No abstract

Tetrachloroaurate reduction with α-, β-, and γ-cyclodextrin at pH 10.56 was studied in this study by dual-angle dynamic light scattering and spectrophotometry. The nanoparticles were also characterized by scanning electron microscopy. In contrast with our previous study, the nanoparticles were purified by centrifugation prior to characterization. The reaction is considered to be a promising one-step method for preparation of gold nanoparticles with immobilized cyclodextrins without the need for seeding. Unlike in our previous study, the reaction mixture was boiled under reflux conditions instead of an open vial. This change sped up the reaction, and extensive aggregation was avoided. For the first time, this study demonstrated that all three cyclodextrins were able to reduce tetrachloroaurate at room temperature as well, but long incubation periods were necessary. This is the first publication discussing the mechanism of tetrachloroaurate reduction by cyclodextrins. The first stage of the reaction involved tetrachloroaurate hydrolysis despite presence of hydrochloric acid in the commercial preparation of tetrachloroauric acid (HAuCl4). Tetrachloroaurate was therefore the precursor but not the actual oxidant. The previous hypothesis on autocatalytic decarboxylation of cyclodextrins was therefore proven wrong. Particle growth was accompanied by nucleation, leading to coexistence of nanoparticles and nanoclusters. The resulting nanoparticles contained a small fraction of aggregates, probably because of sodium chloride generated from hydrochloric acid. However, besides playing this detrimental role, chloride ions facilitated nucleation by stabilizing gold intermediates. The nanoparticles solutions could be stored at least for three months, which contrasted with our previous work, where the nanoparticles were stable for only three days. For the first time, freeze-drying and reconstitution of the resulting nanoparticles were investigated, and they were shown to be free from aggregation. The synthesized gold nanoparticles are recommended for use as drug carriers.

Cyclodextrin-capped gold nanoparticles are promising drug-delivery vehicles, but the technique of their preparation without trace amounts of aggregates is still lacking, and the size-manipulation possibility is very limited. In the present study, gold nanoparticles were synthesized by means of 0.1% (w/w) tetrachloroauric acid reduction with cyclodextrins at room temperature, at cyclodextrin concentrations of 0.001 M, 0.002 M and 0.004 M, and pH values of 11, 11.5 and 12. The synthesized nanoparticles were characterized by dynamic light scattering in both back-scattering and forward-scattering modes, spectrophotometry, X-ray photoelectron spectroscopy, transmission electron microscopy and Fourier-transform infrared spectroscopy. These techniques revealed 14.9% Au1+ on their surfaces. The Finke–Watzky kinetics of the reaction was demonstrated, but the actual growth mechanism turned out to be multistage. The synthesis kinetics and the resulting particle-size distribution were pH-dependent. The reaction and centrifugation conditions for the recovery of aggregate-free nanoparticles with different size distributions were determined. The absorbances of the best preparations were 7.6 for α-cyclodextrin, 8.9 for β-cyclodextrin and 7.5 for γ-cyclodextrin. Particle-size distribution by intensity was indicative of the complete absence of aggregates. The resulting preparations were ready to use without the need for concentration, filtration, or further purification. The synthesis meets the requirements of green chemistry.