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41.
L. Timperman A. Lewera W. Vogel N. Alonso-Vante 《Electrochemistry communications》2010,12(12):1772-1775
We report on Pt selectively photodeposited on oxides sites of Ti-, and W-carbon composites. The change of the lattice parameter strongly suggests that the metal center alloys with the metal centers of the oxides with a concomitant change of electronic properties favorable for oxygen reduction reaction in acid medium. 相似文献
42.
Badr Benmansour Ludovic Stephan Jean-Yves Cabon Laure Deschamps Philippe Giamarchi 《Journal of fluorescence》2011,21(3):843-850
This work presents spectroscopic properties of some Endocrine Disrupting Compounds (EDCs), frequently found in food and in
natural water. Studied molecules belong to the groups of phenolic and phthalate EDCs. In a first part, we have examined their
absorption and fluorescence properties. Fluorescence emission wavelengths are about 300 nm for phenolic compounds and 360 nm
for phtalate compounds; main excitation wavelengths being comprised between 210 nm and 230 nm. Fluorescence lifetimes measured
are short (about 4 ns) and the fluorescence quantum yield has been determined. In a second part, to avoid the time consuming
solvent extraction step, an analytical application to evaluate the performance of a direct analysis by laser induced fluorescence
spectroscopy of ECDs traces in tap water and in raw water is presented. Good detection limits have been obtained, i.e.: 0.35 μg.L−1 of chlorophenol in tap water, which are always lower than the reported Predictive Non Efficient Concentration (PNEC). 相似文献
43.
In this Letter, we present a new experimental approach to investigate the effective temperature concept as a generalization of the fluctuation-dissipation theorem (FDT) for nonequilibrium systems. Simultaneous measurements of diffusion coefficient and sedimentation velocity of heavy colloids, embedded in a Laponite clay suspension, are performed with a fluorescence-recovery-based setup. This nonperturbative dual measurement, performed at a single time in a single sample, allows for a direct application of the FDT to the tracer velocity observable. It thus provides a well-defined derivation of the effective temperature in this ageing colloidal gel. For a wide range of concentrations and ageing times, we report no violation of the FDT, with effective temperature agreeing with bath temperature. This result is consistent with recent theoretical predictions on the coupling between the velocity observable and nonequilibrium gels dynamics. 相似文献
44.
My-Loan-Phung Le Fannie Alloin Pierre Strobel Jean-Claude Lepr��tre Laure Cointeaux Carlos P��rez del Valle 《Ionics》2011,18(9):817-827
Ionic liquids, ILs, based on fluorinated pyrrolidinium and piperidinium ammonium cations and imide anion were prepared and characterized. The physicochemical and electrochemical properties of these ILs including melting point, glass transition and degradation temperatures, viscosity, ionic conductivity, and electrochemical stability were determined and compared to alkyl pyrrolidinium and piperidinium ILs. The incorporation of a CF3 group instead of a CH3 induces an increase of the IL viscosity, thus a conductivity decrease. However, good ionic conductivity is obtained with fluorinated pyrrolidinium IL. Cyclic amine ILs with propyl alkyl chain or fluorinated ammonium exhibit very high electrochemical stability toward oxidation. The effect of the addition of LiTFSI on the IL properties was studied with the same methodology. 相似文献
45.
Dr. Christophe André Dr. Baptiste Legrand Laure Moulat Emmanuel Wenger Dr. Claude Didierjean Dr. Emmanuel Aubert Dr. Marie Christine Averlant‐Petit Prof. Jean Martinez Dr. Muriel Amblard Dr. Monique Calmes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):16963-16971
The combination of a non‐functionalized constrained bicyclo[2.2.2]octane motif along with urea linkages allowed the formation of a highly rigid 2.512/14 helical system both in solution and the solid state. In this work, we aimed at developing stable and functionalized systems as promising materials for biological applications in investigating the impact of this constrained motif and its configuration on homo and heterochiral mixed‐oligourea helix formation. Di‐, tetra‐, hexa‐, and octa‐oligoureas alternating the highly constrained bicyclic motif of (R) or (S) configuration with acyclic (S)‐β3‐amino acid derivatives were constructed. Circular dichroism (CD), NMR experiments, and the X‐ray crystal structure of the octamer unequivocally proved that the alternating heterochiral R/S sequences form a stable left‐handed 2.5‐helix in contrast to the mixed (S/S)‐oligoureas, which did not adopt any defined secondary structure. We observed that the (?)‐synclinal conformation around the Cα? Cβ bond of the acyclic residues, although sterically less favorable than the (+)‐synclinal conformation, was imposed by the (R)‐bicyclic amino carbamoyl (BAC) residue. This highlighted the strong ability of the BAC residue to drive helical folding in heterochiral compounds. The role of the stereochemistry of the BAC unit was assessed and a model was proposed to explain the misfolding of the S/S sequences. 相似文献
46.
Thibault Dutronc Dr. Emmanuel Terazzi Dr. Laure Guénée Kerry‐Lee Buchwalder Aurore Spoerri Dr. Daniel Emery Dr. Jiri Mareda Dr. Sébastien Floquet Prof. Claude Piguet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8447-8456
This work illustrates how minor structural perturbations produced by methylation of 4′‐(dodecyloxy)‐4‐cyanobiphenyl leads to enthalpy–entropy compensation for their melting processes, a trend which can be analyzed within the frame of a simple intermolecular cohesive model. The transformation of the melting thermodynamic parameters collected at variable temperatures into cohesive free‐energy densities expressed at a common reference temperature results in a novel linear correlation, from which melting temperatures can be simply predicted from molecular volumes. 相似文献
47.
