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101.
Dipl.‐Chem. Sascha A. Erhardt Dr. Florian Hoffmann Dr. Jürgen O. Daiß Dr. Jürgen Stohrer Dr. Eberhardt Herdtweck Prof. Dr. Bernhard Rieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(15):4818-4825
(Acetoxymethyl)silanes 2 , 7 a – c , and 10 a – c with at least one alkoxy group, of the general formula (AcOCH2)Si(OR)3?n(CH3)n (R: Me, Et, iPr; n=0, 1, 2), were synthesized from the corresponding (chloromethyl)silanes 1 , 6 a – c , and 9 a – c by treatment with potassium acetate under phase‐transfer‐catalysis conditions. These compounds were found to provide 2,2,5,5‐organo‐substituted 1,4‐dioxa‐2,5‐disilacyclohexanes 3 , 8 a – c , and 11 a – c if treated with organotin(IV) catalysts such as dioctyltin oxide. The reaction proceeds through transesterification of the acetoxy and alkoxy units followed by ring‐closure to form a dimeric six‐membered ring. The corresponding alkyl acetates are formed as the reaction by‐products. With these mild conditions, the method overcomes the drawbacks of previously reported synthetic routes to furnish 2,2,5,5‐tetramethyl‐1,4‐dioxa‐2,5‐disilacyclohexane ( 3 ) and even allows the synthesis of 1,4‐dioxa‐2,5‐disilacyclohexanes bearing hydrolytically labile alkoxy substituents at the silicon atom in good yields and high purity. These new materials were fully characterized by NMR spectroscopy, elemental analysis, mass spectrometry, and X‐ray analysis (trans‐ 8 a ). 相似文献
102.
Qiuqin Zhou Florian Grundmann Marcel Kaiser Matthias Schiell Dr. Sophie Gaudriault Dr. Andreas Batzer Dr. Michael Kurz Prof. Dr. Helge B. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16772-16779
During the search for novel natural products from entomopathogenic Xenorhabdus doucetiae DSM17909 and X. mauleonii DSM17908 novel peptides named xenoamicins were identified in addition to the already known antibiotics xenocoumacin and xenorhabdin. Xenoamicins are acylated tridecadepsipeptides consisting of mainly hydrophobic amino acids. The main derivative xenoamicin A ( 1 ) was isolated from X. mauleonii DSM17908, and its structure elucidated by detailed 1 D and 2 D NMR experiments. Detailed MS experiments, also in combination with labeling experiments, confirmed the determined structure and allowed structure elucidation of additional derivatives. Moreover, the xenoamicin biosynthesis gene cluster was identified and analyzed in X. doucetiae DSM17909, and its participation in xenoamicin biosynthesis was confirmed by mutagenesis. Advanced Marfey’s analysis of 1 showed that the absolute configuration of the amino acids is in agreement with the predicted stereochemistry deduced from the nonribosomal peptide synthetase XabABCD. Biological testing revealed activity of 1 against Plasmodium falciparum and other neglected tropical diseases but no antibacterial activity. 相似文献
103.
104.
Functional molecular nanoarchitectures (FMNs) are highly relevant for the development of future nanotechnology devices. Profound knowledge about the atomically controlled construction of such nanoscale assemblies is an indispensable requirement to render the implementation of such components into a real product successful. For exploiting their full potential the architectures’ functionalities have to be characterized in detail including the ways to tailor them. In recent years a plethora of sophisticated constructs were fabricated touching a wide range of research topics. 相似文献
105.
Michael Langeloth Taisuke Sugii Michael C. Böhm Florian Müller-Plathe 《Soft Materials》2014,12(4):S71-S79
Mesoscale molecular dynamics simulations are performed to analyze the curing process of an epoxy resin with polyfunctional amines on a generic surface. The coarse grained potentials were derived from all-atomistic molecular dynamics simulations using iterative Boltzmann inversion. The reactive scheme incorporates cross-linking between an epoxy resin and an amine, as well as amine adsorption on the surface. The structure of the cured network is examined and compared with equilibrium properties of the uncured system. Special attention has been paid on the implications of the surface that is believed to play a crucial role in the performance of epoxy systems. 相似文献
106.
