One-pot green synthesis of luminescent gold nanoparticles using imidazole derivative of chitosan.

Water soluble luminescent gold nanoparticles with average size 2.3nm were for the first time synthesized by completely green method of Au(III) reduction using chitosan derivative-biocompatible nontoxic N-(4-imidazolyl)methylchitosan (IMC) as both reducing and stabilizing agent. Reduction of Au(III) to gold nanoparticles in IMC solution is a slow process, in which coordination power of biopolymer controls both reducing species concentration and gold crystal growth rate.

Role of Au(III) coordination by polymer in "green" synthesis of gold nanoparticles using chitosan derivatives.

Here we report "green" synthesis of gold nanoparticles in solutions of heterocyclic chitosan derivatives (N-(4-imidazolyl)methylchitosan (IMC), N-2-(2-pyridyl)ethylchitosan (2-PEC), and N-2-(4-pyridyl)ethylchitosan (4-PEC)) and show how efficiency of Au(III) binding to polymer influences the Au(III) reduction rate and the size of the gold nanoparticles formed using only the reducing power of these chitosan derivatives. Rheology measurements and (1)H NMR spectroscopy data have confirmed that cleavage of glycosidic bond is a common mechanism of reducing species generation in solutions of chitosan and its N-heterocyclic derivatives. However, the emerging additional reducing species in 2-PEC and 4-PEC solutions due to vinylpyridine elimination promotes Au(III) reduction and gold nanoparticles growth despite lower efficiency of glycosidic bond cleavage in pyridyl derivatives.

Mechanism of Au(III) reduction by chitosan: comprehensive study with 13C and 1H NMR analysis of chitosan degradation products.

The mechanism of Au(III) reduction by chitosan has been proposed on the basis of comprehensive study of kinetics of Au(III) reduction and chitosan chain degradation using UV-vis spectroscopy and viscosimetry, and identification of reaction products using colloid titration and (13)C, (1)H NMR spectroscopy. We have shown that formation of gold nanoparticles in H[AuCl4]/chitosan solutions starts with hydrolysis of chitosan catalyzed by Au(III). The products of chitosan hydrolysis rather than chitosan itself act as the main reducing species.