Numerical analysis of a model of cure process for composites

We consider a composite material composed of fibres included in a resin which becomes solid when it is heated up (reaction of reticulation). The mathematical modelling of the cure process is given by a kinetic equation describing the evolution of the reaction of reticulation coupled with the heat equation. In this paper, we are interested in the computation of approximate solutions. We propose a family of discretized problems depending on two parameters (β₁, β₂) ε [0, 1]² which split the linear and non‐ linear terms in implicit and explicit parts. We prove the stability and convergence of the discretization for any (β₁, β₂) ε [½, 1 ] × [0, 1]. We present also some numerical results. Copyright © 2006 John Wiley & Sons, Ltd.     

Comparison of sulphur and sulphur–oxygen ligands as ionophores for liquid–liquid extraction and facilitated transport of silver and palladium

The reactivity of new ligands described as S₁, S₅, S₂O₉ (in respect to character and amount of donors) towards metal ions was examined by extraction from HNO₃ and HCl media. These ligands were next utilised as carriers for Ag and Pd transport through a supported liquid membrane (SLM). The effect of collecting a greater number of S donors in one molecule and the influence of type of donors (O–S versus S) on efficiency and selectivity of Ag and Pd(II) extraction and transport were examined.

The extraction of Ag from HNO₃ solutions increased with increasing amount of S-donors in one molecule (S₁2O₉5). For palladium the sequence was different (S₅12O₉). The transport of Ag through SLM impregnated with m-chlorotoluene solution of ionophore increased in the same order as in the case of extraction, whereas for Pd the row was different: S₅2O₉1. The highest fluxes of Ag and Pd transported from HNO₃ equalled to 5.25×10⁻⁷ and 1.37×10⁻⁷ mol/m² s, respectively. Palladium flux depended on stripping solution type (Na₂S₂O₃相似文献   

KINETICS AND MECHANISM OF THE REACTION BETWEEN OLIGOSILOXANES AND P-TRICHLORO-N-DICHLOROPHOSPHORYL MONOPHOSPHAZENE (Cl3P[dbnd]N-POCl2)

Abstract

³¹P NMR investigation has been made of the action of Cl₃P[dbnd]N-POCl₂(I) first on hexamethyldisiloxane (Me₃Si)₂O and then on oligosiloxanes Me₃Si-(OSiMe₂)_n-OSiMe₃ n = 2 and n=3. The reactions were carried out in bulk or in solution with molar ratios siloxane/(I) varying from I to 5. It was demonstrated that only the monosubstitution of a chlorine atom by the -(OSiMe₂)_n,-OSiMe₃ species n = 0, 2, 3 with elimination of trimethylchlorosilane occurred leading to the derivatives Cl₂OP-N[dbnd]PCl₂O(SiMe₂-O)_nSiMe₃ (II). For n=2, 3 the siloxane redistribution reactions were observed by ²⁹Si NMR analysis. A two steps mechanism is proposed. consisting in a nucleophilic substitution, involving a tricoordinate phosphazenium intermediate, followed by the formation of an active ionic centre probably an oxonium ion, arising from the solvatation by the siloxane of this phosphazeniurn ion and /or of (II) leading to the redistribution reactions. The influences of the solvent, of trimethylchlorosilane, of the temperature, and of the addition of a protonated species (MDH) were investigated.     

Quantitative and sensitive detection of rare mutations using droplet-based microfluidics

Somatic mutations within tumoral DNA can be used as highly specific biomarkers to distinguish cancer cells from their normal counterparts. These DNA biomarkers are potentially useful for the diagnosis, prognosis, treatment and follow-up of patients. In order to have the required sensitivity and specificity to detect rare tumoral DNA in stool, blood, lymph and other patient samples, a simple, sensitive and quantitative procedure to measure the ratio of mutant to wild-type genes is required. However, techniques such as dual probe TaqMan(?) assays and pyrosequencing, while quantitative, cannot detect less than ～1% mutant genes in a background of non-mutated DNA from normal cells. Here we describe a procedure allowing the highly sensitive detection of mutated DNA in a quantitative manner within complex mixtures of DNA. The method is based on using a droplet-based microfluidic system to perform digital PCR in millions of picolitre droplets. Genomic DNA (gDNA) is compartmentalized in droplets at a concentration of less than one genome equivalent per droplet together with two TaqMan(?) probes, one specific for the mutant and the other for the wild-type DNA, which generate green and red fluorescent signals, respectively. After thermocycling, the ratio of mutant to wild-type genes is determined by counting the ratio of green to red droplets. We demonstrate the accurate and sensitive quantification of mutated KRAS oncogene in gDNA. The technique enabled the determination of mutant allelic specific imbalance (MASI) in several cancer cell-lines and the precise quantification of a mutated KRAS gene in the presence of a 200,000-fold excess of unmutated KRAS genes. The sensitivity is only limited by the number of droplets analyzed. Furthermore, by one-to-one fusion of drops containing gDNA with any one of seven different types of droplets, each containing a TaqMan(?) probe specific for a different KRAS mutation, or wild-type KRAS, and an optical code, it was possible to screen the six common mutations in KRAS codon 12 in parallel in a single experiment.     

