Crystallization of Arthrobacter sp. strain 1C N-(1-D-carboxyethyl)-L-norvaline dehydrogenase and its complex with NAD+

The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres.     

Comparison of combustion sources for sulfur chemiluminescence detection

Three different types of SCD combustion source have been evaluated for use in the chromatographic analysis of atmospheric sulfur compounds. The conventional FID source and the newer inverted burner source were found to be less sensitive and less stable than the flameless design. Overall, the flameless source was superior for use with HRGC-SCD.     

Synthesis and structures of a 3-sila-beta-diketiminatomagnesium bromide, ketenimide and triflate

The crystalline compounds [Mg(Br)(L)(thf)].0.5Et2O [L = {N(R)C(C6H3Me2-2,6)}2SiR, R = SiMe3] (1), [Mg(L){N=C=C(C(Me)=CH)2CH2}(D)2] [D = NCC6H3Me2-2,6 (2), thf (3)] and [{Mg(L)}2{mu-OSO(CF3)O-[mu}2] (4) were prepared from (a) Si(Br)(R){C(C6H3Me2-2,6)=NR}2 and Mg for (1), (b) [Mg(SiR3)2(thf)2] and 2,6-Me2C6H3CN (5 mol for (2), 3 mol for (3)), and (c) (2) + Me3SiOS(O)2CF3 for (4); a coproduct from (c) is believed to have been the trimethylsilyl ketenimide Me3SiN=C=C{C(Me)=CH}2CH2 (5).     

Spectral changes in stochastic light beams propagating in turbulent ocean

The behavior of the spectral composition of a typical stochastic beam in a turbulent ocean environ is revealed. The analysis is based on the extended Huygens–Fresnel principle and the coherence theory in the space-frequency domain. The optical source is assumed to be of the Gaussian Schell-model type with a single narrow Gaussian spectral line in the visible region. Optical turbulence in the ocean is assumed to be driven by temperature and salinity fluctuations. It is found that the well-known source correlation-induced spectral shift is compensated by turbulence at sufficiently large distances.     

Effect of oceanic turbulence on polarization of stochastic beams

On the basis of the extended Huygens-Fresnel principle and the unified theory of coherence and polarization of light we determine the changes in various polarization properties of stochastic beams propagating through the turbulent clear-water ocean. The ocean-induced fluctuations in the refractive index are described via the recently developed power spectrum which takes into account both temperature and salinity variations. Numerical examples of changes in the spectral density, the degree of polarization and in the polarization ellipse are given for electromagnetic Gaussian Schell-model beams. We demonstrate, in particular, how polarization of the propagating beam is affected by statistical properties of the source and by several parameters of oceanic turbulence. We find that propagation of light beams in the oceanic turbulence resembles that in the atmospheric turbulence qualitatively, however evolution and asymptotic saturation of polarization in the oceanic turbulence occurs at much shorter distances.     

Performance-based design of permeation test cells for reliable evaluation of chemical protective materials

The test cell constitutes the core functionality of a permeation testing system. Accuracy of an experimental methodology depends on the ability of the test cell to efficiently deliver the challenge agents to the test material, collect all the transported permeate compounds from the test material and transfer those analytes to the online detector. Common test cell designs used in the US and internationally form the basis of their respective testing procedures. However, widespread usage does not necessarily equate to defensible assurance of analytical reliability. Consequently, chemical protective materials characterized with these cells may provide inadequate protection to users whose health and safety depend on barrier garments such as gloves and suits. Permeation test data, including those acquired in our laboratory, have emphasized the significance of test cell design on the accuracy of permeation measurements. This paper describes the key considerations necessary to ensure analytical reliability for a test cell, illustrates quantitative improvements demonstrated by existing prototypes and, finally, proposes a design which further advances the technology of permeation testing.     

The Goodmanham plane: Raman spectroscopic analysis of a Roman ivory artefact

Raman spectroscopy has been applied to the study of the exceptional ivory stock of an archaeological discovery of great importance for the history of woodworking tools: a virtually complete Roman plane that was found in a late fourth century A.D. context in North Yorkshire, UK, in A.D. 2000. An assessment has been made of the viability of Raman spectroscopy for the identification of ivories from archaeological excavations and comparisons made with similar studies of modern specimens. All of the attributed ivory specimens studied have suffered from deterioration in their burial environment, and severe degradation of their proteinaceous component was observed. In addition, spectral quality was affected through the absorption of fluorescent materials from their environment, and from the presence of emergency conservation procedures undertaken to preserve the integrity of very fragile specimens. The spectra of ivories dating from about 2000 years ago varied considerably because some specimens had experienced an almost complete leaching‐out of collagen, whereas in others, the degraded protein was still substantially identifiable. Generally, however, the protocols used successfully for the identification of modern ivories and for an assignment of their mammalian species were not transferable into archaeological ivory identification and classification because of the collagen degradation and decreased spectral quality. Copyright © 2008 John Wiley & Sons, Ltd.     

Asymmetric Enzymatic Synthesis of Allylic Amines: A Sigmatropic Rearrangement Strategy

Sigmatropic rearrangements, while rare in biology, offer opportunities for the efficient and selective synthesis of complex chemical motifs. A “P411” serine‐ligated variant of cytochrome P450_BM3 has been engineered to initiate a sulfimidation/[2,3]‐sigmatropic rearrangement sequence in whole E. coli cells, a non‐natural function for any enzyme, providing access to enantioenriched, protected allylic amines. Five mutations in the enzyme substantially enhance its activity toward this new function, demonstrating the evolvability of the catalyst toward challenging nitrene transfer reactions. The evolved catalyst additionally performs the highly enantioselective imidation of non‐allylic sulfides.     

Vibrational spectroscopic study of the contents of a chest excavated from the wreck of the HMS Pandora

The FT-IR and Raman spectroscopic analysis of a red powder found in a chest from an officer's cabin during the excavation of the wreck of the 18th Century frigate HMS Pandora have confirmed that the pigment is cinnabar, mercury(II) sulphide. Weaker signals in the Raman spectrum are assignable to a proteinaceous material, such as collagen, typical of a degraded vellum or parchment. Comparison of the Raman spectra with that of a pigmented seal from a 1786 Lieutenant's commission demonstrated that the beeswax component of the seal was not observable.     

Raman spectroscopy of 3‐(pent‐1‐enyl) methyl ether and selected deuterium‐labelled analogues

The Raman spectra of 3‐(pent‐1‐enyl) methyl ether (3‐methoxypent‐1‐ene) and four deuterium‐labelled analogues are reported and discussed. Correlations between specific structural features and the associated Raman bands are developed, with a view to enhancing the analytical application of Raman spectroscopy in investigating materials containing an alkenyl group. Particular attention is given to developing means of distinguishing the methyl group attached to the carbon skeleton from that of the methoxy group, to maximize the analytical utility of the signals associated with ν(sp² CH), ν(sp² CH₂) and ν(CC) stretching vibrations, and to interpreting in more detail certain δ(sp² CH) and δ(sp² CH₂) vibrations of the atoms of the double bond. These results establish a definitive spectroscopic protocol for differentiating a methoxy group from a methyl substituent attached directly to a carbon atom in unsaturated ethers. Copyright © 2007 John Wiley & Sons, Ltd.