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991.
Marvin Mendel Indrek Kalvet Daniel Hupperich Guillaume Magnin Franziska Schoenebeck 《Angewandte Chemie (International ed. in English)》2020,59(5):2115-2119
Since 2014, the interest in aryl fluorosulfates (ArOSO2F) as well as their implementation in powerful applications has continuously grown. In this context, the enabling capability of ArOSO2F will strongly depend on the substitution pattern of the arene, which ultimately dictates its overall function as drug candidate, material, or bio‐linker. This report showcases the modular, substrate‐independent, and fully predictable, selective functionalization of polysubstituted arenes bearing C?OSO2F, C?Br, and C?Cl sites, which makes it possible to diversify the arene in the presence of OSO2F or utilize OSO2F as a triflate surrogate. Sequential and triply selective arylations and alkylations were realized within minutes at room temperature, using a single and air‐stable PdI dimer. 相似文献
992.
Dr. Guillaume Mata Bernhard Wölfl Prof. Alois Fürstner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):246-254
A path-scouting investigation into the highly cytotoxic marine macrolide callyspongiolide is reported that capitalizes on the selective formation of the C10−C11 alkene site. While the closure of the macrocycle by ring closing alkyne metathesis (RCAM) with the aid of a molybdenum alkylidyne complex was high yielding, the envisaged semi-reduction of the cycloalkyne to the corresponding E-alkene proved challenging. The reasons are likely steric in origin, in that the methyl branches on either side of the alkyne seem to prevent effective coordination of the substrate to the ruthenium catalyst, which must carry a bulky Cp* ligand to ensure high trans-selectivity. This notion is supported by the preparation of a callyspongiolide analogue, in which the two methyl groups in question are excised; its formation by RCAM followed by trans-hydrostannation/proto-destannation was straightforward. In parallel work the formation of the fully functional building block 54 showed that the presence of an unprotected -OH group allows even hindered substrates to be processed: the protic group adjacent to the triple bond engages with a chloride ligand on the ruthenium catalyst in hydrogen bonding and hence assists in substrate binding. Moreover, the preparation of an alkynylogous callyspongiolide analogue is described. 相似文献
993.
Guillaume Houzeaux Marta Garcia Juan Carlos Cajas Antoni Artigues Edgar Olivares Jesús Labarta 《International Journal of Computational Fluid Dynamics》2016,30(6):408-418
This work presents a parallel numerical strategy to transport Lagrangian particles in a fluid using a dynamic load balance strategy. Both fluid and particle solvers are parallel, with two levels of parallelism. The first level is based on a substructuring technique and uses message passing interface (MPI) as the communication library; the second level consists of OpenMP pragmas for loop parallelisation at the node level. When dealing with transient flows, there exist two main alternatives to address the coupling of these solvers. On the one hand, a single-code approach consists in solving the particle equations once the fluid solution has been obtained at the end of a time step, using the same instance of the same code. On the other hand, a multi-code approach enables one to overlap the transport of the particles with the next time-step solution of the fluid equations, and thus obtain asynchronism. In this case, different codes or two instances of the same code can be used. Both approaches will be presented. In addition, a dynamic load balancing library is used on the top of OpenMP pragmas in order to continuously exploit all the resources available at the node level, thus increasing the load balance and the efficiency of the parallelisation and uses the MPI. 相似文献
994.
Michael Kogan Lucie Ducloué Julie Goyon Xavier Chateau Olivier Pitois Guillaume Ovarlez 《Rheologica Acta》2013,52(3):237-253
We study the rheological behavior of mixtures of foams and pastes, which can be described as suspensions of bubbles in yield stress fluids. Model systems are designed by mixing monodisperse aqueous foams and concentrated emulsions. The elastic modulus of the bubble suspensions is found to depend on the elastic capillary number $\textit{Ca}_{_G}$ , defined as the ratio of the paste elastic modulus to the bubble capillary pressure. For values of $\textit{Ca}_{_G}$ larger than $\simeq 0.5$ , the dimensionless elastic modulus of the aerated material decreases as the bubble volume fraction $\phi $ increases, suggesting that bubbles behave as soft elastic inclusions. Consistently, this decrease is all the sharper as $\textit{Ca}_{_G}$ is high, which accounts for the softening of the bubbles as compared to the paste. By contrast, we find that the yield stress of most studied materials is not modified by the presence of bubbles. This suggests that their plastic behavior is governed by the plastic capillary number $\textit{Ca}_{\tau_y}$ , defined as the ratio of the paste yield stress to the bubble capillary pressure. At low $\textit{Ca}_{\tau_y}$ values, bubbles behave as nondeformable inclusions, and we predict that the suspension dimensionless yield stress should remain close to unity, in agreement with our data up to $\textit{Ca}_{\tau_y}=0.2$ . When preparing systems with a larger target value of $\textit{Ca}_{\tau_y}$ , we observe bubble breakup during mixing, which means that they have been deformed by shear. It then seems that a critical value $\textit{Ca}_{\tau_y}\simeq 0.2$ is never exceeded in the final material. These observations might imply that, in bubble suspensions prepared by mixing a foam and a paste, the suspension yield stress is always close to that of the paste surrounding the bubbles. Finally, at the highest $\phi $ investigated, the yield stress is shown to increase abruptly with $\phi $ : this is interpreted as a “foamy yield stress fluid” regime, which takes place when the paste mesoscopic constitutive elements (here, the oil droplets) are strongly confined in the films between the bubbles. 相似文献
995.
