CN1332775C - Gold nanometer particle grain size control method based on glutathione - Google Patents
Gold nanometer particle grain size control method based on glutathione Download PDFInfo
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- CN1332775C CN1332775C CNB2005100275715A CN200510027571A CN1332775C CN 1332775 C CN1332775 C CN 1332775C CN B2005100275715 A CNB2005100275715 A CN B2005100275715A CN 200510027571 A CN200510027571 A CN 200510027571A CN 1332775 C CN1332775 C CN 1332775C
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Abstract
Description
技术领域technical field
本发明涉及的是一种纳米技术领域的方法，特别是一种基于谷胱甘肽对金纳米粒子粒径的控制方法。The invention relates to a method in the field of nanotechnology, in particular to a method for controlling the particle size of gold nanoparticles based on glutathione.
背景技术Background technique
近年来，随着纳米科技的兴起，纳米尺度的金颗粒以其独特的光学、电学性质在许多领域表现出潜在的应用价值，引起了人们浓厚的研究兴趣。纳米金粒子的粒径及尺寸强烈影响着其在化学、生物、电子器件等方面的潜在应用。当粒子小于100nm时，其光学、电学及磁学特性强烈依赖粒子尺寸，因此通过控制金纳米粒子的粒径可以间接的得到所期望的物理性能。金纳米粒子粒径的控制方法有多种，如液相萃取法，晶种法，电化学法等。但这些方法通常操作步骤复杂，条件不易控制，粒径分布较宽。In recent years, with the rise of nanotechnology, nanoscale gold particles have shown potential application value in many fields due to their unique optical and electrical properties, which has aroused people's strong research interest. The size and size of gold nanoparticles strongly affect their potential applications in chemistry, biology, and electronic devices. When the particle is smaller than 100nm, its optical, electrical and magnetic properties strongly depend on the particle size, so the desired physical properties can be obtained indirectly by controlling the particle size of gold nanoparticles. There are many methods to control the particle size of gold nanoparticles, such as liquid phase extraction, seed crystal method, electrochemical method and so on. However, these methods usually have complex operation steps, difficult conditions to control, and wide particle size distribution.
经对现有技术的文献检索发现，2001年Gen T等人在《日本应用物理杂志》(Jpn.J.Appl.Phys.，2001，40(1)346-349)上发表了“Well-size-controlledColloidal Gold Nanoparticles Dispersed in Organic Solvents”(分散在有机溶剂中尺寸可控的金纳米粒子)的文章，该文采用在制备金溶胶的过程中加入丹宁酸，通过改变加入丹宁酸的体积获得不同粒径的金纳米颗粒的方法，并将金溶胶溶液离心后溶入多种有机溶剂中。这一方法操作简单，可控制金纳米粒子的尺寸在5-18纳米之间。但这一方法所制得的金纳米粒子生物兼容性相对较低，金纳米粒子的可控尺寸范围较窄。Found through document retrieval to prior art, in 2001, people such as Gen T published " Well-size -ControlledColloidal Gold Nanoparticles Dispersed in Organic Solvents"(Au nanoparticles dispersed in organic solvents with controllable size) article, this article uses tannic acid in the process of preparing gold sol, obtained by changing the volume of tannic acid added A method for gold nanoparticles with different particle sizes, and centrifuging the gold sol solution and dissolving it in various organic solvents. This method is simple to operate and can control the size of gold nanoparticles between 5-18 nanometers. However, the biocompatibility of gold nanoparticles prepared by this method is relatively low, and the controllable size range of gold nanoparticles is narrow.
发明内容Contents of the invention
本发明的目的在于针对现有技术中的不足，提供一种基于谷胱甘肽对金纳米粒子粒径的控制方法，使其通过谷胱甘肽的加入，直接获得谷胱甘肽修饰的金纳米粒子，方法简单、实用，所得纳米颗粒分散性好、粒径均一，粒径可控制在8-40nm范围内。The purpose of the present invention is to address the deficiencies in the prior art, to provide a method for controlling the particle size of gold nanoparticles based on glutathione, so that glutathione-modified gold can be directly obtained by adding glutathione. Nanoparticles, the method is simple and practical, and the obtained nanoparticles have good dispersion and uniform particle size, and the particle size can be controlled within the range of 8-40nm.
