Search results for "Kinetic"

Temperature dependent mechanical unfolding of calixarene nanocapsules studied by molecular dynamics simulations.

2019

Using atomistic molecular dynamics simulations, we study the temperature dependence of the mechanical unfolding of a model supramolecular complex, a dimer of interlocked calixarene capsules. This system shows reversible transitions between two conformations that are stabilized by different networks of hydrogen bonds. We study the forced dissociation and formation of these networks as a function of temperature and find a strong impact of the nonequilibrium conditions imposed by pulling the system mechanically. The kinetics of the transition between the two conformations is ideally suited to investigate the range of validity of the stochastic models employed in the analysis of force dependent…

A theoreticalab initiostudy on the H2NO + O3reaction

2003

The deviation of the NH2 pseudo-first-order decay Arrhenius plots of the NH2 + O3 reaction at high ozone pressures measured by experimentalists, has been attributed to the regeneration of NH2 radicals due to the subsequent reactions of the products of this reaction with ozone. Although these products have not yet been characterized experimentally, the radical H2NO has been postulated, because it can regenerate NH2 radicals through the reactions: H2NO + O3 NH2 + O2 and H2NO + O3 HNO + OH + O2. With the purpose of providing a reasonable explanation from a theoretical point of view to the kinetic observed behaviour of the NH2 + O3 system, we have carried ab initio electronic structure calculat…

A Contradiction between Pulsed and Steady-State Studies in the Recombination Kinetics of Close Frenkel Defects in KBr and KCl Crystals

1994

Theoretical study of the kinetics of the correlated annealing of pairs of close (geminate) F-H centers in KCl and KBr crystals controlled by their diffusion and elastic attraction shows that the multi-step (kink) decay in defect concentrations observed more than once in thermostimulated experiments takes place only for very close F-H center pairs which are no further than fourth nearest neighbors. On the other hand, it is demonstrated (both theoretically and experimentally) that such F-H center pairs should be destroyed by the tunneling recombination already at time ≤10 -4 s, i.e. much before beginning of the thermostimulated experiments. Possible explanations of this contradiction are sugg…

1986

The aminolysis of diphenyl terephthalate by means of hexylamine was studied in dimethyl sulfoxide as a model reaction for polyamidation. The kinetic analysis showed that the two ester groups of the diphenyl ester do not react independently. Furthermore, the reaction of the first ester group was of mixed second and third order, while the reaction of the second ester group contained only a second order term. The rate constants found were used to determine the Arrhenius activation parameters.

Speciation and oxidation kinetics of arsenic in the thermal springs of Wiesbaden spa, Germany.

2001

Since 1886 arsenic has been known to be present as a trace component in the Wiesbaden thermal waters at concentrations of over 100 microg L(-1). In this study for the first time molecular level speciation of arsenic was measured both in the water (by HG-AAS) and in wellstone scale deposits (by XANES). Most of the arsenic in the anoxic NaCl-type waters is in the reduced arsenite form. Hydrous ferric oxide (HFO) precipitates in the scale deposits scavenge only the minor dissolved arsenate portion which is, however, accumulated up to 3% w/w. Isothermal precipitation experiments at in-situ temperatures showed a difference between the progress of both arsenic and iron oxidation and precipitation…

Atherogenic properties of enzymatically degraded LDL: selective induction of MCP-1 and cytotoxic effects on human macrophages.

1998

Abstract —The mechanisms underlying the selective accumulation of macrophages in early atherosclerotic lesions are poorly understood but are likely to be related to specific properties of altered low density lipoprotein (LDL) deposited in the subendothelium. Enzymatic, nonoxidative degradation of LDL converts the lipoprotein to a potentially atherogenic moiety, enzymatically altered LDL (E-LDL), which activates complement and is rapidly taken up by human macrophages via a scavenger receptor–dependent pathway. Immunohistological evidence indicates that E-LDL is present in an extracellular location in the early lesion. We report that E-LDL causes massive release of monocyte chemotactic prote…

Measurement of gas transport kinetics in high-frequency oscillatory ventilation (HFOV) of the lung using hyperpolarized 3He magnetic resonance imaging

2010

PURPOSE: To protect the patient with acute respiratory distress syndrome from ventilator associated lung injury (VALI) high-frequency oscillatory ventilation (HFOV) is used. Clinical experience has proven that HFOV is an efficient therapy when conventional artificial ventilation is insufficient. However, the optimal settings of HFOV parameters, eg, tidal volumes, pressure amplitudes and frequency for maximal lung protection, and efficient gas exchange are not established unambiguously. METHODS: In this work magnetic resonance imaging (MRI) with hyperpolarized (3)He was employed to visualize the redistribution of gas within the cadaver pig lung during HFOV. The saturated slice method was use…

Aryl azides formation under mild conditions: a kinetic study in some ionic liquid solutions.

2009

The kinetics of nucleophilic aromatic substitution of three nitrothiophene derivatives in different [1-butyl-3-methylimidazolium][N(3)]/ionic liquid binary mixtures was studied spectrophotometrically at 298 K. Ionic liquids differing for cation structure (imidazolium or pyrrolidinium) and for size, shape, and coordination ability of the anion ([BF(4)(-)], [PF(6)(-)], [SbF(6)(-)], and [NTf(2)(-)]) were used. Furthermore, in order to have a comparison with conventional organic solvents, the target reaction was also carried out in DMF solution at increasing concentration of NaN(3) or [bmim][N(3)]. Data collected show that the reaction occurs faster in DMF than in ionic liquid solution. Further…

Effect of storage conditions (relative humidity, duration, and temperature) on the germination time of Aspergillus carbonarius and Penicillium chryso…

2012

Fungal conidia are disseminated, often in the air, for a certain period of time, prior to contaminating food products. The objective of this study was to examine the effects of the relative humidity, RH (%), time (day), and temperature (°C) during this period of time, called "storage", on the germination time, τ (h), of Aspergillus carbonarius and Penicillium chrysogenum. A Doehlert design was used in the range, 20-100% RH, 2-28 days, and 5-25 °C. As compared to un-stored conidia, the germination time of conidia stored at 60% RH, 15 days, 5 °C was increased by 23 and 28%, for A. carbonarius and P. chrysogenum, respectively. Stored conidia exhibited a minimum τ value at 60% RH, and 100% RH f…

Oxygen depletion in dense molecular clouds: a clue to a low O2 abundance?

2011

Context: Dark cloud chemical models usually predict large amounts of O2, often above observational limits. Aims: We investigate the reason for this discrepancy from a theoretical point of view, inspired by the studies of Jenkins and Whittet on oxygen depletion. Methods: We use the gas-grain code Nautilus with an up-to-date gas-phase network to study the sensitivity of the molecular oxygen abundance to the oxygen elemental abundance. We use the rate coefficient for the reaction O + OH at 10 K recommended by the KIDA (KInetic Database for Astrochemistry) experts. Results: The updates of rate coefficients and branching ratios of the reactions of our gas-phase chemical network, especially N + C…