Organic reactions and nanoparticle preparation in CO(2)-induced water/P104/p-xylene microemulsions

Nanometer-sized gold particles are synthesized by the reduction of HAuCl(4) with KBH(4) in the CO(2)-induced microemulsion of (EO)(27)(PO)(61)(EO)(27) (P104; EO=ethylene oxide, PO=propylene oxide)/p-xylene/CO(2)/H(2)O. The recovery of gold particles from the microemulsion can be easily accomplished by the venting of CO(2), while the surfactant remains in the organic phase. The effect of the molar ratio of the reductant to HAuCl(4), the concentration of the reactants, and the molar ratio of water to EO segments (W(0)) in the reverse micelles on the size of the gold particles is studied. The hydrolysis of benzoyl chloride (BzCl) and p-nitrophenyl chloroformate (NPhCl) has also been carried out in the microemulsion. The results show that the observed rate constants k(obs) of both substrates increase significantly with W(0), and that W(0) has a larger influence on the hydrolysis of BzCl. The different extents of the influence of W(0) on the two reactions can be ascribed to the different reaction mechanisms and the expected changes in nucleophilicity and polarity of water in the reverse micelles.