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31.
L. Semichon M. Flanzy A. Boidin E. Martin A. Wanscheidt O. Ieremejewa Al. Ionescu-Matiu Const Popesco H. S. King A. C. Bell C. Kollo N. Crisan G. Klein H. Linser O. Noetzel F. M. Archibald C. M. Beamer I. M. Korenman L. Palfray S. Sabetay Denise Sontag M. C. Brockmann C. H. Werkman C. Neuberg F. F. Nord C. R. Breden E. I. Fulmer L. Malaprade J. H. Birkinshaw J. H. V. Charles P. W. Clutterbuck C. B. van Niel und K. Száhlender 《Fresenius' Journal of Analytical Chemistry》1934,98(5-6):210-220
Ohne Zusammenfassung 相似文献
32.
Membrane activity of biomimetic facially amphiphilic antibiotics 总被引:1,自引:0,他引:1
Arnt L Rennie JR Linser S Willumeit R Tew GN 《The journal of physical chemistry. B》2006,110(8):3527-3532
Membranes are a central feature of all biological systems, and their ability to control many cellular processes is critically important. As a result, a better understanding of how molecules bind to and select between biological membranes is an active area of research. Antimicrobial host defense peptides are known to be membrane-active and, in many cases, exhibit discrimination between prokaryotic and eukaryotic cells. The design of synthetic molecules that capture the biological activity of these natural peptides has been shown. In this report, the interaction between our biomimetic structures and different biological membranes is reported using both model vesicle and in vitro bacterial cell experiments. Compound 1 induces 12% leakage at 20 microg/mL against phosphatidylglycerol (PG)-phosphatidylethanolamine (PE) vesicles vs only 3% leakage at 200 microg/mL against phosphatidyl-L-serine (PS)-phosphatidylcholine (PC) vesicles. Similarly, a 40% reduction in fluorescence is measured in lipid movement experiments for PG-PE compared to 10% for PS-PC at 600 s. A 30 degrees C increase in the phase transition of stearoyl-oleoyl-phosphatidylserine is observed in the presence of 1. These results show that lipid composition is more important for selectivity than overall net charge. Additionally, the overall concentration of a given lipid is another important factor. An effort is made to connect model vesicle studies with in vitro data and naturally occurring lipid compositions. 相似文献
33.
34.
Proton-detected scalar coupling based assignment strategies in MAS solid-state NMR spectroscopy applied to perdeuterated proteins 总被引:1,自引:0,他引:1
Assignment of proteins in MAS (magic angle spinning) solid-state NMR relies so far on correlations among heteronuclei. This strategy is based on well dispersed resonances in the 15N dimension. In many complex cases like membrane proteins or amyloid fibrils, an additional frequency dimension is desirable in order to spread the amide resonances. We show here that proton detected HNCO, HNCA, and HNCACB type experiments can successfully be implemented in the solid-state. Coherences are sufficiently long lived to allow pulse schemes of a duration greater than 70 ms before incrementation of the first indirect dimension. The achieved resolution is comparable to the resolution obtained in solution-state NMR experiments. We demonstrate the experiments using a triply labeled sample of the SH3 domain of chicken α-spectrin, which was re-crystallized in H2O/D2O using a ratio of 1/9. We employ paramagnetic relaxation enhancement (PRE) using EDTA chelated CuII to enable rapid data acquisition. 相似文献
35.
Avinash S. Bhat Sven M. Elbert Wen‐Shan Zhang Frank Rominger Michael Dieckmann Rasmus R. Schrder Michael Mastalerz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8911-8915
In recent years, interest in shape‐persistent organic cage compounds has steadily increased, not least because dynamic covalent bond formation enables such structures to be made in high to excellent yields. One often used type of dynamic bond formation is the generation of an imine bond from an aldehyde and an amine. Although the reversibility of the imine bond formation is advantageous for high yields, it is disadvantageous for the chemical stability of the compounds. Amide bonds are, in contrast to imine bonds much more robust. Shape‐persistent amide cages have so far been made by irreversible amide bond formations in multiple steps, very often accompanied by low yields. Here, we present an approach to shape‐persistent amide cages by exploiting a high‐yielding reversible cage formation in the first step, and a Pinnick oxidation as a key step to access the amide cages in just three steps. These chemically robust amide cages can be further transformed by bromination or nitration to allow post‐functionalization in high yields. The impact of the substituents on the gas sorption behavior was also investigated. 相似文献
36.
L. Semichon M. Flanzy A. Boidin E. Martin A. Wanscheidt O. Ieremejewa Al. Ionescu-Matiu Const Popesco H. S. King A. C. Bell C. Kollo N. Crisan G. Klein H. Linser O. Noetzel F. M. Archibald C. M. Beamer I. M. Korenman L. Palfray S. Sabetay Denise Sontag M. C. Brockmann C. H. Werkman C. Neuberg F. F. Nord C. R. Breden E. I. Fulmer L. Malaprade J. H. Birkinshaw J. H. V. Charles P. W. Clutterbuck C. B. van Niel K. Száhlender 《Analytical and bioanalytical chemistry》1934,97(5-6):210-220
37.
