Characterization of the early stage aminoshikimate pathway in the formation of 3-amino-5-hydroxybenzoic acid: the RifN protein specifically converts kanosamine into kanosamine 6-phosphate

The biosynthesis of 3-amino-5-hydroxybenzoic acid (AHBA), precursor of the ansamycin and mitomycin antibiotics, proceeds by the aminoshikimate pathway from 3,4-dideoxy-4-amino-D-arabino-heptulosonic acid 7-phosphate (aminoDAHP). Identification of RifN, product of one of three genes from the rifamycin biosynthetic gene cluster known to be essential for aminoDAHP formation, as a specific kanosamine (3-deoxy-3-amino-D-glucose) 6-kinase establishes kanosamine and its 6-phosphate as specific intermediates in AHBA formation. This suggests a hypothetical reaction sequence for aminoDAHP formation, and thus for the early steps of AHBA biosynthesis, starting from UDP-D-glucose and introducing the nitrogen by oxidation and transamination at C-3.     

Synthesis and properties of conjugated oligoyne-centered π-extended tetrathiafulvalene analogues and related macromolecular systems

Alkynyl-substituted phenyldithiafulvenes have been found to act as versatile building blocks for the construction of π-conjugated molecular rods, shape-persistent macrocycles (SPMs), and conducting polymers. Through Cu(I)-catalyzed alkynyl homocoupling, a series of linear-shaped π-extended tetrathiafulvalene analogues (exTTFs) carrying conjugated oligoynes (ranging from diyne to hexayne) as the central π-bridge were readily prepared. The solid-state properties and reactivities of diyne- and tetrayne-centered exTTFs were characterized by X-ray crystallography and differential scanning calorimetry (DSC), while the electronic properties of the oligoyne-exTTFs were elucidated by UV-vis absorption spectroscopy and density functional theory (DFT) calculations. Cyclic voltammetric analysis showed that the terminal phenyldithiafulvene groups of the oligyne-exTTFs could undergo oxidative coupling to form tetrathiafulvalene vinylogue (TTFV)-linked polymer wires. Through a different synthetic route involving oxidative dimerization and Pd/Cu-catalyzed alkynyl homocoupling, the acetylenic phenyldithiafulvene precursors led to shape-persistent macrocycles where the formation of trimeric macrocycles was particularly favored due to the small ring strain incurred. Finally, spectroelectrochemical studies on these oligoyne and TTF hybrid materials disclosed electrochromic and molecular redox-controlled switching properties applicable to molecular electronic and optoelectronic devices.     

Polymerization of Ion-Pair Comonomers of Related Structures

Two ion-pair comonomers of 2-methacryloyloxyethyltrimethyl-ammonium 2-methacryloyloxyethanesulfonate (METMAMES) and 3-acrylamido-3-methylbutyltrimethylammonium 2-acrylamido-2-methylpropanesulfonate have been synthesized. The spontaneous and radical homocopolymerizations of these monomer pairs, wherein no nonpolymerizable counterions are present, have also been studied. Moreover, the intrinsic viscosity of the homocopolymer derived from METMA MES was found to increase with increasing KCl concentration in aqueous solutions.     

An updated overview of diamond-like carbon coating in tribology

During the last two decades, the industry (including scientists) has focused on diamond-like carbon (DLC) coating because of its wide range of application in various fields. This material has numerous applications in mechanical, electrical, tribological, biomedical, and optical fields. Severe friction and wear in some machine parts consumes high amount of energy, which makes the process energy inefficient. Thus, DLC coating can be an effective means to lower the friction and wear rate. Some important process variables that affect the tribological characteristics of DLC coating are adhesion promoter intermediate layer, substrate surface roughness, hydrogen incorporation or hydrogen non involvement, and coating deposition parameters (e.g., bias voltage, etching, current, precursor gas, time, and substrate temperature). Working condition of DLC-coated parts also affects the tribological characteristics, such as temperature, sliding speed and load, relative humidity, counter surface, and lubrication media (DLC additive interaction). Different types of lubricated oils and additives are used in engine parts to minimize friction and wear. DLC can be coated to the respective engine parts; however, DLC does not behave accordingly after coating because of lubricant oil and additive interaction with DLC. Some additive interacts positively and some behave negatively because of the tribochemical reactions between DLC coating and additives. Numerous conflicting views have been presented by several researchers regarding this coating additive interaction, resulting in unclear determination of true mechanism of such interaction. However, lubricant additive has been established to be more inert to DLC coating compared with uncoated metal surface because the additive is fabricated in such a way that it can react with metal surfaces. In this article, the tribological characteristics of different types of DLC coating in dry and lubricated conditions will be presented, and their behavior will be discussed in relation to working condition and processing parameters.     

