CN102806357A - Preparation method of high-stability nano-gold particles - Google Patents
Preparation method of high-stability nano-gold particles Download PDFInfo
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- CN102806357A CN102806357A CN2011101472294A CN201110147229A CN102806357A CN 102806357 A CN102806357 A CN 102806357A CN 2011101472294 A CN2011101472294 A CN 2011101472294A CN 201110147229 A CN201110147229 A CN 201110147229A CN 102806357 A CN102806357 A CN 102806357A
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Abstract
The invention relates to the field of synthesis and preparation of nano-gold materials, in particular to a preparation method of high-stability nano-gold particles. The preparation method includes steps of (1), preparing solution of polyoxyethylene-polypropylene oxide-polyoxyethylene polymer, regulating pH (potential of hydrogen) value of the solution to be 8-12, heating the solution to be 30-40DEG C and then keeping the temperature constant; and 2), adding chloroauric acid aqueous solution, enabling the molar ratio of chloroauric acid to the polymer to be 1:(19.8-87), uniformly stirring and mixing, reacting and separating to obtain the high-stability nano-gold particles. The preparation method has the advantages that nano-gold polyhedrons or nano-gold ellipsoids which are obtained by regulating the pH value of the reaction solution have high stability; and the preparation method requires mild reaction conditions, is simple in operation and can be completed within two hours.
Description
Technical field
The present invention relates to the synthetic preparation field of metal nano material, particularly, the present invention relates to a kind of preparation method of high-stability nano gold grain.
Background technology
The develop rapidly of nanometer technology is that the application of nano particle in fields such as biological medicine, analysis catalysis provides good prospect.Because its unique physicochemical properties, nano particle has caused scientific worker's very big concern.
The basic characteristics (small-size effect, skin effect, tunnel-effect) of gold nano grain except having nano material also have remarkable optics, electricity, catalysis characteristics, have demonstrated great using value in a lot of fields.And factors such as the size, size, stability of particle are depended in the performance of its performance, through simple method preparation singly disperse, particle diameter is controlled and the gold nano grain of homogeneous, is the focus of research always.
Gold nano grain is because surface area is very little, and the surface can be high, so in solution, reunite easily.Generally need to add reducing agent (like sodium borohydride, natrium citricum etc.) gold ion is reduced to simple substance; Through physical absorption or the chemical bonding with gold grain such as surfactant (like lauryl sodium sulfate, cetab etc.), macromolecule, prevent its reunion then.Because add several kinds of compositions of different effects, so the pattern regulative mode of gold grain is complicated, and the stability that adds is generally toxic, has limited the application at biomedicine field.Amphiphilic block copolymer PEO-PPO-PEO (trade name Pluronic) is as the macromolecular compound of a kind of commercialization, relative low price, low bio-toxicity, has wide practical use in fields such as medicine carrying, gene transmission, mesoporous material are synthetic.With the synthetic gold nano grain of PEO-PPO-PEO, wherein, the ether-oxygen bond of hydrophilic PEO segment has certain reducing power; Can be reduced to golden simple substance with the gold ion combination and with it, hydrophobic PPO segment is adsorbed in the gold grain surface through hydrophobic interaction simultaneously, makes its stable existence in the aqueous solution; Need not add reducing agent in addition, operating procedure is simple, regulates the size of gold grain through the ratio of the molecular weight of control block copolymer, close hydrophobic section; But generally speaking; Particle less stable in the aqueous solution of preparation, wide range of particle sizes limits its application in practical systems.At present, improved measure has the hydrophobic microenvironment that adds inorganic ion adjusting PEO-PPO-PEO micelle kernel, because effectively improved the stability of gold grain in the aqueous solution, particle is all once further strengthened.But in the practical application of the gold grain aqueous solution, often need regulate the physical-chemical parameters,, and can reunite because of the change of external condition with the synthetic gold grain of inorganic salts regulation and control like pH and ionic strength etc.Therefore the gold grain requirement to acid-base value and ionic strength in application for preparing by this method is very high, and its application is restricted.
