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121.
Philipp Niermeier Sebastian Blomeyer Younes K. J. Bejaoui J. Louis Beckmann Beate Neumann Hans‐Georg Stammler Norbert W. Mitzel 《Angewandte Chemie (International ed. in English)》2019,58(7):1965-1969
Bidentate boron Lewis acids based on 1,8‐diethynylanthracene were synthesised in two steps by initial stannylation of the terminal alkynes and subsequent tin–boron exchange with different chloroboranes. The reactions were very selective, and the target compounds were obtained in high purity and good to excellent yields. Complexation experiments of 1,8‐bis[(diphenylboranyl)ethynyl]anthracene with nitrogen bases (pyridine, pyrimidine, TMEDA) afforded three stable adducts, which were structurally characterised by X‐ray diffraction. Competition experiments demonstrated the selective exchange of guests, and quantum‐chemical calculations provided information on their energetics. NMR experiments at low temperature gave insight into the dynamic behaviour of the TMEDA adduct. 相似文献
122.
Simon Bailleul Dr. Sven M. J. Rogge Dr. Louis Vanduyfhuys Prof. Veronique Van Speybroeck 《ChemCatChem》2019,11(16):3993-4010
The methylation of hexamethylbenzene with methanol is one of the key reactions in the methanol-to-olefins hydrocarbon pool reaction cycle taking place over the industrially relevant H-SAPO-34 zeolite. This methylation reaction can occur either via a concerted or via a stepwise mechanism, the latter being the preferred pathway at higher temperatures. Herein, we systematically investigate how a complex reaction environment with additional water molecules and higher concentrations of Brønsted acid sites in the zeolite impacts the reaction mechanism. To this end, first principle molecular dynamics simulations are performed using enhanced sampling methods to characterize the reactants and products in the catalyst pores and to construct the free energy profiles. The most prominent effect of the dynamic sampling of the reaction path is the stabilization of the product region where water is formed, which can either move freely in the pores of the zeolite or be stabilized through hydrogen bonding with the other protic molecules. These protic molecules also stabilize the deprotonated Brønsted acid site, created due to the formation of the heptamethylbenzenium cation, via a Grotthuss-type mechanism. Our results provide fundamental insight in the experimental parameters that impact the methylation of hexamethylbenzene in H-SAPO-34, especially highlighting and rationalizing the crucial role of water in one of the main reactions of the aromatics-based reaction cycle. 相似文献
123.
Robert A. Skutnik Louis Lehmann Sergej Püschel-Schlotthauer George Jackson Martin Schoen 《Molecular physics》2019,117(20):2830-2845
ABSTRACTMonte Carlo simulations in the isothermal-isobaric ensemble are used to investigate the formation of an ordered, biaxial nematic phase in a binary mixture of thermotropic liquid crystals. The orientational dependence of the interaction between molecules of each pure component is the same as in the well-known Maier-Saupe model; each pure component of the mixture is therefore capable of forming a uniaxial nematic phase. For the interaction between molecules of different components, we use the same Maier-Saupe model but change the sign of the coupling constant. As a consequence a T-shaped arrangement of these molecules is energetically favoured. The formation of the biaxial phase occurs in two steps. At higher temperatures T, one of the components forms a uniaxial nematic phase whereas the other is in a quasi two-dimensional restricted isotropic liquid state. We develop a simple theoretical model to understand the high degree of (ostensible) nematic order in the latter. At lower T, the second component becomes nematic and then the entire mixture of the two compounds has biaxial symmetry. The biaxial nematic phase does not demix into domains rich in molecules of one or the other species. 相似文献
124.
Nylon 6 and nylon 6,6 reaction equilibria depend in a complex way on water concentration and temperature. For example, data sets from six research groups reveal that the apparent equilibrium constant for polycondensation increases with water at low water concentrations, reaches a maximum, and then decreases as the water concentration rises further. In this article, semi‐empirical expressions are proposed to describe the experimentally observed equilibrium behavior for the five main reactions that occur during nylon 6 and nylon 6,6 polymerization. Nine side reactions involving amidine ends, cyclopentanone ends, and hydrated carboxyl ends are used to develop expressions that account for the influence of both water and temperature on these equilibrium constants. Excellent fit to the data, over the entire range of the available nylon 6 and nylon 6,6 literature data, suggests that the proposed equations will be helpful for modeling reaction equilibria for nylon 6/6,6 copolymerization. 相似文献
125.
