Lipase activity of Lecitase® Ultra: characterization and applications in enantioselective reactions

The general properties of Lecitase® Ultra, a phospholipase manufactured and marketed by Novozymes, Denmark, have been studied after purification by ultrafiltration. The enzyme has a molecular mass of 35 KD, pH-optimum of 8.5, and appears to possess a single active site which exhibits both the lipase and phospholipase activities that increase in the presence of Ca²⁺ and Mg²⁺ ions. The enzyme is inhibited by heavy metal ions and surfactants, and does not accept p-nitrophenyl acetate and glycerol triacetate. Substrates, such as glycerol tributyrate and p-nitrophenyl palmitate, esters of N-acetyl-α-amino acids and α-hydroxy acids are readily accepted. Amino acids with aliphatic residues, such as alanine, isoleucine, and methionine, are hydrolyzed with high enantioselectivity for the l-enantiomer (E >100), but amino acids with aromatic residues such as phenylalanine and phenylglycine, and esters of α-hydroxy acids are hydrolyzed with low enantioselectivity (E = 1–5). Immobilization of the enzyme in a gelatin matrix (gelozyme) leads to a marginal improvement in the enantioselectivity for these substrates. However, a dramatic improvement in enantioselectivity is observed for ethyl 2-hydroxy-4-oxo-4-phenylbutyrate (E value increases from 4.5 to 19.5 with S-selectivity). Similarly, glycidate esters, such as ethyl trans-(±)-3-phenyl glycidate and methyl trans-(±)-3-(4-methoxyphenyl) glycidate, are selectively hydrolyzed with a remarkable selectivity towards the (2S,3R)-enantiomer providing unreacted (2R,3S)-glycidate esters (ee >99%, conversion 52–55%) by the immobilized enzyme.     

Generation of zonal magnetic fields by drift waves in a current carrying nonuniform magnetoplasma

It is shown that zonal magnetic fields (ZMFs) can be nonlinearly excited by incoherent drift waves (DWs) in a current carrying nonuniform magnetoplasma. The dynamics of incoherent DWs in the presence of ZMFs is governed by a wave-kinetic equation. The governing equation for ZMFs in the presence of nonlinear advection force of the DWs is obtained from the parallel component of the electron momentum equation and the Faraday law. Standard techniques are used to derive a nonlinear dispersion relation, which depicts instability via which ZMFs are excited in plasmas. ZMFs may inhibit the turbulent cross-field particle and energy transport in a nonuniform magnetoplasma.     

Chemo-enzymatic synthesis of both enantiomers of rugulactone

The synthesis of both the (R)- and (S)-enantiomers of the natural product rugulactone has been achieved. Candida rugosa lipase hydrolyzes the butyrate ester of the protected 3-hydroxy homoallylic alcohol with very high enantioselectivity (E = 244) and provides the key intermediates with high enantiomeric purity (ee 98–99%) and excellent yields.     

A convenient synthesis of pyrrolopyridines and 2-substituted indoles by gold-catalyzed cycloisomerization

We have developed a gold-catalyzed intramolecular cyclization of variously substituted acetylenic amines under mild conditions, which yields pyrrolopyridines and 2-substituted indoles, quantitatively. The cycloisomerization of acetylenic amines was achieved with AuCl₃ as catalyst without the use of base, acid or N-protecting group.     

Wave reflection in slightly compressible, finitely deformed elastic media

Summary  In this paper, the reflection of a plane wave at an incrementally traction-free boundary of a half-space composed of nearly incompressible elastic material is considered. It is shown that two distinct cases exist, these being dependent on the underlying primary deformation. In the first case, the appropriate slowness sections are each approximately elliptical, and the corresponding reflection phenomena closely mirrors that associated with the corresponding linear isotropic theory. Specifically, an angular range of direction of incident wave exists, for which both a quasi-longitudinal and quasi-shear wave are reflected, the former being replaced by a surface wave outside this angular range. In the second case, the outer slowness section is re-enrant and, in addition to the scenarios previously mentioned, it is possible for two quasi-shear waves to be reflected. Numerical illustrations of reflection coefficients are presented in respect of a modified Varga material and the case of increasing bulk modulus is investigated. Received 17 January 2000; accepted for publication 22 February 2000     

Asymmetric synthesis of Goniothalesdiol A from (R)-2,3-O-cyclohexylidine glyceraldehyde

Goniothalesdiol A 1 has been synthesized from (R)-2,3-O-cyclohexylidine glyceraldehyde with high stereoselectivity and 22% overall yield in 11 simple steps. The key features of the synthetic strategy include the stereocontrolled allylation of (R)-2,3-O-cyclohexylidine glyceraldehydes; the cross-metathesis with a Grubbs’s second generation catalyst, and the intramolecular base-catalyzed oxy-Michael addition for the formation of the tetrahydropyran ring.     

Synthesis of a novel uracil-2,6-diaminopyridine-lithocholic acid conjugate that self-assembles into a cyclic dimer

Synthesis and self-association studies of a uracil-2,6-diaminopyridine-lithocholic acid conjugate are described. The dimeric supramolecular structure is characterized by NMR spectroscopic, ESI-MS, and size exclusion chromatographic studies.     

Scope for Exploitation of Consumers Through Speculation: A Dynamic- Programming Approach to the Case of the Indian Sugar Industry

The Government of India (G.O.I.) controls the quantity of sugar released into the domestic market on a monthly basis. This forms a part of the package of public policies affecting the development of the Indian sugar industry, which includes protection from foreign competition, simultaneous existence of an open market for sugar and distribution of sugar at subsidized prices to consumers through the public distribution system (P.D.S.), minimum support prices for the farmers producing sugar-cane, and differential prices paid to sugar factories for the sugar taken over by G.O.I. for the P.D.S.Using a dynamic-programming approach, this paper describes a worst case analysis of the scope for the traders to exploit the consumers under the current policy of controls over releases into the domestic market. The results show the marginal importance of such controls in saving the consumers from the exploitation by traders. Secondly, on the basis of wider research done by the authors, it is concluded that the scope provided to the traders for the exploitation of consumers through the other policies of the package is of such a magnitude as to make the controls over the releases into the market a relatively insignificant policy intervention for protecting the consumers.     

Oxidation reactions of 1,3-diphenylpropane-1,3-dione

The free radical scavenging properties and possible antioxidant activity of 1,3-diphenylpropane-1,3-dione (1) are reported. Pulse radiolysis technique was employed to study the one-electron oxidation of 1 with various radicals viz. CCl₃O₂ ^•, N₃ ^• and^•OH in homogeneous aqueous solution. All these radicals reacted with 1 under ambient conditions at almost diffusion controlled rates producing transient species with an absorption maximum around 420 nm that decayed at first order rates. The transient absorption peak was shifted in the case of CCl₃OO^• radical reaction with 1 due to change in the polarity of the medium. Formation of a stable product with a broad absorption band starting from 400 nm and cut off at 230 nm was observed in the oxidation of 1 with^•OH and^•N₃ radicals. In a biological system also, 1 showed significant inhibitory activity against Fe²⁺-mediatedlipidperoxidation. Based on these observations, a suitable mechanism for the oxidation of 1 has been proposed.