Development of the parametric tolerance modeling and optimization schemes and cost-effective solutions

Most of previous research on tolerance optimization seeks the optimal tolerance allocation with process parameters such as fixed process mean and variance. This research, however, differs from the previous studies in two ways. First, an integrated optimization scheme is proposed to determine both the optimal settings of those process parameters and the optimal tolerance simultaneously which is called a parametric tolerance optimization problem in this paper. Second, most tolerance optimization models require rigorous optimization processes using numerical methods, since closed-form solutions are rarely found. This paper shows how the Lambert W function, which is often used in physics, can be applied efficiently to this parametric tolerance optimization problem. By using the Lambert W function, one can express the optimal solutions to the parametric tolerance optimization problem in a closed-form without resorting to numerical methods. For verification purposes, numerical examples for three cases are conducted and sensitivity analyses are performed.     

Influence of Molar Mass and Concentration on the Thermogelation of Methylcelluloses

In this study, thermogelation of methylcelluloses is investigated in relation to the molar mass and concentration in aqueous medium. A large hysteresis between heating and cooling ramps was observed whatever the conditions. The heating process in particular was studied to analyze the two steps of gelation using rheometry. At low temperature, in the sol state, viscosity depends on the concentration and molar mass. Over 30°C a gel-like behavior was observed including two steps (the second step is a strong gel with phase separation) having storage moduli that are nearly independent of polymer molar mass but are directly related to polymer concentration.     

Thermoset modified with polyethersulfone: Characterization and control of the morphology

Thermoset (TS) epoxy resins can be toughened with a thermoplastic (TP) for high-performance applications. The final structure morphology has to be controlled to achieve high mechanical properties and high impact resistance. Four polyethersulfone-modified epoxy resins are considered. They consist of different epoxy monomer structure (TGAP, triglycidyl-p-aminophenol and TGDDM, tetraglycidyl diaminodiphenylmethane) and a fixed amount of thermoplastic, and they are cured with two different amounts of curing agent. A reaction-induced phase separation occurs for all formulations generating morphologies, different in shapes and scales. The aim is to control the final morphology and in particular its dominant length scale. This morphology depends on the phase separation process, from the initiation to its final stage. The initiation relies on the relative miscibility of the components and on the stoichiometry between epoxy and curing agent. The kinetics depends on the viscosity of the systems. The different morphologies are characterized by electron microscopy or neutron scattering. Dynamic mechanical analysis allows confirming the presence of a phase separation even when it is not observable by electron microscopy. Vermicular morphologies with few hundreds nanometer width are obtained for the systems containing the TGAP as epoxy monomer. Systems formulated with TGDDM presents morphologies on much smaller scale of order a few tens of nanometers. We interpret the different sizes of the morphologies as a consequence of a larger viscosity for the TGDDM systems as compared to the TGAP ones rather than by a latter initiation of phase separation.     

Enzyme-catalyzed synthesis of furanosyl nucleotides

A bacterial alpha-d-glucopyranosyl-1-phosphate thymidylyltransferase was found to couple four hexofuranosyl-1-phosphates, as well as a pentofuranosyl-1-phosphate, with deoxythymidine 5'-triphosphate, providing access to furanosyl nucleotides. The enzymatic reaction mixtures were analyzed by electrospray ionization mass spectrometry and NMR spectroscopy to determine the anomeric stereochemistry of furanosyl nucleotide products. This is the first demonstration of a nucleotidylyltransferase discriminating between diastereomeric mixtures of sugar-1-phosphates to produce stereopure, biologically relevant furanosyl nucleotides.     

A useful Pd-catalyzed Negishi coupling approach to benzylic sulfonamide derivatives

A mild catalytic system to access diversely functionalized benzylic sulfonamides has been developed. Palladium-catalyzed alpha-arylation by Negishi cross-coupling of sulfonamide-stabilized anions and a wide range of aryl iodides, bromides, and triflates constitutes a practical strategy for the synthesis of various benzylic sulfonamides.     

Underpotential surface reduction of mesoporous CeO<Subscript>2</Subscript> nanoparticle films

The formation of variable-thickness CeO₂ nanoparticle mesoporous films from a colloidal nanoparticle solution (approximately 1–3-nm-diameter CeO₂) is demonstrated using a layer-by-layer deposition process with small organic binder molecules such as cyclohexanehexacarboxylate and phytate. Film growth is characterised by scanning and transmission electron microscopies, X-ray scattering and quartz crystal microbalance techniques. The surface electrochemistry of CeO₂ films before and after calcination at 500 °C in air is investigated. A well-defined Ce(IV/III) redox process confined to the oxide surface is observed. Beyond a threshold potential, a new phosphate phase, presumably CePO₄, is formed during electrochemical reduction of CeO₂ in aqueous phosphate buffer solution. The voltammetric signal is sensitive to (1) thermal pre-treatment, (2) film thickness, (3) phosphate concentration and (4) pH. The reversible ‘underpotential reduction’ of CeO₂ is demonstrated at potentials positive of the threshold. A transition occurs from the reversible ‘underpotential region’ in which no phosphate phase is formed to the irreversible ‘overpotential region’ in which the formation of the cerium(III) phosphate phase is observed. The experimental results are rationalised based on surface reactivity and nucleation effects.     

The effect of chronic ultraviolet radiation on the human immune system

A single or a limited number of UVR exposures is recognized to suppress cell-mediated immunity in human subjects. The complex pathway leading from the absorption of photons by chromophores in the skin to the generation of T regulatory cells has been, at least partially, elucidated. However, the effect of repeated UV exposures on immune responses and associated mediators is not well studied, particularly to assess whether they lead, first, to the development of photoprotection so that these immune changes are reduced or no longer occur, and, secondly, to the development of photoprotection against the normal downregulation of immunity induced by a high UV dose. For almost all the parameters evaluated in this review--epidermal DNA damage/erythema, urocanic acid, Langerhans and dendritic cells, natural killer cells, macrophages, mast cells, contact and delayed hypersensitivity responses--none, aside from epidermal DNA damage/erythema and macrophage phagocytic activity, show convincing evidence of photoadaptation or, where appropriate, photoprotection. It is concluded that repeatedly irradiating individuals with UVR is likely to continue to result in downregulation of immunity.     

Synthesis and regioselective substitution of C-6 alkoxy derivatives of (S)-nicotine

Enantiopure (S)-6-alkoxynicotine derivatives have been synthesized in two steps from (S)-nicotine via (S)-6-iodonicotine. Deprotonation and substitution at the C-5 position of the pyridine ring of (S)-6-methoxynicotine were achieved using mesityllithium as the base at 0 °C. Conditions for the C-4 lithiation/substitution of (S)-6-isopropoxynicotine and (S)-5-chloro-6-methoxynicotine were also developed.