Guillaume A Rousselet Jesse S Husk Cyril R Pernet Carl M Gaspar Patrick J Bennett Allison B Sekuler 《BMC neuroscience》2009,10(1):114-20
Background
In this study, we quantified age-related changes in the time-course of face processing by means of an innovative single-trial ERP approach. Unlike analyses used in previous studies, our approach does not rely on peak measurements and can provide a more sensitive measure of processing delays. Young and old adults (mean ages 22 and 70 years) performed a non-speeded discrimination task between two faces. The phase spectrum of these faces was manipulated parametrically to create pictures that ranged between pure noise (0% phase information) and the undistorted signal (100% phase information), with five intermediate steps. 相似文献996.
Takashi Nagano Dr. Jiři Pospíšil Dr. Guillaume Chollet Dr. Saskia Schulthoff Volker Hickmann Dipl.‐Chem. Emilie Moulin Dr. Jennifer Herrmann Dipl.‐Chem. Rolf Müller Prof. Alois Fürstner Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(38):9697-9706
A multitasking C‐silylation strategy using the readily available compound 26 as a surrogate for cinnamic acid represents the key design element of a total synthesis of all known members of the ipomoeassin family of resin glyosides. This protecting group maneuver allows the unsaturated acids decorating the glucose subunit of the targets to be attached at an early phase of the synthesis, prevents their participation in the ruthenium‐catalyzed ring‐closing metathesis (RCM) used to form the macrocyclic ring, and protects them against reduction during the hydrogenation of the resulting cycloalkene over Wilkinson’s catalyst. As the C‐silyl group can be concomitantly removed with the O‐TBS substituent using tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF) in acetonitrile, no separate protecting group manipulations were necessary in the final stages, thus contributing to a favorable overall “economy of steps”. In addition to the naturally occurring ipomoeassins, a small set of synthetic analogues has also been prepared by “diverted total synthesis”. The cytotoxicity of these compounds was assayed with two different cancer cell lines. The recorded data confirm previous findings that the acylation‐ and oxygenation pattern of these amphiphilic glycoconjugates is highly correlated with their biological activity profile. Ipomoeassin F turned out to be the most promising member of the series, showing IC50 values in the low nanomolar range. 相似文献
997.
998.
Younes Makoudi Judicaël Jeannoutot Frank Palmino Frédéric Chérioux Guillaume Copie Christophe Krzeminski Fabrizio Cleri Bruno Grandidier 《Surface Science Reports》2017,72(4):316-349
Understanding the physical and chemical processes in which local interactions lead to ordered structures is of particular relevance to the realization of supramolecular architectures on surfaces. While spectacular patterns have been demonstrated on metal surfaces, there have been fewer studies of the spontaneous organization of supramolecular networks on semiconductor surfaces, where the formation of covalent bonds between organics and adatoms usually hamper the diffusion of molecules and their subsequent interactions with each other. However, the saturation of the dangling bonds at a semiconductor surface is known to make them inert and offers a unique way for the engineering of molecular patterns on these surfaces. This review describes the physicochemical properties of the passivated B-Si(111)-(√3x√3) R30° surface, that enable the self-assembly of molecules into a rich variety of extended and regular structures on silicon. Particular attention is given to computational methods based on multi-scale simulations that allow to rationalize the relative contribution of the dispersion forces involved in the self-assembled networks observed with scanning tunneling microscopy. A summary of state of the art studies, where a fine tuning of the molecular network topology has been achieved, sheds light on new frontiers for exploiting the construction of supramolecular structures on semiconductor surfaces. 相似文献
999.
Felix Houard Frederic Gendron Yan Suffren Thierry Guizouarn Vincent Dorcet Guillaume Calvez Carole Daiguebonne Olivier Guillou Boris Le Guennic Matteo Mannini Kevin Bernot 《Chemical science》2021,12(31):10613
The careful monitoring of crystallization conditions of a mixture made of a TbIII building block and a substituted nitronyl-nitroxide that typically provides infinite coordination polymers (chains), affords a remarkably stable linear hexanuclear molecule made of six TbIII ions and five NIT radicals. The hexanuclear units are double-bridged by water molecules but ab initio calculations demonstrate that this bridge is inefficient in mediating any magnetic interaction other than a small dipolar antiferromagnetic coupling. Surprisingly the hexanuclears, despite being finite molecules, show a single-chain magnet (SCM) behavior. This results in a magnetic hysteresis at low temperature whose coercive field is almost doubled when compared to the chains. We thus demonstrate that finite linear molecules can display SCM magnetic relaxation, which is a strong asset for molecular data storage purposes because 1D magnetic relaxation is more robust than the relaxation mechanisms observed in single-molecule magnets (SMMs) where under-barrier magnetic relaxation can operate.A stable hexanuclear molecule made of a TbIII building block and a substituted nitronyl-nitroxide radical show a single-chain magnet behavior despite being a finite molecule. 相似文献
1000.
A straightforward synthesis of fluorescent tris-meta-substituted triphenylamines (m-TPAs) is presented. These new fluorophores display a unique feature that is a remarkably high Stokes shift up to 250 nm, as compared to their para counterparts. Although the meta substitution is made at the expense of the quantum yield, the latter is maintained at an appreciable level (5%) making the m-TPAs a new class of fluorophores adaptable to a large range of applications from biology to materials science. 相似文献