Epoxide-opening and group-transfer reactions mediated by monomeric zirconium imido complexes

N-tert-Butylimidozirconocene (Cp2Zr=Nt-Bu) and its analogue (ebthi)Zr=NAr (ebthi = ethylenebis(tetrahydroindenyl), Ar = 2,6-dimethylphenyl) undergo overall cycloaddition reactions at ambient temperature with epoxides that lack accessible beta-hydrogens. The process results in addition of the Zr=N bond to an epoxide C-O bond, leading to azazirconacyclopentanes. The regio- and stereochemistry of the products implicate a stepwise mechanism, with the intermediacy of zwitterions having substantial carbocation character at the substituted carbon of the ring-opened epoxide-derived fragment. The azametallacycles undergo facile cleavage to beta-amino alcohols upon addition of mild acid.     

Synthesis of some 4-carboxy-3- and 5-(2-hydroxyalkyl)pyrazole lactone derivatives

The synthesis and biological activities of some 4-oxo-1-or-2-substituted 1H-or-2H-pyrano[4,3-c]pyrazole derivatives are described.     

ADSORPTION OF SURFACE-ACTIVE AGENTS FROM AQUEOUS SOLUTION: HYDROPHOBIC SUBSTRATES∗

Isotherms for the adsorption of sodium dodecyl benzene sulfonate, sodium POE (4) nonyl phenol sulfate, and POE (25) nonyl phenol, on the hydrophobic crystalline herbicides atrazine and cyanazine were determined. Anionic surfactants were measured at 5°, 25°, and 50° C; the nonionic surfactant at 25° C only. Low degrees of surface coverage were observed; in only one case (atra-zine/NaDBS) was monolayer coverage approached. On the other hand, adsorption was accompanied by a significant increase in negative zeta potential. Although DLVO calculations suggest that this adsorption should lead to stable aggregates, these are of such size that gravitational effects overpower the DLVO terms.     

Structural basis for thrombin activation of a protease-activated receptor: inhibition of intramolecular liganding

Protease-activated G protein-coupled receptors (PAR1-4) are tethered-ligand receptors that are activated by proteolytic cleavage of the extracellular domain (exodomain) of the receptor. PAR1, the prototypic member of the PAR family, is the high-affinity thrombin receptor of platelets and vascular endothelium and plays a critical role in blood coagulation, thrombosis, and inflammation. Here, we describe the solution structure of the thrombin-cleaved exodomain of PAR1. The side chains of a hydrophobic hirudin-like (Hir) sequence and adjacent anionic motif project into solution. Docking of the exodomain Hir sequence to exosite I of thrombin reveals that the tethered ligand in the cleaved exodomain bends away from thrombin, leaving its active site available to another large macromolecular substrate. The N-terminal ligand is longer than anticipated and forms an intramolecular complex with a region located in the C terminus of the exodomain. Mutational analysis confirmed that this C-terminal region is a ligand binding site for both intra- and intermolecular ligands. A lipidated-ligand binding site peptide was found to be an effective inhibitor of thrombin-induced platelet aggregation.     

Fundamental role of the fostriecin unsaturated lactone and implications for selective protein phosphatase inhibition

Key derivatives and analogues of fostriecin were prepared and examined that revealed a fundamental role for the unsaturated lactone and confirmed the essential nature of the phosphate monoester. Thus, an identical 200-fold reduction in protein phosphatase 2A (PP2A) inhibition is observed with either the saturated lactone (7) or with an analogue that lacks the entire lactone (15). This 200-fold increase in PP2A inhibition attributable to the unsaturated lactone potentially may be due to reversible C269 alkylation within the PP beta12-beta13 active site loop accounting for PP2A/4 potency and selectivity.     

Spectroscopic analysis of bacterial biological warfare simulants and the effects of environmental conditioning on a bacterial spectrum

The ability to distinguish bacteria from mixed samples is of great interest, especially in the medical and defence arenas. This paper reports a step towards the aim of differentiating pathogenic endospores in situ, to aid any required response for hazard management using infrared spectroscopy combined with multivariate analysis. We describe a proof-of-principle study aimed at discriminating biological warfare simulants from common environmental bacteria. We also report an evaluation of multiple pre-processing techniques and subsequent differences in cross-validation of two pattern recognition models (Support Vector Machines and Principal Component–Linear Discriminant Analysis) for a six-class classification (bacterial classification). These classifications were possible with an average sensitivity of 88.0 and 86.9?%, and an average specificity of 97.6 and 97.5?% for the SVM and the PC-LDA models, respectively. Most spectroscopic models are built upon spectra from bacteria that have been specifically prepared for analysis by a particular method; this paper will comment upon the differences in the bacterial spectrum that occur between specific preparations when the bacteria have spent 30?days in the simulated weather conditions of a hot dry climate.

The regioselectivity of the formation of 2-pyrazolylthiazoles and their precursors from the reaction of 2-hydrazinothiazoles with 4,4,4-trifluoro-1-hetaryl-1,3-butanediones

Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c.     

