N-Levulination of Guanosine

A procedure have been developed for the synthesis of the N-levulinoyl derivative of guanosine.     

Influence of hydrophobe content on the solution rheology of hydrophobically modified terpolymer of SO2, N,N-diallyl-N-carboethoxymethylammonium chloride

Rheological properties of hydrophobically modified copolymer of SO₂, N,N-diallyl-N-carboethoxymethylammonium chloride and the hydrophobic monomer N,N-diallyl-N-octadecylammonium chloride were studied. The influence of hydrophobe content (HP) and polymer concentration was investigated. Polymers with HP content in the range 1.5-5% were examined and the concentration was varied in the range 2-5 wt%. Both dynamic and steady-shear experiments were performed in ARES rheometer. Copolymers were observed to exhibit typical viscoelastic behavior even with low HP content. Both the dynamic viscosity, η′ and storage modulus, G′, increase with the increase of both the polymer concentration and the HP content of the system. The viscosity of the high HP content polymer showed a strong shear dependency, while G′ was a weak function of frequency and gel-like behavior was observed. The zero-shear viscosity, η₀, showed a strong concentration dependency (η₀ ∼ ?^α; 1.1 < α < 5.9). The concentration dependency of η₀ suggests that intermolecular association is dominant in the high HP content polymer. Control of the HP content and polymer concentration of this class of polymers can lead to a wide range of interesting rheological properties.     

Confirmation of eprinomectin, moxidectin, abamectin, doramectin, and ivermectin in beef liver by liquid chromatography/positive ion atmospheric pressure chemical ionization mass spectrometry

A liquid chromatographic (LC) multiresidue screening procedure was developed for determination of eprinomectin, moxidectin, abamectin, doramectin, and ivermectin in beef liver at 0, 25, 50, and 100 ppb levels. A procedure using low resolution LC/atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) was developed with further purification steps added to the quantitative LC method to confirm residues. Acetonitrile extracts of liver, prior to derivatization for LC analysis, were further purified by using a C8 solid-phase extraction cartridge and an alumina-B cartridge. The purified extract was analyzed by injection into an LC/positive ion APCI MS. Identity of the compound was confirmed by comparison of its retention time and relative intensity data with those of a standard or recovery from a fortified control liver sample. Anthelmintic drugs in acetonitrile extracts of liver containing eprinomectin, moxidectin, abamectin, doramectin, and ivermectin at 25 ppb, the lowest level of fortification used in the LC determinative method, were successfully confirmed.     

Synthesis of trimethyl (2S,3R)- and (2R,3R)-[2-H1]-homocitrates and the corresponding dimethyl ester lactones—towards elucidating the stereochemistry of the reaction catalysed by homocitrate synthase and by the Nif-V protein

Trimethyl (2S,3R)- and (2R,3R)-[2-²H₁]-homocitrates, 10b and 10c respectively, and dimethyl (2S,3R)- and (2R,3R)-[2-²H₁]-homocitric lactones, 11b and 11c respectively, have been synthesised from shikimic acid and [2-²H]-shikimic acid by a route which defines the stereochemistry of the two chiral centres in each compound. The NMR spectra of these products will enable the stereochemistry of the biological reaction catalysed by homocitrate synthase and by the protein from the nifV gene to be elucidated.     

Solventless synthesis of monodisperse Cu2S nanorods, nanodisks, and nanoplatelets

Cu(2)S nanocrystals with disklike morphologies were synthesized by the solventless thermolysis of a copper alkylthiolate molecular precursor. The nanodisks ranged from circular to hexagonal prisms from 3 to 150 nm in diameter and 3 to 12 nm in thickness depending on the growth conditions. High resolution transmission electron microscopy (HRTEM) revealed the high chalcocite (hexagonal) crystal structure oriented with the c-axis ([001] direction) orthogonal to the favored growth direction. This disk morphology is thermodynamically favored as it allows the extension of the higher energy [100] and [110] surfaces with respect to the [001] planes. The hexagonal prism morphology also appears to relate to increased C-S bond cleavage of adsorbed dodecanethiol along the more energetic [100] facets relative to [001] facets. Monodisperse Cu(2)S nanodisks self-assemble into ribbons of stacked platelets. This solventless approach provides a new technique to synthesize anisotropic metal chalcogenide nanostructures with shapes that depend on both the face-sensitive thermodynamic surface energy and the surface reactivity.     

