948 resultados para reaction kinetics
Resumo:
Gemini viral assembly and transport of viral DNA into nucleus for replication, ssentially involve DNA-coat protein interactions. The kinetics of interaction of Cotton LeafCtirl Kokhran Virus-Dabawali recombinant coat protein (rCP) with DNA was studied by electrophoretic mobility shift assay (EMSA) and Surface plasmon resonance (SPR). The rCP interacted with ssDNA with a K-A, of 2.6 +/- 0.29 x 10(8) M-1 in a sequence non-specific manner. The CP has a conserved C2H2 type zinc finger motif composed of residues C68, C72, H81 and H85. Mutation of these residues to alanine resulted in reduced binding to DNA probes. The H85A mutant rCP showed the least binding with approximately 756 fold loss in the association rate and a three order magnitude decrease in the binding affinity as compared to rCP. The CP-DNA interactions via the zinc finger motif could play a Crucial role ill Virus assembly and in nuclear transport. (C) 2009 Elsevier Inc.
Influence of Solvent on Photoinduced Electron-Transfer Reaction: Time-Resolved Resonance Raman Study
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Time-resolved resonance Raman spectroscopy (TR3) has been used to study the effect of solvent polarity on the mechanism and nature of intermediates formed in photoinduced electron-transfer reaction between triplet flouranil ((FL)-F-3) and tetramethylbenzene (TMB). Comparison of the TR3 spectra in polar, nonpolar, and medium polar media suggests that formation of radical anion due to electron-transfer reaction between (FL)-F-3 and TMB is favored in more polar solvents, whereas ketyl radical formation is more favored in less polar media. Compared to ketyl radical, the extent of radical anion formation is negligible in nonpolar solvents. Therefore, it is inferred that in nonpolar media ketyl radical is mainly generated by hydrogen-transfer reaction in the encounter complex between (FL)-F-3 and TMB. In solvents of medium polarity, the ion-pair decay leads to the formation of both ketyl radical and ketyl radical formed from the encounter between triplet state and the donor. Thus, competition between the formation of ketyl radical and ion pair is influenced by the solvent polarity. The nature of the ion pair in different solvent polarity has been investigated from the changes observed in the vibrational frequency of (fluoranil) FL part of the complex.
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The oxides of cobalt have recently been shown to be highly effective electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. In general species such as Co3O4 and CoOOH have been investigated that often require an elevated temperature step during their synthesis to create crystalline materials. In this work we investigate the rapid and direct electrochemical formation of amorphous nanostructured Co(OH)2 on gold electrodes under room temperture conditions which is a highly active precursor for the OER. During the OER some conversion to crystalline Co3O4 occurs at the surface, but the bulk of the material remains amorphous. It is found that the underlying gold electrode is crucial to the materials enhanced performance and provides higher current density than can be achieved using carbon, palladium or copper support electrodes. This catalyst exhibits excellent activity with a current density of 10 mA cm-2 at an overpotential of 360 mV with a high turnover frequency of 2.1 s-1 in 1 M NaOH. A Tafel slope of 56 mV dec-1 at low overpotentials and a slope of 122 mV dec-1 at high overpotentials is consistent with the dual barrier model for the electrocatalytic evolution of oxygen. Significantly, the catalyst maintains excellent activity for up to 24 hr of continuous operation and this approach offers a facile way to create a highly effective and stable material.
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A generalized mass transport model is developed for predicting the rate ofdeposition in chemical vapor deposition (CVD) systems. This combines thegeneralized method of obtaining equilibrium composition, with elemental fluxbalance expressions. This procedure avoids the usual problems encountered incalculating the rates in multicomponent systems, like writing overall reactionschemes. The dependence of multicomponent diffusivities on the fluxes is accountedin this model using an iterative procedure. The model developed isapplied to the deposition of titanium carbide on cemented carbide tool bitsfrom a gas mixture of titanium tetrachloride, toluene, and hydrogen. Experimentaldeposition rates were obtained using a thermogravimetric assembly.Mass transport controlled rates give an order of magnitude estimates of theobserved rates.
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Many processes during embryonic development involve transport and reaction of molecules, or transport and proliferation of cells, within growing tissues. Mathematical models of such processes usually take the form of a reaction-diffusion partial differential equation (PDE) on a growing domain. Previous analyses of such models have mainly involved solving the PDEs numerically. Here, we present a framework for calculating the exact solution of a linear reaction-diffusion PDE on a growing domain. We derive an exact solution for a general class of one-dimensional linear reaction—diffusion process on 0
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A change-over from SN2(P) to SN1(P) mechanism is established for the chlorine replacement reactions of halogenocyclophosphazenes; this mechanistic change-over helps in rationalising the diverse findings reported for this class of reactions.