At present, though it is a lot of to prepare the method for nanoscale gold grain, all there are problems such as stability, bio-toxicity in the particle for preparing, and therefore, the gold nano grain that preparation has good stability and biocompatibility has important value to advancing its application.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-stability nano gold grain.
Preparation method according to high-stability nano gold grain of the present invention said method comprising the steps of:
1) solution of preparation polyoxyethylene-poly-oxypropylene polyoxyethylene polymer, and adjusting pH is 8～12, is heated to 30～40 ℃ of constant temperature;
2) add aqueous solution of chloraurate, make gold chloride and polymer mol ratio 1: 19.8～87, mix, react, separate, obtain the high-stability nano gold grain.
According to the preparation method of high-stability nano gold grain of the present invention, constant temperature time is 1～2h in the said step 1).
Preparation method according to high-stability nano gold grain of the present invention; The molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene polymer is 5750～12600g/mol in the said step 1); Wherein polyoxypropylene accounts for 30%～70% of polyoxyethylene-poly-oxypropylene polyoxyethylene polymer; Be specially P123 or F127, its molecular weight is respectively 5750,12600, and its concentration is 5～10wt%.
According to the preparation method of high-stability nano gold grain of the present invention, pH is 8.1～11.6. in the said step 1)
According to the preparation method of high-stability nano gold grain of the present invention, said step 2) concentration of aqueous solution of chloraurate is 2mmol/L in.
Preparation method according to high-stability nano gold grain of the present invention; Said step 2) the nanogold particle form for preparing in is polyhedron particle, spheroid particle, nano golden cluster; The images of transmissive electron microscope statistics draws, and its particle diameter is respectively 13nm, 8.9～10.7nm and 54～70nm.
According to the preparation method of high-stability nano gold grain of the present invention, said step 2) separating step is in: in the nm of gold aqueous solution, add the mixture of propyl alcohol, hexane, its volume ratio is 2: 1, uses centrifuge under the 12000rpm rotating speed, to move 20 minutes.
According to one embodiment of the invention, its concrete preparation process may further comprise the steps:
1) the preparation Pluronic aqueous solution is regulated its pH with certain density NaOH.
2) the P123 aqueous solution of getting different pH heated in water-bath one hour in advance, and temperature is set at 40 ℃.
3) get certain density chlorauric acid solution and be injected into fast in the P123 aqueous solution, mix, place the medium question response of water-bath to accomplish, naturally cool to room temperature.
4) the Pluronic series of products are preferably got the strong P123 of hydrophobicity (molecular weight 5750), and the P123 aqueous solution and aqueous solution of chloraurate optimum volume ratio scope are 20: 1-5: 1, and pH value optimum range is 8.10-11.63.
Preparation method according to high-stability nano gold grain of the present invention; Block copolymer Pluronic has temperature sensitivity; (the critical micelle temperature of 5wt%P123 is 18 ℃) block copolymer exists with the micelle form more than the critical micelle temperature; The hydrophobic side is adsorbed on the gold grain, and water-wet side and water can guarantee fund's particle good stable property in the aqueous solution with hydrogen bond structure.Simultaneously, temperature raises, and helps accelerating reaction rate, and therefore testing reaction temperature is good at 30～40 ℃, further improves reaction temperature, and the block copolymer phase behavior changes, and micelle is destructurized, also is unfavorable for the controlledly synthesis of gold grain.
Simultaneously, improve the ratio of initator (gold chloride) with the reducing agent (block copolymer) of gold ion, can improve the rate of reduction of gold ion, the gold grain particle diameter of acquisition is less.
