
Embodiment 10
It is prepared according to the method for embodiment 4, unlike, polyethylene pyrrole is replaced using polystyrolsulfon acid aqueous solution
Pyrrolidone aqueous solution, N, N- dimethyl selenourea replace thioacetamide, finally obtained Au Cu2-xThe super nanoparticle B4 of Se.
Embodiment 11
It is prepared according to the method for embodiment 5, unlike, polyethylene pyrrole is replaced using polystyrolsulfon acid aqueous solution
Pyrrolidone aqueous solution, N, N- dimethyl selenourea replace thioacetamide, finally obtained Au Cu2-xThe super nanoparticle B5 of Se.
Embodiment 12
It is prepared according to the method for embodiment 6, unlike, polyethylene pyrrole is replaced using polystyrolsulfon acid aqueous solution
Pyrrolidone aqueous solution, N, N- dimethyl selenourea replace thioacetamide, finally obtained Au Cu2-xThe super nanoparticle B6 of Se.
Au@Cu obtained2-xThe partial size of S super nanoparticle A1, A2, A3 and A4 are respectively 2.2nm, 5.3nm, 8.8nm
And 13.5nm, Au@Cu obtained2-xThe partial size of Se super nanoparticle B1, B2, B3 and B4 be respectively 2.2nm, 5.3nm,
8.8nm and 13.5nm.By Fig. 1-Fig. 3 can be seen that the extinction spectra of Au nanoparticle after PVP modification, dynamic light scattering and
Zeta electric potential changes, it was demonstrated that PVP has successfully been modified on Au nanoparticle.From Fig. 4 and Fig. 5 as can be seen that with
Au@Cu2-xBlue shift has occurred in the variation of the super nanoparticle thickness of the shell of S, ultraviolet spectra, and Fig. 6 is the Au@that partial size is 13.5nm
Cu2-xThe Au@Cu that the super nanoparticle of S and partial size are 13.5nm2-xThe transmission electron microscope picture of the super nanoparticle of Se, Fig. 7 are partial sizes
For the Au@Cu of 13.5nm2-xThe Zeta electric potential figure of the super nanoparticle of S, Fig. 8 are the Au@Cu that partial size is 13.5nm2-xS is super to be received
The infrared figure of rice corpuscles.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (8)
1. a kind of synthesis in water Au@Cu2-xThe method of the super nanoparticle of E, which is characterized in that the described method includes:
(1) will aqueous solution of chloraurate and the first trisodium citrate mix after heat, mixture M 1 is obtained, in Xiang Suoshu mixture M 1
Aqueous povidone solution is added, Au nano-particle solution is made；
(2) Au nano-particle solution obtained in step (1), the second trisodium citrate and mantoquita are mixed, mixture M 2 are made,
Mixture M 2 is adjusted to pH as after 9.2-9.4, after thioacetamide and hydroxylamine hydrochloride is added into mixture M 2, heating is made
Au@Cu2-xThe super nanoparticle of S；Alternatively,
The described method includes:
(A) it is heated after mixing aqueous solution of chloraurate and the first trisodium citrate, obtains mixture M 1；Into the mixture M 1
Polystyrolsulfon acid aqueous solution is added, Au nano-particle solution is made；
(B) Au nano-particle solution obtained in step (A), the second trisodium citrate and mantoquita are mixed, mixture M 4 are made,
Mixture M 4 is adjusted to after pH is 9.2-9.4, is added N into mixture M 4, after N- dimethyl selenourea and hydroxylamine hydrochloride, heating
Au@Cu is made afterwards2-xThe super nanoparticle of Se；Wherein,
E is S or Se；
Wherein, in step (1) and step (A), the aqueous solution of chloraurate the preparation method comprises the following steps: gold chloride and water are stirred in magnetic force
Under conditions of mixing, heating is boiled, and aqueous solution of chloraurate is made；
The method that Au nano-particle solution is made in step (1) specifically includes: being added first into the aqueous solution of chloraurate boiled
After trisodium citrate, continue heat 28-32min, obtain mixture M 1, to the mixture M 1 be cooled to 20-25 DEG C it is backward its
