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61.
62.
J. A. Muller C. Reinhardt C. Fischbach A. Siebenschub V. Stanek N. M. Randall K. Bogoluboff H. Wdowiszewski F. Garrat D. J. Demorest J. R. Cain H. E. Walters F. C. T. Daniels A. J. Field A. Terni P. Malaguti B. S. Evans L. W. Winkler O. L. Barnebey G. L. Kelley J. A. Wiley E. Little J. Costa M. Gröger H. O. Ward P. Slawik W. Hild und F. Simion 《Fresenius' Journal of Analytical Chemistry》1923,63(9):348-359
Ohne Zusammenfassung 相似文献
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A cyclic evolution of a pure quantum state is characterized by a closed curve γ in the projective Hilbert space
, equipped with the Fubini-Study geometry. It is known that the geometric phase
for this evolution is given by the integral of the symplectic form of the Fubini-Study geometry over an arbitrary surface spanning γ. This result extends to an infinite-dimensional Hilbert space for a bosonic quantum field. We prove that
is bounded above by the infimum area over all surfaces spanning γ, and that the bound is attained if γ can be spanned by a holomorphic curve. Using an earlier result concerning the intrinsic Euclidean geometry of the coherent state submanifold
, we derive an expression for the geometric phase for a cyclic evolution amongst coherent states. We indicate how the intensity of a classical configuration can be inferred from the winding number of the exponential geometric phase about the origin in the complex plane. In the case of photon states we present group theoretic and 2-component spinor representations of
. We derive an expression for
in the case of a sequence of measurements such that the resulting states are coherent at each step, in terms of a sequence of projection operators. The situation in relation to some earlier experiments of Pancharatnam and Tomita–Chiao is explained. 相似文献
65.
Harrison JA Kartha KP Fournier EJ Lowary TL Malet C Nilsson UJ Hindsgaul O Schenkman S Naismith JH Field RA 《Organic & biomolecular chemistry》2011,9(5):1653-1660
Systematically modified octyl galactosides and octyl N-acetyllactosamines were assessed as inhibitors of, and substrates for, T. cruzi trans-sialidase (TcTS) in the context of exploring its acceptor substrate binding site. These studies show that TcTS, which catalyses the α-(2→3)-sialylation of non-reducing terminal β-galactose residues, is largely intolerant of substitution of the galactose 2 and 4 positions whereas substitution of the galactose 6 position is well tolerated. Further studies show that even the addition of a bulky sugar residue (glucose, galactose) does not impact negatively on TcTS binding and turnover, which highlights the potential of 'internal' 6-substituted galactose residues to serve as TcTS acceptor substrates. Results from screening a 93-membered thiogalactoside library highlight a number of structural features (notably imidazoles and indoles) that are worthy of further investigation in the context of TcTS inhibitor development. 相似文献
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Merer AJ Steeves AH Baraban JH Bechtel HA Field RW 《The Journal of chemical physics》2011,134(24):244310
A systematic analysis of the S(1)-trans (A?(1)A(u)) state of acetylene, using IR-UV double resonance along with one-photon fluorescence excitation spectra, has allowed assignment of at least part of every single vibrational state or polyad up to a vibrational energy of 4200 cm(-1). Four observed vibrational levels remain unassigned, for which no place can be found in the level structure of the trans-well. The most prominent of these lies at 46?175 cm(-1). Its (13)C isotope shift, exceptionally long radiative lifetime, unexpected rotational selection rules, and lack of significant Zeeman effect, combined with the fact that no other singlet electronic states are expected at this energy, indicate that it is a vibrational level of the S(1)-cis isomer (A?(1)A(2)). Guided by ab initio calculations [J. H. Baraban, A. R. Beck, A. H. Steeves, J. F. Stanton, and R. W. Field, J. Chem. Phys. 134, 244311 (2011)] of the cis-well vibrational frequencies, the vibrational assignments of these four levels can be established from their vibrational symmetries together with the (13)C isotope shift of the 46?175 cm(-1) level (assigned here as cis-3(1)6(1)). The S(1)-cis zero-point level is deduced to lie near 44?900 cm(-1), and the ν(6) vibrational frequency of the S(1)-cis well is found to be roughly 565 cm(-1); these values are in remarkably good agreement with the results of recent ab initio calculations. The 46?175 cm(-1) vibrational level is found to have a 3.9 cm(-1) staggering of its K-rotational structure as a result of quantum mechanical tunneling through the isomerization barrier. Such tunneling does not give rise to ammonia-type inversion doubling, because the cis and trans isomers are not equivalent; instead the odd-K rotational levels of a given vibrational level are systematically shifted relative to the even-K rotational levels, leading to a staggering of the K-structure. These various observations represent the first definite assignment of an isomer of acetylene that was previously thought to be unobservable, as well as the first high resolution spectroscopic results describing cis-trans isomerization. 相似文献
68.
Cross-linking mechanisms of arginine and lysine with α,β-dicarbonyl compounds in aqueous solution 总被引:1,自引:0,他引:1
Nasiri R Field MJ Zahedi M Moosavi-Movahedi AA 《The journal of physical chemistry. A》2011,115(46):13542-13555
Cross-linking in proteins by α,β-dicarbonyl compounds is one of the most damaging consequences of reactive carbonyl species in vivo and in foodstuffs. In this article we investigate computationally the cross-linking of glyoxal and methylglyoxal with lysine and arginine residues using density functional theory and the wB97XD dispersion-corrected functional. Five pathways, A-E, have been characterized. In pathways A and B, the reaction proceeds via formation of the Schiff base, aldimine, followed by addition of arginine. In contrast, in pathways C-E, direct addition of arginine to the dicarbonyl compounds occurs first, leading to a dihydroxyimidazolidine intermediate, which then reacts with lysine after dehydration and proton transfer reactions. The results reveal that pathways A, C, and E are competitive whereas reactions via pathways B and D are much less favorable. Inclusion of up to five explicit water molecules in the proton transfer and dehydration steps is found to lower the energy barriers in the feasible pathways by about 5-20 kcal/mol. Comparison of the mechanisms of methylglyoxal-derived imidazolium cross-linking (MODIC) and glyoxal-derived imidazolium cross-linking (GODIC) shows that the activation barriers are lower for GODIC than MODIC, in agreement with experimental observations. 相似文献
69.
Health psychology has studied the cross-sectional, stationary relationships linking stress, social support, and health. Levels of stress-related illness are generally modeled by including a nonlinear multiplicative or 'buffering' effect, corresponding to the interaction of stressor levels with social support from family and friends. The motivation of the present research is to extend an iterative, dynamic model of this well-investigated psychological process using a dynamical systems model expressed as a set of continuous, nonlinear differential equations similar to those of the 'Oregonator,' a model of a nonlinear dynamic chemical system. This model of the behavior of an individual is amenable to numerical investigation of its stationary-state stability properties, temporal evolution, and cause-effect relationships. The continuous variables in this new approach refer to varying states of an individual; they are Perceived stress (X), Symptoms (Y), and Social support (Z). It is expected that poor health in this model, represented by Symptoms (Y), is directly related to Perceived stress, as well as being tied in more complicated ways to Social support. A number of such models may be envisioned, some including a multiplicative, 'buffering' (- X x Z) effect of social support dependent on stress levels. We explore the behavior of this model over ranges of parameter values and initial conditions and relate these results to how an individual reacts to environmental challenges at various levels of stressors and social-support recruitment. Data generated by the model are in turn analyzed with a traditional cross-sectional statistical technique. Similarities and differences between chemical and psychological systems are discussed. 相似文献
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