The potential of organic polymer-based hydrogen storage materials

The challenge of storing hydrogen at high volumetric and gravimetric density for automotive applications has prompted investigations into the potential of cryo-adsorption on the internal surface area of microporous organic polymers. A range of Polymers of Intrinsic Microporosity (PIMs) has been studied, the best PIM to date (a network-PIM incorporating a triptycene subunit) taking up 2.7% H(2) by mass at 10 bar/77 K. HyperCrosslinked Polymers (HCPs) also show promising performance as H(2) storage materials, particularly at pressures >10 bar. The N(2) and H(2) adsorption behaviour at 77 K of six PIMs and a HCP are compared. Surface areas based on Langmuir plots of H(2) adsorption at high pressure are shown to provide a useful guide to hydrogen capacity, but Langmuir plots based on low pressure data underestimate the potential H(2) uptake. The micropore distribution influences the form of the H(2) isotherm, a higher concentration of ultramicropores (pore size <0.7 nm) being associated with enhanced low pressure adsorption.     

Stochastic Finite Element Analysis for Multiphase Flow in Heterogeneous Porous Media

This study is concerned with developing a two-dimensional multiphase model that simulates the movement of NAPL in heterogeneous aquifers. Heterogeneity is dealt with in a probabilistic sense by modeling the intrinsic permeability of the porous medium as a stochastic process. The deterministic finite element method is used to spatially discretize the multiphase flow equations. The intrinsic permeability is represented in the model via its Karhunen–Loeve expansion. This is a computationally expedient representation of stochastic processes by means of a discrete set of random variables. Further, the nodal unknowns, water phase saturations and water phase pressures, are represented by their stochastic spectral expansions. This representation involves an orthogonal basis in the space of random variables. The basis consists of orthogonal polynomial chaoses of consecutive orders. The relative permeabilities of water and oil phases, and the capillary pressure are expanded in the same manner, as well. For these variables, the set of deterministic coefficients multiplying the basis in their expansions is evaluated based on constitutive relationships expressing the relative permeabilities and the capillary pressure as functions of the water phase saturations. The implementation of the various expansions into the multiphase flow equations results in the formulation of discretized stochastic differential equations that can be solved for the deterministic coefficients appearing in the expansions representing the unknowns. This method allows the computation of the probability distribution functions of the unknowns for any point in the spatial domain of the problem at any instant in time. The spectral formulation of the stochastic finite element method used herein has received wide acceptance as a comprehensive framework for problems involving random media. This paper provides the application of this formalism to the problem of two-phase flow in a random porous medium.     

On the numerical study of an obstacle optimal control problem with source term

In the present work, we study the numerical aspect of the optimality system given by R. Ghanem (Positivity 13:321–338, 2009). A numerical algorithm is given and its practical feasibility is investigated by several numerical tests in one and two dimensional spaces.     

Synthesis and powder X-ray diffraction of new Schiff-base liquid crystal

Liquid crystals (LCs) are soft materials that combine the fluidity of disordered liquids and the long-range orientational or positional order of crystalline solids, along one or two directions of space. A search for better stationary phases, including highly selective ones, is an important trend in chromatography development. Among the stationary phases under investigation are LC stationary phases that have been recently generated much interest. A variety of isomeric molecules were separated with high accuracy. Successfully, X-ray scattering is widely used to investigate and characterise the microscopic structure of most LCs. In this paper, a new liquid crystalline material that can be used potentially as stationary phase in gas chromatography was synthesised and characterised by means of nuclear magnetic resonance (NMR), infrared (IR) spectra, elemental analysis and X-ray diffraction.     

Amine groups functionalized gel-type resin supported Pd catalysts: Physicochemical and catalytic properties in hydrogenation of alkynes