本发明是通过以下技术方案实现的，本发明的具体步骤如下：The present invention is achieved through the following technical solutions, and the concrete steps of the present invention are as follows:
a.将柠檬酸三钠溶液和谷胱甘肽溶液混合。a. Mix trisodium citrate solution and glutathione solution.
b.将步骤a中所得的溶液与氯金酸溶液分别加热，然后混合。b. The solution obtained in step a and the chloroauric acid solution are heated respectively, and then mixed.
c.待步骤b中所得的溶液变色后，将溶液加热至沸腾，使反应充分，然后将溶液冷却得到金纳米粒子溶胶溶液。c. After the solution obtained in step b changes color, the solution is heated to boiling to make the reaction fully, and then the solution is cooled to obtain a gold nanoparticle sol solution.
在步骤a中，本发明所使用的谷胱甘肽为氧化型谷胱甘肽或者还原型谷胱甘肽。谷胱甘肽与氯金酸的质量比控制为(0.01-2)∶1，由于极少量的谷胱甘肽对金纳米粒子粒径的影响较小，而且当谷胱甘肽超过一定比例之后，氯金酸还原速度减慢，对金粒子的粒径影响作用减弱，因此谷胱甘肽与氯金酸的最佳质量比为(0.1-0.8)∶1。In step a, the glutathione used in the present invention is oxidized glutathione or reduced glutathione. The mass ratio of glutathione and chloroauric acid is controlled as (0.01-2): 1, because a very small amount of glutathione has little effect on the particle size of gold nanoparticles, and when glutathione exceeds a certain ratio, , the reduction rate of chloroauric acid slows down, and the effect on the particle size of gold particles is weakened, so the optimal mass ratio of glutathione to chloroauric acid is (0.1-0.8):1.
在步骤b中，为了使氯金酸全部还原，需要加入过量的柠檬酸三钠，因此控制柠檬酸三钠和氯金酸的质量比大于1∶1，优选比例(3-4)∶1，加热温度控制在50-75℃之间。In step b, in order to make chloroauric acid all reduce, need to add excessive trisodium citrate, therefore control the mass ratio of trisodium citrate and chloroauric acid to be greater than 1: 1, preferred ratio (3-4): 1, The heating temperature is controlled between 50-75°C.
在步骤c中，加热沸腾时间为5～20分钟，为了使粒径分布均匀，反应充分，同时减少金纳米粒子的团聚，最佳时间为8-15分钟，所得金纳米粒子的粒径为8-40nm。In step c, the heating and boiling time is 5 to 20 minutes. In order to make the particle size distribution uniform, the reaction is sufficient, and at the same time reduce the aggregation of gold nanoparticles, the optimal time is 8-15 minutes, and the particle diameter of the gained gold nanoparticles is 8 -40nm.
本发明利用柠檬酸三钠还原氯金酸获得金粒子，同时在制备过程中直接加入谷胱甘肽，利用谷胱甘肽的包覆作用，控制金纳米粒子的粒径，并形成谷胱甘肽对金纳米粒子表面的修饰和分散。The present invention utilizes trisodium citrate to reduce chloroauric acid to obtain gold particles, and at the same time directly adds glutathione in the preparation process, utilizes the coating effect of glutathione to control the particle size of gold nanoparticles, and forms glutathione Modification and dispersion of peptides on the surface of gold nanoparticles.
本发明采用在金纳米粒子制备过程中加入谷胱甘肽制备粒径可控的金纳米粒子。由于在反应过程中直接加入谷胱甘肽可以方便地实现谷胱甘肽对金纳米粒子的修饰。本发明所提供的方法具有简单易行，效率高， 颗粒尺寸方便可调，生物兼容性好等特点。由此制得的金纳米粒子可应用在DNA检测、生物及医药等领域，便于推广和应用。The invention adopts adding glutathione in the preparation process of gold nanoparticles to prepare gold nanoparticles with controllable particle size. The modification of gold nanoparticles by glutathione can be conveniently realized by directly adding glutathione in the reaction process. The method provided by the present invention has the characteristics of simplicity, high efficiency, convenient and adjustable particle size, and good biocompatibility. The thus prepared gold nanoparticles can be applied in fields such as DNA detection, biology and medicine, and are convenient for popularization and application.
