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41.
Dr. Samir Safi Dr. Gaëlle Creff Dr. Aurélie Jeanson Lei Qi Christian Basset Dr. Jérome Roques Dr. Pier Lorenzo Solari Prof. Eric Simoni Dr. Claude Vidaud Prof. Christophe Den Auwer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11261-11269
Herein, we describe the structural investigation of one possible uranyl binding site inside a nonstructured protein. This approach couples spectroscopy, thermodynamics, and theoretical calculations (DFT) and studies the interaction of uranyl ions with a phosphopeptide, thus mimicking a possible osteopontin (OPN) hydroxyapatite growth‐inhibition site. Although thermodynamical aspects were investigated by using time‐resolved laser fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC), structural characterization was performed by extended X‐ray absorption fine structure (EXAFS) at the U LIII‐edge combined with attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopy. From the vibrational and fluorescence spectra, several structural models of a UO22+/peptide complex were developed and subsequently refined by using theoretical calculations to fit the experimental EXAFS obtained. The structural effect of the pH value was also considered under acidic to moderately acidic conditions (pH 1.5–5.5). Most importantly, the uranyl/peptide coordination environment was similar to that of the native protein. 相似文献
42.
Gañán-Calvo AM 《Physical review letters》2007,98(13):134503
Electro-flow focusing, a technique combining the features of electrospray (ES) and flow focusing (FF), provides a reliable tool to reach parametrical microjetting ranges not attainable by ES or FF alone under specific operational regimes (liquid properties and flow rate). In this Letter, we provide not only a closed theoretical model predicting the diameter of a high electrical conductivity electro-flow focused liquid microjet, but also its convective or absolute instability, linked to the jetting-to-dripping transition and the minimum liquid flow rate that can be ejected in steady jetting regime, in which the smallest droplets are issued. Good agreement is found with experimental values. 相似文献
43.
The structure of the double layer on the boundary between solid and liquid phases is described by various models, of which the Stern–Gouy–Chapman model is still commonly accepted. Generally, the solid phase is charged, which also causes the distribution of the electric charge in the adjacent diffuse layer in the liquid phase. We propose a new mathematical model of electromigration considering the high deviation from electroneutrality in the diffuse layer of the double layer when the liquid phase is composed of solution of weak multivalent electrolytes of any valence and of any complexity. The mathematical model joins together the Poisson equation, the continuity equation for electric charge, the mass continuity equations, and the modified G-function. The model is able to calculate the volume charge density, electric potential, and concentration profiles of all ionic forms of all electrolytes in the diffuse part of the double layer, which consequently enables to calculate conductivity, pH, and deviation from electroneutrality. The model can easily be implemented into the numerical simulation software such as Comsol. Its outcome is demonstrated by the numerical simulation of the double layer composed of a charged silica surface and an adjacent liquid solution composed of weak multivalent electrolytes. The validity of the model is not limited only to the diffuse part of the double layer but is valid for electromigration of electrolytes in general. 相似文献
44.
Self‐Assembly of a Highly Organized,Hexameric Supramolecular Architecture: Formation,Structure and Properties 下载免费PDF全文
Dr. Gaël Schaeffer Dr. Olaf Fuhr Prof. Dieter Fenske Prof. Jean‐Marie Lehn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):179-186
Two derivatives, 3 L and 9 L , of a ditopic, multiply hydrogen‐bonding molecule, known for more than a decade, have been found, in the solid state as well as in solvents of low polarity at room temperature, to exist not as monomers, but to undergo a remarkable self‐assembly into a complex supramolecular species. The solid‐state molecular structure of 3 L , determined by single‐crystal X‐ray crystallography, revealed that it forms a highly organized hexameric entity 3 L 6 with a capsular shape, resulting from the interlocking of two sets of three monomolecular components, linked through hydrogen‐bonding interactions. The complicated 1H NMR spectra observed in o‐dichlorobenzene (o‐DCB) for 3 L and 9 L are consistent with the presence of a hexamer of D3 symmetry in both cases. DOSY measurements confirm the hexameric constitution in solution. In contrast, in a hydrogen‐bond‐disrupting solvent, such as DMSO, the 1H NMR spectra are very simple and consistent with the presence of isolated monomers only. Extensive temperature‐dependent 1H NMR studies in o‐DCB showed that the L 6 species dissociated progressively into the monomeric unit on increasing th temperature, up to complete dissociation at about 90 °C. The coexistence of the hexamer and the monomer indicated that exchange was slow on the NMR timescale. Remarkably, no species other than hexamer and monomer were detected in the equilibrating mixtures. The relative amounts of each entity showed a reversible sigmoidal variation with temperature, indicating that the assembly proceeded with positive cooperativity. A full thermodynamic analysis has been applied to the data. 相似文献
45.
Reglucosylation of the Benzoxazinoid DIMBOA with Inversion of Stereochemical Configuration is a Detoxification Strategy in Lepidopteran Herbivores 总被引:1,自引:0,他引:1 下载免费PDF全文
Felipe C. Wouters Dr. Michael Reichelt Dr. Gaétan Glauser Eugen Bauer Dr. Matthias Erb Prof. Jonathan Gershenzon Dr. Daniel G. Vassão 《Angewandte Chemie (International ed. in English)》2014,53(42):11320-11324
Benzoxazinoids are chemical defenses against herbivores and are produced by many members of the grass family. These compounds are stored as stable glucosides in plant cells and require the activity of glucosidases to release the corresponding toxic aglucones. In maize leaves, the most abundant benzoxazinoid is (2R)‐DIMBOA‐Glc, which is converted into the toxic DIMBOA upon herbivory. The ways in which three Spodoptera species metabolize this toxin were investigated. (2S)‐DIMBOA‐Glc, an epimer of the initial plant compound, was observed in the insect frass, and the associated glucosyltransferase activity was detected in the insect gut tissue. The epimeric glucoside produced by the insect was found to be no longer reactive towards plant glucosidases and thus cannot be converted into a toxin. Stereoselective reglucosylation thus represents a detoxification strategy in Spodoptera species that might help to explain their success as agricultural pests on benzoxazinoid‐containing crops. 相似文献
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48.
We prove the vanishing of the (possibly twisted) orbital integrals of certain functions on real Lie groups at non-semisimple elliptic elements. This applies to Euler–Poincaré functions and makes some results of [7] (Chenevier and Clozel, 2009) unconditional. 相似文献
49.
50.
The transverse mass spectra of Omega, J/psi, and psi' in Pb+Pb collisions at 158A GeV are studied within a hydrodynamical model of the quark-gluon-plasma expansion and hadronization. The model reproduces the existing data with the common hadronization parameters: temperature T = T(H) congruent with 170 MeV and average collective transverse velocity v(T) congruent with 0.2. 相似文献