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271.
Palaprat G Marty JD Routaboul C Lattes A Mingotaud AF Mauzac M 《The journal of physical chemistry. A》2006,110(47):12887-12890
A hydrogen-bonded complex between an aromatic acid and an enantiopure chiral amine has been dissolved in a nematic solvent, giving rise to a cholesteric medium. Fourier transform infrared (FT-IR) experiments have been performed at various temperatures on both sides of the cholesteric-isotropic transition. Liquid crystalline order provides significant enhancement to the strength of interaction, inducing a discontinuous jump in concentration of the complex at the cholesteric-isotropic transition. 相似文献
272.
Dondoi MP Bucur B Danet AF Toader CN Barthelmebs L Marty JL 《Analytica chimica acta》2006,578(2):162-169
This paper presents an analysis method for organophosphorus insecticides based on AChE biosensors coupled with a preconcentration and oxidation on a solid phase column. Three organic solvents, acetonitrile (ACN), ethanol and methanol were tested for their influence on AChE activity, insecticide inhibition and their ability to elute the adsorbed insecticides. Our results showed that ACN in a concentration of 5% (v/v) had the less negative effect on biosensor analysis and was the most appropriate organic solvent for the column elution. The presence of the organic solvent in the incubation media of the biosensor was found to induce a reduction of the inhibition percentages. The inhibition of the biosensors was performed in phosphate buffer with 5% (v/v) ACN, while the initial and remaining response of the biosensors were measured in PBS. In these conditions, the LODs of paraoxon and dichlorvos were measured with or without a preconcentration step. The LODs of the AChE biosensor without sample preconcentration were 8 × 10−8 M for paraoxon and 1 × 10−7 M dichlorvos and the LOD obtained after the preconcentration step were 2.5 × 10−8 M for paraoxon and 2.5 × 10−8 M for dichlorvos. Moreover, the use of the column allowed the heterogeneous oxidation of organophosphorus insecticides for improved LOD. 相似文献
273.
We present a detailed comparison of computational efficiency and precision for several free energy difference (DeltaF) methods. The analysis includes both equilibrium and nonequilibrium approaches, and distinguishes between unidirectional and bidirectional methodologies. We are primarily interested in comparing two recently proposed approaches, adaptive integration, and single-ensemble path sampling to more established methodologies. As test cases, we study relative solvation free energies of large changes to the size or charge of a Lennard-Jones particle in explicit water. The results show that, for the systems used in this study, both adaptive integration and path sampling offer unique advantages over the more traditional approaches. Specifically, adaptive integration is found to provide very precise long-simulation DeltaF estimates as compared to other methods used in this report, while also offering rapid estimation of DeltaF. The results demonstrate that the adaptive integration approach is the best overall method for the systems studied here. The single-ensemble path sampling approach is found to be superior to ordinary Jarzynski averaging for the unidirectional, "fast-growth" nonequilibrium case. Closer examination of the path sampling approach on a two-dimensional system suggests it may be the overall method of choice when conformational sampling barriers are high. However, it appears that the free energy landscapes for the systems used in this study have rather modest configurational sampling barriers. 相似文献
274.
Goj LA Lail M Pittard KA Riley KC Gunnoe TB Petersen JL 《Chemical communications (Cambridge, England)》2006,(9):982-984
Stoichiometric reactions of TpRu(CO)(NCMe)(Ph) with electron-rich olefins result in metal-mediated cleavage of C-S and C-O bonds. 相似文献