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Query: UMLS:C0027960 (mole)
 21,279 document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)

The physical, electrophoretic and chromatographic properties (mean diameter, electroosmotic flow, electrophoretic mobility, elution range, efficiency, retention, and hydrophobic, shape, and chemical selectivity) of three surfactant vesicles and one phospholipid vesicle were investigated and compared to a conventional micellar pseudostationary phase comprised of sodium dodecyl sulfate (SDS). Chemical selectivity (solute-pseudostationary phase interactions) was discussed from the perspective of linear solvation energy relationship (LSER) analysis. Two of the surfactant vesicles were formulated from nonstoichiometric aqueous mixtures of oppositely charged, single-tailed surfactants, either cetyltrimethylammonium bromide (CTAB) and sodium octyl sulfate (SOS) in a 3:7 mole ratio or octyltrimethylammonium bromide (OTAB) and SDS in a 7:3 mole ratio. The remaining surfactant vesicle was comprised solely of bis(2-ethylhexyl)sodium sulfosuccinate (AOT) in 10% v/v methanol, and the phospholipid vesicle consisted of 1-palmitoyl-2-oleyl-sn-glycero-3-phosphocholine (POPC) and phosphatidyl serine (PS) in 8:2 mole ratio. The mean diameters of the vesicles were 76.3 nm (AOT), 86.9 nm (CTAB/SOS), 90.1 nm (OTAB/SDS), and 108 nm (POPC/PS). Whereas the coefficient of electroosmotic flow (10(-4) cm2 V(-1) s(-1)) varied considerably (1.72 (OTAB/SDS), 3.77 (CTAB/SOS), 4.05 (AOT), 5.26 (POPC/PS), 5.31 (SDS)), the electrophoretic mobility was fairly consistent (-3.33 to -3.87 x 10(-4) cm2 V(-1) s(-1)), except for the OTAB/SDS vesicles (-1.68). This resulted in elution ranges that were slightly to significantly larger than that observed for SDS (3.12): 3.85 (POPC/PS), 8.6 (CTAB/SOS), 10.1 (AOT), 15.2 (OTAB/SDS). Significant differences were also noted in the efficiency (using propiophenone) and hydrophobic selectivity; the plate counts were lower with the OTAB/SDS and POPC/PS vesicles than the other pseudostationary phases (< or = 75,000/m vs. > 105,000/m), and the methylene selectivity was considerably higher with the CTAB/SOS and OTAB/SDS vesicles compared to the others (ca. 3.10 vs. < or = 2.6). In terms of shape selectivity, only the CTAB/SOS vesicles were able to separate all three positional isomers of nitrotoluene with near-baseline resolution. Finally, through LSER analysis, it was determined that the cohesiveness and hydrogen bond acidity of these pseudostationary phases have the greatest effect on solute retention and selectivity.
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PMID:Characterization of surfactant and phospholipid vesicles for use as pseudostationary phases in electrokinetic chromatography. 1467 70

A clarification of the retention mechanism of non-polar solutes in octadecyl reversed-phase chromatographic columns is attempted based on a systematic comparison of the retention in C18 and C2 columns under the assumption that the retention in C2 columns is due to adsorption. The comparison involves curve fitting procedures and tests based on the properties of special functions suggested in the present paper. For the application of this approach the retention behaviour of six non-polar solutes, benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene and tert-butylbenzene, is studied from aqueous mobile phases modified with methanol, isopropanol, acetonitrile and tetrahydrofuran using C18 and C2 reversed-phase columns. It was found that the retention mechanism in C18 columns is not the same in the four modifiers. In particular, our results show that the adsorption mechanism has a significant contribution in mobile phases modified by acetonitrile and tetrahydrofuran, the partition mechanism is likely to predominate in isopropanol-water mobile phases provided that the mole fraction of isopropanol is higher than 0.2, whereas the case of MeOH is rather obscure, since the various tests did not give a clear picture about the retention mechanism in methanol-water mobile phases.
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PMID:New insights on the retention mechanism of non-polar solutes in reversed-phase liquid chromatographic columns. 1511 13