Palladium catalysts (0.125–0.5 wt.% Pd) supported by amine groups—functionalized gel-type resin (FCN) were studied in the hydrogenation of alkynes reagents, 2-butyne-1,4-diol and phenylacetylene. The catalysts were prepared by two routes. The first, “OAc” is based on the immobilization of Pd-precursor in the pre-swollen resin from THF solution of Pd(OAc)₂, followed by chemical reduction of the Pd-centers. This method produces Pd particles of size in nano-scale. The second procedure, “aq” implies the deposition of Pd-species on dry resin beads using aqueous solution of PdCl₂. Reduction of these Pd-species gives relatively large Pd particles, dominating are 30–50 nm in size. The SEM studies performed over the cross-section of catalysts grains showed location of Pd in outer shell of polymer beads in both “OAc” and “aq” catalysts; however, thinner layer of Pd appears in “aq” series catalysts. In the presence of all catalysts, prepared by “OAc” and “aq” methods the selectivity towards alkenes is high, above 90%. The catalysts of “aq’ series are much more active and more selective than “OAc” analogues giving selectivity to alkene ca. 94% at almost complete conversion of alkynes. Moreover, catalytic performance of “aq’ series catalyst is unchanged under recycling use. The catalyst was recovered and reused 4 times, maintaining its catalytic efficiency.     

Prenatal diagnosis of hemoglobinopathies.

Hemoglobinopathies are the most frequent and severe inherited diseases worldwide. Prenatal diagnosis is an effective way of controlling severe hemoglobin disorders for which effective treatments are not yet available everywhere. It is a multidisciplinary process requiring knowledge of the spectrum of molecular defects and involving laboratory investigations and genetic counseling. Hematological screening for these disorders is simple, rapid, and reliable. Carrier screening in populations at risk and genetic counseling are part of a number of European health programs, offering many couples at risk the chance of having a healthy child. This article describes the current molecular biology techniques for prenatal diagnosis of hemoglobinopathies.     

Lipase-catalyzed Irreversible Transesterification of Secondary Alcohols Using Isopropenyl Acetate

Summary. Asymmetric acetylation of a set of secondary alcohols with the innocuous acyl donor isopropenyl acetate catalyzed by a lipase from Pseudomonas cepacia immobilized on ceramic particles (PSL-C) in toluene as organic medium afforded the chiral alcohols and the corresponding acetates in high enantiomeric excess (up to 99%). An effective baseline separation of the enantiomers of both substrate and product was performed in one analysis without derivatization using gas chromatography on a new chiral stationary phase (CSP) Chirasil--Dex containing an undecamethylene spacer (C11-Chirasil-Dex).Received November 27, 2002; accepted (revised) January 9, 2003 Published online June 2, 2003     

Reduced models for the medium-frequency dynamics of stochastic systems

In this paper, a frequency domain vibration analysis procedure of a randomly parametered structural system is described for the medium-frequency range. In this frequency range, both traditional modal analysis and statistical energy analysis (SEA) procedures well-suited for low- and high-frequency vibration analysis respectively, lead to computational and conceptual difficulties. The uncertainty in the structural system can be attributed to various reasons such as the coupling of the primary structure with a variety of secondary systems for which conventional modeling is not practical. The methodology presented in the paper consists of coupling probabilistic reduction methods with dynamical reduction methods. In particular, the Karhunen-Loeve and Polynomial Chaos decompositions of stochastic processes are coupled with an operator decomposition scheme based on the spectrum of an energy operator adapted to the frequency band of interest.     

Rh(II)-catalyzed enantioselective cyclopropanation of olefins with dimethyl malonate via in situ generated phenyliodonium ylide

Olefins are cyclopropanated with dimethyl malonate (1a) iodosylbenzene (PhI=O) and a Rh(II) carboxylate catalyst via an in situ generated phenyliodonium ylide (1c). Enantioselectivities of up to 90% for 4-bromostyrene and 98% for pent-1-ene have been observed with (S)-N-4-bromo-1,8-naphthanoyl-tert-leucine (4c) as the chiral ligand. The same catalyst was effective for olefin cyclopropanation with Meldrum's acid, giving cyclopropanes with 96% (with styrene) and 87% ee (with pent-1-ene), respectively.     

Radiation effects on polymers—XII. Molecular weight and molecular weight distribution of cellulose acetate-grafted polyacrylamide side-chains and homopolyacrylamide using gel permeation chromatography

Calibration of gel permeation chromatography was carried out to determine molecular weight and molecular weight distribution of the side-chains and homopolymer formed during grafting of cellulose acetate with acrylamide monomer using accelerated electrons. Polyacrylamide in side-chains and in homopolymer was found to be of very high molecular weight; the grafting event was found to be as low as 1–10 polyacrylamide chains per 10³ cellulose acetate chains.