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Employing a specific radioimmunoassay for quantification, the kinetics of estrogen-induced elevation in the plasma concentration of biotin-binding protein (BBP) in immature male chicks was investigated. A single injection of the steroid hormone enhanced the plasma BBP content several-fold at 6 h, reaching peak levels around 48 h and declining thereafter. A 2-fold amplification of the response was evident during secondary stimulation with the hormone. The magnitude of the response was hormonal dose-dependent while the initial lag phase and the time of peak protein accumulation were unaltered within the hormonal doses tested. The circulatory half-life of the specific protein in normal and estrogenized birds was 10 h. Hyperthyroidism markedly decreased the hormonal response while the opposite effect was seen during hypothyroidism. The antiestrogens E- and Z-clomiphene citrate effectively blocked the protein induction whereas progesterone, either alone or in combination with estrogen, was ineffective in modulating the induction. Cycloheximide administration drastically inhibited the inductive response. The above observations clearly suggest that the genes corresponding to the two isofunctional proteins of chicken egg, viz. BBP and avidin, are differentially regulated.
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The free radical polymerization of acrylonitrile (AN) initiated by Cu(II) 4-anilino 2-one [Cu(II) ANIPO] Cu(II), 4-p-toluedeno 3-pentene 2-one [Cu(II) TPO], and Cu(II) 4-p-nitroanilino 3-pentene 2-one [Cu(II) NAPO] was studied in benzene at 50 and 60°C and in carbon tetrachloride (CCl4), dimethyl sulfoxide (DMSO), and methanol (MeOH) at 60°C. Although the polymerization proceeded in a heterogeneous phase, it followed the kinetics of a homogeneous process. The monomer exponents were 2 at two different temperatures and in different solvents. The square-root dependence of Rp on initiator concentration and higher monomer exponents accounted for a 1:2 complex formation between the chelate and monomer. The complex formation was shown by ultraviolet (UV) study. The activation energies, kinetics, and chain transfer constants were also evaluated.
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We present a theoretical analysis of the dynamics of crystal growth from a supercooled melt. A molecular theory of crystal growth that pays proper attention to the structure at the liquid-solid interface is discussed.
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A quantitative expression has been obtained for the equivalent resistance of an internal short in rechargeable cells under constant voltage charging.
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The water-gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nanosized catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2, and Ce1-xTixO2-delta. These catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS), and it has been shown that Pt2+ in these reducible oxides result in solid solutions like Ti0.99Pt0.01O2-delta, Ce0.8Ti0.15Pt0.02O2-delta, and Ce0.98Pt0.02O2-delta. These catalysts were tested for the water gas shift reaction both ill the presence and absence of hydrogen. It was shown that Ti0.99Pt0.01O2-delta exhibited higher catalytic activity than Ce0.83Ti0.15Pt0.02O2-delta and Ce0.98Pt0.02O2-delta. Further, experiments were conducted to determine the deactivation of these catalysts. There was no sintering of Pt and no carbonate formation; therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ti4+ ions in the catalysts.
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Effect of lime:silica ratio on the kinetics of the reaction of silica with saturated lime has been investigated. Below C/S=0.65 the reaction does not proceed to completion and even in the presence of a large excess of silica only 90% lime is consumed. A parameter, lime reactivity index, has been defined to quantity the reactive silica present in rice husk ash. The product of the reaction between rice husk ash and saturated lime is a calcium hydrosilicate, C---S---H(I)**. The fibrilar structure and the hollow tubular morphology of the fibres of C---S---H, have been explained by a growth mechanism, where the driving force is osmotic pressure.
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The reaction of hexachlorocyclotriphosphazene (N3P3Cl6) with sodium p-cresoxide proceeds by a predominantly nongeminal pathway. The presence of geminal isomers at the bis- and tris-stages of substitution in tiny quantities (< 5%) has also been observed. All the chloro(p-cresoxy)cyclotriphosphazenes and their dimethylamino derivatives have been characterized by 1H-, 13C{1H}-, and 31P{1H}-NMR spectroscopy. The reaction of N3P3Cl6 with sodium phenoxide has been reinvestigated. The relative yields of the products at various stages of substitution and their isomeric compositions are almost the same for both phenoxy and p-cresoxy systems. Possible mechanisms to explain the observed isomeric compositions are discussed. A through-space interaction involving oxygen-2p and phosphorus-3d orbitals is invoked to explain the greater yield of the cis isomer of N3P3Cl4(OAr)2 than that of its trans isomer.
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A multiplex real-time PCR was developed for the detection and differentiation of two closely related bovine herpesviruses 1 (BoHV-1) and 5 (BoHV-5). The multiplex real-time PCR combines a duplex real-time PCR that targets the DNA polymerase gene of BoHV-1 and BoHV-5 and a real-time PCR targeting mitochondrial DNA, as a house-keeping gene, described previously by Cawthraw et al. (2009). The assay correctly identified 22 BoHV-1 and six BoHV-5 isolates from the Biosecurity Sciences Laboratory virus collection. BoHV-1 and BoHV-5 were also correctly identified when incorporated in spiked semen and brain tissue samples. The detection limits of the duplex assay were 10 copies of BoHV-1 and 45 copies of BoHV-5. The multiplex real-time PCR had reaction efficiencies of 1.04 for BoHV-1 and 1.08 for BoHV-5. Standard curves relating Ct value to template copy number had correlation coefficients of 0.989 for BoHV-1 and 0.978 for BoHV-5. The assay specificity was demonstrated by testing bacterial and viral DNA from pathogens commonly isolated from bovine respiratory and reproductive tracts. The validated multiplex real-time PCR was used to detect and differentiate BoHV-1 and BoHV-5 in bovine clinical samples with known histories.