Surface-pressure (Pi) and surface-area isotherms as a function of surface area were measured for monolayers of amphotericin B (AmB) and cholesterol mixtures at the air/water interface at 10, 20, and 30 degrees C. When chloroform/methanol was used as a spreading solvent, the Pi-A isotherms of the mixed monolayers exhibited characteristic transitions from the gas to liquid-expanded, then liquid-condensed, and finally the solid state. The expanding effect in monolayers was accompanied by a large Pi-A hysteresis and a positive excess of free energy of mixing at high Pi. At low Pi, a condensing effect was observed with the most significant deviation from ideality occurring at a mole fraction of AmB (XAmB) of 0.67. Free energy calculations revealed a condensing effect at low Pi and an expanding effect at high Pi except at 30 degrees C, where a condensing effect was observed for XAmB around 0.33. In contrast, when 2-propanol/water was used as spreading solvent, the mixed monolayers at 20 degrees C exhibited Pi-A isotherms which obey van der Waals equation of state, with no visible transitions, low hysteresis, a condensing effect, and a negative free energy of mixing. The most stable monolayers were produced from mixtures of AmB and cholesterol with a 2:1 stoichiometry.
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PMID:Thermodynamic characteristics of mixed monolayers of amphotericin B and cholesterol. 1521 30

The nature of the rate enhancements caused by gradually increasing the mole fraction of water in the solvent (from 0 to 1) for the cycloaddition reactions of pyridazinium-dicyanomethanide 1,3-dipole, 2, with the dipolarophiles ethyl vinyl ketone (a water-super dipolarophile) and methyl acrylate (a water-normal dipolarophile) in the organic solvents acetonitrile, acetone, methanol, ethanol, and tert-butyl alcohol at 37 degrees C are explored. In each case as the mole fraction of water surpassed ca. 0.9, exponential rate enhancements were triggered. When methanol replaced water, the rate enhancements were smaller, and no triggering effect was observed. The dramatic rate enhancement triggered for the water-super dipolarophile was significantly reduced as the temperature was raised in the range 29-64 degrees C. The results suggest that a dominant hydrogen-bonding effect operates in water-induced rate enhancements of 1,3-dipolar cycloaddition reactions with water-super dipolarophiles as well as the hydrophobic effect. The hydrogen-bonding effect involves secondary bridging hydrogen bonding from the primary water-solvation shell of the transition state and the growth of structured water clusters. Theoretical calculations strongly support these conclusions.
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PMID:The influence of water on the rates of 1,3-dipolar cycloaddition reactions: trigger points for exponential rate increases in water-organic solvent mixtures. Water-super versus water-normal dipolarophiles. 1538 27

Considerable purification of streptolysin S has been achieved by fractionation of crude bacterial filtrates with methanol, under controlled conditions of pH, ionic strength, and temperature. The final material (P III) consisted of two electrophoretic components. The purified material was employed for kinetic studies, the results of which were confirmed with hemolysin isolated electrophoretically from P III. The heat of activation (temperature characteristic) of streptolysin S was found to be 17,900 calories per mole. Time dilution curves of the hemolysin were found to be sigmoid. The influence of certain ions and lipids on the course of hemolysis was investigated. The significance of the prolonged lag period and of the deviation in the behavior of streptolysin S from Ponder's equation has been discussed.
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PMID:The purification and properties of streptolysin S. 1543 32

An extensive series of neutron diffraction experiments and molecular dynamics simulations has shown that mixtures of methanol and water exhibit extended structures in solution despite the components being fully miscible in all proportions. Of particular interest is a concentration region (methanol mole fraction between 0.27 and 0.54) where both methanol and water appear to form separate, percolating networks. This is the concentration range where many transport properties and thermodynamic excess functions reach extremal values. The observed concentration dependence of several of these material properties of the solution may therefore have a structural origin.
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PMID:Methanol-water solutions: a bi-percolating liquid mixture. 1544 45

