Selective oxidation using gold

This critical review covers the recent development of the catalytic properties of gold in the selective oxidation of organic compounds, highlighting the exciting contribution to the art of catalysis. The unique, outstanding properties of nanometre-scale particles of gold, a biocompatible non-toxic metal, have allowed the development of a new generation of stable and selective catalysts for the conversion of many organic feedstocks to valuable chemicals. A critical discussion of the results of different research groups is presented along with attempts to correlate the catalytic properties with catalyst morphology in non-equivalent series of experiments.Particular emphasis has been given to the international efforts towards optimised synthesis of products of industrial appeal such as propylene oxide, vinyl acetate monomer, cyclohexanol/cyclohexanone, gluconic acid and glyceric acid (168 references).     

Update on selective oxidation using gold

This critical review aims to update the recent development in the selective oxidation of organic compounds by gold catalysis, highlighting the progress in the last three years. Following the impressive developments in the last decades, several protocols for catalytic oxidation are today available, which are based on the extraordinary properties of gold in terms of catalytic activity, selectivity, reusability and resistance to poisons. Beside many other applications, gold can be recommended for green processes dedicated to fine chemicals, pharmaceuticals and the food industry owing to its recognized bio-compatibility. The collected literature is focused on experiments concerning the oxidation of different chemical groups and could be of interest, in the wide area of organic chemistry, for improving previous processes or for exploring new catalytic pathways (174 references).     

A tri-block copolymer templated synthesis of gold nanostructures

Stable ultra-small gold nanoparticles have been synthesized in aqueous phase by using a tri-block copolymer (BMB) as a templating agent consisting of two PEG-methylacrylate chains (B blocks) anchored to a poly(methacrylic) moiety containing a trithiocarbonate unit (M block). The effect of the BMB/Au molar ratios on the final particle size, shape and monodispersity has been investigated. The synthesized nanosols have been characterized by means of Visible Absorption, Small Angle X-ray Scattering (SAXS), and Transmission Electron Microscopy (TEM). Results clearly indicate that the polymer plays a key role in determining the size and shape of gold particles, from fractal-like structures to monodisperse spherical particles with a mean diameter of about 3 nm. The aggregation behavior of these nanostructures has been characterized both in solution (SAXS) as well as on mica substrate (AFM) and has been proven to be driven by the polymer to gold concentration ratio.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

Rotational isomerism in acetic acid: the first experimental observation of the high-energy conformer

The high-energy conformer of acetic acid (cis-AA) is produced in an Ar matrix by vibrational excitation of the OH stretching overtone of the ground conformational state (trans-AA). IR-absorption spectroscopy provides a clear identification of the reaction product. cis-AA converts back to trans-AA in a time scale of minutes at 8 K by tunneling.     

Interactions between hairy rod anionic conjugated polyelectrolytes and nonionic alkyloxyethylene surfactants in aqueous solution: observations from cloud point behaviour

The effect of three anionic, hairy-rod fluorene based conjugated polyelectrolytes on the cloud points of the alkyloxyethylene surfactants C10E3, C12E4, C12E5, and C12E6 has been studied in aqueous solution. Although the association behaviour of these rigid polymers with surfactants is different from that of more flexible polyelectrolytes, both types of polymers are seen to increase the cloud points, probably as a consequence of associative interactions. The possible importance of Coulombic interactions is suggested by the decrease in cloud points with these systems in the presence of NaCl. With the conjugated polyelectrolytes, the effect appears to be most pronounced with poly[9,9-bis(4-phenoxybutylsulfonate)fluorene-co-2,5-thienylene], which may result from specific interactions between oxyethylene groups and the thiophene ring. The value of cloud point behaviour in designing water based formulations for preparation of devices of these conjugated polyelectrolytes is discussed.