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81.
Ing. Günter Seidel Barbara Gabor Dr. Richard Goddard Dipl.‐Ing. Berit Heggen Prof. Walter Thiel Prof. Alois Fürstner 《Angewandte Chemie (International ed. in English)》2014,53(3):879-882
Carbophilic catalysts that are based on AuI allow a host of different nucleophiles to be added across various π systems. 1 – 3 Although many of these reactions are thought to proceed via gold carbenoids, the challenge to observe and characterize these putative intermediates has basically been unmet. 4 The current mechanistic interpretation therefore largely relies on indirect evidence and computational data, some of which are subject to debate. 5 In an attempt to fill this gap, we pursued a potential route to gold carbenoids by formal transmetalation of chromium or tungsten Fischer carbene complexes with [LAu]+. Whereas this transformation proceeds with exceptional ease as long as a stabilizing heteroelement is present on the carbene center, it stops half‐way in its absence. Rather unusual bimetallic arrays are formed, which allow the charge density to delocalize over several positions. The obvious difficulty of releasing an “unstabilized” gold carbenoid has potential mechanistic implications for the understanding of π‐acid catalysis in general. 相似文献
82.
Ruthenium‐Catalyzed Reductive Methylation of Imines Using Carbon Dioxide and Molecular Hydrogen 下载免费PDF全文
Dr. Kassem Beydoun Ghazi Ghattas Katharina Thenert Prof. Dr. Jürgen Klankermayer Prof. Dr. Walter Leitner 《Angewandte Chemie (International ed. in English)》2014,53(41):11010-11014
The use of the well‐defined [Ru(triphos)(tmm)] catalyst, CO2 as C1 source, and H2 as reducing agent enabled the reductive methylation of isolated imines, as well as the direct coupling of amines with aldehydes and the subsequent reductive methylation of the in situ formed imines. The method, which afforded the corresponding N‐methyl amines in very good to excellent yields, was also used for the preparation of the antifungal agent butenafine in one step with no apparent waste, thus increasing the atom efficiency of its synthesis. 相似文献
83.
Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein 下载免费PDF全文
Dr. Qiangqiang Zhang Prof. Xuebo Chen Dr. Ganglong Cui Prof. Wei‐Hai Fang Prof. Dr. Walter Thiel 《Angewandte Chemie (International ed. in English)》2014,53(33):8649-8653
Fluorescence emission of wild‐type green fluorescent protein (GFP) is lost in the S65T mutant, but partly recovered in the S65T/H148D double mutant. These experimental findings are rationalized by a combined quantum mechanics/molecular mechanics (QM/MM) study at the QM(CASPT2//CASSCF)/AMBER level. A barrierless excited‐state proton transfer, which is exclusively driven by the Asp148 residue introduced in the double mutant, is responsible for the ultrafast formation of the anionic fluorescent state, which can be deactivated through a concerted asynchronous hula‐twist photoisomerization. This causes the lower fluorescence quantum yield in S65T/H148D compared to wild‐type GFP. Hydrogen out‐of‐plane motion plays an important role in the deactivation of the S65T/H148D fluorescent state. 相似文献
84.
Salt,Shake, Fuse—Giant Hybrid Polymer/Lipid Vesicles through Mechanically Activated Fusion 下载免费PDF全文
Ian M. Henderson Walter F. Paxton 《Angewandte Chemie (International ed. in English)》2014,53(13):3372-3376
Large (200 nm) poly(ethylene oxide)‐b‐poly(butadiene) polymer vesicles fuse into giant (>1 μm) vesicles with mild agitation in dilute aqueous NaCl solutions. This unusual effect is attributed to the salt‐induced contraction of the poly(ethylene oxide) corona, reducing steric resistance between vesicles and, with agitation, increasing the probability of contact between the hydrophobic cores of adjacent membranes. In addition, NaCl and agitation facilitated the creation of giant hybrid vesicles from much smaller homogeneous polymersomes and liposomes. Whereas lipid vesicles do not readily fuse with each other under the same circumstances, they did fuse with polymersomes to produce hybrid polymer/lipid vesicles. 相似文献
85.
Niels De Meirleir Linda Pellens Walter Broeckx Guy van Assche Wim De Malsche 《Colloid and polymer science》2014,292(10):2539-2547
The present study focuses on the rheological performance of a surfactant-rich aqueous suspension containing hydrogenated castor oil (HCO) crystals. HCO can be typically crystallized in five distinct shapes: spherically shaped, irregularly shaped, star-shaped (also called rosettes), short needles, and thick or thin fibers. The effect of the differences in shape on the rheological performance is studied, and the rheological properties are compared to the behavior of other triacylglycerol’s (TAG) suspensions. A suspension of TAG crystals usually behaves as a colloidal gel wherein a colloidal gel is defined as a network of flocs, with each floc being an aggregate of smaller subunits. All of these surfactant-rich aqueous suspensions of HCO crystals behaved according to a colloidal gel in the transient regime, independent of the studied crystal shapes, except the long thin fibers at a concentration above 0.1 wt% HCO transitioning from a heterogeneous fractal rod network to a homogeneous rod network, shifting from a colloidal gel to a glass. 相似文献
86.