We have conducted wave packet simulations of excited-state dynamics of 1,3-dibromopropane (DBP) with the aim of reproducing the experimental results of the gas-phase pump-probe experiment by Kotting et al. [ Kotting, C. ; Diau, E. W.-G. ; S?lling, T. I. ; Zewail, A. H. J. Phys. Chem. A 2002, 106, 7530 ]. In the experiment, DBP is excited to a Rydberg state 8 eV above the ground state. The interpretation of the results is that a torsional motion of the bromomethylene groups with a vibrational period of 680 fs is activated upon excitation. The Rydberg state decays to a valence state, causing a dissociation of one of the carbon bromine bonds on a time scale of 2.5 ps. Building the theoretical framework for the wave packet propagation around this model of the reaction dynamics, the simulations reproduce, to a good extent, the time scales observed in the experiment. Furthermore, the simulations provide insight into how the torsion motion influences the bond breakage, and we can conclude that the mechanism that delays the dissociation is solely the electronic transition from the Rydberg state to the valence state and does not involve, for example, intramolecular vibrational energy redistribution (IVR). 相似文献
38.
More than one multi-informative analytical technique is often applied when describing the condition of a set of samples. Often a part of the information found in these data blocks is redundant and can be extracted from more blocks. This study puts forward a method (multiblock variance partitioning—MVP) to compare the information/variation in different data blocks using simple quantitative measures. These measures are the unique part of the variation only found in one data block and the common part that can be found in more data blocks. These different parts are found using PLS models between predictor blocks and a common response. MVP provides a different view on the information in different blocks than normal multiblock analysis. It will be shown that this has many applications in very diverse fields such as process control, assessor performance in sensory analysis, efficiency of preprocessing methods and as complementary information to an interval PLS analysis. Here the ideas of the MVP approach are presented in detail using a study of red wines from different regions measured with GC-MS and FT-IR instruments providing different kinds of data representations. 相似文献
39.
Poulsen RD Jørgensen MR Overgaard J Larsen FK Morgenroth W Graber T Chen YS Iversen BB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9775-9790
Three high-quality single-crystal X-ray diffraction data sets have been measured under very different conditions on a structurally simple, but magnetically complex, coordination polymer, [Mn(HCOO)(2)(H(2)O)(2)](infinity) (1). The first data set is a conventional 100(2) K Mo(Kalpha) data set, the second is a very high resolution 100(2) K data set measured on a second-generation synchrotron source, while the third data set was measured with a tiny crystal on a high brilliance third-generation synchrotron source at 16(2) K. Furthermore, the magnetic susceptibility (chi) and the heat capacity (C(p)) have been measured from 2 to 300 K on pressed powder. The charge density of 1 was determined from multipole modeling of the experimental structure factors, and overall there is good agreement between the densities obtained separately from the three data sets. When considering the fine density features, the two 100 K data sets agree well with each other, but show small differences to the 16 K data set. Comparison with ab initio theory suggests that the 16 K APS data set provides the most accurate density. Topological analysis of the metal-ligand bonding, experimental 3d orbital populations on the Mn atoms, and Bader atomic charges indicate quite ionic, high-spin metal atoms. This picture is supported by the effective moment estimated from the magnetization measurements (5.840(2) mu(B)), but it is at variance with earlier spin density measurements from polarized neutron diffraction. The magnetic ordering originates from superexchange involving covalent interactions with the ligands, and non-ionic effects are observed in the static deformation density maps as well as in plots of the valence shell charge concentrations. Overall, the present study provides a benchmark charge density that can be used in comparison with future metal formate dihydrate charge densities. 相似文献
40.
Balmes O Resta A Wermeille D Felici R Messing ME Deppert K Liu Z Grass ME Bluhm H van Rijn R Frenken JW Westerström R Blomberg S Gustafson J Andersen JN Lundgren E 《Physical chemistry chemical physics : PCCP》2012,14(14):4796-4801
The structure and chemical composition of Pd nanoparticles exposed to pure CO and mixtures of CO and O(2) at elevated temperatures have been studied in situ by a combination of X-ray Diffraction and X-ray Photoelectron Spectroscopy in pressures ranging from ultra high vacuum to 10 mbar and from room temperature to a few hundred degrees celsius. Our investigation shows that under CO exposure, above a certain temperature, carbon dissolves into the Pd particles forming a carbide phase. Upon exposure to CO and O(2) mixtures, the carbide phase forms and disappears reversibly, switching at the stoichiometric ratio for CO oxidation. This finding opens new scenarios for the understanding of catalytic oxidation of C-based molecules. 相似文献