Kinetic and thermodynamic acidities of substituted 1-benzyl-1-methoxy-2-nitroethylenes. Strong reduction of the transition state imbalance compared to other nitroalkanes

Acidity constants of six substituted 1-benzyl-1-methoxy-2-nitroethylenes (2-Z with Z = m-NO(2), m-CF(3), m-Cl, H, p-Me, p-MeO) and their respective nitronic acids were determined in 50% DMSO-50% water (v/v) at 20 degrees C. Kinetic data were obtained on the reversible deprotonation of all six 2-Z by OH(-) and piperidine and on the reversible deprotonation of 2-NO(2)() by piperazine, 1-(2-hydroxyethyl)piperazine, and morpholine in the same solvent. These data allowed a determination of the Br?nsted coefficients alpha (dependence on acidity of 2-Z) and beta (dependence on amine basicity). The fact that alpha > beta indicates the presence of a transition state imbalance which, however, is much smaller than that for the deprotonation of arylnitromethanes. The reasons for this reduction in the imbalance and their relevance to a recent study of the deprotonation of Fischer carbene complexes are discussed.     

Effect of anion concentration on the stability of the uranyl-ascorbate complex

The effect of anion concentration and the dependence of uranyl ascorbate on the nature of anion present is systematically studied for nine different anions over the concentration range (0.2–2.0) × 10⁻² M. These anions, commonly encountered in pharmaceutical preparations with ascorbic acid (vitamin C) are nitrate, sulfate, chloride, bromide, fluoride, phosphate, citrate, oxalate, and tartrate. Based on the absorbance data, and on the value of the replacement constant K calculated, the studied anions may be arranged according to their complexing power on uranium as follows: citrate > tartrate > phosphate > oxalate > fluoride > sulfate > nitrate > chloride > bromide.This order is substantiated by the calculated values of the side reaction coefficients α_M of the uranyl ligand complex or the conditional stability constant of uranyl-ascorbate calculated at different ligand concentrations.     

Four-jet production in e+e−-annihilation

We investigate the four-jet production processes $e^{+}{e}^{?}\to q\overline{q}ggand{e}^{+}{e}^{?}\to q\overline{q}q\overline{q}$ in lowest order QCD perturbation theory. We estimate that four-jet events should be detectable at a rate of about 5% at the highest PETRA energy. The acoplanarity distribution is calculated and compared to nonperturbative effects.     

Smart Biopolymer-Based Nanocomposite Materials Containing pH-Sensing Colorimetric Indicators for Food Freshness Monitoring

Nanocomposite biopolymer materials containing colorimetric pH-responsive indicators were prepared from gelatin and chitosan nanofibers. Plant-based extracts from barberry and saffron, which both contained anthocyanins, were used as pH indicators. Incorporation of the anthocyanins into the biopolymer films increased their mechanical, water-barrier, and light-screening properties. Infrared spectroscopy and scanning electron microscopy analysis indicated that a uniform biopolymer matrix was formed, with the anthocyanins distributed evenly throughout them. The anthocyanins in the composite films changed color in response to alterations in pH or ammonia gas levels, which was used to monitor changes in the freshness of packaged fish during storage. The anthocyanins also exhibited antioxidant and antimicrobial activity, which meant that they could also be used to slow down the degradation of the fish. Thus, natural anthocyanins could be used as both freshness indicators and preservatives in biopolymer-based nanocomposite packaging materials. These novel materials may therefore be useful alternatives to synthetic plastics for some food packaging applications, thereby improving the environmental friendliness and sustainability of the food supply.     

Euphorbiasteroid Abrogates EGFR and Wnt/β-Catenin Signaling in Non-Small-Cell Lung Cancer Cells to Impart Anticancer Activity

EGFR and Wnt/β-catenin signaling pathways play a prominent role in tumor progression in various human cancers including non-small-cell lung carcinoma (NSCLC). Transactivation and crosstalk between the EGFR and Wnt/β-catenin pathways may contribute to the aggressiveness of cancers. Targeting these oncogenic pathways with small molecules is an attractive approach to counteract various types of cancers. In this study, we demonstrate the effect of euphorbiasteroid (EPBS) on the EGFR and Wnt/β-catenin pathways in NSCLC cells. EPBS induced preferential cytotoxicity toward A549 (wildtype EGFR-expressing) cells over PC-9 (mutant EGFR-expressing) cells. EPBS suppressed the expression of EGFR, Wnt3a, β-catenin, and FZD-1, and the reduction in β-catenin levels was found to be mediated through the activation of GSK-3β. EPBS reduced the phosphorylation of GSK-3β^S9 with a parallel increase in β-TrCP and phosphorylation of GSK-3β^Y216. Lithium chloride treatment increased the phosphorylation of GSK-3β^S9 and nuclear localization of β-catenin, whereas EPBS reverted these effects. Forced expression or depletion of EGFR in NSCLC cells increased or decreased the levels of Wnt3a, β-catenin, and FZD-1, respectively. Overall, EPBS abrogates EGFR and Wnt/β-catenin pathways to impart its anticancer activity in NSCLC cells.