Search results for "atomic and molecular physics"
showing 10 items of 4501 documents
Interaction of quinine with negatively charged lipid vesicles studied by fluorescence spectroscopy Influence of the pH
1997
Abstract The interaction of quinine with dimyristoylphosphatidic acid (DMPA) and dimyristoylphosphatidyl glycerol (DMPG) small unilamellar vesicles in the gel phase was studied by steady-state fluorescence spectroscopy at pHs 7, 6, 5 and 4 and 20°C. In aqueous solution, with excitation at 335 nm, the emission fluorescence spectrum of quinine varied with pH reflecting the occurrence of different charged species of the drug. In all cases, the emission maximum centered at 383 or 443 nm shifted to lower wavelength in the presence of vesicles. This indicates that the membrane-bound state quinine is in an environment of low polarity. Drug monocationic species were deeply buried in DMPG relative t…
Physical origin of Na+/Cl− selectivity of tight junctions between epithelial cells. Nonlocal electrostatic approach
2020
Abstract Tight junctions (TJs) of epithelial cells play a key role in regulation of the ion exchange between NaCl solutions separated by the layer of these cells. Their functioning is based on a strong difference in the permeabilities of these channels for Na+ and Cl− ion migrational fluxes owing to specific properties of the protein network inside TJs. It has been assumed in this study that this phenomenon originates from combination of two effects related to this specific TJ protein (claudin) which segments are partially located inside the TJ space. First, their ionogenic groups create a negative charge distributed inside TJs, thus inducing a difference between the Na+ and Cl− concentrati…
A simple model for barrier frequencies for enzymatic reactions.
2010
We present a simple model to rationalize the effects of environment on the reaction barrier frequencies derived from free energy profiles. These frequencies are relevant in deviations of a rate constant from its transition state theory value and in determining which environmental dynamics participate in the reaction. In particular, this simple model can be used to understand the changes in the reaction barrier frequencies of an enzymatic catalyzed reaction and the corresponding uncatalyzed process in aqueous solution, a change which has implications for dynamical environmental effects on the enzymatic reaction. Two possible cases are analyzed, in which the polarity (charge separation/locali…
Dioxygen reduction by cobalt(II) octaethylporphyrin at liquid|liquid interfaces.
2010
Oxygen reduction catalyzed by cobalt(II) (2,3,7,8,12,13,17,18-octaethylporphyrin) [Co(OEP)] at soft interfaces is studied by voltammetry and biphasic reactions. When Co(OEP) is present in a solution of 1,2-dichloroethane in contact with an aqueous acidic solution, oxygen is reduced if the interface is positively polarized (water phase versus organic phase). This reduction reaction is facilitated when an additional electron donor, here ferrocene, is present in excess in the organic phase.
Design, Synthesis and Evaluation of Enzyme-Responsive Fluorogenic Probes Based on Pyridine-Flanked Diketopyrrolopyrrole Dyes
2020
The ever-growing demand for fluorogenic dyes usable in the rapid construction of analyte-responsive fluorescent probes, has recently contributed to a revival of interest in the chemistry of diketopyrrolopyrrole (DPP) pigments. In this context, we have explored the potential of symmetrical and unsymmetrical DPP derivatives bearing two or one 4-pyridyl substituents acting as optically tunable group(s). The unique fluorogenic behavior of these molecules, closely linked to N-substitution/charge state of their pyridine unit (i.e., neutral pyridine or cationic pyridinium), has been used to design DPP-based fluorescent probes for detection of hypoxia-related redox enzymes and penicillin G acylase …
Study of separation of water + 2-propanol mixture using different ionic liquids: 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-b…
2018
Abstract The liquid–liquid equilibria data of water (1) + 2-propanol (2) + [bmim][Tf2N] (3) and water (1) + 2-propanol (2) + [bmp][Tf2N] (3) at 283.2, 303.2 and 323.2 K and atmospheric pressure were measured with the objective of understanding the behavior of these two systems and to try to improve the extraction of 2-propanol from water from economical and environmental points of view. The thermodynamic parameters were determined using the non-random two-liquid (NRTL) and universal quasichemical (UNIQUAC) models, and excellent results were achieved in both cases (the maximum root-mean-square deviation was 0.433%). Lastly, the capability of the two ionic liquids to separate 2-propanol from …
Measurements of transition probabilities for two N I infrared transitions and their application for diagnostics of low temperature plasmas
2010
Abstract Spectra emitted from a wall-stabilized arc, running in a gas mixture of helium, argon, nitrogen, oxygen and traces of hydrogen have been studied. Intensities of selected spectral transitions of neutral nitrogen and oxygen have been measured. Applying the Boltzmann plot method and using a reliable set of O I transition probabilities of spectral lines, originating from levels considerably spread in excitation energies, the temperatures of arc plasmas have been determined. Line intensities of two N I infrared transitions, originating from doubly excited terms 3p′ 2 F o and 3p′ 2 G have been measured. In order to obtain the corresponding transition probabilities ( A ki ) for these line…
Dependence of O2 diffusion dynamics on pressure and temperature in silica nanoparticles
2013
An experimental study of the molecular O2 diffusion process in high purity non-porous silica nanoparticles having 50 m2/g BET specific surface and 20 nm average radius was carried out in the temperature range from 127 to 177 °C at O2 pressure in the range from 0.2 to 66 bar. The study was performed by measuring the volume average interstitial O2 concentration by a Raman and photoluminescence technique using a 1,064 nm excitation laser to detect the singlet to triplet emission at 1,272 nm of the molecular oxygen in silica. A dependence of the diffusion kinetics on the O2 absolute pressure, in addition to temperature dependence, was found. The kinetics can be fit by the solution of Fick’s dif…
Mössbauer relaxation spectra in arbitrarily ordered absorbers—Line shape analysis for an iron(II) spincrossover complex in the presence of texture
1989
The stochastic theory of Mossbauer line shapes is formulated in a fashion which allows the evaluation of the spectral shapes for absorbers of arbitrary thickness, texture, and an anisotropic Lamb—Mossbauer factor. The results are specialized to a two-state-relaxation model of fluctuating electric hyperfine interaction in the case of an absorber of axially symmetric texture. The formalism is applied to the line shape analysis of Mossbauer spectra of a textured sample of the spin-crossover complex [Fe(mtz)6] (PF6)2 (mtz=1-methyltetrazole). It is found that between 185 and 240 K the rate constants for the HS→LS conversion are temperature independent, whereas an Arrhenius behaviour is found for…
Dynamics of spin state conversion processes in the solid state
1989
High spin (HS) ⇌ low spin (LS) conversions in transition metal complexes are nonradiative transitions between spin states. In this contribution, we present a study of the temperature and pressure dependence of the HS ⇌ LS intersystem crossing dynamics. For some iron(II) spin-crossover complexes, the rate constants were determined by line shape analysis of57Fe Mossbauer spectra. Their temperature dependence is described by an Arrhenius equation, their pressure dependence is interpreted within absolute rate theory. HS → LS conversion rates at low temperatures were determined from the relaxation of light-induced formation of HS states, monitored by optical spectroscopy. Deviations from a simpl…