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21.
Claudia R. Herbers Chunli Li Nico F. A. van der Vegt 《Journal of computational chemistry》2013,34(14):1177-1188
A detailed understanding of the adsorption of small molecules or macromolecules to a materials surface is of importance, for example, in the context of material and biomaterial research. Classical atomistic simulations in principle provide microscopic insight in the complex entropic and enthalpic interplay at the interface. However, an application of classical atomistic simulation techniques to such interface systems is a nontrivial problem, mostly because commonly used force fields cannot be straightforwardly applied, as they are usually developed to reproduce bulk properties of either solids or liquids but not the interfacial region between two phases. Therefore, a dual‐scale modeling approach has often been the method of choice in the past, in which the classical force field is parameterized such that quantum chemical information on near‐surface conformations and adsorption energies is reproduced by the classical force field. We will discuss in this review the current state‐of‐the‐art of quantum‐classical modeling of molecule–surface interactions and outline the major challenges in this field. In this context, we will, among other things, lay emphasis on discussing ways to obtain representable force fields and propose systematic and system‐independent strategies to optimize the quantum‐classical fitting procedure. © 2013 Wiley Periodicals, Inc. 相似文献
22.
Natalia Tiessen Dr. Nico Schwarze Mira Keßler Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Berthold Hoge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(43):11041-11044
While alkyl-substituted siloxanes are widely known, virtually nothing is known about perfluoroalkyl siloxanes and their congener species, the silanols and silanolates. We recently reported on the tris(pentafluoroethyl)silanide ion, [Si(C2F5)3]−, which features Lewis amphoteric character deriving from the pentafluoroethyl substituents and their strong electron-withdrawing properties. Transferring this knowledge, we investigated the Lewis amphoteric behavior of the tris(pentafluoroethyl)silanolate, [Si(C2F5)3O]−. In order to examine such Lewis amphoteric behavior, we first developed a strategy for the synthesis of the corresponding silanol Si(C2F5)3OH, which readily condenses at room temperature to the hexakis(pentafluoroethyl)disiloxane, (C2F5)3SiOSi(C2F5)3. Deprotonation of Si(C2F5)3OH employing a sterically demanding phosphazene base allows the characterization of the first example of a dimeric triorganosilanolate: the dianionic hexakis(pentafluoroethyl)disilanolate, [{Si(C2F5)3O}2]2−, implies Lewis amphoteric character of the monomeric [Si(C2F5)3O]− anion. 相似文献
23.
Nico Fleck Caspar A. Heubach Tobias Hett Florian R. Haege Pawel P. Bawol Helmut Baltruschat Olav Schiemann 《Angewandte Chemie (International ed. in English)》2020,59(24):9767-9772
The understanding of biomolecular function is coupled to knowledge about the structure and dynamics of these biomolecules, preferably acquired under native conditions. In this regard, pulsed dipolar EPR spectroscopy (PDS) in conjunction with site‐directed spin labeling (SDSL) is an important method in the toolbox of biophysical chemistry. However, the currently available spin labels have diverse deficiencies for in‐cell applications, for example, low radical stability or long bioconjugation linkers. In this work, a synthesis strategy is introduced for the derivatization of trityl radicals with a maleimide‐functionalized methylene group. The resulting trityl spin label, called SLIM, yields narrow distance distributions, enables highly sensitive distance measurements down to concentrations of 90 nm , and shows high stability against reduction. Using this label, the guanine‐nucleotide dissociation inhibitor (GDI) domain of Yersinia outer protein O (YopO) is shown to change its conformation within eukaryotic cells. 相似文献
24.
25.
Albert J. R. Heck Nico M. M. Nibbering 《Journal of the American Society for Mass Spectrometry》1995,6(1):11-18
The gas phase chemistry of C3H6Br+ cations generated via low energy electron impact on various dibromopropanes has been studied by using Fourier transform ion cyclotron resonance mass spectrometry. Neutral substrate molecules that have been selected to probe the bimolecular reactivity of the C3H6Br+ isomers are ammonia, methylamine, trimethylamine, cis-butene, and 2, 3-dimethyl-2-butene. At least three different isomers are characterized on the basis of their different reactivity toward the various substrate molecules. It is suggested that these isomers have (a) the 2-bromo-2-propyl cation structure, (b) the propylenebromomum ion structure, and (c) the cyclic four-membered trimethylenebromonium ion structure. The 2-bromo-2-propyl cations react predominantely via proton transfer. This reaction is hampered for the propylenebromonium ions, which react mainly as electrophiles or bromanyl cation donors. Cyclic trimethylenebromoruum ions react predominantly via adduct formation, even under low pressure conditions, which implies that tturd body collisions are not the only stabilization mechanism. 相似文献
26.
