Search results for "kinetics"
showing 10 items of 2224 documents
Local dynamics of DNA probed with optical absorption spectroscopy of bound ethidium bromide
1997
We have studied the local dynamics of calf thymus double-helical DNA by means of an "optical labeling" technique. The study has been performed by measuring the visible absorption band of the cationic dye ethidium bromide, both free in solution and bound to DNA, in the temperature interval 360-30 K and in two different solvent conditions. The temperature dependence of the absorption line shape has been analyzed within the framework of the vibronic coupling theory, to extract information on the dynamic properties of the system; comparison of the thermal behavior of the absorption band of free and DNA-bound ethidium bromide gave information on the local dynamics of the double helix in the prox…
Mechanical unfolding pathway of a model β-peptide foldamer.
2015
Foldamers constructed from oligomers of β-peptides form stable secondary helix structures already for small chain lengths, which makes them ideal candidates for the investigation of the (un)folding of polypeptides. Here, the results of molecular simulations of the mechanical unfolding of a β-heptapeptide in methanol solvent revealing the detailed unfolding pathway are reported. The unfolding process is shown to proceed via a stable intermediate even for such a small system. This result is arrived at performing non-equilibrium force ramp simulations employing different pulling velocities and also using standard calculations of the potential of mean force, i.e., the free energy as a function …
Quaternary relaxations in sol-gel encapsulated hemoglobin studied via NIR and UV spectroscopy.
2007
In this work, we study the kinetics of the R --T transition in hemoglobin using a combination of near-infrared and near-ultraviolet spectroscopy. We use a sol-gel encapsulation protocol to decelerate the conformational transitions and to avoid spectral perturbations arising from ligand migration and recombination. We monitor two spectroscopic markers: band III in the near-IR, which is a fine probe of the heme pocket conformation, and the tryptophan band in the near-UV, which probes the formation of the Trpbeta37-Aspalpha94 hydrogen bond, characteristic of the T structure, at the critical alpha1beta2 subunit interface. The time evolution of these two bands is monitored after deoxygenation of…
Biopartitioning micellar chromatoraphy to predict blood to lung, blood to liver, blood to fat and blood to skin partition coefficients of drugs
2009
[EN] Biopartitioning micellar chromatography (BMC), a mode of micellar liquid chromatography that uses micellar mobile phases of Brij35 in adequate experimental conditions, has demonstrated to be useful in mimicking the drug partitioning process into biological systems. In this paper, the usefulness of BMC for predicting the partition coefficients from blood to lung, blood to liver. blood to fat and blood to skin is demonstrated. PLS2 and multiple linear regression (MLR) models based on BMC retention data are proposed and compared with other ones reported in bibliography. The proposed models present better or similar descriptive and predictive capability. (C) 2008 Elsevier B.V. All rights r…
Use of molecular topology for the prediction of physico-chemical, pharmacokinetic and toxicological properties of a group of antihistaminic drugs
2002
We used molecular connectivity to search mathematical models for predicting physico-chemical (e.g. the partition coefficient, P), pharmacokinetic (e.g. the time of maximum plasma level, and toxicological properties (lethal dose, LD) for a group of antihistaminic drugs. The results obtained clearly reveal the high efficiency of molecular topology for the prediction of these properties. Randomization and cross-validation by use of leave-one-out tests were also performed in order to assess the stability and the prediction ability of the connectivity functions selected.
Opioid analgetics retention–pharmacologic activity models using biopartitioning micellar chromatography
2002
Opioids are drugs used in medicine for pain control. In this paper, retention-pharmacokinetics and retention-pharmacodynamics relationships of opioids are proposed and statistically validated. These models are based on the compound retention in the biopartitioning micellar chromatography system (BMC), a new methodology which has successfully been used to develop QRAR models for many other families of compounds. The obtained results are compared to the traditional QSAR models using lipophilicity data. The adequacy of QRAR models is due to the fact that the characteristics of the compounds such as the hydrophobicity, electronic charge and steric effects determine both their retention in BMC a…
Modeling of interactions between xenobiotics and cytochrome P450 (CYP) enzymes
2015
The adverse effects to humans and environment of only few chemicals are well known. Absorption, distribution, metabolism, and excretion (ADME) are the steps of pharmaco/toxicokinetics that determine the internal dose of chemicals to which the organism is exposed. Of all the xenobiotic-metabolizing enzymes, the cytochrome P450 (CYP) enzymes are the most important due to their abundance and versatility. Reactions catalyzed by CYPs usually turn xenobiotics to harmless and excretable metabolites, but sometimes an innocuous xenobiotic is transformed into a toxic metabolite. Data on ADME and toxicity properties of compounds are increasingly generated using in vitro and modeling (in silico) tools.…
A theoretical study of the gas-phase chemi-ionization reaction between uranium and oxygen atoms
2005
The U+O chemi-ionization reaction has been investigated by quantum chemical methods. Potential-energy curves have been calculated for several electronic states of UO and UO+. Comparison with the available spectroscopic and thermodynamic values for these species is reported and a mechanism for the chemi-ionization reaction U+O -> UO++e(-) is proposed. The U+O and Sm+O chemi-ionization reactions are the first two metal-plus-oxidant chemi-ionization reactions to be studied theoretically in this way.
Non-isothermal crystallization kinetics of PET
2000
The crystallization kinetics of poly(ethylene terephthalate) was studied using constant cooling rate, isothermal and quenching experiments. A non-isothermal crystallization kinetics equation based on a single mechanism was used to analyze the data. Different mechanisms of crystallization at low, intermediate, and high cooling rates were hypothesized based on deviation of the experimental data from the single mechanism model.
Interpretation of the photoluminescence decay kinetics in metal halide perovskite nanocrystals and thin polycrystalline films
2020
Abstract In this paper we present critical analysis of different points of view on interpretation of the photoluminescence (PL) decay kinetics in lead halide perovskites prepared in the form of well passivated nanocrystals (PNCs) or thin polycrystalline layers. In addition to the literature data, our own measurements are also considered. For PNCs, a strong dependence of the PL lifetimes on the type of passivating ligand was observed with a consistently high PL quantum yield. It is shown that such ligand effects, as well as a decrease in the PL lifetime with decreasing temperature, are well qualitatively explained by the phenomenological model of thermally activated delayed luminescence, in …