[R(+) OC Cl(-)] ion pairs were generated in methanol/dichloroethane solutions, with R(+) as the 1-bicyclo[2.2.2]octyl, 1-adamantyl, or 3-homoadamantyl cation. Ion pairs were produced either by the direct fragmentation of alkoxychlorocarbenes (ROCCl), with R = 1-bicyclo[2.2.2]octyl, 1-adamantyl, or 3-homoadamantyl, or by the ring expansion-fragmentation of R'CH(2)OCCl, with R' = 1-norbornyl, 3-noradamantyl, or 1-adamantyl. Correlations of the [ROMe]/[RCl] product ratios as a function of the mole fraction of MeOH in dichloroethane showed that the homoadamantyl chloride ion pairs, produced by either the direct or ring expansion-fragmentations, were identical, solvent- and anion-equilibrated, and precursor independent. Laser flash photolysis experiments gave 20-30 ps as the time required for solvent equilibration and precursor independence. Methanol/chloride selectivities of the (less-stable) 1-adamantyl chloride and 1-bicyclo[2.2.2]octyl chloride ion pairs were not independent of their ROCCl or R'CH(2)OCCl precursors. Computational studies provided transition states for the fragmentations and for the structures of the ion pairs.
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PMID:Solvent-equilibrated ion pairs from carbene fragmentation reactions. 1545 76

In multicomponent mixtures, a much richer variety of phenomena can occur than in simple (single-component) fluids. Natural convection in single-component fluids is due to buoyancy forces caused by temperature gradients. In multicomponent mixtures, buoyancy forces may also be caused by concentration gradients. Because natural convection, molecular diffusion, and thermal conduction have different relaxation time scales, a wide variety of resulting convective motions and heat and mass distributions might occur. In some fluid mixtures such as water-ethanol system, for instance, ethanol diffuses much more slowly than heat, and because of this difference in time scales oscillatory convection might occur. In a multicomponent mixture, the total molar flux consists of two parts: the convective molar flux and the diffusive molar flux (resulting from the difference between the component velocity and the bulk velocity). The diffusion molar flux of a component depends, not only on its own mole fraction gradient (Fickian diffusion), but also on the gradient of all the components present in the mixture (cross-molecular diffusion). The diffusion flux depends also on the pressure gradient (pressure diffusion; the so-called gravitational effect) and temperature gradient (thermal diffusion; the so-called Soret effect). Firoozabadi's thermal diffusion model was applied to calculate the Soret coefficient, as well as the thermal diffusion coefficient and molecular diffusion coefficient for methanol-water and ethanol-water mixtures at 310.65 K temperature and 1 bar pressure with 10% water mass fraction. The results were compared with experimental data (J.K. Platten, in Proceedings of the 5th International Meeting on Thermodiffusion (IMT5), Lyngby, Aug. 2002, Philos. Mag. 83, Nos. 17-18 (2003)), as well as theoretical predictions with other models. A better agreement with the experimental data using the Firoozabadi model was achieved.
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PMID:Theoretical and experimental comparison of the Soret coefficient for water-methanol and water-ethanol binary mixtures. 1559 63

Time-resolved fluorescence spectroscopy of the solvent-sensitive molecule 1,8-anilinonaphthalene sulfonate (ANS) is used to probe the structure and dynamics of an aqueous methanol solution (mole fraction = 0.5). The intensity decay of ANS in the mixed solvent displays single exponential kinetics under ambient conditions. At low temperature, a simple two-state solvent relaxation model describes the fluorescence decay for ANS in both methanol and the mixed solvent. The temperature dependence of ANS fluorescence in the mixed solvent is attributed to the onset of glassy dynamics in the aqueous component at higher temperature, implying a partial demixing of the water and methanol due to self-association. We discuss the absence of more complicated fluorescence decays in such a heterogeneous solvent system.
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PMID:Probing the liquid-state structure and dynamics of aqueous solutions by fluorescence spectroscopy. 1562 67

The acid ionization constants of some pyrimidine bases of nucleic acids were determined pH-metrically at 25 degrees C and at the constant ionic strength I = 0.10 mol l(-1) (KNO3) in pure water as well as in aqueous media containing variable mole percentages (5-30%) of organic solvents. The organic solvents used were methanol, ethanol, N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetonitrile, acetone and dioxane. The results obtained indicated that the acidity constants are generally decreased as the content of an organic solvent in the medium is increased. It was deduced that the hydrogen bonding interactions and the solvent basicity in addition to the electrostatic effect are the major effects influencing significantly the acid ionization process of pyrimidine bases in the different water-organic solvent media. Some thermodynamic parameters (deltaH, deltaG degrees, deltaS degrees) of the ionization process over the temperature range 5-45 degrees C in pure water were also determined and discussed.
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PMID:The acidity constants of some pyrimidine bases in various water-organic solvent media. 1562 45


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