Prof. Eric Collet Dr. Maciej Lorenc Dr. Marco Cammarata Dr. Laurent Guérin Dr. Marina Servol Dr. Antoine Tissot Dr. Marie‐Laure Boillot Prof. Hervé Cailleau Prof. Marylise Buron‐Le Cointe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(7):2051-2055
We study by 100 picosecond X‐ray diffraction the photo‐switching dynamics of single crystal of the orthorhombic polymorph of the spin‐crossover complex [(TPA)Fe(TCC)]PF6, in which TPA=tris(2‐pyridyl methyl)amine, TCC2?=3,4,5,6‐Cl4‐Catecholate2?. In the frame of the emerging field of dynamical structural science, this is made possible by using optical pump/X‐ray probe techniques, which allow following in real time structural reorganization at intra‐ and intermolecular levels associated with the change of spin state in the crystal. We use here the time structure of the synchrotron radiation generating 100 picosecond X‐ray pulses, coupled to 100 fs laser excitation. This study has revealed a rich variety of structural reorganizations, associated with the different steps of the dynamical process. Three consecutive regimes are evidenced in the time domain: 1) local molecular photo‐switching with structural reorganization at constant volume, 2) volume relaxation with inhomogeneous distribution of local temperatures, 3) homogenization of the crystal in the transient state 100 µs after laser excitation. These findings are fundamentally different from those of conventional diffraction studies of long‐lived photoinduced high spin states. The time‐resolution used here with picosecond X‐ray diffraction probes different physical quantities on their intrinsic time‐scale, shedding new light on the successive processes driving macroscopic switching in a functionalized material. These results pave the way for structural studies away from equilibrium and represent a first step toward femtosecond crystallography. 相似文献
48.
Putkunz CT D'Alfonso AJ Morgan AJ Weyland M Dwyer C Bourgeois L Etheridge J Roberts A Scholten RE Nugent KA Allen LJ 《Physical review letters》2012,108(7):073901
Ptychographic coherent diffractive imaging (CDI) has been extensively applied using both x rays and electrons. The extension to atomic resolution has been elusive. This Letter demonstrates ptychographic electron diffractive imaging at atomic resolution, permitting identification of structure in a boron nitride helical cone at a resolution of order 1 ?, beyond that of comparative Z-contrast images. A scanning transmission electron microscope is used to create a diverging illumination in a defocused Fresnel CDI geometry, providing a robust strategy leading to a unique solution. 相似文献
49.
Matthieu Tissot Daniele Poggiali Dr. Hélène Hénon Daniel Müller Dr. Laure Guénée Dr. Marc Mauduit Prof. Alexandre Alexakis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(28):8731-8747
The copper‐catalyzed conjugate addition of various Grignard reagents to polyconjugated enones (dienone and enynone derivatives) is reported. The catalyst system, composed of copper triflate and an NHC ligand, led to the unusual selective formation of the 1,4‐addition products. This reaction allows for the creation of all‐carbon chiral quaternary centers with enantiomeric excesses up to 99 %. The remaining unsaturation on the 1,4 adducts give access to valuable synthetic transformations. 相似文献
50.
Lahcen Hssaini Francisca Hernandez Manuel Viuda-Martos Jamal Charafi Rachid Razouk Karim Houmanat Rachida Ouaabou Said Ennahli Driss Elothmani Ilham Hmid Marie Laure Fauconnier Hafida Hanine 《Molecules (Basel, Switzerland)》2021,26(9)
In the present study, chromatic coordinates, phenolic acids, flavonoids and antioxidant capacity assessed by 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonate (ABTS) and lipid peroxidation inhibition capacity (LPIC) essays and their relative IC50 were investigated in 25 fig cultivars growing in Morocco. The aims of this study were to determine (i) the variation in these compounds among light and dark-colored cultivars, (ii) their partitioning between fruit peel and pulp and (iii) to display network connections among these variables. Twelve phenolic compounds (PCs) were isolated in peel extract versus eight in pulp samples. Anthocyanins, mainly cyanidin-3,5-diglucoside and cyanidin-3-O-rutinoside, were the predominant compounds in peels, where the mean concentrations were 75.90 ± 18.76 and 77.97 ± 18.95 µg/g dw, respectively. On the other hand, (−)-epicatechin and cyanidin-3-O-rutinoside were the major compounds in the pulp extracts, where the mean values were 5.23 ± 4.03 and 9.01 ± 5.67 µg/g dw, respectively. A two-dimensional hierarchically clustered heatmap was applied to the dataset to explore correlations in the dataset and similarities between cultivars, without dimensionality reduction. Results showed that anthocyanins, particularly pelargonidin-3-O-rutinoside, cyanidin-3,5-diglucoside and cyanidin-3-O-rutinoside, were the main contributors to the peels’ free radical scavenging capacity. This capacity was particularly higher in the peel of dark-colored figs compared to the fruit pulp. The local cultivar “INRA 1301” showed the most promising phenolic profile due to its very high levels of almost all detected PCs, especially (−)-epicatechin, quercetin-3-O-rutinoside, quercetin-3-O-glucoside, cyanidine-3,5-diglucoside, cyanidine-3-O-rutinoside and pelargonidin-3-O-rutinoside (54.66, 141.08, 35.48, 494.08, 478.66, 12.56 µg/g dw, respectively). Having the darkest figs in the collection (L* = 25.72, c* = 22.09 and h° = 20.99), this cultivar has also combined promising IC50 values, which were of 19.85, 40.58 and 124.78 µg/mL for DPPH, ABTS and LPIC essays, respectively. 相似文献