Tribocatalysis: challenges and perspectives

正With an increasing global energy demands and environmental pollution, the development of alternative clean energy technologies has aroused widespread research interest.Harvesting and converting natural energy from the environment, such as solar energy, mechanical energy, thermal energy, chemical and biological energy, is one of the main sources of clean energy. Among these energy sources,     

Phospha-organic chemistry: panorama and perspectives

Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.     

Additions radicalaires—XV : Addition du tetrahydrofuranne au propadiene

Free-radical addition of tetrahydrofuran to propadiene involves addition of α-tetrahydrofuryl radicals to both the terminal and the central carbon of propadiene. Attack at the terminal positions yields the monadduct 2-allyl tetrahydrofuran and the di-adducts 1,2- and 1,3-ditetrahydrofuryl propanes. Attack at the central position yields mainly a dehydrodimer, 2,5-ditetrahydrofuryl hexa-1,5 diene. The ratio of adducts and dehydrodimer depends on the relative concentrations of reactants.     

Peptide-lipid interactions: insights and perspectives

As the number of membrane proteins in the Protein Data Bank increases, efforts to understand how they interact with their natural environment are increasing in importance. A number of membrane proteins crystallise with lipid molecules implicitly bound at discrete locations that are consistent with the transmembrane regions of the protein. Bioinformatics studies also point to the specific interactions of some amino acids with membrane lipids. The results of experiments using model systems are revealing how these interactions contribute to the stability of both the protein and the membrane in which it is embedded. From a different perspective, the processes involved in the binding of peptides to membrane surfaces to produce a variety of effects are being understood in ever-increasing detail. This review describes current research efforts and thinking in this area.     

Alkylations allyliques catalysees au nickel

Stable enolates such as diethyl malonate enolate can be smoothly substituted by allylic acetates (or sulfones) in the presence of nickel complexes. Sulfinate ions convert allylic acetates into sulfones.     

Semiempirical methods: current status and perspectives

Semiempirical methods for calculating potential surfaces are reviewed, with particular emphasis on MNDO and related methods. Topics include the rigorous derivation of semiempirical methods from first principles, the analysis of correlation effects, a comparison between semiempirical and ab initio transition states, and a survey of applications. Possible improvements for MNDO-type methods are discussed, and specific refinements are suggested.     

Selenium-containing enzymes in mammals: Chemical perspectives

The chemical and biochemical route to the synthesis of the 21st amino acid in living systems, selenocysteine, is described. The incorporation of this rare amino acid residue into proteins is described with emphasis on the role of monoselenophosphate as selenium source. The role of selenocysteine moiety in natural mammalian enzymes such as glutathione peroxidase (GPx), iodothyronine deiodinase (ID) and thioredoxin reductase (TrxR) is highlighted and the effect of other amino acid residues located in close proximity to selenocysteine is described. It is evident from various studies that two amino acid residues, tryptophan and glutamine, appear in identical positions in all known members of the GPx family. According to the three-dimensional structure established for bovine GPx, these residues could constitute a catalytic triad in which the selenol group of the selenocysteine is both stabilized and activated by hydrogen bonding with the imino group of the tryptophan (Trp) residue and with the amido group of the glutamine (Gln) residue. The ID enzymes, on the other hand, do not possess any Trp or Gln residues in close proximity to selenium, but contain several histidine residues, which may play important roles in the catalysis. The TrxR enzymes also possess some basic histidines, but the most important amino acid residues are the cysteines which constitute the internal cofactor systems along with the catalytically active selenocysteine. The catalytic activity and substrate specificity of all three selenoenzymes are described. The reactivity of selenocysteine residues in selenoenzymes towards metal-based drugs such as goldthioglucose is also described.     

Simulating enzyme reactions: challenges and perspectives

Elucidating how enzymes enhance the rates of the reactions that they catalyze is a major goal of contemporary biochemistry, and it is an area in which computational and theoretical techniques can make a major contribution. This article outlines some of the processes that need to be investigated if enzyme catalysis is to be understood, reviews the current state-of-the-art in enzyme simulation work, and highlights challenges for the future.     

