Reactions of NO3 with the man-made emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone

Rate coefficients for reactions of nitrate radicals (NO3) with the anthropogenic emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene.. ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone (pent-1-en-3-one) were determined to be (9.3 +/- 1.1) x 10(-12), (9.3 +/- 3.2) x 10(-12), (1.7 +/- 1.3) x 10(-12) and (9.4 + 2.7) x 10(-17) cm(3) molecule(-1) s(-1). We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC-FID analysis. Experiments with ethyl vinyl ether required a modification of our established procedure that might introduce additional uncertainties, and the errors suggested reflect these difficulties. Rate coefficients are discussed in terms of electronic and steric influences. Atmospheric lifetimes with respect to important oxidants in the troposphere were calculated. NO3-initiated oxidation is found to be the strongly dominating degradation route for 2-methylpent-2-ene, (Z)-3-methylpent-2-ene and ethyl vinyl ether. Atmospheric concentrations of the alkenes and their relative contribution to the total NMHC emissions from trucks can be expected to increase if plans for the introduction of particle filters for diesel engines are implemented on a global scale. Thus more kinetic data are required to better evaluate the impact of these emissions.

Reactions of methylvinyl and phenylvinyl ketones with a tricyclic ketone derived from 2-tetralone: characterization of crystalline products by X-ray diffraction

Base catalysed reaction of the tricyclic ketone (6 ⇌ 7) with methylvinyl ketone gave the tetracyclic ketols, 11, 13, 15, 16, and the pentacyclic ketols, 12, 17. With phenylvinyl ketone, the tetracyclic ketol (18) was formed. The stereostructures of the ketols were identified by X-Ray diffraction. The base-catalysed title reactions gave the cyclic ketols and derived compounds shown below whose structures were identified by X-ray diffraction.

Complexes of palladium using di-2-pyridyl ketone as ligand: synthesis, structure and, spectral and catalytic properties

During the reaction of di-2-pyridyl ketone (dpk) with Na(2)[PdCl(4)] in alcoholic media, the C=O fragment of dpk undergoes facile solvolysis and the transformed di-2-pyridyl ketone (dpk(ROH), R = Me or H) binds to palladium as NN-donor. When the reaction is carried out in refluxing methanol, a mono-complex of type [Pd(dpk(MeOH))Cl(2)] is obtained. A similar reaction in ethanol affords a bis-complex of type [Pd(dpk(ROH))(2)]Cl(2). Structure of both the complexes have been determined by X-ray crystallography. In acetonitrile solution the [pd(dpk(MeOH))Cl(2)] and [pd(dpk(ROH))(2)]Cl(2) complexes show intense absorptions in the visible and ultraviolet region, origin of which has been probed through uvr calculations. These two palladium complexes are found to be efficient catalysts for Suzuki cross-coupling reactions.

Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s

The effects of varying the alkali metal cation in the high-temperature nucleophilic synthesis of a semi-crystalline, aromatic poly(ether ketone) have been systematically investigated, and striking variations in the sequence-distributions and thermal characteristics of the resulting polymers were found. Polycondensation of 4,4'-dihydroxybenzophenone with 1,3-bis(4-fluorobenzoyl)benzene in diphenylsulfone as solvent, in the presence of an alkali metal carbonate M2CO3 (M= Li, Na, K, or Rb) as base, affords a range of different polymers that vary in the distribution pattern of 2-ring and 3-ring monomer units along the chain. Lithium carbonate gives an essentially alternating and highly crystalline polymer, but the degree of sequence-randomisation increases progressively as the alkali metal series is descended, with rubidium carbonate giving a fully random and non-thermally-crystallisable polymer. Randomisation during polycondensation is shown to result from reversible cleavage of the ether linkages in the polymer by fluoride ions, and an isolated sample of alternating-sequence polymer is thus converted to a fully randomised material on heating with rubidium fluoride.

Combined Crystallographic and Solution Molecular Dynamics Study of Allosteric Effects in Ester and Ketone p-tert-Butylcalix[4]arene Derivatives and Their Complexes with Acetonitrile, Cd(II), and Pb(II)

We describe here a procedure to bridge the gap in the field of calixarene physicochemistry between solid-state atomic-resolution structural information and the liquid-state low-resolution thermodynamics and spectroscopic data. We use MD simulations to study the kinetics and energetics involved in the complexation of lower rim calix[4]arene derivatives (L), containing bidentate ester (1) and ketone (2) pendant groups, with acetonitrile molecule (MeCN) and Cd2+ and Pb2+ ions (M2+) in acetonitrile solution. On one hand, we found that the prior inclusion of MeCN into the calix to form a L(MeCN) adduct has only a weak effect in preorganizing the hydrophilic cavity toward metal ion binding. On the other hand, the strong ion-hydrophilic cavity interaction produces a wide open calix which enhances the binding of one MeCN molecule (allosteric effect) to stabilize the whole (M2+)1(MeCN) bifunctional complex. We reach two major conclusions: (i) the MD results for the (M2+)1(MeCN) binding are in close agreement with the ""endo"", fully encapsulated, metal complex found by X-ray diffraction and in vacuo MD calculations, and (ii) the MD structure for the more flexible 2 ligand, however, differs from the also endo solid-state molecule. In fact, it shows strong solvation effects at the calixarene lower bore by competing MeCN molecules that share the metal coordination sphere with the four C=O oxygens of an ""exo"" (M2+)2(MeCN) complex.