Peter Fechner Oliver Bleher Melanie Ewald Kathrin Freudenberger Dominik Furin Urs Hilbig Felix Kolarov Katrin Krieg Lothar Leidner Goran Markovic Günther Proll Florian Pröll Sabrina Rau Johannes Riedt Barbara Schwarz Patricia Weber Julia Widmaier 《Analytical and bioanalytical chemistry》2014,406(17):4033-4051
This review is focused on methods for detecting small molecules and, in particular, the characterisation of their interaction with natural proteins (e.g. receptors, ion channels). Because there are intrinsic advantages to using label-free methods over labelled methods (e.g. fluorescence, radioactivity), this review only covers label-free techniques. We briefly discuss available techniques and their advantages and disadvantages, especially as related to investigating the interaction between small molecules and proteins. The reviewed techniques include well-known and widely used standard analytical methods (e.g. HPLC-MS, NMR, calorimetry, and X-ray diffraction), newer and more specialised analytical methods (e.g. biosensors), biological systems (e.g. cell lines and animal models), and in-silico approaches. 相似文献
107.
Mohammad Vatankhah‐Varnoosfaderani Amin GhavamiNejad Saud Hashmi Florian J. Stadler 《Macromolecular rapid communications》2015,36(5):447-452
Copolymers of N‐isopropylacrylamide (NIPAM) and dopamine methacrylate can establish a reversible, self‐healing 3D network in aprotic solvents based on hydrogen bonding. The reactivity and hydrogen bonding formation of catechol groups in copolymer chains are studied by UV–vis and 1H NMR spectroscopy, while reversibility from sol to gel and inverse as well as self‐healing properties are tested rheologically. The produced reversible organogel can self‐encapsulate physically interacting or chemically bonded solutes such as drugs due to thermosensitivity of the used copolymer. This system offers dual‐targeted and controlled drug delivery and release—by slowing down release kinetics by supramolecular bonding of the drug and by reducing diffusion rates due to modulus increase.
108.
Florian E. Golling Amelie H. R. Koch George Fytas Klaus Müllen 《Macromolecular rapid communications》2015,36(10):898-902
3,6‐Connected cyclohexadienes as precursors for polyphenylenes are synthesized and characterized by mass spectrometry and NMR spectroscopy. Pure fractions of trimers, hexamers, and nonamers are collected after separation of the product mixture by recycling GPC. The anticipated formation of rigid linear structures, due to the trans‐configuration of the monomeric units, is supported by density functional theory and experimentally confirmed by dynamic light scattering from dilute solution at low scattering angles. The obtained translational diffusion coefficients are represented by rigid rod‐like or prolate ellipsoid‐like molecular shapes. The measurements of diffusion coefficients reveal a length‐dependent ratio of 1:2:3 between the three oligomers, which directly correlates to the expected length extension from trimer to nonamer.
109.
Friction influences metal forming processes both in economic and technical terms. A precise understanding of friction is inevitable as friction restricts the potential of the product design. Friction depends on the occurring contact loads which is especially true for sheet-bulk metal forming (SBMF) as the incorporated contact loads appear in a very broad range. Numerical simulations, which are verified experimentally, are carried out to analyse contact interactions which typically appear in SBMF. On the one hand the multi-scale character of rough surfaces requires a very fine resolution of the contact area, on the other hand a large contact area is necessary to be representative. A half-space model is chosen for the contact analysis, because it only depends on the two-dimensional surface boundary which consumes less computing capacity than the finite element method (FEM) with its three-dimensional volume approach for the same surface resolution and area. The outcome is a constitutive friction law (CFL) consisting of two equations. The law is implemented into the framework of FEM to see the impact in a typical SBMF-process which aims to form metal sheet into cups with integrated gearing teeth. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
110.
This contribution presents the characterisation of an incompressible carbon black-filled elastomer as one characteristical example for highly filled rubber. It shows a strongly pronounced non-linear viscoelastic behaviour and the most important characteristic is the extremely long relaxation time which has to be taken into account. The material model is developed with respect to uniaxial tension data. The basis in the development of a phenomenological model is given by the basic elasticity. For this evaluation the long term relaxation behaviour results in a complex experimental procedure. Therefore, special attention has to be paid according to an optimised experimental process in order to get the necessary reference data in an adequate and reproduceable way [1]. With this model basis further investigations are taken into account concerning the time-dependent viscoelasticity. Therefore, cyclic deformations from zero up to a maximum of deformation are considered for different strain rates. Furthermore, the relaxation behaviour is investigated for multiple strain levels. The phenomena which are observed in the experimental results yield in a purely viscoelastic model, based on a rheological analogous model consisting of an equilibrium spring and several Maxwell-elements which contain nonlinear relations for the relaxation times of the dashpot elements [1,2]. The material model's numerical realisation is accomplished in two ways. Because of its numerical simplicity especially according to the parameter identification the model is restricted only to the simple case of uniaxial tension. A second, alternative implementation is executed providing the benefit that more complex deformation conditions can also be taken into account. Therefore, the general, three-dimensional finite model is implemented in an open-source Finite Element library [3]. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献