Synthesis of gold and silver nanoparticles by use of arabinoglucan from Lallemantia royleana.

Highly stable gold and silver nanoparticles were synthesized by use of an arabinoglucan from Lallemantia royleana seeds without additional use of reducing or stabilizing agents. The mechanism involved the reduction potential of the hemicellulose as verified by cyclic voltammetry. The arabinoglucan used was substantially free from ferulic acid and phenolic content, suggesting the inherent reducing potential of arabinoglucan for gold and silver ions. The synthesized nanoparticles exhibited surface plasmon resonance maxima at 515 nm (gold) and 397 nm (silver) corresponding to sizes of 10 nm and 8 nm, respectively. The zeta potential values were -24.1 mV (gold) and -22.3 mV (silver). The silver nanoparticles showed potential for application in surface-enhanced Raman spectroscopy. Gold nanoparticles were found to be non-toxic, whereas silver nanoparticles exhibited dose-dependent biological activities and found to be cytotoxic against brine shrimps and HeLa cell lines and the tumours caused by A. tumefaciens.

Ligand Exchange/Scrambling Study of Gold(I)-Phosphine Complexes in the Solid Phase by DESI-MS Analysis.

Only a few analytical techniques are available for the characterization of mechanochemical synthetic reaction products. We demonstrate here that DESI-MS is a powerful technique for this purpose, combining the selectivity of MS-based assays with the simplicity and in situ analysis capability of ambient ionization methods. In this work, we report that auranofin, a gold-based drug, and its precursor triethylphosphine gold(I) chloride undergo a complex array of ligand exchange/scrambling reactions with thiol-containing amino acids in the solid state. The products were readily characterized by DESI-MS analysis from the solid-phase reaction, clearly exhibiting ligand exchange and scrambling, with independent confirmation by solid state 13C-NMR. The thioglucose and triethylphosphine moieties exchanged with cysteine and its derivatives, whereas the glutathione replaced 2,3,4,6-tetra-o-acetyl-ß-1-D-glucopyranose only. It was concluded that ligand exchange and scrambling reactions can be carried out in the solid state, and some of the unique products reported in this study can be conveniently prepared through mechanochemical synthesis in good yields (> 98%), as demonstrated by synthesis of (L-cysteinato-S)-triethylphosphine gold(I) from triethylphosphine gold(I) chloride and L-cysteine.

A Spectroscopic Study of Interaction of Auricyanide with n-Acetylcysteine.

Interaction of auricyanide, an important metabolite of anti-arthritic gold-based drug auranofin, was studied in vitro with a pharmacologically active ligand n-acetylcysteine with a view to understand reactivity of gold in vivo. Formation of reduction product aurocyanide occurred through mono- and di-n-acetylcysteine-substituted intermediates. The product and intermediates were identified and monitored spectrophotometrically and by electrospray ionization mass spectrometry. This study suggests successive substitution with n-acetylcysteine through trans effect. At equimolar concentrations of auricyanide and n-acetylcysteine, only mono-substituted mixed-ligand complex was formed. Substitution of the data obtained to various kinetic models suggested that the reaction orders are 0.6 in terms of n-acetylcysteine, 1.5 in terms of auricyanide, and 2 overall. The intermediates detected in this work may help to synthesize more effective and less toxic gold drugs.