Preparation of a deoxynucleoside thiophosphoramidite intermediate in the synthesis of nucleoside phosphorodithioates

A general synthetic scheme for preparation of thiophosphoramidite intermediates, chloro-N,N-diisopropylaminothiomethoxyphosphine, 2, and 3′-O-deoxythymidine derivatives of N,N-diisopropylaminothiomethoxyphosphine, 4, is described. These intermediates can be used to synthesize dithiophosphate deoxyoligonucleotide analogues.     

Conformation of acetate derivatives of sugars and other cyclic alcohols. Crystal structures, NMR studies, and molecular mechanics calculations of acetates. When is the exocyclic C-O bond eclipsed?

[reaction: see text] A study of published crystal structures (of O-acetylated sugars for the most part) suggests that the exocyclic C-O bond in acetate esters of cyclic alcohols intrinsically prefers a staggered conformation, although the eclipsed conformation is only slightly less stable. When the acetate is flanked by two equatorial substituents the preferred conformation is close to eclipsed. Over 1500 C-OAc bonds have been analyzed. Diagnostic NMR criteria for torsion angles and MM3 calculations are reported and confirm these conclusions.     

Dicyclopentadienylnickel-alkyne complexes: photochemical formation and mass spectra

Irradiation of toluence or n-hexanne solutions of dicyclopentadienyldicarbonyldinickel complexes at λ ? 350 nm gives good yields of bridged dinuclear complexes (RCCR′)(CpNi)₂. Their bonding and mass spectra are discussed.     

A redetermination of the lifetime of the 4s 5s (3S1) level in Ca by high-rate electron—photon stepwise pulse excitation

The radiative lifetime of the 4s 5s (³S₁) level in Ca was measured using two-step excitation of atoms in a beam which traverses a cold-cathode Penning discharge, where, by electron impact the atoms are excited to the metastable 4s 5p (³P_{2, 1, 0}) states. Immediately thereafter, the beam is crossed with a pulse-modulated cw dye laser beam to populate the final state selectively. Using a pulse-modulation frequency of 0.5 MHz, a preliminary value of 12.4 ± 0.5 ns was obtained with a statistical error of 0.4%. The wide limits of systematic error reflect an assumed uncertainty in the excitation function and possible distortion in the fluorescence decay requiring further study.     

Die ionisierenden Potentialwellen beim Funkendurchschlag

Extending earlier studies on spark breakdown, the development of the impulse prebreakdown streamers leading to complete breakdown were investigated. By taking advantage of the proportionality between point potential and length of the positive Lichtenberg figure produced, the potential of the streamer tips progressing from a point anode towards a plane cathode were determined. It was found that the streamer tip potential decreases as streamer advances. At voltages much lower than sparking potential this decrease is rapid. By approaching the sparking potential the loss of tip potential diminishes considerably near the anode. The decrease of potential remains very rapid near the cathode until sparking potential is reached. At the cathode the tip potential increases with the applied potential. At a certain value electrons are emitted from the cathode under the influence of high tip fields. These electrons are accelerated towards the tips forming avalanches by collision. These avalanches appear on the photographic film as minute dots whose number and density depend on the intensity of tip fields. If the applied potential exceeds the sparking voltage, tip potentials are recorded on the cathode between 15 and 25 kV. The avalanches formed in the high intensity field region reach the critical size and form negative, anode — directed streamers. These streamers appear on the film as negative Lichtenberg figures. This ionising potential wave, known as return stroke, travels along the channel of the positive primary streamer. It increases its ionisation to such a degree that the main stroke can take place.     

Investigation of the structural directing effect of (2-hydroxyethyl)trimethylammonium on distribution of the silicate anions using 29Si NMR spectroscopy

The effect of (2-hydroxyethyl)trimethylammonium (2-HETMA) cation on the equilibrium of silicate oligomers in aqueous alkaline silicate solutions was investigated using (29)Si NMR spectra. The results indicate role of structural directing of 2-HETMA in which it particularly directs the silicate species to the Q(4)(1)Q(4)(3)Q(4)(4) silicate anion. Results reveal that composition of the alcohols in solution affect the distribution of anionic species. The effect of methanol concentration is also discussed.     

Effects of pulsatile flow and straight length on low-density lipoprotein transport in a curved arterial wall

Abnormal accumulation of macromolecules such as low-density lipoproteins (LDLs) in the arterial wall causes narrowing and blockage of vessels, which leads to atherosclerosis. Effects of pulsatile nature of blood flows as well as the initial length on transport of the LDL species in the arterial boundary layer region are analyzed numerically in the present work. The set of governing equations consisting of continuity, Navier-Stokes, and species transport is solved using a projection method based on the second-order central difference discretization. The obtained results are in excellent agreement with the pertinent data. The computational results imply that the flow field and concentration distribution are time dependent but the variation of the filtration velocity can be ignored. The LDL concentration boundary layer thickness decreases in the outer part and increases in the inner part for both with or without straight length. Presence of initial straight length generates about 26% growth in the boundary layer thickness, although its effect on the LDL surface concentration (LSC) is negligible. The maximum LSC is related to the regions with minimum wall shear stress in the inner part of the curved artery, which have more potential for formation of atherosclerosis. A new numerical correlation between the LSC and boundary layer thickness is proposed and examined.     

Heavy Vacuum Gas Oil Upregulates the Rhamnosyltransferases and Quorum Sensing Cascades of Rhamnolipids Biosynthesis in Pseudomonas sp. AK6U

We followed a comparative approach to investigate how heavy vacuum gas oil (HVGO) affects the expression of genes involved in biosurfactants biosynthesis and the composition of the rhamnolipid congeners in Pseudomonas sp. AK6U. HVGO stimulated biosurfactants production as indicated by the lower surface tension (26 mN/m) and higher yield (7.8 g/L) compared to a glucose culture (49.7 mN/m, 0.305 g/L). Quantitative real-time PCR showed that the biosurfactants production genes rhlA and rhlB were strongly upregulated in the HVGO culture during the early and late exponential growth phases. To the contrary, the rhamnose biosynthesis genes algC, rmlA and rmlC were downregulated in the HVGO culture. Genes of the quorum sensing systems which regulate biosurfactants biosynthesis exhibited a hierarchical expression profile. The lasI gene was strongly upregulated (20-fold) in the HVGO culture during the early log phase, whereas both rhlI and pqsE were upregulated during the late log phase. Rhamnolipid congener analysis using high-performance liquid chromatography-mass spectrometry revealed a much higher proportion (up to 69%) of the high-molecularweight homologue Rha–Rha–C₁₀–C₁₀ in the HVGO culture. The results shed light on the temporal and carbon source-mediated shifts in rhamonlipids’ composition and regulation of biosynthesis which can be potentially exploited to produce different rhamnolipid formulations tailored for specific applications.