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21.
Renaud Barbeyron Jean-Jacques Vasseur Carine Baraguey Michael Smietana 《Tetrahedron》2017,73(17):2468-2475
The iminodiacetic acid and aminodiethanol moieties are known for their ability to generate with boronic acids bicyclic structures having a strong intramolecular NB coordination. We describe here the convergent synthesis of 3′-deoxy-3′-iminodiacetic acid and 3′-deoxy-3′-aminodiethanol thymidine analogues. The abilities of these compounds to form boronate complexes with aliphatic or aromatic boronic acids were established by 1D and 2D 1H and 13C NMR. Moreover, conformational analysis of the newly synthesized compounds revealed a marked preference for an N-type sugar puckering. 相似文献
22.
Nguyen Tle A Devic T Mialane P Rivière E Sonnauer A Stock N Demir-Cakan R Morcrette M Livage C Marrot J Tarascon JM Férey G 《Inorganic chemistry》2010,49(22):10710-10717
A high-throughput methodology combined with X-ray powder diffraction measurements was used to investigate the reactivity of the TetraThiaFulvalene TetraCarboxylic acid ((TTF-TC)H(4)) with divalent metals (M = Ni, Co) under various reaction conditions (stoichiometry, pH, temperature). Two new crystalline phases were identified and then studied by single crystal X-ray diffraction. Whereas the first one appears to be a simple salt, the second one, formulated {[M(H(2)O)(4)](2)(TTF-TC)}·4H(2)O, is built of 2:1 M:TTF-TC molecular complexes and labeled MIL-136(Ni, Co) (MIL stands for Materials Institute Lavoisier). The combination of thermogravimetric analysis and thermodiffraction studies reveals that MIL-136(Ni) exhibits a complex dehydration behavior. Indeed, a partial dehydration/rehydration process led to the single-crystal-to-single-crystal transformation of the molecular compound in a two-dimensional coordination polymer formulated {[Ni(2)(H(2)O)(5)(TTF-TC)]}·H(2)O (MIL-136'(Ni)). Magnetic and redox properties of MIL-136(Ni, Co) were investigated. Magnetic measurements indicate that all the magnetic coupling, intra- and intermolecular, are very weak; thus, the magnetic data of MIL-136(Ni, Co) have been interpreted in term of single-ion spin orbit coupling. Solid state cyclic voltammetry of MIL-136(Ni, Co) presents three reversible waves which were assigned to the redox activity of the TTF core and the metallic cations. In contrast to solids based on TTF linkers and alkaline ions, the MIL-136(Ni, Co) complexes do not act as excellent positive electrode materials for Li batteries, but present two reversible electron oxidation of the TTF core. These observations were tentatively related to the strength of the metal-carboxylate bond. 相似文献
23.
David Semrouni O. Petru Balaj Florent Calvo Catarina F. Correia Carine Clavaguéra Gilles Ohanessian 《Journal of the American Society for Mass Spectrometry》2010,21(5):728-738
The structure of the sodiated peptide GGGGGGGG-Na+ or G8-Na+ was investigated by infrared multiple photon dissociation (IRMPD) spectroscopy and a combination of theoretical methods.
IRMPD was carried out in both the fingerprint and N—H/O—H stretching regions. Modeling used the polarizable force field AMOEBA
in conjunction with the replica-exchange molecular dynamics (REMD) method, allowing an efficient exploration of the potential
energy surface. Geometries and energetics were further refined at B3LYP-D and MP2 quantum chemical levels. The IRMPD spectra
indicate that there is no free C-terminus OH and that several N—Hs are free of hydrogen bonding, while several others are
bound, however not very strongly. The structure must then be either of the charge solvation (CS) type with a hydrogen-bound
acidic OH, or a salt bridge (SB). Extensive REMD searches generated several low-energy structures of both types. The most
stable structures of each type are computed to be very close in energy. The computed energy barrier separating these structures
is small enough that G8-Na+ is likely fluxional with easy proton transfer between the two peptide termini. There is, however, good agreement between
experiment and computations in the entire spectral range for the CS isomer only, which thus appears to be the most likely
structure of G8-Na+ at room temperature. 相似文献
24.
Bernard Masereel Mustapha Dinguizli Caroline Bouzin Nicolas Moniotte Olivier Feron Bernard Gallez Thierry Vander Borght Carine Michiels Stéphane Lucas 《Journal of nanoparticle research》2011,13(4):1573-1580
Nanoscale materials are used in the biomedical field for magnetic resonance imaging, protein detection and drug/gene delivery.
Gold nanoparticles (AuNPs) are particularly investigated in cancer treatment and imaging. In this study, we described a simple
and reliable liquid method to coat AuNPs (diameter: 21 nm) layer-by-layer with alternative cationic polyallylamine and anionic
polystyrenesulfonate. The C-terminal amino acid of the antibody directed against anti-bovine serum albumin was activated by
EDC/NHS, and then condensed with the amino functions of the external polyallylamine layer. An ELISA test confirmed that the
antigen recognition of the bioconjugate antibody was conserved. This AuNP coating and the covalently coupling could be used
as a generic process for binding other specific antibodies, particularly those overexpressed in cancer cells and angiogenesis. 相似文献
25.
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27.
