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101.
Hydrosilylation is an important process, not only in the silicon industry to produce silicon polymers, but also in fine chemistry. In this review, the development of rhenium-based catalysts for the hydrosilylation of unsaturated bonds in carbonyl-, cyano-, nitro-, carboxylic acid derivatives and alkenes is summarized. Mechanisms of rhenium-catalyzed hydrosilylation are discussed. 相似文献
102.
The rheology of F-actin networks has attracted a great attention during the last years. In order to gain a complete understanding of the rheological properties of these novel materials, it is necessary the study in a large deformations regime to alter their internal structure. In this sense, Schmoller et al. (2010) showed that the reconstituted networks of F-actin crosslinked with α-actinin unexpectedly harden when they are subjected to a cyclical shear. This observation contradicts the expected Mullins effect observed in most soft materials, such as rubber and living tissues, where a pronounced softening is observed when they are cyclically deformed.We think that the key to understand this stunning effect is the gelation process. To define it, the most relevant constituents are the chemical crosslinks – α-actinin –, the physical crosslinks – introduced by the entanglement of the semiflexible network – and the interaction between them. As a consequence of this interaction, a pre-stressed network emerges and introduces a feedback effect, where the pre-stress also regulates the adhesion energy of the α-actinin, setting the structure in a metastable reference configuration. Therefore, the external loads and the evolvement of the trapped stress drive the microstructural changes during the cyclic loading protocol. In this work, we propose a micromechanical model into the framework of nonlinear continuum mechanics. The mechanics of the F-actin filaments is modelled using the wormlike chain model for semiflexible filaments and the gelation process is modelled as mesoscale dynamics for the α-actinin and physical crosslink. The model has been validated with reported experimental results. 相似文献
103.
Chlorophyll‐Derived Yellow Phyllobilins of Higher Plants as Medium‐Responsive Chiral Photoswitches 下载免费PDF全文
Dr. Chengjie Li Dr. Klaus Wurst Dr. Steffen Jockusch Prof. Karl Gruber Dr. Maren Podewitz Prof. Klaus R. Liedl Prof. Bernhard Kräutler 《Angewandte Chemie (International ed. in English)》2016,55(51):15760-15765
The fall colors are signs of chlorophyll breakdown, the biological process in plants that generates phyllobilins. Most of the abundant natural phyllobilins are colorless, but yellow phyllobilins (phylloxanthobilins) also occur in fall leaves. As shown here, phylloxanthobilins are unique four‐stage photoswitches. Which switching mode is turned on is controlled by the molecular environment. In polar media, phylloxanthobilins are monomeric and undergo photoreversible Z/E isomerization, similar to that observed for bilirubin. Unlike bilirubin, however, the phylloxanthobilin Z isomers photodimerize in apolar solvents by regio‐ and stereospecific thermoreversible [2+2] cycloadditions from self‐assembled hydrogen‐bonded dimers. X‐ray analysis revealed the first stereostructure of a phylloxanthobilin and its hydrogen‐bonded self‐templating architecture, helping to rationalize its exceptional photoswitch features. The chemical behavior of phylloxanthobilins will play a seminal role in identifying biological roles of phyllobilins. 相似文献
104.
Weak Intermolecular Hydrogen Bonds with Fluorine: Detection and Implications for Enzymatic/Chemical Reactions,Chemical Properties,and Ligand/Protein Fluorine NMR Screening 下载免费PDF全文
Dr. Claudio Dalvit Dr. Anna Vulpetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(22):7592-7601
It is known that strong hydrogen‐bonding interactions play an important role in many chemical and biological systems. However, weak or very weak hydrogen bonds, which are often difficult to detect and characterize, may also be relevant in many recognition and reaction processes. Fluorine serving as a hydrogen‐bond acceptor has been the subject of many controversial discussions and there are different opinions about it. It now appears that there is compelling experimental evidence for the involvement of fluorine in weak intramolecular or intermolecular hydrogen bonds. Using established NMR methods, we have previously characterized and measured the strengths of intermolecular hydrogen‐bond complexes involving the fluorine moieties CH2F, CHF2, and CF3, and have compared them with the well‐known hydrogen‐bond complex formed between acetophenone and the strong hydrogen‐bond donor p‐fluorophenol. We now report evidence for the formation of hydrogen bonds involving fluorine with significantly weaker donors, namely 5‐fluoroindole and water. A simple NMR method is proposed for the simultaneous measurement of the strengths of hydrogen bonds between an acceptor and a donor or water. Important implications of these results for enzymatic/chemical reactions involving fluorine, for chemical and physical properties, and for ligand/protein 19F NMR screening are analyzed through experiments and theoretical simulations. 相似文献
105.
