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Roger D. Farrant John C. Hollerton Sean M. Lynn Stefano Provera Philip J. Sidebottom Richard J. Upton 《Magnetic resonance in chemistry : MRC》2010,48(10):753-762
We have developed QUANTAS (QUANTification by Artificial Signal), which is a software‐based protocol for concentration measurement by NMR. QUANTAS is an absolute intensity external standard method for quantification by NMR that compensates for various experimental parameters. It is applicable to all nuclei and modern spectrometers. QUANTAS is demonstrated here for 1H and 19F NMR, enabling heteronuclear integrals to be compared. It can be applied using fixed probe tuning, matching and pulse length, for samples with the same effective loading on the probe coil as the appropriate reference spectrum. Otherwise, an optimised tuning and matching approach is adopted for every sample together with explicit PULCON (PUlse Length‐based CONcentration measurements) absolute intensity corrections. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
84.
Sree V. Chintapalli Boon K. Yew Christopher J. R. Illingworth Graham J. G. Upton Philip J. Reeves Kevin E. B. Parkes Christopher R. Snell Christopher A. Reynolds 《Journal of computational chemistry》2010,31(15):2689-2701
Nonoverlapping closed loops of around 25–35 amino acids formed via nonlocal interactions at the loop ends have been proposed as an important unit of protein structure. This hypothesis is significant as such short loops can fold quickly and so would not be bound by the Leventhal paradox, giving insight into the possible nature of the funnel in protein folding. Previously, these closed loops have been identified either by sequence analysis (conservation and autocorrelation) or studies of the geometry of individual proteins. Given the potential significance of the closed loop hypothesis, we have explored a new strategy for determining closed loops from the insertions identified by the structural alignment of proteins sharing the same overall fold. We determined the locations of the closed loops in 37 pairs of proteins and obtained excellent agreement with previously published closed loops. The relevance of NMR structures to closed loop determination is briefly discussed. For cytochrome c, cytochrome b562 and triosephophate isomerase, independent folding units have been determined on the basis of hydrogen exchange experiments and misincorporation proton‐alkyl exchange experiments. The correspondence between these experimentally derived foldons and the theoretically derived closed loops indicates that the closed loop hypothesis may provide a useful framework for analyzing such experimental data. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
85.
Nathan J. Van Zee Veljko Dragojlovic Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(27):7950-7958
Phase‐vanishing reactions utilize a perfluorinated solvent as a liquid membrane to separate a substrate and a reagent. Since their introduction less than ten years ago, phase‐vanishing reactions have become a valuable alternative to reactions that require a slow addition of a reagent. A variety of experimental designs allow reactions to be carried out under anhydrous conditions, under photolytic conditions, under solvent‐free conditions, with a gas as a reagent, and under reflux. 相似文献
86.
Zangmeister CD Robey SW van Zee RD Kushmerick JG Naciri J Yao Y Tour JM Varughese B Xu B Reutt-Robey JE 《The journal of physical chemistry. B》2006,110(34):17138-17144
Photoelectron spectroscopy was used to explore changes in Fermi level alignment, within the pi-pi* gap, arising from modifications to the coupling chemistry of conjugated phenylene ethynylene oligomers to the Au surface. Self-assembled monolayers were formed employing either thiol (4,4'-ethynylphenyl-1-benzenethiol or OPE-T) or isocyanide (4,4'-ethynylphenyl-1-benzeneisocyanide or OPE-NC) coupling. The electronic density of states in the valence region of the two systems are nearly identical with the exception of a shift to higher binding energy by about 0.5 eV for OPE-NC. Corresponding shifts appear in C(1s) spectra and in the threshold near E(F). The lack of change in the optical absorption suggests that a rigid shift of the Fermi level within the pi-pi* gap is the major effect of modifying the coupling chemistry. Qualitative consideration of bonding in each case is used to suggest the influence of chemisorption-induced charge transfer as a potential explanation. Connections to other theoretical and experimental work on the effects of varying coupling chemistries are also discussed. 相似文献
87.
The total syntheses of DAB1 (1) and (-)-lentiginosine (2) were concisely accomplished from D-lyxose via regioselective and diastereoselective NHCbz introduction using CSI, chemoselective removal of the Cbz protection, and ring-closing metathesis as key steps. 相似文献
88.
Attempts to derive the Born rule, either in the Many Worlds or Copenhagen interpretation, are unsatisfactory for systems with only a finite number of degrees of freedom. In the case of Many Worlds this is a serious problem, since its goal is to account for apparent collapse phenomena, including the Born rule for probabilities, assuming only unitary evolution of the wavefunction. For finite number of degrees of freedom, observers on the vast majority of branches would not deduce the Born rule. However, discreteness of the quantum state space, even if extremely tiny, may restore the validity of the usual arguments. 相似文献
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We introduce Higgs democracy in the Yukawa sector by constructing a model with a private Higgs and a dark scalar for each fermion thus addressing the large hierarchy among fermion masses. The model has interesting implications for the LHC, while the Standard Model phenomenology is recovered at low energies. We discuss some phenomenological implications such as FCNC, new Higgses at the TeV scale and dark matter candidates. 相似文献