具体实施方式Detailed ways
结合本发明的内容提供以下实施例：Provide following embodiment in conjunction with content of the present invention:
实施例1Example 1
将1ml 1％(w/v)氯金酸溶液加入到79ml超纯水中(a溶液)。取柠檬酸三钠溶液和氧化型谷胱甘肽溶液，加超纯水至20ml(b溶液)，控制谷胱甘肽与氯金酸的质量比为0.1∶1，柠檬酸三钠和氯金酸的质量比3∶1。把a、b溶液均加热到60℃，然后把b溶液快速倒入a溶液中混合。混合溶液变色后，将溶液加热至沸腾。保持沸腾15分钟，使反应充分，然后将溶液冷却得到38nm金纳米粒子溶胶溶液，体积分布91.6％。Add 1ml of 1% (w/v) chloroauric acid solution to 79ml of ultrapure water (solution a). Get trisodium citrate solution and oxidized glutathione solution, add ultrapure water to 20ml (b solution), control the mass ratio of glutathione and chloroauric acid to be 0.1:1, trisodium citrate and chloroauric acid The mass ratio of acid is 3:1. Heat both solutions a and b to 60°C, then quickly pour solution b into solution a and mix. After the color of the mixed solution changed, the solution was heated to boiling. Keep boiling for 15 minutes to make the reaction fully, and then cool the solution to obtain a 38nm gold nanoparticle sol solution with a volume distribution of 91.6%.
实施例2Example 2
将1ml氯金酸溶液加入到79ml超纯水中(a溶液)。取柠檬酸三钠溶液和还原型谷胱甘肽溶液，加超纯水至20ml(b溶液)，控制谷胱甘肽与氯金酸的质量比为0.5∶1，柠檬酸三钠和氯金酸的质量比4∶1。把a、b溶液均加热到75℃，然后把b溶液快速倒入a溶液中混合。混合溶液变色后，将溶液加热至沸腾。保持沸腾5分钟，使反应充分，然后将溶液冷却得到8纳米金纳米粒子溶胶溶液，体积分布97.6％。Add 1 ml of chloroauric acid solution to 79 ml of ultrapure water (a solution). Get trisodium citrate solution and reduced glutathione solution, add ultrapure water to 20ml (b solution), control the mass ratio of glutathione and chloroauric acid to be 0.5:1, trisodium citrate and chloroauric acid The mass ratio of acid is 4:1. Heat both solutions a and b to 75°C, then quickly pour solution b into solution a and mix. After the mixed solution changed color, the solution was heated to boiling. Keep boiling for 5 minutes to make the reaction fully, and then cool the solution to obtain a 8-nm gold nanoparticle sol solution with a volume distribution of 97.6%.
实施例3Example 3
将1ml氯金酸溶液加入到79ml超纯水中(a溶液)。取柠檬酸三钠溶液和氧化型谷胱甘肽溶液，加超纯水至20ml(b溶液)，控制谷胱甘肽与氯金酸的质量比为0.8∶1，柠檬酸三钠和氯金酸的质量比4∶1。把a、b溶液均加热到50℃，然后把b溶液快速倒入a溶液中混合。混合溶液变色后，将溶液加热至沸腾。保持沸腾约8分钟，使反应充分，然后将溶液冷却得到15纳米金纳米粒子溶胶溶液，体积分布99.2％。Add 1 ml of chloroauric acid solution to 79 ml of ultrapure water (a solution). Get trisodium citrate solution and oxidized glutathione solution, add ultrapure water to 20ml (b solution), control the mass ratio of glutathione and chloroauric acid to be 0.8:1, trisodium citrate and chloroauric acid The mass ratio of acid is 4:1. Heat both solutions a and b to 50°C, then quickly pour solution b into solution a and mix. After the color of the mixed solution changed, the solution was heated to boiling. Keep boiling for about 8 minutes to make the reaction fully, and then cool the solution to obtain a 15nm gold nanoparticle sol solution with a volume distribution of 99.2%.