The bimolecular hydrogen-deuterium exchange behavior of protonated alkyl dipeptides in the gas phase
Erez H. Gur Leo J. de Koning Nico M. M. Nibbering 《Journal of the American Society for Mass Spectrometry》1995,6(6):466-477
As part of an ongoing characterization of the intrinsic chemical properties of peptides, thermal hydrogen-deuterium exchange has been studied for a series of fast-atom-bombardment-generated protonated alkyldipeptides and related model compounds in the reaction with D2O, CH3OD, and ND3 in a Fourier transform ion cyclotron resonance mass spectrometer. Despite the very large basicity difference between the dipeptides and the D2O and CH3OD exchange reagents, efficient exchange of all active hydrogen atoms occurs. From the kinetic data it appears that exchange of the amino, amide, and hydroxyl hydrogens proceeds with different efficiencies, which implies that the proton in thermal protonated dipeptides is immobile. The selectivity of the exchange at the different basic sites is governed by the nature of both the dipeptide and the exchange reagent. The results indicate that reversible proton transfer in the reaction complexes, which effectuates the deuterium incorporation, is assisted by formation of multiple hydrogen bonds between the reagents. Exchange is considered to proceed via the intermediacy of different competing intermediate complexes, each of which specifically leads to deuterium incorporation at different basic sites. The relative stabilization of the competing intermediate complexes can be related to the relative efficiencies of deuterium incorporation at different basic sites in the dipeptide. For all protonated dipeptides studied, the exchange in the reaction with ND3 proceeds with unit efficiency, whereas all active hydrogen atoms are exchanged equally efficiently. Evidently specific multiple hydrogen bond formations are far less important in the reversible proton transfers with the relatively basic ammonia, which allows effective randomization of all active hydrogen atoms in the reaction complexes. 相似文献
27.
28.
Beulah E. McKenzie Simon J. Holder Nico A.J.M. Sommerdijk 《Current Opinion in Colloid & Interface Science》2012,17(6):343-349
The self-assembly behaviour of block copolymers in solution has been of significant interest over the past two decades for a number of applications — for example, as delivery vectors and micro-reactors. More recently, attention has turned to the formation of aggregates with complex internal structure, such as multi-compartment micelles and the so-called “Janus” particles (biphasic aggregates) for their promising application as vectors for the simultaneous inclusion of chemically-different encapsulates and their possible catalytic and templating properties. The challenge has been to observe these complex aggregates in such a way as to be able to characterise their internal morphology whilst preserving their intricate structure. To this end, cryogenic transmission electron microscopy (cryoTEM) has become a powerful and indeed a necessary tool for the elucidation and observation of self-assembled polymer systems. Through its use, a new class of complex micelles has been discovered: amphiphilic block copolymer nanospheres with internal bicontinuous structure. These structures have been observed from a variety of block copolymer amphiphiles, although rarely. Intriguingly, there is no seemingly obvious unifying blueprint for their formation. This review will present the importance of cryoTEM in the elucidation and characterisation of internally-structured polymeric aggregates in recent years and highlight its significance in the definition of bicontinuous dispersions. 相似文献
29.
Integral representations are considered of solutions of the Airy differential equation w
–zw=0 for computing Airy functions for complex values of z. In a first method contour integral representations of the Airy functions are written as non-oscillating integrals for obtaining stable representations, which are evaluated by the trapezoidal rule. In a second method an integral representation is evaluated by using generalized Gauss–Laguerre quadrature; this approach provides a fast method for computing Airy functions to a predetermined accuracy. Comparisons are made with well-known algorithms of Amos, designed for computing Bessel functions of complex argument. Several discrepancies with Amos' code are detected, and it is pointed out for which regions of the complex plane Amos' code is less accurate than the quadrature algorithms. Hints are given in order to build reliable software for complex Airy functions. 相似文献
30.
Improved contrast to tissue ratio at higher harmonics 总被引:4,自引:0,他引:4
The challenge in ultrasound contrast imaging is a better discrimination between the perfused tissue and the contrast bubbles, which is usually expressed by contrast to tissue ratio (CTR). Imaging based on the second harmonic frequency showed a higher CTR than imaging at the fundamental frequency. However, because of nonlinear propagation of ultrasound waves, harmonic frequencies are generated. These harmonic frequencies will be linearly reflected by the tissue and therefore limit the CTR at the second harmonic frequency. In order to reduce the scattering of tissue at harmonic frequencies and by that increase the CTR, nonlinear distortion has to be reduced. We demonstrate in this study that the CTR increases with the harmonic number. The increase is substantial when transmitting at lower frequencies. To take advantage of the higher harmonics (third, fourth, fifth and the ultraharmonics and termed here super harmonics), we have developed a new phased array transducer with a wide frequency band. In-vitro measurements using the new probe show an increase of 40 dB of the CTR for super harmonic components over the conventional second harmonic system. The increase in CTR is in agreement with the calculations using existing models for the response of encapsulated bubbles and known theory of nonlinear propagation. 相似文献