In addition; Improve the joint efficiency that pH can promote block copolymer and gold ion; The gold grain that simultaneously also can strengthen generating and the hydrophobic interaction between the block copolymer; Therefore the gold grain particle diameter that under alkali condition, synthesizes is less, and stability is high in the aqueous solution, can adapt to the change (as regulating pH value and ionic strength) of external environment under the certain condition.At acid condition, pH is in 1.97～6.64 scopes, promptly occurs muddyly in the course of reaction, places that a large amount of gold grains precipitate from solution after one day, explain that gold grain under this condition interacts with block copolymer a little less than, easy reunion.And if pH under high alkali condition for example more than the pH=13, then block copolymer exists with gel form, is unfavorable for the reduction of gold ion, the output of gold grain is very low.
Therefore; Need control the temperature of reaction, the initator (gold chloride) of raising gold ion and the ratio of reducing agent (block copolymer) in the present invention; And the pH of reaction, be that the nanogold particle for preparing not only has good bio-compatibility, all possess good stability simultaneously.PEO-PPO-PEO pH value of aqueous solution to certain alkaline range (8.1～11.6) is at first regulated in this experiment, then with the gold chloride reaction, and the gold grain of preparation certain size, pattern.The gold grain that synthesizes of experiment combines with block copolymer with forms such as nucleocapsid structure or groups bunch, can adapt to the change (like adjusting pH value, inorganic salt concentration etc.) of external environment.The maximum characteristics of the present invention are not only can pass through to regulate the stability in the pH value aqueous solution, and can control the combining form of gold grain and block copolymer.Therefore simultaneously, PEO-PPO-PEO has excellent biological compatibility, inanimate object toxicity, and the nm of gold of different shapes such as the nuclear-shell through this method preparation, group bunch has wide practical use in analyzing and testing, medicine carrying field.
Advantage of the present invention is:
1) obtains the polyhedron or the spheroid of nm of gold through the pH value of conditioned reaction solution, all possess good stability;
2) reaction condition is gentle, and is simple to operate, can in 2 hours, accomplish.
Description of drawings
Fig. 1 is the TEM figure of the nm of gold polyhedron sample of embodiment 1 preparation, and scale is 100nm;
Fig. 2 is the TEM figure of the nm of gold spheroid sample of embodiment 2 preparations, and scale is 50nm;
Fig. 3 is the TEM figure of the nano golden cluster sample of embodiment 3 preparations, and scale is 100nm;
Fig. 4 is the TEM figure of the nm of gold sample of embodiment 4 preparations, and scale is 100nm;
Fig. 5 is adjusting pH value or the ultraviolet-visible light spectrogram behind the inorganic salt concentration of the sample of embodiment 2 preparation, the pH value of sample 2 by react preceding 11.6 become reacted 10.87, curve a.
The specific embodiment
Embodiment 1
1) preparation mass and size mark is the Pluronic P123 sample of 5wt%; Pluronic P123 molecular weight is 5750; Polyoxypropylene accounts for 30% of polyoxyethylene-poly-oxypropylene polyoxyethylene polymer; The NaOH aqueous solution of configuration 5mol/L mixes with volume ratio with the NaOH aqueous solution with deionized water at 1: 9;
2) get the Pluronic P123 aqueous solution of 5mL 5wt%, add the NaOH aqueous solution after the above-mentioned dilution of 5uL, mix, measuring its pH value is 8.1, in thermostat water bath, heats one hour, and temperature is set at 40 ℃.
3) chlorauric acid solution of getting 0.5mL, 2mM with liquid-transfering gun is injected in the above-mentioned solution fast; Wherein the mass ratio of gold chloride and Pluronic P123 and mol ratio were respectively 1: 634.8 and 1: 43.5; After mixing 10 seconds with the vortex vortex mixer; Be heated to reaction under continuing 40 ℃ and accomplish, promptly gold nano grain SPR (surfaceplasmon resonance) absworption peak on uv-vis spectra keeps stable.The nm of gold polyhedron average grain diameter that obtains is at 13nm.
