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991.
992.
993.
Caroline Chauvin Pierre Thibault Daniel Plusquellec Joseph Banoub 《Journal of carbohydrate chemistry》2013,32(4-5):459-475
Abstract Structural characterization and differentiation of distinct regioisomenc esters of sucrose were obtained using lonspray ionization and low energy tandem mass spectrometry. Low energy CAD MS/MS analyses of the protonated molecules [M + H]+ provided characteristic fingerprint patterns, and permitted differentiation of the various regioisomers. MS/MS analyses of selected intermediate fragment ions formed during the ionization process provided additional structural data, and established the fragmentation routes of their [M + H]+ precursors. 相似文献
994.
Roman M Cannizzo C Pinault T Isare B Andrioletti B van der Schoot P Bouteiller L 《Journal of the American Chemical Society》2010,132(47):16818-16824
Gathering precise knowledge on weak supramolecular interactions is difficult yet is of utmost importance for numerous scientific fields, including catalysis, crystal engineering, ligand binding, and protein folding. We report on a combined theoretical and experimental approach showing that it is possible to vastly improve the sensitivity of current methods to probe weak supramolecular interactions in solution. The concept consists of using a supramolecular platform involving a highly cooperative configurational transition, the perturbation of which (by the modification of the molecular building blocks) can be monitored in a temperature scanning experiment. We tested this concept with a particular bisurea platform, and our first results show that it is possible to detect the presence of interaction differences as low as 60 J/mol, which may be due to steric repulsion between vinyl and alkyl groups or may be the result of solvation effects. 相似文献
995.
Clarke CS Jornet-Somoza J Mota F Novoa JJ Deumal M 《Journal of the American Chemical Society》2010,132(50):17817-17830
The magnetic bistability present in some molecule-based magnets is investigated theoretically at the microscopic level using the purely organic system TTTA (1,3,5-trithia-2,4,6-triazapentalenyl). The TTTA crystal is selected for being one of the best-studied molecule-based systems presenting magnetic bistability. The magnetic properties of the high- and low-temperature structures (HT and LT phases, respectively) are accurately characterized by performing a First-Principles Bottom-Up study of each phase. The changes that the magnetic exchange coupling constants (J(AB)) undergo when the temperature is raised (LT → HT) or lowered (HT → LT) are also fully explored in order to unravel the reasons behind the presence of these two different pathways. The triclinic LT phase is diamagnetic due to the fact that the nearly eclipsed π dimer is effectively magnetically silent and not to formation of a covalent bond between two TTTA molecules. It is also shown that bistability in TTTA results from the coexistence of the monoclinic HT and triclinic LT phases in the temperature range studied. 相似文献
996.
Caroline Costa Moraes Marcio A. Mazutti Maria Isabel Rodrigues Francisco Maugeri Filho Susana Juliano Kalil 《Journal of chromatography. A》2009,1216(20):4395-4401
A mathematical model for an expanded bed column was developed to predict breakthrough curves for inulinase adsorption on Streamline SP ion-exchange adsorbent, using a crude fermentative broth with cells as the feedstock. The kinetics and mass transfer parameters were estimated using the PSO (particle swarm optimization) heuristic algorithm. The parameters were estimated for each expansion degree (ED) using three breakthrough curves at initial inulinase concentrations of 65.6 U mL−1. In sequence, the model parameters for an ED of 2.5 were validated using the breakthrough curve at an initial concentration of 114.4 U mL−1. The applicability of the validated model in process optimization was investigated, using the model as a process simulator and experimental design methodology to optimize the column and process efficiencies. The results demonstrated the usefulness of this methodology for expanded bed adsorption processes. 相似文献
997.
Khelil Slimani Caroline Aymes-Chodur Denis Labarre 《Polymer Degradation and Stability》2009,94(4):584-590
The aim of this work was to investigate the impact of electron beam irradiation at different dose rates on the molecular structure of linear methacrylate-acrylamide copolymer. In the first part, the radiation chemical yields of scission (Gs) and crosslinking (Gx) have been determined after irradiation for various initial molecular weights CL1 (40?000 g/mol), CL2 (90?000 g/mol) and CL3 (425?000 g/mol). Based on this calculation, solvent (ethanol) was found to increase the impact of irradiation especially at low concentration of copolymer. In the second part, the presence of branching in samples before and after e-beam irradiation was explored, and branching calculation was performed. 相似文献
998.