实施例4Example 4
将1ml氯金酸溶液加入到79ml超纯水中(a溶液)。取柠檬酸三钠溶液和氧化型谷胱甘肽溶液，加超纯水至20ml(b溶液)，控制谷胱甘肽与氯金酸的质量比为2∶1，柠檬酸三钠和氯金酸的质量比4∶1。把a、b溶液均加热到60℃，然后把b溶液快速倒入a溶液中混合。混合溶液变色后，将溶液加热至沸腾。保持沸腾20分钟，使反应充分，然后将溶液冷却得到13纳米金纳米粒子溶胶溶液，体积分布92.8％。Add 1 ml of chloroauric acid solution to 79 ml of ultrapure water (a solution). Get trisodium citrate solution and oxidized glutathione solution, add ultrapure water to 20ml (b solution), control the mass ratio of glutathione and chloroauric acid to be 2:1, trisodium citrate and chloroauric acid The mass ratio of acid is 4:1. Heat both solutions a and b to 60°C, then quickly pour solution b into solution a and mix. After the color of the mixed solution changed, the solution was heated to boiling. Keep boiling for 20 minutes to make the reaction fully, and then cool the solution to obtain a 13nm gold nanoparticle sol solution with a volume distribution of 92.8%.
实施例5Example 5
将1ml氯金酸溶液加入到79ml超纯水中(a溶液)。取柠檬酸三钠溶液和还原型谷胱甘肽溶液，加超纯水至20ml(b溶液)，控制谷胱甘肽与氯金酸的质量比为0.01∶1，柠檬酸三钠和氯金酸的质量比4∶1。把a、b溶液均加热到55℃，然后把b溶液快速倒入a溶液中混合。混合溶液变色后，将溶液加热至沸腾。保持沸腾约10分钟，使反应充分，然后将溶液冷却得到25纳米金纳米粒子溶胶溶液，体积分布97.1％。Add 1 ml of chloroauric acid solution to 79 ml of ultrapure water (a solution). Get trisodium citrate solution and reduced glutathione solution, add ultrapure water to 20ml (b solution), control the mass ratio of glutathione and chloroauric acid to be 0.01:1, trisodium citrate and chloroauric acid The mass ratio of acid is 4:1. Heat both solutions a and b to 55°C, then quickly pour solution b into solution a and mix. After the color of the mixed solution changed, the solution was heated to boiling. Keep boiling for about 10 minutes to make the reaction fully, and then cool the solution to obtain a 25nm gold nanoparticle sol solution with a volume distribution of 97.1%.
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| CN100531972C (en) * | 2008-02-20 | 2009-08-26 | 厦门大学 | A kind of preparation method of photosensitive metal nanomaterial |
| CN101875132B (en) * | 2010-05-31 | 2012-01-11 | 武汉大学 | Method for bionically preparing water-soluble gold nanoclusters |
| CN101987364B (en) * | 2010-09-14 | 2012-06-20 | 江南大学 | Method for preparing functional gold nanoparticles with high stability |
| CN103128309B (en) * | 2013-03-14 | 2015-03-11 | 山东大学 | Synthetic method of water-solubility biocompatibility monodisperse spherical gold nanometer crystals |
| CN103143722B (en) * | 2013-03-21 | 2014-12-17 | 江西农业大学 | Method for preparing multipod-like gold nanoparticles by chemical method |
| CN103212056B (en) * | 2013-05-07 | 2015-07-08 | 东南大学 | Preparation based on gold, silver, gold-silver mixture and glutathione/chitosan, and application of preparation |
| CN106984828B (en) * | 2017-03-28 | 2019-03-12 | 东南大学 | A kind of fluorescence gold nanoclusters fast synthesis method based on chemical etching |
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| JPH07204493A (en) * | 1994-01-18 | 1995-08-08 | Kanebo Ltd | Gold colloid solution |
| WO2004012855A2 (en) * | 2002-08-01 | 2004-02-12 | E.I. Du Pont De Nemours And Company | Ethylene glycol monolayer protected nanoparticles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07204493A (en) * | 1994-01-18 | 1995-08-08 | Kanebo Ltd | Gold colloid solution |
| WO2004012855A2 (en) * | 2002-08-01 | 2004-02-12 | E.I. Du Pont De Nemours And Company | Ethylene glycol monolayer protected nanoparticles |
Non-Patent Citations (3)
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| Controlled Nucleation for the Regulation of the Particle SizeinMonodisperse Gold Suspensions Frens G,Nature Physical Science,Vol.241 No.105 1973 * |
| Controlled Nucleation for the Regulation of the Particle SizeinMonodisperse Gold Suspensions Frens G,Nature Physical Science,Vol.241 No.105 1973;Well-size-controlled Colloidal Gold NanoparticlesDispersedinOrganic Solvents Gen Tsutsui et al,Japanese Journal of Applied Physics,Vol.40 No.1 2001 * |
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