True and false reversal of the elution order of barbiturates on a bonded cellulose-based chiral stationary phase

A set of racemic N-alkylated barbiturates were investigated for their direct enantioselective HPLC separation on a new chiral stationary phase (CSP) containing cellulose tris(3,5-dimethylphenylcarabamate) immobilized onto silica gel (Chiralpak IB) and its coated version (Chiralcel OD). They were online detected by UV and optical rotation detectors to trace the elution order of their enantiomers. Surprisingly, examples of false and true reversal of the elution order of enantiomers of barbiturates were observed and reported.     

Chiral separations of piperidine-2,6-dione analogues on Chiralpak IA and Chiralpak IB columns by using HPLC

Recently, two new immobilized polysaccharides based CSPs, namely tris-(3,5-dimethylphenylcarbamate) derivatives of amylose and cellulose known as Chiralpak IA and Chiralpak IB were introduced, which may be used with a wide range of solvents including standard and prohibited ones. Several racemic piperidine-2,6-dione analogues [aminoglutethimide, p-nitro-glutethimide, p-nitro-5-aminoglutethimide, cyclohexylaminoglutethimide, phenglutarimide and thalidomide] have been resolved on Chiralpak IA and Chiralpak IB columns (25 cm × 0.46 cm). The non-conventional mobile phases used were methyl-tert-butyl ether-THF (90:10, v/v) [I], 100% dichloromethane [II] and 100% acetonitrile [III] separately at a flow rate of 1.0 mL/min using a UV detector at 254 nm. The resolution factors for Chiralpak IA and Chiralpak IB columns were 1.00-5.33 and 0.33-0.67, respectively. Chiralpak IA column gave better results than Chiralpak IB column for the reported molecules using the developed HPLC conditions. Experimental conditions and the possible chiral recognition mechanisms have been discussed.     

Microwave induced jet boiling investigated via voltammetry at ring-disk microelectrodes

High intensity microwave radiation is (self-)focused at metal electrodes immersed in aqueous electrolyte solutions to generate highly localized superheating and convection effects. It is shown that, for an electrode pointing downward, low intensity microwave radiation causes density driven convective flow (upward), which at the onset of boiling abruptly switches to a fast jet of liquid moving away from the electrode surface (downward). This "jet-boiling" phenomenon allows extremely high rates of mass transport and mixing to be realized at the electrode surface. Cyclic voltammograms obtained at electrodes placed into a microwave field show very strong mass transport enhancement effects. Cyclic voltammograms recorded at a Pt/Pt ring-disk electrode system (r(1) = 25 microm, r(2) = 32 microm, r(3) = 32.4 microm) in the presence of microwave radiation are employed to further explore mass transport effects under microwave conditions. Mass transport coefficients, collection efficiencies, and temperatures are determined as a function of microwave intensity.     

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.     

Polynomial chaos expansions for optimal control of nonlinear random oscillators

The polynomial chaos decomposition of stochastic variables and processes is implemented in conjunction with optimal polynomial control of nonlinear dynamical systems. The procedure is demonstrated on a base-excited system whereby ground motion is modeled as a stochastic process with a specified correlation function and is approximated by its Karhunen-Loeve expansion. An adaptive scheme for stochastic approximation with polynomial chaos bases is proposed which is based on a displacement-velocity norm and is applied to the identification of phase orbits of nonlinear oscillators. This approximation is then integrated in the design of an optimal polynomial controller, allowing for the efficient estimation of statistics and probability density functions of quantities of interest. Numerical investigations are carried out employing the polynomial chaos expansions and the Lyapunov asymptotic stability condition based control policy. The results reveal that the performance, as gaged by probabilistic quantities of interest, of the controlled oscillators is greatly improved. A comparative study is also presented against the classical stochastic optimal control, whereby statistical linearization based LQG is employed to design the optimal controller. It is remarked that the proposed polynomial chaos expansion is a preferred approach to the optimal control of nonlinear random oscillators.     

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.     

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.     

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.     

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     

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.