Etude des systemes ternaires: polymere-polymere-solvant. Application au systeme polystyrene-polydimethylsiloxane-benzene

The ternary system benzene-polydimethylsiloxane-polystyrene has been investigated by light scattering. Apparent molecular weight and solvation coefficient have been determined by applying the relations established for the ternary system of polymer in mixed solvents. The range of validity of these relations for our system has been discussed. We have also determined the χ₂₃ parameter (interaction between the both polymers), following the variations of apparent molecular weight or the compositions at the spinodal.     

Nanotextured au microelectrodes: Electrodeposition-based fabrication and their cyclic voltammograms study

In this letter, the fabrication of nanotextured Au microelectrodes was demonstrated for the first time, carried out by electrodeposition of Au starting from the bottom of a 500-nanometer pore pre-fabricated by microfabrication technology. It was found both the size and the surface nanotexture can be controlled by the potential used. The electrochemical cyclic voltammograms (CVs) response of electroactive species toward such Au microelectrodes was also studied and it was found that the electroactive species used underwent a diffusion-controlled process.     

Bimolecular radical termination: New perspectives and insights

The reversible addition‐fragmentation chain transfer‐chain length dependent termination (RAFT‐CLD‐T) method has allowed us to answer a number of fundamental questions regarding the mechanism of diffusion‐controlled bimolecular termination in free‐radical polymerization (FRP). We carried out RAFT‐mediated polymerizations of methyl acrylate (MA) in the presence of a star matrix to develop an understanding of the effect of polymer matrix architecture on the termination of linear polyMA radicals and compared this to polystyrene, polymethyl methacrylate, and polyvinyl acetate systems. It was found that the matrix architecture had little or no influence on termination in the dilute regime. However, due to the smaller hydrodynamic volumes of the stars in solution compared to linear polymer of the same molecular weight, the gel onset point occurred at greater conversions, and supported the postulate that chain overlap (or c*) is the main cause for the observed autoacceleration observed in FRP. Other theories based on “short–long” termination or free‐volume should be disregarded. Additionally, since our systems are well below the entanglement molecular weight, entanglements should also be disregarded as the cause of the gel onset. The semidilute regime occurs over a small conversion range and is difficult to quantify. However, we obtain accurate dependencies for termination in the concentrated regime, and observed that the star polymers (through the tethering of the arms) provided constriction points in the matrix that significantly slow the diffusion of linear polymeric radicals. Although, this could at first sight be postulated to be due to reptation, the dependencies showed that reptation could be considered only at very high conversions (close to the glass transition regime). In general, we find from our data that the polymer matrix is much more mobile than what is expected if reptation were to dominate. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3155–3173, 2008     

Glycan characterization of biopharmaceuticals: Updates and perspectives

Therapeutic proteins are rapidly becoming the most promising class of pharmaceuticals on the market due to their successful treatment of a vast array of serious diseases, such as cancers and immune disorders. Therapeutic proteins are produced using recombinant DNA technology. More than 60% of therapeutic proteins are posttranslationally modified following biosynthesis by the addition of N- or O-linked glycans. Glycosylation is the most common posttranslational modifications of proteins. However, it is also the most demanding and complex posttranslational modification from the analytical point of view. Moreover, research has shown that glycosylation significantly impacts stability, half-life, mechanism of action and safety of a therapeutic protein. Considering the exponential growth of biotherapeutics, this present review of the literature (2009–2015) focuses on the characterization of protein glycosylation, which has witnessed an improvement in methodology. Furthermore, it discusses current issues in the fields of production and characterization of therapeutic proteins. This review also highlights the problem of non-standard requirements for the approval of biosimilars with regard to their glycosylation and discusses recent developments and perspectives for improved glycan characterization.     

Rice proteomics: current status and future perspectives

Rice, the first cereal crop genome to be decoded, has attracted the attention of researchers worldwide because of its immense socio-economic impact on human existence. With the availability of the draft genome sequence of two major types, japonica- and indica-rice, "rice proteomics" has entered into the era of functional genomics. Although during the last decade an important but limited progress (mainly construction of protein datafiles) has been made in the field of rice proteomics, it is only recently that dedicated research groups have taken this challenge to systematically analyze the rice proteome at the cell (and organelle), tissue, and whole plant level. Important gains achieved by the accelerated technological progress in protein separation and identification will help in going beyond the simple cataloguing of rice proteins in realistic terms. In this review, we discuss the progress made in the field of rice proteomics to date and dwell upon the future direction/problems/approaches towards defining the rice proteome.