The structure of acetonitrile−water mixtures has been investigated by X-ray diffraction with an imaging plate detector and IR spectroscopy over a wide range of acetonitrile mole fractions (0.0 ≤ X AN ≤ 1.0). Reichardt E T N and Sone-Fukuda D II,I values were also measured for the mixtures. It has been found from the X-ray data that in pure acetonitrile an acetonitrile molecule interacts with two nearest neighbors by antiparallel dipole−dipole interaction together with a small shift of the two molecular centers and that two acetonitrile molecules in the second-neighbor shell interact with a central molecule through parallel dipole−dipole interaction. Thus, acetonitrile molecules are alternately aligned to form a zigzag cluster. On addition of water into pure acetonitrile, water molecules interact with acetonitrile molecules through a dipole−dipole interaction in an antiparallel orientation. The IR spectra of O−D and C⋮N stretching vibrations, observed for mixtures of acetonitrile AN and water containing 20% D2O, suggested that hydrogen bonds are also formed between acetonitrile and water molecules in the mixtures at X AN ≤ 0.8. The average numbers of the first- and second-neighbor acetonitrile molecules gradually increase with increasing water content with an almost constant first-neighbor distance and slightly decreased second-neighbor ones. Thus, acetonitrile molecules are assembled to form three-dimensionally expanded clusters; the acetonitrile clusters are surrounded by water molecules through both hydrogen bonding and dipole−dipole interaction. The X-ray radial distribution functions and IR spectra suggest that the hydrogen bond network of water is enhanced in the mixtures at X AN < 0.6. The concentration dependence of E T N and D II,I values determined reflects well the above-mentioned behavior of water molecules in the mixtures. These findings suggest that both water and acetonitrile clusters coexist in the mixtures in the range of 0.2 ≤ X AN < 0.6, i.e., “microheterogeneity” occurs in the acetonitrile−water mixtures.

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Gold nanoparticle formation was found from tetrachloroaurate(III) in the presence of Good’s Buffers, such as 2-morpholinoethanesulfonic acid (MES) and 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES), which are used widely in laboratories for studies of analytical, inorganic, physical, and bio-chemistry as well as biology. The obtained gold nanoparticles were examined by Ultraviolet–Visible Spectroscopy (UV–vis), Dynamic Light Scattering (DLS) and Electrophoretic Light Scattering (ELS) in an aqueous system and by transmission electron microscopy (TEM) for particle morphologies. UV–vis spectra showed absorption maxima at ∼530 and ∼750 nm, depending on the buffer reagents and their concentration, pH, and ionic strength. The size and the surface zeta potential of the formed nanoparticles were 23 to 73 nm and −30 to −12 mV, respectively. The TEM pictures clearly indicated the formation of finely dispersed, chained, or aggregated gold nanoparticles, depending on the experimental conditions. The mechanism of gold nanoparticle formation was studied by the measurements of cyclic voltammetry (CV) and electron spin resonance (ESR). MES and HEPES showed a positive anodic peak at approximately +800 mV vs Ag/AgCl electrode, which indicated that these buffering agents have mild reducing ability. ESR results indicated the generation of nitrogen-centered cationic free radicals from these Good’s Buffers in the presence of Au(III), resulting in the formation of gold nanoparticles. A reaction mechanism is proposed.

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