INSECT CHYMOTRYPSINS: CHLOROMETHYL KETONE INACTIVATION AND SUBSTRATE SPECIFICITY RELATIVE TO POSSIBLE COEVOLUTIONAL ADAPTATION OF INSECTS AND PLANTS

Insect digestive chymotrypsins are present in a large variety of insect orders but their substrate specificity still remains unclear. Ewer insect chymotrypsins from 3 different insect orders (Dictyoptera, Coleoptera and two Lepidoptera) were isolated using affinity chromatography. Enzymes presented molecular masses in the range of 20 to 31 kDa and pH optima in the range of 7.5 to 10.0. Kinetic characterization. using different, colorimetric and fluorescent substrates indicated that insect chymotrypsins differ from, bovine chymotrypsin in their primary specificity toward small substrates (like N-benzoyl-L-Tyr p-nitroanilide) rather than on their preference for large substrates (exemplified by Succynil-Ala-Ala-Pro-Phe P-nitroanilide). Chloromethyl ketones (TPCK, N-alpha-tosyl-L-Phe chloromethyl ketone and Z-GGF-CK, N-carbobenzoxy-Gly-Gly-phe-CK) inactivated all chymotrypsins legated. Inactivation rates follow apparent first-order kinetics with variable second order rates (TPCK, 42 to 130 M(-1)s(-1); Z-GGF-CK, 150 to 450 M(-1)s(-1) that may be remarkably low for S. frugiperda chymotrypsin (TPCK, 6 M(-1)s(-1); Z-GGF-CK, 6.1 M(-1) s(-1)). Homology modelling and sequence alignment showed that. in lepidopteran chymotrypsins, differences in the amino acid residues in the neighborhood of the catalytic His 57 may affect its pKa, value. This is Proposed as the cause of the decrease in His 57 reactivity toward chloromethyl ketones. Such amino acid replacement in the active site is proposed. to be an adaptation to the presence of dietary ketones. (C) 2009 Wiley Periodicals, Inc.

Adsorption of di-2-pyridyl ketone salicyloylhydrazone on Amberlite XAD-2 and XAD-7 resins: Characteristics and isotherms

The adsorption of DPKSH onto Amberlite XAD-2 (styrene resin) and XAD-7 (acrylic ester resin) has been investigated, at (25 +/- 1)degrees C and pH 4.7. The experimental equilibrium data were fitted to the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) models. These three models provide a very good fit for both resins and the respective constants K(L), K(F), and K(DR) were calculated. For the same DPKSH concentration interval, the minimum time of contact for adsorption maximum at XAD-7 was smaller than at XAD-2 and the maximum amount of DPKSH adsorbed per gram of XAD-2 is smaller than at XAD-7. The investigation indicates that the mean sorption energy (E) characterizes a physical adsorption and the surfaces of both resins are energetically heterogeneous. The constants obtained in these studied systems were correlated and compared with those obtained for the silica gel/DPKSH system. (C) 2008 Published by Elsevier Inc.

Spectrophotometric determination of zinc in pharmaceutical and biological samples with di-2-pyridyl ketone benzoylhydrazone: A simple, fast, accurate and sensitive method

A simple, fast, accurate, and sensitive spectrophotometric method was developed to determine zinc(II). This method is based on the reaction of Zn(II) with di-2-pyridyl ketone benzoylhydrazone (DPKBH), at pH=5.5 and 50% (v/v) ethanol. Beers law was obeyed in the range 0.020-1.82 mu g mL(-1) with a molar apsorptivity of 3.64 x 10(4) L mol(-1) cm(-1), and a detection limit (3) of 2.29 mu g L-1. The action of some interfering ions was verified and the developed method applied to pharmaceutical and biological samples. The results were then compared with those obtained by using a flame atomic absorption technique.