Embodiment 2
1) preparation mass and size mark is the Pluronic P123 sample of 5wt%, and Pluronic P123 molecular weight is 5750, and polyoxypropylene accounts for 30% of polyoxyethylene-poly-oxypropylene polyoxyethylene polymer.The NaOH aqueous solution of configuration 5mol/L mixes with volume ratio with the NaOH aqueous solution with deionized water at 4: 6;
2) get the Pluronic P123 aqueous solution of 5mL 5wt%, add the NaOH aqueous solution after the above-mentioned dilution of 5uL, mix, measuring its pH value is 11.6, in thermostat water bath, heats 2 hours, and temperature is set at 40 ℃.
3) chlorauric acid solution of getting 0.5mL, 2mM with liquid-transfering gun is injected in the above-mentioned solution fast; Wherein the mass ratio of gold chloride and Pluronic P123 and mol ratio were respectively 1: 634.8 and 1: 43.5; After mixing 10 seconds with the vortex vortex mixer; Be heated to reaction under continuing 40 ℃ and accomplish, promptly gold nano grain SPR (surfaceplasmon resonance) absworption peak on uv-vis spectra keeps stable.The nm of gold spheroid average grain diameter that obtains is at 10nm.
Synthetic sample pH value is that 10.87 (Fig. 4 a) under this condition; The aqueous hydrochloric acid solution that adds variable concentrations with pH value be adjusted to respectively 7.09 perhaps regulate sample with 2.44. ionic strength; Add sodium chloride to concentration for after the 1M. sample leaves standstill 24 hours, do the ultraviolet-visible spectrum of sample, its surface plasma resonance absworption peak (SPR) does not take place significantly mobile; And the sample that has changed materialization environment at room temperature still can keep stablizing more than one month, does not produce deposition.
Embodiment 3
1) preparation mass and size mark is the Pluronic P123 sample of 5wt%, and Pluronic P123 molecular weight is 5750, and polyoxypropylene accounts for 30% of polyoxyethylene-poly-oxypropylene polyoxyethylene polymer.The NaOH aqueous solution of configuration 5mol/L mixes with volume ratio with the NaOH aqueous solution with deionized water at 4: 6;
2) get the Pluronic P123 aqueous solution of 5mL 5wt%, add the NaOH aqueous solution after the above-mentioned dilution of 5uL, mix, measuring its pH value is 11.6, in thermostat water bath, heats one hour, and temperature is set at 30 ℃.
3) chlorauric acid solution of getting 0.25mL, 2mM with liquid-transfering gun is injected in the above-mentioned solution fast; Wherein the mass ratio of gold chloride and Pluronic P123 and mol ratio were respectively 1: 1269.6 and 1: 87; After mixing 10 seconds with the vortex vortex mixer; Be heated to reaction under continuing 30 ℃ and accomplish, promptly gold nano grain SPR (surfaceplasmon resonance) absworption peak on uv-vis spectra keeps stable.The nano golden cluster average grain diameter that obtains is at 50nm.
Embodiment 4
1) preparation mass and size mark is the Pluronic F127 sample of 5wt%, and Pluronic P123 molecular weight is 12600, and polyoxypropylene accounts for 70% of polyoxyethylene-poly-oxypropylene polyoxyethylene polymer.The NaOH aqueous solution of configuration 5mol/L mixes with volume ratio with the NaOH aqueous solution with deionized water at 4: 6;
2) get the Pluronic F127 aqueous solution of 5mL 5wt%, add the NaOH aqueous solution after the above-mentioned dilution of 5uL, mix, measuring its pH value is 12.0, in thermostat water bath, heats one hour, and temperature is set at 30 ℃;
3) chlorauric acid solution of getting 0.5mL, 2mM with liquid-transfering gun is injected in the above-mentioned solution fast; Wherein the mass ratio of gold chloride and Pluronic F127 and mol ratio were respectively 1: 634.8 and 1: 19.8; After mixing 10 seconds with the vortex vortex mixer; Be heated to reaction under continuing 30 ℃ and accomplish, promptly gold nano grain SPR (surfaceplasmon resonance) absworption peak on uv-vis spectra keeps stable.The nano golden cluster average grain diameter that obtains is at 10.3nm.