Erick Kindt Sandra Bak Mueller Christine Castle Carine M. Boustany‐Kari 《Biomedical chromatography : BMC》2010,24(7):752-758
Biomarkers are an increasingly important constituent of the drug development process, offering the potential of increased efficiency through reduced compound attrition and earlier proof of mechanism and/or efficacy. Assays developed for compound screening that can be directly translated for clinical trials are especially valuable, but their successful adoption requires a careful balance between assay performance and implementation costs. One such ‘fit‐for‐purpose’ biomarker assay, the indirect measurement of pharmacological modulation of sphingolipid biosynthesis and disposition, is presented here. Among spingolipids, numerous ceramide species are readily detectable in different lipoprotein fractions of mammalian plasma, but their parallel quantification can be prohibitively expensive and time consuming. Ceramides differ in their fatty acid moiety, which is readily removed by hydrolysis, yielding a common sphingosine derivative, the measurement of which serves as an indicator of total ceramide. When followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for detection, robust analyte quantification becomes relatively straightforward. The practical utility of a method developed to be fit for the purpose of rapidly and quantitatively measuring treatment‐induced variations in total ceramide from hamster plasma and individual lipoprotein fractions is described. With a linear calibration range from 0.003 to 33.4 μm sphingosine, precision and accuracy error in plasma‐based quality controls spiked with ceramides was less than 15%. The specificity of the assay for ceramides was also assessed. The simplicity of the method would allow for its potential translation to other preclinical species, as well as for clinical applications in later‐stage drug development. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
28.
Auneau F Michel C Delbecq F Pinel C Sautet P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(50):14288-14299
We report herein a detailed and accurate study of the mechanism of rhodium-catalysed conversion of glycerol into 1,2-propanediol and lactic acid. The first step of the reaction is particularly debated, as it can be either dehydration or dehydrogenation. It is expected that these elementary reactions can be influenced by pH variations and by the nature of the gas phase. These parameters were consequently investigated experimentally. On the other hand, there was a lack of knowledge about the behaviour of glycerol at the surface of the metallic catalyst. A theoretical approach on a model Rh(111) surface was thus implemented in the framework of density functional theory (DFT) to describe the above-mentioned elementary reactions and to calculate the corresponding transition states. The combination of experiment and theory shows that the dehydrogenation into glyceraldehyde is the first step for the glycerol transformation on the Rh/C catalyst in basic media under He or H(2) atmosphere. 相似文献
29.
Abdellah I Boggio-Pasqua M Canac Y Lepetit C Duhayon C Chauvin R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(18):5110-5115
The configurational stability of biaryl motifs is addressed for the 1-naphthyl-N-benzimidazolyl motif substituted by a single diphenylphosphinyl group at the 2-position. The atropoenantiomers of the N-methylated cation H-MIOP, a less sterically locked analogue of the neutral H-MOP ligand, were resolved by enantiospecific cleavage of the N(2)C-P bond of the resolved enantiomers of BIMIONAP. The latter were obtained by enantiospecific N-methylation of the previously resolved enantiomers of neutral BIMINAP. PdCl(2) complexes of the P,C-chelating N-heterocyclic carbene (NHC)-phosphine ligands derived from (R)- and (S)-H-MIOP were prepared by two enantiospecific routes: by N(2)C-P bond cleavage from the (R)- and (S)-BIMIONAP-PdCl(2) complexes, or by simultaneous coordination of the P and C atoms of the in situ generated free NHC-phosphine. The enantiomerization pathways of H-MOP, H-MIOP, and corresponding NHC-phosphine have been investigated at the B3PW91/6-31G(d,p) level of theory. The calculated enantiomerization barriers of H-MOP and H-MIOP in acetonitrile are equal to 176.0 and 146.4 kJ mol(-1), respectively, and are mainly determined by the distortion of the naphthalene and/or benzimidazole motifs in the transition state. Beyond the stability of their optical rotation at room temperature, the respective calculated Oki's racemization temperatures of 334 and 225 °C allowed us to consider both ligands as configurationally stable. 相似文献
30.
The influence of the formal electrostatic interaction on the cis/trans coordination mode at a PdCl(2) center is investigated in a family of isostructural flexible diphosphine ligands Ph(2)P-X-C(6)H(4)-Y-PPh(2), where X and Y stand for neutral or cationic N,C-imidazolylene linkers. While the neutral and monocationic diphosphine spontaneously behave as classical cis-chelating ligands, only the dicationic diphosphine, where the electrostatic repulsion between the formal positive charges specifically takes place, is observed to behave as a trans-chelating ligand. The crucial role of electrostatics is analyzed on the basis of (31)P NMR data in solution and X-ray diffraction data in the crystal state. Comparative theoretical studies of the cis- and trans-chelated complexes, including EDA, static (31)P NMR, MESP, and AIM analyses, have been undertaken on the basis of DFT calculations in the gas phase or in the acetonitrile continuum. Whereas the cis-coordination mode is shown to be thermodynamically favored for the neutral ligand, the trans-coordination mode is found to be preferred for the dicationic homologue. The stereochemical preference is thus shown to be parallel to the expected effect of the formal electrostatic interaction. The results open perspectives for control of the cis- and trans-chelating behavior of flexible bidentate ligands by more or less reversible charge transfer at the periphery of the coordination sphere of a metallic center. 相似文献