Acid promoted enantioselective oxygen-atom transfer from N-alkyl binaphthyl-derived oxaziridines onto sulfides

Acid-promoted asymmetric sulfoxidations of prochiral sulfides using binaphthyl-derived oxaziridines have been studied. The reactions of dialkyl or aryl-alkyl sulfides gave good yields of the corresponding sulfoxides with enantiopurities ranging from 20% to 80%. The influence of temperature and strength of the acid catalyst on enantioselectivity was studied. The absolute configuration of the resulting major enantiomer varied with the structure of the sulfide.     

On the divisorial spectrum of a Noetherian domain

For a Noetherian domain, the sets of divisorial primes, t-primes, and associated primes of principal ideals coincide. We study the divisorial primes of a Noetherian domain as a partially ordered set. In particular, we show that it is possible to have arbitrarily long chains and any finite amount of noncatenarity.     

Theoretical investigation of the Cl and CH3 substitutions effect on structural and energy behavior of benzodiazepine

In this study, heat energy, atomic charges and dipole moments permit qualitative predictions about the substituent effects by a chlorine or methyl group on the benzodiazepine properties in the ground state. AM1 and MNDO semi-empirical methods of calculation are used to obtain information on the structural and energy properties for some benzodiazepine derivatives.     

(Vapor + liquid) equilibrium data for (carbon dioxide + 1,1-difluoroethane) system at temperatures from (258 to 343) K and pressures up to about 8 MPa

Accurate thermo-physical data are of utmost interest for the development of new efficient refrigeration systems. Carbon dioxide (R744) and 1,1-difluoroethane (R152a) are addressed here. Isothermal (vapor + liquid) equilibrium data are reported herein for (R744 + R152a) binary system in the (258–343) K temperature range and in the (0.14 to 7.65) MPa pressure range. A reliable “static-analytic” method taking advantage of two online ROLSI? micro capillary samplers is used for all thermodynamic measurements. The data are correlated using our in-house ThermoSoft thermodynamic model using the Peng–Robinson equation of state, the Mathias–Copeman alpha function, the Wong–Sandler mixing rules, and the NRTL model.     

Microfluidic platform for combinatorial synthesis in picolitre droplets

This paper presents a droplet-based microfluidic platform for miniaturized combinatorial synthesis. As a proof of concept, a library of small molecules for early stage drug screening was produced. We present an efficient strategy for producing a 7 × 3 library of potential thrombin inhibitors that can be utilized for other combinatorial synthesis applications. Picolitre droplets containing the first type of reagent (reagents A(1), A(2), …, A(m)) were formed individually in identical microfluidic chips and then stored off chip with the aid of stabilizing surfactants. These droplets were then mixed to form a library of droplets containing reagents A(1-m), each individually compartmentalized, which was reinjected into a second microfluidic chip and combinatorially fused with picolitre droplets containing the second reagent (reagents B(1), B(2), …, B(n)) that were formed on chip. The concept was demonstrated with a three-component Ugi-type reaction involving an amine (reagents A(1-3)), an aldehyde (reagents B(1-7)), and an isocyanide (held constant), to synthesize a library of small molecules with potential thrombin inhibitory activity. Our technique produced 10(6) droplets of each reaction at a rate of 2.3 kHz. Each droplet had a reaction volume of 3.1 pL, at least six orders of magnitude lower than conventional techniques. The droplets can then be divided into aliquots for different downstream screening applications. In addition to medicinal chemistry applications, this combinatorial droplet-based approach holds great potential for other applications that involve sampling large areas of chemical parameter space with minimal reagent consumption; such an approach could be beneficial when optimizing reaction conditions or performing combinatorial reactions aimed at producing novel materials.