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31.
Yella-Reddy Nelli Céline Douat-Casassus Paul Claudon Brice Kauffmann Claude Didierjean Gilles Guichard 《Tetrahedron》2012,68(23):4492-4500
A new N-Boc-protected monomer for the synthesis of oligourea foldamers containing the (1H-imidazolyl-4yl)methyl side chain of histidine, has been prepared in seven steps from Trt-His(τ-Trt)-OMe. This protecting group combination on histidine was found to be critical to ensure efficient access to the requisite activated building block. This new derivative, suitable for solid phase synthesis, expands the current arsenal of building blocks with proteinogenic side chains useful for the design of peptidomimetic oligourea foldamers. 相似文献
32.
The design of the mold and the choice of the injection parameters for metal injection molding (MIM) is required to maintain homogeneity of the filled mixture. However, powder segregation is unavoidable in MIM because of the significant difference in densities of the metallic powder and the polymer binder. To achieve an effective prediction of segregation effect, a biphasic model based on mixture theory is employed. The viscous behaviors of each phase and the interaction coefficient between the flows of the two phases should be determined. The solution of two coupled Navier–Stokes equations results in a tremendous computation effort. The previous development of an explicit algorithm makes the biphasic simulation much faster than that of the classic methods. However, it is strongly desired to reduce or even eliminate the numerous global solutions for pressure fields at each time step. Hence, a new vectorial algorithm is proposed and developed to perform the simulation only by vectorial operations. It provides the anticipated efficiency in the simulation of biphasic modeling, and the advantage to use the classic elements of equal‐order interpolations. Some results produced by the two algorithms are compared with the experimental values to validate the new vectorial algorithm. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
33.
Dr. Matthieu Autillo Md. Ashraful Islam Julie Héron Laetitia Guérin Dr. Eleonor Acher Dr. Christelle Tamain Dr. Marie-Claire Illy Dr. Philippe Moisy Dr. Eric Colineau Dr. Jean-Christophe Griveau Dr. Claude Berthon Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(24):7138-7153
Actinide +VI complexes ( = , and ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, and complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the 1H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans’ method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the complex. The temperature dependence of the pNMR chemical shifts has a strong contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the complex and a non-Kramers-doublet model for the complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center. 相似文献
34.
Dr. Julie Jung M. Ashraful Islam Dr. Vincent L. Pecoraro Dr. Talal Mallah Dr. Claude Berthon Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(66):15112-15122
Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn16(picHA)16 series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)3](C3H5N2)3 ⋅ 3H2O series (Ln=Ce–Yb; dpa=2,6-dipicolinic acid) with approximate three-fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many-electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second-order parameter differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects. 相似文献
35.
High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene 下载免费PDF全文
Dr. Marie Betou Nicolas Kerisit Esme Meledje Dr. Yann R. Leroux Dr. Claudine Katan Dr. Jean‐François Halet Dr. Jean‐Claude Guillemin Dr. Yann Trolez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9553-9557
A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings. 相似文献
36.
Dr. Samuel Stolz Dr. Aliaksandr V. Yakutovich Dr. Jan Prinz Dr. Thomas Dienel Dr. Carlo A. Pignedoli Prof. Dr. Harald Brune Dr. Oliver Gröning Dr. Roland Widmer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18336-18340
Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on-surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9-ethynylphenanthrene (9-EP) upon annealing to 500 K on the chiral Pd3-terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9-EP propellers. The observed behavior strongly contrasts the reaction of 9-EP on the chiral Pd1-terminated PdGa{111} surfaces, where 9-EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level. 相似文献
37.
In this work, the influence of metallic dopant addition in 10 wt % Ni/γ-Al2O3 catalyst on the material physico-chemical properties and catalytic activity for the toluene steam reforming was studied. Seventeen doped Ni/γ-Al2O3 catalysts were synthesized by the sol–gel process. The aim of this study was to determine which elements were the most suitable for the doping of 10 wt % Ni/γ-Al2O3 catalysts. The influence of the dopants was studied through different physico-chemical techniques. It appeared that some dopants showed lower catalytic performances due to high carbon deactivation. On the contrary, some dopants increased the resistance to coking while also improving the catalytic activity. Different mechanisms were proposed to explain these modifications of catalytic behavior. Among all doped Ni/γ-Al2O3 catalysts, the samples that combined Mn + Mo or Co + Mo dopants showed the best catalytic performances at 650 °C. Both samples showed high toluene reforming activity and low amounts of carbon deposit. 相似文献
38.
Claude Tournut 《Macromolecular Symposia》1994,82(1):99-109
After a brief presentation of the standard non-functionalized copolymers of vinylidene fluoride, the preparation of new functionalized copolymers is described, by copolymerization of vinylidene fluoride, with other fluoromonomers and non-fluorinated monomers including at least one hydroxy or other functional group. The copolymers are analysed by the conventional methods. Examples of formulation show that these new copolymers are able to give coatings applicable outdoors and offering the same excellent durability as PVDF. 相似文献
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