Stabilité analytique et convergence locale de translatées en dynamique homogène S-arithmétique

We present the main result of Richard and Zamojski [14] concerning, in homogeneous dynamics, the general problem of the dynamics of sequences of translates of a certain measure in a space of S-arithmetic lattices.     

pH‐controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways

The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH‐controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3‐dihydroxy‐oxalosuccinate, 3 , in the reaction with glyoxylate and 2‐hydroxy‐2‐hydroxymethyl‐3‐oxosuccinate, 14 , in the reaction with formaldehyde). At pH 7–8, products ( 7 , 8 , and 15 ) exclusively from a decarboxylation of the intermediate are observed, while at pH 13–14, products ( 9 , 10 , and 16 ) solely derived from a hydroxide‐promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7–14) conditions investigated. Herein, we employ a combination of quantitative ¹³C NMR measurements and density functional theory calculations to provide a rationale for this pH‐driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide‐mediated dimerization of glyoxylate. In addition, the non‐enzymatic decarboxylation and fragmentation transformations of these central intermediates ( 3 and 14 ) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism – the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright © 2016 John Wiley & Sons, Ltd.     

Current status of automotive fuel cells for sustainable transport

Automotive proton-exchange membrane fuel cells (PEMFCs) have finally reached a state of technological readiness where several major automotive companies are commercially leasing and selling fuel cell electric vehicles, including Toyota, Honda, and Hyundai. These now claim vehicle speed and acceleration, refueling time, driving range, and durability that rival conventional internal combustion engines and in most cases outperform battery electric vehicles. The residual challenges and areas of improvement which remain for PEMFCs are performance at high current density, durability, and cost. These are expected to be resolved over the coming decade while hydrogen infrastructure needs to become widely available. Here, we briefly discuss the status of automotive PEMFCs, misconceptions about the barriers that platinum usage creates, and the remaining hurdles for the technology to become broadly accepted and implemented.     

Surface Modified Single Molecules Free-Diffusion Evidenced by Fluorescence Correlation Spectroscopy

We report on the free diffusion of single molecule near an interface studied using fluorescence correlation spectroscopy. In particular, we show that the chemical nature of the substrate may modify the free diffusion of a widely used molecule (rhodamine 6G), thus inducing unexpected effects in fluorescence correlation spectroscopy measurements. Our results show a strong influence, up to a few micrometer from the interface, of the surface polarity. This effect is assessed through the relative weight of the two dimensions diffusion process observed close to the surface. Our results are discussed in terms of competition between surface-solvent, solvent-molecule and molecule-surface specific interactions.     

Copper(I/II) complexes of a bis(tetrathiafulvalene)-2,2'-bipyridine: synthesis, characterization, magnetic and electrochemical properties

The coordination ability of the electroactive TTF-based chelating ligand 5,5'-bis(4,5-bis(thiomethyl)-4'-carbamoyltetrathiafulvalene)-2,2'-bipyridine (L) has been tested with Cu(I) and Cu(II) centres. [(L)2Cu(I)](PF6), [(L)2Cu(II)](OTf)2 and [(L)Cu(II)(DMF)3](OTf)2 have been synthesized. A single-crystal X-ray analysis was performed on [(L)Cu(II)(DMF)3](OTf)2, showing a distorted octahedral geometry around the Cu(II) centre, and the formation of dimeric units in the solid state through weak coordination in apical position of an amide oxygen atom from a neighbouring complex. Magnetic data show that the paramagnetic metallic centres are isolated, in agreement with the solid-state structure. Electrochemical measurements were performed on the three complexes and in all cases the Cu(I)/Cu(II) and TTF/TTF+*/TTF2+ redox processes were observed.