The effect of solvent uptake on the relaxation behaviour, morphology and mechanical properties of a poly(ether ether ketone)/poly(etherimide) blend

The effects of solvent uptake on the relaxation behaviour, morphology and mechanical properties of poly(ether ether ketone) (PEEK), poly(etherimide) (PEI) and a 50/50 PEEK/PEI blend have been investigated. Amorphous films were immersed in acetone at 25°C, 35°C and 45°C until equilibrium uptake was achieved. The films were then examined by wide angle X-ray scattering (WAXS), differential scanning calorimetry (d.s.c.), dynamic mechanical relaxation spectroscopy and mechanical testing. WAXS and d.s.c. revealed that the degree of solvent induced crystallinity in PEEK is constant with immersion temperature, whereas the degree of induced crystallinity in the 50/50 blend is strongly temperature dependent. The dynamic mechanical studies confirmed that a significant decrease in glass transition temperature results from the plasticizing effect of the solvent and that solvent and thermally crystallized samples have different relaxation characteristics. Mechanical property tests showed that the yield stress and tensile strength of the blend are dominated by PEEK and the degree of crystallinity, while the modulus is more sensitive to the extent of plasticization.

Solvent diffusion in poly(ether ether ketone)/poly(ether imide) blends

Solvent uptake in thin, amorphous samples of poly(ether ether ketone), poly(ether imide) and a 50/50 blend has been measured as a function of temperature. Diffusion coefficients, percentage weight increase and apparent activation energies have been calculated. The 50/50 blend shows anomalous diffusion behaviour which may be attributed to specific interactions between the homopolymers and density changes on blending.

One-dimensional polyelectrolyte/polymeric semiconductor core/shell structure : sulfonated poly(arylene ether ketone)/polyaniline nanofibers for organic field-effect transistors

A polyelectrolyte/polymeric semiconductor core/shell structure is developed for organic field-effect transistors (OFETs) based on sulfonated poly(arylene ether ketone)/polyaniline core/shell nanofibers via electrospinning and solution-phase selective polymerization. The polyelectrolyte does not work as a gate dielectric, but can provide an internal modulation from the nanointerface of the 1D core/shell nanostructure. The transistor devices display very high mobilities.

Sulfonated poly(ether ether ketone)/polypyrrole core–shell nanofibers : a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form onedimensional polymeric adsorbent/conducting polymer core−shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH3 can facilitate the mass diffusion of NH3 through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH3 (20 ppb) at room temperature.

Dielectric percolative composites with high dielectric constant and low dielectric loss based on sulfonated poly(aryl ether ketone) and a-MWCNTs coated with polyaniline

Acidified multi-walled carbon nanotubes (a-MWCNTs) coated with polyaniline (PANI) (a-MWCNTs@PANI) nanofiller were prepared by in situ polymerization. Novel dielectric percolative composites, sulfonated poly(aryl ether ketone) (SPAEK)/a-MWCNTs@PANI, with high dielectric constant and low dielectric loss were fabricated using simple solution blending technique. A SPAEK/a-MWCNTs@PANI composite prepared in this fashion exhibited a high dielectric constant above 800, a dielectric loss tangent less than 1.1 at 10 kHz and room temperature. The morphological study of composites by SEM suggested that the in situ polymerization method of preparing a-MWCNTs@PANI nanofillers was useful to achieve good dispersion of fillers in SPAEK matrix.

Preparation and dielectric properties of sulfonated poly(aryl ether ketone)/acidified graphite nanosheet composites

Percolative dielectric composites of sulfonated poly(aryl ether ketone) (SPAEK) and acidified graphite nanosheets (AGSs) were fabricated by a solution method. The dielectric constant of the as-prepared composite with 4.01 vol % AGSs was found to be 330 at 1000 Hz; this was a significant increase compared to that of pure SPAEK. Through the calculation, a low percolation threshold of the AGS/SPAEK composite was confirmed at 3.18 vol % (0.0318 volume fraction) AGSs; this was attributed to the large surface area and high conductivity of the AGSs. Additionally, our percolative dielectric composites also exhibited good mechanical performances and good thermostability, with a tensile strength of 71.7 MPa, a tensile modulus of 1.91 GPa, a breaking elongation of 16.4%, and a mass loss temperature at 5% of 336°C.

Ternary graphite nanosheet/copper phthalocyanine/sulfonated poly(aryl ether ketone) dielectric percolative composites: Preparation, micromorphologies and dielectric properties

Novel ternary dielectric percolative composites, consisting of acidified graphite nanosheets (a-GNs)/copper phthalocyanine (CuPc)/sulfonated poly (aryl ether ketone) (SPAEK), were fabricated using a simple solution blending technique. A functional intermediate CuPc layer was introduced and coated on a-GNs to ensure a good dispersion of a-GNs in the SPAEK matrix and suppress the mobility of free charge carriers effectively, resulting in significant improvement of the dielectric properties of a-GNs@CuPc/SPAEK in contrast to a-GNs/SPAEK. Furthermore, enhanced mechanical properties of a-GNs@CuPc/SPAEK compared to SPAEK have been also achieved. © 2014 the Partner Organisations.