Formation and stability of gold nanoparticles in colloids prepared by citrate method

N. Vityuk, A. Eremenko, N. Rusinchuk, V. Lozovski, M. Lokshyn, V. Lysenko, I. Mukha
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Abstract

Gold nanoparticles (Au NPs) have found a variety of applications in different areas, particularly in biomedical practices. The activity of Au NPs strongly depends on the size and association of particles in colloid, that in turn are greatly affected by experimental parameters of the reaction. The obtaining of Au NPs even via classical procedure of citrate method can be a challenge. In the present work we applied different experimental approaches to affect the process of Au NPs formation in the presence of sodium citrate. Au NPs were obtained using different experimental procedures and varying the ratio of reagents, their concentrations, temperature of reaction, duration of heating, the order of introduction of reagents into the reaction mixture, pH, and so on. Comparative analyses of UV-vis spectra with DLS data by number, volume and intensity basis allowed to trace the changes in Au NPs colloid, find optimal experimental conditions and predict prolonged stability of colloids. Applying size-dependent Hamaker constant to DLVO theory explains experimental results. The formation of Au NPs strongly depends on the ratio of the functional groups of the molecule involved simultaneously in the reduction of metal ions, the binding to the surface of Au NPs and the formation of a charge for stabilization due to electrostatic repulsion. The change in the ratio of components is not enough to get a different size of Au NPs. Big concentration of the reagents mostly affects the aggregation process and colloid aging. Temperature is a critical activation factor, that should be about 100 °C, but prolonged heating causes collision induced aggregation. The initial stage of particles growth (the mechanism) can be affected with the change of pH of the system due to formation of deprotonated carboxyl groups and gold hydroxocomplexes.
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柠檬酸盐法制备胶体金纳米颗粒的形成及稳定性
金纳米颗粒(Au NPs)在不同领域,特别是在生物医学实践中有各种各样的应用。Au NPs的活性很大程度上取决于胶体中颗粒的大小和结合体,而这些又受到反应的实验参数的很大影响。即使通过经典的柠檬酸盐法也很难得到Au NPs。在目前的工作中,我们采用不同的实验方法来影响金NPs在柠檬酸钠存在下的形成过程。采用不同的实验方法,通过改变试剂的比例、浓度、反应温度、加热时间、将试剂引入反应混合物的顺序、pH等,得到金纳米粒子。紫外-可见光谱与DLS数据在数量、体积和强度基础上的对比分析,可以追踪Au NPs胶体的变化,找到最佳的实验条件,预测胶体的长期稳定性。将大小相关的Hamaker常数应用于DLVO理论,解释了实验结果。Au NPs的形成强烈依赖于同时参与金属离子还原的分子官能团的比例,与Au NPs表面的结合以及由于静电排斥而形成的稳定电荷。组分比例的变化不足以得到不同尺寸的Au NPs。大浓度的试剂主要影响胶体的聚集过程和老化。温度是一个关键的激活因素,应该在100°C左右,但长时间加热会导致碰撞诱导聚集。由于去质子化羧基和金羟基配合物的形成,pH的变化会影响颗粒生长的初始阶段(机理)。
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