Claims (7)
1. the preparation method of a high-stability nano gold grain is characterized in that, said method comprising the steps of:
1) solution of preparation polyoxyethylene-poly-oxypropylene polyoxyethylene polymer, and adjusting pH is 8～12, is heated to 30～40 ℃ of constant temperature;
2) add aqueous solution of chloraurate, making the mol ratio of gold chloride and polymer is 1: 19.8～87, mixes, and reacts, separates, and obtains the high-stability nano gold grain.
2. the preparation method of high-stability nano gold grain according to claim 1 is characterized in that, constant temperature time is 1～2h in the said step 1).
3. the preparation method of high-stability nano gold grain according to claim 1; It is characterized in that; The molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene polymer is 5750～12600g/mol in the said step 1), and wherein polyoxypropylene accounts for 30%～70% of polyoxyethylene-poly-oxypropylene polyoxyethylene polymer.
4. the preparation method of high-stability nano gold grain according to claim 1; It is characterized in that; The polyoxyethylene-poly-oxypropylene polyoxyethylene polymer is P123 or F127 in the said step 1), and its molecular weight is respectively 5750 and 12600, and preparing its concentration is 5～10wt%.
5. the preparation method of high-stability nano gold grain according to claim 1 is characterized in that, in the said step 1), regulating pH is 8.1～11.6.
6. the preparation method of high-stability nano gold grain according to claim 1 is characterized in that, said step 2) in the concentration of aqueous solution of chloraurate be 2mmol/L.
7. the preparation method of high-stability nano gold grain according to claim 1; It is characterized in that; Said step 2) in, in the reacted mixed solution of aqueous solution of chloraurate, add the mixture of propyl alcohol, hexane, its volume ratio is 2: 1; Use centrifuge under the 12000rpm rotating speed, to move 20 minutes, separate.
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| CN107200336A (en) * | 2017-06-29 | 2017-09-26 | 中国科学院青岛生物能源与过程研究所 | The preparation method of inorganic salts nano wire |
| CN107902674A (en) * | 2016-12-23 | 2018-04-13 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the cube potassium chloride nano particle of high stability |
| CN110842214A (en) * | 2019-12-18 | 2020-02-28 | 中国科学院青岛生物能源与过程研究所 | Preparation method of gold nanorods |
| CN112719285A (en) * | 2020-12-18 | 2021-04-30 | 黑龙江省能源环境研究院 | Sacrificial template agent coated nano-gold particles and preparation method thereof |
| CN116769480A (en) * | 2023-06-21 | 2023-09-19 | 桑若(厦门)光伏产业有限公司 | Preparation method of high-stability perovskite heterojunction quantum dot |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902674A (en) * | 2016-12-23 | 2018-04-13 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the cube potassium chloride nano particle of high stability |
| CN107902674B (en) * | 2016-12-23 | 2019-10-15 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the cube potassium chloride nano particle of high stability |
| CN107200336A (en) * | 2017-06-29 | 2017-09-26 | 中国科学院青岛生物能源与过程研究所 | The preparation method of inorganic salts nano wire |
| CN110842214A (en) * | 2019-12-18 | 2020-02-28 | 中国科学院青岛生物能源与过程研究所 | Preparation method of gold nanorods |
| CN112719285A (en) * | 2020-12-18 | 2021-04-30 | 黑龙江省能源环境研究院 | Sacrificial template agent coated nano-gold particles and preparation method thereof |
| CN112719285B (en) * | 2020-12-18 | 2022-12-13 | 黑龙江省能源环境研究院 | Sacrificial template agent coated nano-gold particles and preparation method thereof |
| CN116769480A (en) * | 2023-06-21 | 2023-09-19 | 桑若(厦门)光伏产业有限公司 | Preparation method of high-stability perovskite heterojunction quantum dot |
| CN116769480B (en) * | 2023-06-21 | 2023-12-05 | 桑若(厦门)光伏产业有限公司 | Preparation method of high-stability perovskite heterojunction quantum dot |
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Application publication date: 20121205 |