Zieba AA Richardson C Lucero C Dieng SD Gindt YM Schelvis JP 《Journal of the American Chemical Society》2011,133(20):7824-7836
Proton-coupled electron-transfer (PCET) is a mechanism of great importance in protein electron transfer and enzyme catalysis, and the involvement of aromatic amino acids in this process is of much interest. The DNA repair enzyme photolyase provides a natural system that allows for the study of PCET using a neutral radical tryptophan (Trp(?)). In Escherichia coli photolyase, photoreduction of the flavin adenine dinucleotide (FAD) cofactor in its neutral radical semiquinone form (FADH(?)) results in the formation of FADH(-) and (306)Trp(?). Charge recombination between these two intermediates requires the uptake of a proton by (306)Trp(?). The rate constant of charge recombination has been measured as a function of temperature in the pH range from 5.5 to 10.0, and the data are analyzed with both classical Marcus and semi-classical Hopfield electron transfer theory. The reorganization energy associated with the charge recombination process shows a pH dependence ranging from 2.3 eV at pH ≤ 7 and 1.2 eV at pH(D) 10.0. These findings indicate that at least two mechanisms are involved in the charge recombination reaction. Global analysis of the data supports the hypothesis that PCET during charge recombination can follow two different mechanisms with an apparent switch around pH 6.5. At lower pH, concerted electron proton transfer (CEPT) is the favorable mechanism with a reorganization energy of 2.1-2.3 eV. At higher pH, a sequential mechanism becomes dominant with rate-limiting electron-transfer followed by proton uptake which has a reorganization energy of 1.0-1.3 eV. The observed 'inverse' deuterium isotope effect at pH < 8 can be explained by a solvent isotope effect that affects the free energy change of the reaction and masks the normal, mass-related kinetic isotope effect that is expected for a CEPT mechanism. To the best of our knowledge, this is the first time that a switch in PCET mechanism has been observed in a protein. 相似文献
999.
Caroline Costa Moraes Joana da Costa Ores Jorge Alberto Vieira Costa Susana Juliano Kalil 《Chromatographia》2011,73(3-4):307-312
In order to study the relationship between spinal cord injury and the change of nerve growth factor (NGF), an analytical method for NGF by capillary electrophoresis-based immunoassay (CEIA) with laser-induced fluorescence (LIF) was developed. Having been dissolved in phosphate buffer solution and concentrated with vacuum freeze-drying, NGF in spinal cord of rat was allowed to react with NGF monoclonal antibody labeled with fluorescence isothiocyanate (FITC). Then the immuno-complex, FITC-labeled anti-NGF and FITC were separated and determined by LIF-CEIA using Kiton red as the internal standard. The linear range of the method was 2?C30?ng?mL?1 and the limit of detection was 0.35?ng?mL?1. The relative standard derivations for relative migration time and relative fluorescence intensity ratio were 7.98% and 6.52%, respectively. The contents of NGF from spinal cord of rat were determined by both the proposed method and Western blotting. The results with the two methods agreed well. The spiked recoveries of the samples were 88.5?C116.3%. The proposed method was rapid, precise and inexpensive. 相似文献
1000.
Caroline?VanderghemEmail author Nicolas?Jacquet Sabine?Danthine Christophe?Blecker Michel?Paquot 《Applied biochemistry and biotechnology》2012,166(6):1423-1432
The effect of two types of cellulose, microcrystalline cellulose and paper pulp, on enzymatic hydrolysis for cellobiose production
was investigated. The particle size, the relative crystallinity index and the water retention value were determined for both
celluloses. A previously studied multistage hydrolysis process that proved to enhance the cellobiose production was studied
with both types of celluloses. The cellobiose yield exhibited a significant improvement (120% for the microcrystalline cellulose
and 75% for the paper pulp) with the multistage hydrolysis process compared to continuous hydrolysis. The conversion of cellulose
to cellobiose was greater for the microcrystalline cellulose than for the paper pulp. Even with high crystallinity, microcrystalline
cellulose achieved the highest cellobiose yield probably due to its highest specific surface area accessible to enzymes and
quantity of adsorbed protein. 相似文献