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641.
Two-dimensional (1)H-(13)C INEPT MAS NMR experiments utilizing a (1)H-(1)H magnetization exchange mixing period are presented for characterization of lipid systems. The introduction of the exchange period allows for structural information to be obtained via (1)H-(1)H dipolar couplings but with (13)C chemical shift resolution. It is shown that utilizing a RFDR recoupling sequence with short mixing times in place of the more standard NOE cross-relaxation for magnetization exchange during the mixing period allowed for the identification and separation of close (1)H-(1)H dipolar contacts versus longer-range inter-molecular (1)H-(1)H dipolar cross-relaxation. These 2D INEPT experiments were used to address both intra- and inter-molecular contacts in lipid and lipid/cholesterol mixtures. 相似文献
642.
We report the synthesis, spectroscopy, and structural characterization of iron-alkyne and -alkene complexes of the type L(Me)Fe(ligand) [L(Me) = bulky beta-diketiminate, ligand = HCCPh, EtCCEt, CH2CHPh, EtCHCHEt, HCC(p-C6H4OCH3), HCC(p-C6H4CF3)]. The neutral ligand exchanges rapidly at room temperature, and the equilibrium constants have been measured or estimated. The binding affinity toward the low-coordinate Fe follows the trend HCCPh > EtCCEt > CH2CHPh > EtCHCHEt approximately PPh3 > benzene > N2. This trend is consistent with a model in which pi back-bonding from the formally Fe(I) center is the dominant interaction in determining the relative binding affinities. In nitrogenase, alkynes are reduced while alkenes are unreactive, and this work suggests that the different binding affinities to low-coordinate Fe might explain the differential activity of the enzyme toward these two substrates. 相似文献
643.
Williams JP Patel VJ Holland R Scrivens JH 《Rapid communications in mass spectrometry : RCM》2006,20(9):1447-1456
Three ionisation techniques that require no sample preparation or extraction prior to mass analysis have been used for the rapid analysis of pharmaceutical tablets and ointments. These methods were (i) the novel direct analysis in real time (DART), (ii) desorption electrospray ionisation (DESI), and (iii) desorption atmospheric pressure chemical ionisation (DAPCI). The performance of the three techniques was investigated for a number of common drugs. Significant differences between these approaches were observed. For compounds of moderate to low polarity DAPCI produced more effective ionisation. Accurate DESI and DAPCI tandem mass spectra were obtained and these greatly enhance the selectivity and information content of the experiment. The detection from human skin of the active ingredients from ointments is reported together with the detection of ibuprofen metabolites in human urine. 相似文献
644.
Zoltán Fodor Kieran Holland Julius Kuti Dániel Nógrádi Chris Schroeder Chik Him Wong 《Physics letters. [Part B]》2012
New results are reported from large scale lattice simulations of a frequently discussed strongly interacting gauge theory with a fermion flavor doublet in the two-index symmetric (sextet) representation of the SU(3) color gauge group. We find that the chiral condensate and the mass spectrum of the sextet model are consistent with chiral symmetry breaking in the limit of vanishing fermion mass. In contrast, sextet fermion mass deformations of spectral properties are not consistent with leading conformal scaling behavior near the critical surface of a conformal theory. A recent paper could not resolve the conformal fixed point of the gauge coupling from the slowly walking scenario of a very small nearly vanishing β-function (DeGrand et al. [3]). It is argued that overall consistency with our new results is resolved if the sextet model is close to the conformal window, staying outside with a very small non-vanishing β-function. The model would exhibit then the simplest composite Higgs mechanism leaving open the possibility of a light scalar state with quantum numbers of the Higgs impostor. It would emerge as the pseudo-Goldstone dilaton state from spontaneous symmetry breaking of scale invariance. We will argue that even without association with the dilaton, the scalar Higgs-like state can be light very close to the conformal window. A new Higgs project of sextet lattice simulations is outlined to resolve these important questions. 相似文献
645.