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51.
Li Zhang Dr. Julie Jung Dr. Peng Zhang Mei Guo Dr. Lang Zhao Prof. Dr. Jinkui Tang Prof. Dr. Boris Le Guennic 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1392-1398
Elaborate chemical design is of utmost importance in order to slow down the relaxation dynamics in single‐molecule magnets (SMMs) and hence improve their potential applications. Much interest was devoted to the study of distinct relaxation processes related to the different crystal fields of crystallographically independent lanthanide ions. However, the assignment of the relaxation processes to specific metal sites remains a challenging task. To address this challenge, a new asymmetric Dy2 SMM displaying a well‐separated two‐step relaxation process with the anisotropic centers in fine‐tuned local environments was elaborately designed. For the first time a one‐to‐one relationship between the metal sites and the relaxation processes was evidenced. This work sheds light on complex multiple relaxation and may direct the rational design of lanthanide SMMs with enhanced magnetic properties. 相似文献
52.
Julie Febvay Dr. Charles S. Demmer Dr. Pascal Retailleau Dr. Jeanne Crassous Dr. Laura Abella Prof. Jochen Autschbach Dr. Arnaud Voituriez Dr. Angela Marinetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(68):15609-15614
Phosphahelicenes with thiophosphinic acid and ester functions have been obtained by the oxidative photocyclisation of olefins bearing both a benzophenanthrene and a benzophosphole unit. When the method has been extended to olefins bearing a partially saturated benzophospholene unit, a divergent regioselectivity of the photocyclisation step has been observed, leading to new helicenes in which the phosphorus function is located on the external rim of the helical backbone. The observed regioselectivity correlates well with the free-valence numbers of the atoms involved in the photocyclisation reaction (DFT calculations). 相似文献
53.
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
54.
55.
Rik H. Verschueren Julie Schmauck Dr. Michael S. Perryman Dr. Hui-Lan Yue Julian Riegger Dr. Bertrand Schweitzer-Chaput Dr. Martin Breugst Dr. Martin Klussmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(38):9088-9097
In this work, the reactivities of acetonyl and benzoyl radicals in aromatic substitution and addition reactions have been compared in an experimental and computational study. The results show that acetonyl is more electrophilic than benzoyl, which is rather nucleophilic. A Hammett plot analysis of the addition reactions of the two radicals to substituted styrenes clearly support the nucleophilicity of benzoyl, but in the case of acetonyl, no satisfactory linear correlation with a single substituent-related parameter was found. Computational calculations helped to rationalize this effect, and a good linear correlation was found with a combination of polar parameters (σ+) and the radical stabilization energies of the formed intermediates. Based on the calculated philicity indices for benzoyl and acetonyl, a quantitative comparison of these two radicals with many other reported radicals is possible, which may help to predict the reactivities of other aromatic radical substitution reactions. 相似文献
56.
Ionizable amino acids in protein‐based hydrogels can confer pH‐responsive behavior. Because elastin‐like polypeptides (ELPs) have an established sequence and can crosslink to form hydrogels, they are an ideal system for creating pH‐sensitive materials. This study examines different parameters that might affect pH‐sensitive behavior and characterizes the mechanical and physical properties between pH 3 and 11 of three ELP‐based crosslinked hydrogels. The first finding is that varying the amount of crosslinker affects the overall stiffness and resilience of the hydrogels but does not strongly affect water content, swelling ratio, or pH sensitivity. Second, the choice of two popular tag sequences, which vary in histidine and aspartic acid content, does not have a strong effect on pH‐sensitive properties. Last, selectively blocking lysine and tyrosine residues through acetylation significantly decreases the pH‐sensitive zeta potential. Acetylated hydrogels also demonstrate different behavior at low pH values with reduced swelling, reduced water content, and higher stiffness. Overall, this work demonstrates that ELP hydrogels with ionizable groups are promising materials for environmentally‐responsive applications such as drug delivery, tissue engineering, and microfluidics. 相似文献
57.
