Enzymatic synthesis of chiral organophosphothioates from prochiral precursors

The phosphotriesterase from Pseudomonas diminuta has been shown to selectively cleave the pro-R p-nitrophenolate substituent from bis-p-nitrophenyl alkyl phosphothioate esters. When the alkyl substituent is methyl, ethyl, or isopropyl the enantiomeric excess of the product is >/=99%. Manipulation of the active site through mutagenesis has enabled the preparation of protein variants that preferentially hydrolyze the pro-S substituent of the target substrates. This methodology thus permits the preparation of chiral products from prochiral precursors.     

Length scales of acceleration for locally isotropic turbulence

Length scales are determined that govern the behavior at small separations of the correlations of fluid-particle acceleration, viscous force, and pressure gradient. The length scales and an associated universal constant are quantified on the basis of published data. The length scale governing pressure spectra at high wave numbers is discussed. Fluid-particle acceleration correlation is governed by two length scales: one arises from the pressure gradient, the other from the viscous force.     

The Monodelphis melanoma model: initial report on large ultraviolet A exposures of suckling young

The objective of this study was to determine whether exposure of early suckling young of the opossum Monodelphis domestica to ultraviolet A (UVA) radiation (320-400 nm) can lead to the development of melanocytic lesions similar to those induced after exposure to ultraviolet B (UVB) radiation (280-320 nm) to total doses as low as 380 J/m2. A total of 576 sucklings received nine exposures of 0.6, 2.6 or 15.5 kJ/m2 per dose (total doses approximately 6, 23 and 140 kJ/m2, respectively) from a Blak Ray lamp source with a narrow range emission at 365 nm. A further 280 sucklings were exposed in the same way to doses of 2.6 kJ/m2 per dose (total approximately 23 kJ/m2) broad-band UVA with visible wavelengths from a Dermalight lamp. Frequency of litter loss following all of the UVA-exposure protocols was similar to that within the same stocks in the colony at large. Only one of the 856 UVA-exposed individuals possessed a melanocytic lesion at the 5 month assessment point. No radiation-induced lesions of any type were evident on the skin of the other animals exposed as sucklings. The affected male was from a group of 70 individuals exposed to the highest total dose (140 kJ/m2) from the Blak Ray light source. The melanocytic hyperplasia was provisionally identified as a potential melanoma but it slowly regressed as the animal aged. We conclude that in the opossum suckling exposure system, the potency of UVA for melanoma induction is extremely low compared with that of UVB. Possible explanations, amenable to further investigations, are given for the low UVA sensitivity of the suckling model compared to the adult exposure model of Ley (Ley, R. D. [1997] Cancer Res. 57, 3682-3684).     

Caps and codes

The packing problem in the theory of caps is that of finding, or at least bounding, the size m(r, q) of an ovaloid (cap of largest size) in the projective space S_r,q of dimension r over a field of q elements. This problem and that of constructing and classifying ovaloids are approached by consideration of certain codes associated with caps. Improved general upper bounds on m(r, q) are found, which give m(5, 3)?56 as a particular case. A 56-cap in S_5,3 is constructed via its code and its uniqueness as an ovaloid is demonstrated.     

Gelation and the production of surface grown polyethylene fibres

Summary In the course of examining the limiting conditions for growth of polyethylene fibres by the surface growth method (1, 2) an unexpected gelation effect was observed. Accordingly a solution, after having been stirred at such elevated temperatures where no visible crystallization can take place, is found to set as a gel after cooling under quiescent conditions. It is established that the ability to form this gel is a necessary condition for fibre production byPennings andZwijnenburg's surface growth method which by the new findings essentially should consist of the stretching of such gels. We verified that material indeed accumulates at the surface of the rotor used in the surface growth method as was originally envisaged, but we now infer that this material consists of gel particles formed during the preceding treatments. This adhesion of the gel to a rotating surface enables it to be readily stretched by an externally introduced fibre as done in the surface growth method. The gel precursor is of interest in its own right. We find that it is a transient structure but with long, up to several hours, persistence time during which the solution `remembers' that it has been stirred. The structure itself is presumably an incipient network forming crystallization induced by localised chain stretching, where the crystal junctions are likely to provide the nuclei for the more permanent fibrous crystals which arise on cooling causing the gel to set. Electron microscopy indeed identified smooth fibres in the gel which could develop into shish-kebabs on appropriate treatment, while the bulk of the gel consists of large single crystal platelets which arise within the network on final cooling to room temperature. Finally we suggest, that many, if not all, shishkebab structures conventionally observed on stirring arise by the stretching of the gel network formed at a preceding stage of the preparation procedure.