Au nano-particle solution is made in middle addition aqueous povidone solution；
The method that Au nano-particle solution is made in step (A) specifically includes: being added first into the aqueous solution of chloraurate boiled
After trisodium citrate, continue heat 28-32min, obtain mixture M 1, to the mixture M 1 be cooled to 20-25 DEG C it is backward its
Au nano-particle solution is made in middle addition polystyrolsulfon acid aqueous solution；
Wherein, in step (1) and step (2), relative to 2.5 × 10-5Gold chloride in the aqueous solution of chloraurate of mol, institute
The dosage for stating the water in aqueous solution of chloraurate is 95-110mL, and the dosage of first trisodium citrate is 8.7 × 10-5-8.8×
10-5Mol, the dosage of the polyvinylpyrrolidone in the aqueous povidone solution are 0.15-0.25g, the poly- second
The dosage of water in alkene pyrrolidone aqueous solution is 8-12mL, and the dosage of second trisodium citrate is 1.8 × 10-5-2.2×
10-5Mol, the dosage of the mantoquita are 8.8 × 10-6-9.2×10-6Mol, the dosage of the thioacetamide are 2.8 × 10-6-
1.8×10-5Mol, the dosage 2.8 × 10 of the hydroxylamine hydrochloride-5-1.6×10-4mol；
In step (A) and step (B), relative to 2.5 × 10-5Gold chloride in the aqueous solution of chloraurate of mol, the chlorine gold
The dosage of water in aqueous acid is 95-110mL, and the dosage of first trisodium citrate is 8.7 × 10-5-8.8×10- 5Mol, the dosage of the polystyrolsulfon acid in the polystyrolsulfon acid aqueous solution are 0.15-0.25g, the polystyrene sulphur
The dosage of water in aqueous acid is 8-12mL, and the dosage of second trisodium citrate is 1.8 × 10-5-2.2×10-5Mol,
The dosage of the mantoquita is 8.8 × 10-6-9.2×10-6The dosage of mol, the N, N- dimethyl selenourea is 2.8 × 10-6-1.8
×10-5Mol, the dosage 2.8 × 10 of the hydroxylamine hydrochloride-5mol-1.6×10-4mol。
2. according to the method described in claim 1, wherein, the weight average molecular weight of the polyvinylpyrrolidone is 30000-
50000；The weight average molecular weight of the polystyrolsulfon acid is 60000-80000.
3. according to the method described in claim 2, wherein, in step (2), the mixture M 2 adjusts pH's method particularly includes:
The mixture M 2 is adjusted into pH to 9.2-9.4 using the sodium hydroxide of 0.4-0.6mol/L；
In step (B), the mixture M 4 adjusts pH's method particularly includes: will be described using the sodium hydroxide of 0.4-0.6mol/L
Mixture M 4 adjusts pH to 9.2-9.4.
4. in step (2), the mixture M 2 is passed through nitrogen after adjusting pH according to the method described in claim 3, wherein, it
The thioacetamide and the hydroxylamine hydrochloride is added under conditions of magnetic agitation afterwards；
In step (B), the mixture M 4 is passed through nitrogen after adjusting pH, is added under conditions of magnetic agitation later described thio
Acetamide and the hydroxylamine hydrochloride.
5. according to the method described in claim 4, wherein, the heating in step (2) and step (B) all uses the side of oil bath heating
Method, and the temperature heated is 65-75 DEG C.
6. according to the method described in claim 5, wherein, the return time of the oil bath heating is 10-14h.
7. method described in any one of -6 according to claim 1, wherein the mantoquita in step (1) is five water sulfuric acid
One of copper, copper nitrate and copper chloride are a variety of；
The mantoquita in step (B) is one of cupric sulfate pentahydrate, copper nitrate and copper chloride or a variety of.
8. according to the method described in claim 7, wherein, by the Au@Cu obtained2-xThe super nanoparticle of S and the Au@
Cu2-xThe super nanoparticle of Se carries out centrifugal purification, and the time of the centrifugal purification is 25-35min.
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