Davide Toniolo Aurélien R. Willauer Dr. Julie Andrez Yan Yang Dr. Rosario Scopelliti Prof. Laurent Maron Prof. Marinella Mazzanti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7831-7834
The activation of CS2 is of interest in a broad range of fields and, more particularly, in the context of creating new C−C bonds. The reaction of the dinuclear ytterbium(II) complex [Yb2L4], 1 , [L=(OtBu)3SiO−] with carbon disulfide led to the isolation of unprecedented reduction products. In particular, the crystallographic characterization of complex [Yb2L4(μ-C2S2)], 2 , provided the first example of an acetylenedithiolate ligand formed from metal reduction of CS2. Computational studies indicated that this unprecedented reactivity can be ascribed to the unusual binding mode of CS22− in the isolated “key intermediate” [Yb2L4(μ-CS2)], 3 , which results from the dinuclear nature of 1 . 相似文献
58.
Camille Piovesan Anne-Laurence Dupont Isabelle Fabre-Francke Odile Fichet Bertrand Lavédrine Hervé Chéradame 《Cellulose (London, England)》2014,21(1):705-715
Two di-alkoxysilanes, with (AMDES, aminopropylmethyldiethoxysilane) or without (DMDES, dimethyldiethoxysilane) an amine function, and a tri-alkoxy aminosilane (APTES, aminopropyltriethoxysilane) as well as their mixtures were introduced in paper as fiber strengthening agents. The polymerization and copolymerization of these polysiloxanes in the paper were investigated. In all the cases where APTES was present, the formation of networks was established by measuring the soluble fraction amount extracted from the treated papers. A slight decrease of the opacity of the paper sheets when AMDES was part of the treatment was noted. The presence of APTES reduced this opacity loss. The study of the physicochemical properties of the treated paper (mechanical strength and alkalinity) demonstrated that, besides the required deacidification feature, the different treatments allowed an efficient strengthening of the cellulose fibers to various extents. Contact angle measurements indicated a decrease of the hydrophilic character of papers treated with the mixture APTES/AMDES and the occurrence of a hydrophobic character of the papers treated with APTES alone. These results were consistently obtained for both spray and immersion treatment processes. 相似文献
59.
Lynn Vanhaecke Lieven Van MeulebroekNathalie De Clercq Julie Vanden Bussche 《Analytica chimica acta》2013
A prominent trend which has been observed in recent years in the analysis of veterinary drugs and growth-promoting agents is the shift from target-oriented procedures, mainly based on liquid chromatography coupled to triple-quadrupole mass spectrometry (LC-QqQ-MS), towards accurate mass full scan MS (such as time of flight (ToF) and Fourier Transform (FT) Orbitrap MS). In this study the applicability of high resolution single-stage-Orbitrap-MS for confirmatory analysis of growth-promoting agents in meat was compared to that of a QqQ-MS. Validation according to CD 2002/657/EC demonstrated that steroid analysis based on Orbitrap MS, operating at a resolution of 50,000 FWHM, is indeed capable to compete with QqQ-MS in terms of selectivity/specificity, while providing excellent linearity (for most compounds >0.99) but somewhat inferior sensitivity. Indeed, CCαs reached from 0.04–0.88 μg kg−1 for the 34 anabolic steroids upon MS/MS detection, while upon Orbitrap MS detection a range of 0.07–2.50 μg kg−1 was observed. Using QqQ-MS adequate precision was obtained since relative standard deviations, associated with the repeatability and intra-laboratory reproducibility, were below 20%. In the case of Orbitrap MS, for some compounds (i.e. some estrogens) this threshold was exceeded and thus poor precision was observed, which is possibly caused by the lack in sensitivity. Overall, it may be concluded that Orbitrap-MS offers an adequate performance in terms of linearity and precision but lacks in sensitivity for some of the compounds. 相似文献
60.