Thissa N. Siriwardena Alice Capecchi Bee‐Ha Gan Dr. Xian Jin Dr. Runze He Dr. Dengwen Wei Lan Ma Dr. Thilo Köhler Prof. Dr. Christian van Delden Dr. Sacha Javor Prof. Dr. Jean‐Louis Reymond 《Angewandte Chemie (International ed. in English)》2018,57(28):8483-8487
We used nearest‐neighbor searches in chemical space to improve the activity of the antimicrobial peptide dendrimer (AMPD) G3KL and identified dendrimer T7 , which has an expanded activity range against Gram‐negative pathogenic bacteria including Klebsiellae pneumoniae, increased serum stability, and promising activity in an in vivo infection model against a multidrug‐resistant strain of Acinetobacter baumannii. Imaging, spectroscopic studies, and a structural model from molecular dynamics simulations suggest that T7 acts through membrane disruption. These experiments provide the first example of using virtual screening in the field of dendrimers and show that dendrimer size does not limit the activity of AMPDs. 相似文献
126.
AbstractIn strongly alkaline media ([OH?]?≥?0.12 M), nicotinamide (nica) forms a complex with square-planar Ag(OH)4? [nica]?≥?0.05 M. The complex decomposes in seconds to nicotinamide N-oxide. The correlation of maximum absorbance of the complex with concentrations of nicotinamide and hydroxide requires that the complex is either the five-coordinate Ag(OH)4(H-1nica)2? or the six-coordinate Ag(OH)5(nica)2?. Comparison with the reactions of Ag(OH)4? with nicotinate ion (nic?) and acetamide under similar conditions indicates that nicotinamide coordinates with Ag(OH)4? by the amido group rather than the nitrogen on the pyridine ring or the amido oxygen. Kinetics of the Ag(III)-nica redox reaction are consistent with direct reaction between nicotinamide and uncoordinated Ag(OH4)?. Oxidation takes place at the pyridine ring, yielding nicotinamide N-oxide. Silver(III) is reduced to monovalent silver. 相似文献
127.
Maria Chudnovsky Louis Esperet Laetitia Lemoine Peter Maceli Frédéric Maffray Irena Penev 《Journal of Graph Theory》2017,84(3):221-232
We prove that a graph G contains no induced ‐vertex path and no induced complement of a ‐vertex path if and only if G is obtained from 5‐cycles and split graphs by repeatedly applying the following operations: substitution, split unification, and split unification in the complement, where split unification is a new class‐preserving operation introduced here. 相似文献
128.
It is known that in any r‐coloring of the edges of a complete r‐uniform hypergraph, there exists a spanning monochromatic component. Given a Steiner triple system on n vertices, what is the largest monochromatic component one can guarantee in an arbitrary 3‐coloring of the edges? Gyárfás proved that is an absolute lower bound and that this lower bound is best possible for infinitely many . On the other hand, we prove that for almost all Steiner triple systems the lower bound is actually . We obtain this result as a consequence of a more general theorem which shows that the lower bound depends on the size of a largest 3‐partite hole (ie, disjoint sets with such that no edge intersects all of ) in the Steiner triple system (Gyárfás previously observed that the upper bound depends on this parameter). Furthermore, we show that this lower bound is tight unless the structure of the Steiner triple system and the coloring of its edges are restricted in a certain way. We also suggest a variety of other Ramsey problems in the setting of Steiner triple systems. 相似文献
129.
Sutherland M Li SY Hawthorn DG Hill RW Ronning F Tanatar MA Paglione J Zhang H Taillefer L DeBenedictis J Liang R Bonn DA Hardy WN 《Physical review letters》2005,94(14):147004
Low-temperature heat transport was used to investigate the ground state of high-purity single crystals of the lightly doped cuprate YBa2Cu3O6.33. Samples were measured with doping concentrations on either side of the superconducting phase boundary. We report the observation of delocalized fermionic excitations at zero energy in the nonsuperconducting state, which shows that the ground state of underdoped cuprates is a thermal metal. Its low-energy spectrum appears to be similar to that of the d-wave superconductor, i.e., nodal. The insulating ground state observed in underdoped La2-xSrxCuO4 is attributed to the competing spin-density-wave order. 相似文献
130.
Loch RA Dubrouil A Sobierajski R Descamps D Fabre B Lidon P van de Kruijs RW Boekhout F Gullikson E Gaudin J Louis E Bijkerk F Mével E Petit S Constant E Mairesse Y 《Optics letters》2011,36(17):3386-3388
We characterize the phase shift induced by reflection on a multilayer mirror in the extreme UV range (80-93?eV) using two techniques: one based on high order harmonic generation and attosecond metrology (reconstruction of attosecond beating by interference of two-photon transitions), and a second based on synchrotron radiation and measurements of standing waves (total electron yield). We find an excellent agreement between the results from the two measurements and a flat group delay shift (±40?as) over the main reflectivity peak of the mirror. 相似文献