Median lethal dose, antimalarial activity, phytochemical screening and radical scavenging of methanolic Languas galanga rhizome extract

The methanolic extract of Languas galanga rhizomes was investigated for antimalarial activity against Plasmodium berghei (NK65) infections in mice. The median lethal dose was determined to ascertain the safety of the extract in ICR mice of both sexes. The antimalarial activities during early and established infections, as well as the prophylactic activity were evaluated. Phytochemical screening and radical scavenging activity of the extract were also investigated to elucidate the possible mechanism of the antimalarial properties. The acute oral toxicity (LD??) of Languas galanga extract in mice was established to be 4.998 mg/kg. The extract of Languas galanga rhizomes demonstrated significant antiplasmodial activity in all the three models of the antimalarial evaluations. Phytochemical screening revealed the presence of some vital antiplasmodial constituents such as terpenoids and flavonoids. The extract also exhibited a moderate capacity to scavenge the free radicals. The rhizome extract of Languas galanga thus possesses antimalarial activity, which explains the rational usage of this plant in traditional Malaysian medicine.     

Crystallisation progress in Si-rich ultra-soft nanocomposite alloy fabricated by melt spinning

The crystallisation process and the ultras-soft magnetic properties of amorphous/nanocomposite alloy Fe_73.5Si_17.5B₅Nb₃Cu₁ fabricated by conventional melt-spinning technique are systematically investigated in terms of thermal analysis and in-situ measurement of magnetisation dynamics. The thermal analysis using differential scanning calorimetry showed that crystallisation from Fe-based amorphous state to α-Fe(Si) started at . Further heating the sample leads to a transformation from the α-Fe(Si) to Fe-B phases at . Crystallisation activation energies were determined using two models: Kissinger and John-Mehl-Avrami (JMA), which were consistent to each other with a value of . High resolution transmission electron microscopy investigation revealed an ultrafine structure of α-Fe(Si) nanocrystallite with mean size of 12.5 nm embedded in an amorphous matrix. At a volume fraction of 86% of α-Fe(Si) phase, optimum soft magnetic properties were obtained with very high permeability of 110,000 and a very low coercivity of 0.015 Oe by annealing the amorphous alloy at in 40 min.     

Rainwater rivulets on a cable subject to windFilets d'eau de pluie sur un câble soumis au vent

Rainwater rivulets appear on inclined cables of cable-stayed bridges when wind and rain occur simultaneously. In a restricted range of parameters this is known to cause vibrations of high amplitudes on the cable. The mechanism underlying this effect is still under debate but the role of rainwater rivulets is certain. We use a standard lubrication model to analyse the dynamics of a water film on a cylinder under the effect of gravity and wind load. A simple criterion is then proposed for the appearance and position of rivulets, where the Froude number is the control parameter. Experiments with several geometries of cylinder covered with water in a wind tunnel show the evolution of the rivulets with the Froude number. Comparison of the prediction by the model with these experimental data shows that the main mechanism of rivulet formation and positioning is captured. To cite this article: C. Lemaitre et al., C. R. Mecanique 334 (2006).     

Cu(I)-catalyzed, α-selective, allylic alkylation reactions between phosphorothioate esters and organomagnesium reagents

Regiocontrol of allylic alkylation reactions involving hard nucleophiles remains a significant challenge and continues to be an active area of research. The lack of general methods in which α-alkylation is favored underscores the need for the development of new processes for achieving this type of selectivity. We report that Cu(I) catalyzes the allylic substitution of phosphorothioate esters with excellent α-regioselectivity, regardless of the nature of the Grignard reagent that is used. To the best of our knowledge, the Cu-catalyzed allylic alkylation of phosphorothioate esters has never been described. We have also developed a simple protocol for inducing high α selectivity starting from secondary allylic halides. This is accomplished by using sodium phosphorothioates as an additive.     

Intelligent control of surface hydrophobicity.

Switchable surfaces are highly useful materials with surface properties that change in response to external stimuli. These surfaces can be employed in both research and industrial applications, where the ability to actively control surface properties can be used to develop smart materials and intelligent surfaces. Herein, we review a range of surfaces in which hydrophobicity can be controlled. We present the principal ideas of surface switching, discuss recent developments, explore experimental issues and examine factors that influence surface switching, including the nature of the stimuli, the underlying material, the morphology of the surface and the surrounding environment. We have categorised switchable surfaces according to the stimuli that trigger changes in surface hydrophobicity. These are electrically, electrochemically, thermally, mechanically, photo- and environmentally inducible surfaces. In addition, we review the use of chemical reactions to modify the properties of switchable surfaces and produce changes in the molecular structure and nanoscale features of the surface.