Search results for "CONSTANT"
showing 10 items of 1718 documents
Pressure dependence in the methyl vinyl ketone + OH and methacrolein + OH oxidation reactions: an electronic structure study.
2005
High-level electronic structure calculations were carried out for the study of the reaction pathways in the OH-initiated oxidations of methyl vinyl ketone (MVK) and methacrolein (MACR). For the two conformers of MVK (called synperiplanar and antiperiplanar), the addition channels of OH to the terminal and central carbon atom of the double bond dominate the overall rate constant, whereas the abstraction of the methyl hydrogen atoms has no significant kinetic role. In the case of MACR, only the antiperiplanar conformer is important in its reactivity. In addition, the lower Gibbs free energy barrier for MACR corresponds to the aldehydic hydrogen abstraction reaction, which will be somewhat mor…
The impact of Pleurotus ostreatus on organic matter transformation processes.
2012
This study showed the effect of Pleurotus ostreatus on the external organic matter (OM) transformation processes. The kinetics of these changes were determined. The experiment was conducted as 42-day pot experiment done in four combinations (with four replications). The four combinations of different substrates were: (1) organic, (2) composted hay, (3) organic soil + composted hay, (4) organic soil + composted hay + lead. The study results showed that P. ostreatus had the ability to transform external OM as well as metal–organic complexes. These transformations were reflected in the constant rate of characterized changes and correlation coefficients. The study also indicated the direction o…
Environmentally relevant precursors of carbonyl sulfide in aquatic systems
1997
Seawater solutions of environmentally relevant organosulfur compounds, commercial humic acid (HA), and natural dissolved organic matter (DOM) were incubated with and without UV light in order to determine the carbonyl sulfide (COS) producing capabilities of these compounds. COS dark- and photo-production rate constants were determined for dilute solutions of the organosulfur compounds (μmol l−1) and HA/DOM (mg l−1). Dissolved COS was determined using a purge and cryogenic trap method followed by GC/FPD detection. COS was produced in considerable amounts both non-photochemically and photochemically from the reduced form of free acid of glutathione (GSH) and photochemically from cysteine (CYS…
Novel acrylamido monomers with higher hydrophilicity and improved hydrolytic stability: II. Properties of N-acryloylaminopropanol
1996
The physico-chemical properties and the electrophoretic behavior of the novel set of monomers reported by (Simo-Alfonso et al., Electrophoresis 1996, 17, 723-731) have been evaluated. Of utmost importance was the combination of high hydrophilicity and extreme hydrolytic stability, most desired properties for, any electrophoretic matrix, especially for protein fractionation. One of these monomers (N-acryloylaminopropanol, AAP) was found indeed to be extremely hydrophilic (with a partition coefficient P of only 0.10, vs. P = 0.13 for N-acryloylaminoethoxyethanol and P = 0.20 for acrylamide) and to possess excellent stability to alkaline hydrolysis. Its hydrolysis constant (0.008 L mol-1 min-1…
Cyclic voltammetric analysis of pH-dependent complex formation equilibria in anion coordination chemistry
1995
A procedure to analyze pH-dependent complex formation equilibria from cyclic voltammetry is described. Application to adduct formation equilibria between [Fe(CN)(6)](4-) and [Fe(CN)(6)](3-) with different polyammonium receptors is discussed. Extension to the interaction of substrates such as ATP, NAD(+), NADP(+), and carboxylate ions with these receptors by means of competitive interaction with hexacyanoferrate(II) ion is presented.
Stopped-Flow and DFT Studies of Proton Transfer and Isomerization of 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine and Its Related Base 2-(5-Amin…
2001
International audience; A complete kinetic study of pH-dependent isomerization of 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine (HL) and 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (L‘-) in the pH range from −0.5 to +13 in aqueous solution, which spans over 7 orders of magnitude for the pseudo-first-order rates (log k from −4.8 to +2.5), has revealed for the first time the existence of the corresponding conjugate species L- and HL‘. The study has allowed the determination of the acid dissociation constants of HL (pKa) and HL‘ (pKa‘), as well as all of the individual forward and reverse isomerization rates of the acidic (HL/HL‘) and basic (L-/L‘-) forms. Although L…
Assembly of the Major Light-harvesting Chlorophyll-a/b Complex
2006
The major light-harvesting chlorophyll-a/b complex in most higher plants contains three carotenoids, lutein, neoxanthin, and violaxanthin. How these pigments are assembled into the complex during its biogenesis is largely unknown. Here we show that neoxanthin but not lutein can dissociate from the fully assembled complex. Its equilibrium binding constant in a detergent system (0.1% n-dodecyl-beta-D-maltoside) was determined to be > or = 10(6) m(-1). Neoxanthin insertion into light-harvesting chlorophyll-a/b complex prefolded from overexpressed apoprotein (Lhcb1*2 from Pisum sativum) in the presence of chlorophylls a, b, and lutein as the sole carotenoid is kinetically controlled by an activ…
Tuning the Properties of Photonic Films from Polymer Beads by Chemistry
2002
This paper describes the preparation of monodisperse colloids from various methacrylates. These colloids sediment well on glass slides and formin the dried statelarge three-dimensional face-centered cubic photonic crystal films with Bragg reflection in the visible region. Depending on crystallization conditions, the domain sizes vary between 50 and 300 μm. By cross-linking the polymer within the colloids, it is possible to increase the thermal stability of the polymeric photonic structure tremendously (up to 1 h at 200 °C). These photonic structures soften above Tg (rubbery photonic structure), but they cannot fuse. Cross-linked colloids from poly(tert-butyl methacrylate) can either thermal…
A study of the enolization of some alkyl ketones in lyomesophases formed by alkylammonium surfactants
1988
The kinetics of enolization of acetone, 3-pentanone, and 6-undecanone have been studied in lyotropic systems in the isotropic, nematic, and lamellar phases. The data, analysed in terms of spontaneous and acid-catalyzed rate constants, do not show any relevant influence of the physical nature of the phase. Effects are instead observed in relation to the length of the alkyl chains of the ketones and the type of the amphiphilic molecule. 6-undecanone has a surprising effect in stabilizing ordered mesophases.
Simulation of Dense Polymer Systems in Two and Three Dimensions
1991
Dense polymer systems are modeled by self- and mutually avoiding walks on lattices. Both simple models where the step length is one lattice spacing and more complicated models where the step length is distinctly longer and may fluctuate (“bond fluctuation model”) are discussed, and it is shown that the computer simulation of such models gives useful insight to understand the thermodynamic phase behavior and the relaxational dynamics of dense polymer solutions and polymer melts. The huge demands in computing power needed for a successful simulation of such systems can be covered by parallel computers such as the multitransputer facility of the University of Mainz.