Stability of silanols and grafted alkylsilane monolayers on plasma-activated mica surfaces

We investigated the effect of physical and chemical modifications of mica surfaces induced by water vapor-based plasma treatments on the stability of silanols and grafted alkylsilane monolayers. The plasma-activated substrates were characterized using XPS, TOF-SIMS, and contact angle measurements. They revealed a large surface coverage of silanol groups (Si-OH) and a loss of aluminum atoms compared to freshly cleaved mica surfaces. The stability of plasma-induced silanol groups was investigated by contact angle measurements using ethylene glycol as a probe liquid. The Si-OH surface coverage decreased rapidly under vacuum or thermal treatment to give rise to hydrophobic dehydrated surfaces. The stability of end-grafted monofunctionalized n-alkylsilanes was investigated in different solvents and at different pH using water contact angle measurements. The degrafting of alkylsilanes from the activated mica was promoted in acidic aqueous solutions. This detachment was associated with the hydrolysis of covalent bonds between the alkylsilanes and the mica surface. The monolayer stability was enhanced by increasing the length of the alkyl chains that probably act as a hydrophobic protective layer against hydrolysis reactions. Stable alkylsilane monolayers in water with pH greater than 5.5 were obtained on mica surfaces activated at low plasma pressure. We attributed this stability to the loss of surface Al atoms induced by the plasma treatment.     

Ultraviolet-B radiation effects on the structure and function of lower trophic levels of the marine planktonic food web

The impact of UV-B radiation (UVBR; 280-320 nm) on lower levels of a natural plankton assemblage (bacteria, phytoplankton and microzooplankton) from the St. Lawrence Estuary was studied during 9 days using several immersed outdoor mesocosms. Two exposure treatments were used in triplicate mesocosms: natural UVBR (N treatment, considered as the control treatment) and lamp-enhanced UVBR (H treatment, simulating 60% depletion of the ozone layer). A phytoplankton bloom developed after day 3, but no significant differences were found between treatments during the entire experiment for phytoplankton biomass (chlorophyll a and cell carbon) nor for phytoplankton cell abundances from flow cytometry and optical microscopy of three phytoplankton size classes (picoplankton, nanoplankton and microplankton). In contrast, bacterial abundances showed significantly higher values in the H treatment, attributed to a decrease in predation pressure due to a dramatic reduction in ciliate biomass (approximately 70-80%) in the H treatment relative to the N treatment. The most abundant ciliate species were Strombidinium sp., Prorodon ovum and Tintinnopsis sp.; all showed significantly lower abundances under the H treatment. P. ovum was the less-affected species (50% reduction in the H treatment compared with that of the N control), contrasting with approximately 90% for the other ones. Total specific phytoplanktonic and bacterial production were not affected by enhanced UVBR. However, both the ratio of primary to bacterial biomass and production decreased markedly under the H treatment. In contrast, the ratio of phytoplankton to bacterial plus ciliate carbon biomass showed an opposite trend than the previous results, with higher values in the H treatment at the end of the experiment. These results are explained by the changes in the ciliate biomass and suggest that UVBR can alter the structure of the lower levels of the planktonic community by selectively affecting key species. On the other hand, linearity between particulate organic carbon (POC) and estimated planktonic carbon was lost during the postbloom period in both treatments. On the basis of previous studies, our results can be attributed to the aggregation of carbon released by cells to the water column in the form of transparent exopolymer particles (TEPs) under nutrient limiting conditions. Unexpectedly, POC during such a period was higher in the H treatment than in controls. We hypothesize a decrease in the ingestion of TEPs by ciliates, in coincidence with increased DOC release by phytoplankton cells under enhanced UVBR. The consequences of such results for the carbon cycle in the ocean are discussed.     

Fabrication and characterization of TEOS-based silica aerogels prepared using rapid supercritical extraction

Silica aerogels were prepared using the precursor tetraethylorthosilicate (TEOS) via a rapid supercritical extraction (RSCE) method. Multiple consistent batches of monolithic TEOS-based aerogels were fabricated via an 8-h RSCE process. Fabricating TEOS-based aerogels with an RSCE method offers some distinct advantages. One advantage is the relative simplicity of the RSCE approach: liquid precursors are mixed and poured into a metal mold in a hydraulic hot-press, where gelation, aging and extraction of liquid from the pores occur. The precursor recipe employs TEOS, ethanol, water, oxalic acid to catalyze hydrolysis, and ammonia to catalyze the subsequent polycondensation reactions. Another advantage is that reaction of TEOS to form sol gels yields ethanol as a byproduct. A process that releases ethanol, rather than methanol (as in tetramethylorthosilicate (TMOS)-based aerogels) may be more appealing for commercial applications, involving scale-up of the process. The significantly lower cost of TEOS, compared to TMOS, is a considerable advantage. The TEOS-based RSCE aerogels are mesoporous and optically translucent, have bulk densities of 0.099(±0.003) g/cm³ and surface areas of 460(±10) m²/g. Signals observed in infrared and Raman spectra of the aerogels are consistent with Si–O framework bonds. Using scanning electron microscopy imaging, the surface morphology of the aerogel samples was imaged at magnifications up to 150 kX.