New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers 下载免费PDF全文
Prof. Dr. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):6988-7001
The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed. 相似文献
106.
Dawid Lichosyt Dr. Paweł Dydio Prof. Janusz Jurczak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17673-17680
Herein we report the synthesis and detailed studies of the anion‐binding properties of two 20‐membered macrocyclic tetramide receptors: one symmetrical, containing two identical azulene‐based bisamide units, the other a hybrid, containing a dipicolinic bisamide unit and an azulene‐based bisamide unit. Analysis of the crystal structures of the macrocyclic receptors revealed their preference for adopting similar well‐preorganized bent‐sheet conformations, both as free receptors and in their complexes with anions. Studies of the optical properties of both receptors revealed abilities to selectively sense phosphate anions (H2PO4?, HP2O73?), allowing for naked‐eye detection of the presence of these guests in DMSO. Binding studies in solution confirmed that the receptors bind strongly to a series of anions even in highly demanding media, such as mixtures of DMSO with water or with methanol. Comparison of the anion affinity of linear analogues with that of the macrocyclic receptors evidenced the importance of macrocyclic topology. Quantitative analysis revealed that the macrocyclic receptors are selective for H2PO4? over other anions. The affinity to H2PO4? seen for the symmetrical receptor, containing two azulene‐based subunits, is much higher than for the hybrid macrocycle containing both the azulene‐based and pyridine‐derived subunits. This highlights that the azulene‐based building block serves efficiently as both a binding site and a structure‐preorganizing motif. 相似文献
107.
108.
Cover Picture: Alcohol Dimer is Requisite to Form an Alkyl Oxonium Ion in the Proton Transfer of a Strong (Photo)Acid to Alcohol (Chem. Eur. J. 13/2016) 下载免费PDF全文
109.
Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations 下载免费PDF全文
Dr. Naresh K. Jena Ida Josefsson Dr. Susanna K. Eriksson Prof. Anders Hagfeldt Prof. Hans Siegbahn Prof. Olle Björneholm Prof. Håkan Rensmo Dr. Michael Odelius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):4049-4055
Ab initio molecular dynamics (MD) simulations of the solvation of LiI3 in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I3? ion in relation to X‐ray photoelectron spectroscopy (XPS). Simulations show that hydrogen‐bond rearrangement in the solvation shell is coupled to intramolecular bond‐length asymmetry in the I3? ion. By a combination of charge analysis and I 4 d core‐level XPS measurements, the mechanism of the solvent‐induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent‐dependent structure of the I3? ion, and the geometric structure has been correlated with the electronic structure. 相似文献
110.
Experimental and Computational Studies of the Molybdenum‐Flanking Arene Interaction in Quadruply Bonded Dimolybdenum Complexes with Terphenyl Ligands 下载免费PDF全文
Dr. Mario Carrasco Irene Mendoza Dr. Eleuterio Álvarez Dr. Abdessamad Grirrane Dr. Celia Maya Dr. Riccardo Peloso Dr. Amor Rodríguez Andrés Falceto Prof. Dr. Santiago Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):410-421
To clarify the nature of the Mo?Carene interaction in terphenyl complexes with quadruple Mo?Mo bonds, ether adducts of composition [Mo2(Ar′)(I)(O2CR)2(OEt2)] have been prepared and characterized (Ar′=ArXyl2, R=Me; Ar′=ArMes2, R=Me; Ar′=ArXyl2, R=CF3) (Mes=mesityl; Xyl=2,6‐Me2C6H3, from now on xylyl) and their reactivity toward different neutral Lewis bases investigated. PMe3, P(OMe)3 and PiPr3 were chosen as P‐donors and the reactivity studies complemented with the use of the C‐donors CNXyl and CN2C2Me4 (1,3,4,5‐tetramethylimidazol‐2‐ylidene). New compounds of general formula [Mo2(Ar′)(I)(O2CR)2( L )] were obtained, except for the imidazol‐2‐ylidene ligand that yielded a salt‐like compound of composition [Mo2(ArXyl2)(O2CMe)2(CN2C2Me4)2]I. The Mo?Carene interaction in these complexes has been analyzed with the aid of X‐ray data and computational studies. This interaction compensates the coordinative and electronic unsaturation of one of the Mo atoms in the above complexes, but it seems to be weak in terms of sharing of electron density between the Mo and Carene atoms and appears to have no appreciable effect in the length of the Mo?Mo, Mo?X, and Mo? L bonds present in these molecules. 相似文献