Fortunati Alessandro Bacigalupo Andrea Lepidi Marco Arena Andrea Lacarbonara Walter 《Nonlinear dynamics》2022,108(2):765-787
Nonlinear Dynamics - The cellular microstructure of periodic architected materials can be enriched by local intracellular mechanisms providing innovative distributed functionalities. Specifically,... 相似文献
87.
J. Walter C. Hartmann J. H. Maddocks 《The European physical journal. Special topics》2011,200(1):153-181
The most classic approach to the dynamics of an n-dimensional mechanical system constrained by d independent holonomic constraints is to pick explicitly a new set of (n − d) curvilinear coordinatesparametrizingthe manifold of configurations satisfying the constraints, and to compute the Lagrangian
generating the unconstrained dynamics in these (n − d) configuration coordinates. Starting from this Lagrangian an unconstrained Hamiltonian H(q,p) on 2(n−d) dimensional phase space can then typically be defined in the standard way via a Legendre transform. Furthermore, if the
system is in contact with a heat bath, the associated Langevin and Fokker-Planck equations can be introduced. Provided that
an appropriate fluctuation-dissipation condition is satisfied, there will be a canonical equilibrium distribution of the Gibbs
form exp(−βH) with respect to the flat measure dqdp in these 2(n − d) dimensional curvilinear phase space coordinates. The existence of (n − d) coordinates satisfying the constraints is often guaranteed locally by an implicit function theorem. Nevertheless in many
examples these coordinates cannot be constructed in any tractable form, even locally, so that other approaches are of interest.
In ambient space formulations the dynamics are defined in the full original n-dimensional configuration space, and associated 2n-dimensional phase space, with some version of Lagrange multipliers introduced so that the 2(n − d) dimensional sub-manifold of phase space implied by the holonomic constraints and their time derivative, is invariant under
the dynamics. In this article we review ambient space formulations, and explain that for constrained dynamics there is in
fact considerable freedom in how a Hamiltonian form of the dynamics can be constructed. We then discuss and contrast the Langevin
and Fokker-Planck equations and their equilibrium distributions for the different forms of ambient space dynamics. 相似文献
88.
Nathalie Guarnizo Diego Oliveros Walter Murillo-Arango María Bianney Bermúdez-Cardona 《Molecules (Basel, Switzerland)》2020,25(24)
Plants have innate immune systems or defense mechanisms that respond to the attack of pathogenic microorganisms. Unlike mammals, they lack mobile defense cells, so defense processes depend on autonomous cellular events with a broad repertoire of recognition to detect pathogens, which compensates for the lack of an adaptive immune system. These defense mechanisms remain inactive or latent until they are activated after exposure or contact with inducing agents, or after the application of the inductor; they remain inactive only until they are affected by a pathogen or challenged by an elicitor from the same. Resistance induction represents a focus of interest, as it promotes the activation of plant defense mechanisms, reducing the use of chemical synthesis pesticides, an alternative that has even led to the generation of new commercial products with high efficiency, stability and lower environmental impact, which increase productivity by reducing not only losses but also increasing plant growth. Considering the above, the objective of this review is to address the issue of resistance induction with a focus on the potential of the use of oligosaccharides in agriculture, how they are recognized by plants, how they can be used for commercial products and perspectives. 相似文献
89.
Dr. Damien Hudry Dr. Christos Apostolidis Dr. Olaf Walter Dr. Arne Janßen Dr. Dario Manara Dr. Jean‐Christophe Griveau Dr. Eric Colineau Dr. Tonya Vitova Tim Prüßmann Dr. Di Wang Dr. Christian Kübel Dr. Daniel Meyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10431-10438
Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non‐conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium‐based nanomaterials. Here we show that ultra‐small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2(NO3)2] ? 3 H2O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption fine structure (XAFS), X‐ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. 相似文献
90.
Fused Perylene–Phthalocyanine Macrocycles: A New Family of NIR‐Dyes with Pronounced Basicity 下载免费PDF全文
Jörg Schönamsgruber Dr. Harald Maid Prof. Dr. Walter Bauer Prof. Dr. Andreas Hirsch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16969-16979
The synthesis and characterization of a new type of chromophore, namely PePc consisting of a central phthalocyanine core and four fused perylene–bisimide (PBI) units is described for the first time. The entire architecture represents a highly extended conjugated heterocyclic π‐system with C4h symmetry. In order to guarantee pronounced solubility in organic solvents the corresponding PBI units were bay‐functionalized with tert‐butylphenoxy substituents. Next to the metal‐free macrocycle, PePcH2, also metallated macrocycles PePcM (M=Zn, Ni, Pb, Ru, Fe) were synthesized. The extensive fusion of the corresponding aromatic building blocks to the very large extended π‐system leads to a very narrow HOMO–LUMO gap and as a consequence to transparency in the visible but light absorption in the NIR region. Significantly, the azomethine N‐atoms N1?N4 of PePcM and PePcH2 are highly basic. The corresponding tetraprotonated systems can only be deprotonated with very strong non‐nucleophilic bases such as phosphazene bases. In the protonated forms PePcMH44+ and PePcMH64+ the absorption maximum is shifted back to the visible region due to the loss of conjugation. The experimental findings were corroborated with quantum mechanical calculations. 相似文献