Long‐Range Electrostatics‐Induced Two‐Proton Transfer Captured by Neutron Crystallography in an Enzyme Catalytic Site

Neutron crystallography was used to directly locate two protons before and after a pH‐induced two‐proton transfer between catalytic aspartic acid residues and the hydroxy group of the bound clinical drug darunavir, located in the catalytic site of enzyme HIV‐1 protease. The two‐proton transfer is triggered by electrostatic effects arising from protonation state changes of surface residues far from the active site. The mechanism and pH effect are supported by quantum mechanics/molecular mechanics (QM/MM) calculations. The low‐pH proton configuration in the catalytic site is deemed critical for the catalytic action of this enzyme and may apply more generally to other aspartic proteases. Neutrons therefore represent a superb probe to obtain structural details for proton transfer reactions in biological systems at a truly atomic level.     

From incompatible poly(aryl ether sulfone)/polyamide 4.6. blends to new impact resistant alloys by a synergistic combination of a block copolymer emulsifier and an impact modifier

The compatibilization and impact modification of blends of a relatively new engineering plastic polyamide 4.6 (PA 4.6) and a poly(aryl ether sulfone) (PSU) are investigated. PSU-b-PA6 block copolymers, which can be easily synthesized by ring opening polymerization of ϵ-caprolactam in the presence of a commercial PSU, were found to be very efficient emulsifiers for these incompatible blends. Small amounts (1–4%) of copolymer are sufficient to significantly reduce the particle size and to improve the tensile and impact properties. Combinations of the copolymer and an impact modifier (ethylene-propylene rubber grafted with maleic anhydride) are synergistic and high impact PSU/PA 4.6 alloys are obtained in that way.     

New prospects for “living” anionic polymerization of (meth) acrylic esters

The living low temperature polymerization in polar solvents of most methacrylates, even functional ones, can now be performed by direct and experimentally convenient anionic methods, thanks to the use of α-methylstyrene and of complex-purified monomers. A diversified family of block copolymers has thus been generated, that are used as compatibilizing agents in the designing of interesting heterophase materials: i.e. blends of polymers and inorganic fillers, and liquid-solid dispersions. The living polymerization of acrylates (or of methacrylates under more drastic conditions) raises additional requirements: they have been met to a large extent by the use of specific ligands of the growing ion-pair. Resulting structures such as f.i. block copolymers and end-functionalized oligomers of a low dispersity, should have a great interest in the molecular engineering of (meth)acrylate-based products. Finally, these new initiators lend themselves to structural and mechanistic studies which should shed some light on the critical features of these living propagation processes.     

ChemInform Abstract: Evolution of the Electronic Structure of Lithium Clusters Between Four and Eight Atoms

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Raman microspectroscopic mapping: a tool for the characterisation of polymer surfaces

Raman mapping by point illumination of polymer surfaces is discussed with examples taken from the plasma treatment of polypropylene (PP) and subsequent grafting of polystyrene (PS). Maps can be constructed for surface properties such as crystallinity, blend components and distribution of grafted PS. The Raman sampling volume was estimated for confocal operation using a 50x objective lens.