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41.
Wang YN Topol IA Collins JR Burt SK 《Journal of the American Chemical Society》2003,125(43):13265-13273
Phosphate hydrolysis by GTPases plays an important role as a molecular switch in signal transduction and as an initiator of many other biological processes. Despite the centrality of this ubiquitous reaction, the mechanism is still poorly understood. As a first step to understand the mechanisms of this process, the nonenzymatic hydrolysis of mono-phosphate and tri-phosphate esters were systematically studied in gas phase and aqueous solution using hybrid density functional methods. The dielectric effect of the environment on the energetics of these processes was also explored. Theoretical results show that for mono-phosphate ester, the dissociative pathway is much more favorable than the associative pathway. However, the reaction barriers for the dissociative and associative pathways of tri-phosphate hydrolysis are very close in aqueous solution, though the dissociative pathway is more favorable in the gas phase. High dielectric solvents, such as water, significantly lower the activation barrier of the associative pathway due to the greater solvation energy of the associative transition states than that of the reactant complex. By contrast, the barrier of the dissociative pathway, with respect to the gas phase, is less sensitive to the surrounding dielectric. In the associative hydrolysis pathway of the tri-phosphate ester, negative charge is transferred from the gamma-phosphate to beta-phosphate through the bridging ester oxygen and results in Pgamma-O bond dissociation. No analogous charge transfer was observed in the dissociative pathway, where Pgamma-O bond dissociation resulted from proton transfer from the gamma-phosphate to the bridge oxygen. Finally, the active participation of local water molecules can significantly lower the activation energy of the dissociative pathway for both mono-phosphate and tri-phosphate. 相似文献
42.
Summary The provitamin A content of some food samples was determined by methods involving MgO: Hyflosupercel gravityflow column chromatography (GFCC) and reversed phase high performance liquid chromatography (HPLC), the quantitation being done by external standardization (HPLC-ES) or internal standardization (HPLC-IS) with Sudan. The results obtained with - and -carotene in carrots, -carotene and -cryptoxanthin in papaya and -carotene in tomato and kale agreed well, showing that any of the these techniques can be used, provided the analysis is done under optimum conditions. Good separation of the different provitamins using GFCC depends on the analyst's skill and visual acuity. HPLC-ES required a constant supply of provitamin standards, thus the varying purity of commercially available standards and the high instability of these compounds could pose grave problems. Due to the stability of Sudan, HPLC-IS appeared to be the method of choice although passage of the extract through a MgO: Hyflosupercel minicolumn was required prior to injection to separate chlorophylls, dihydroxy- and polyoxycarotenoids which would otherwise elute with Sudan. Nonconformity of the Sudan structure to those of the provitamins did not effect the quantitative results. The chromatographic separation, identity and quantification of the provitamins could be more easily established by using HPLC-IS, complemented with GFCC. 相似文献
43.
Summary In the determination of several perhalogenated compounds after gas chromatographic separation on an Apiezon L column, using
a flame ionization detector, all the compounds tested gave linear area-mass plots although the coefficients observed do not
lead to extrapolations which would permit quantitation of perhalogenated compounds for which no standard is available. Of
the compounds tested, dibromodichloromethane, tetrachloroethene and tetrabromoethene gave good linear correlations of area
ratio-mass ratio (using n-decane as the internal standard). Bromotrichloromethane and tetrabromomethane gave continuously
curving area ratio-mass ratio plots which were very reproducible and could be used for graphical interpolation. 相似文献
44.
Ahmad Waleh Jack R. Collins Gilda H. Loew M. C. Zerner 《International journal of quantum chemistry》1986,29(5):1575-1589
Restricted open-shell ground state properties and electronic spectra of two closely related low-spin, ferric, 6-coordinate, model cytochrome P450 complexes, one with a methyl mercaptide and the other a mercaptan as the second axial ligands, have been calculated with a newly modified, semiempirical INDO-SCF-CI method. The sensitivity of the calculated spectra to protonation of the sixth axial ligand, and the ability of the method to predict characteristic spectral features for the complexes investigated, are determined. Assignment of transitions, including xy- and z-polarized transitions, are made and compared with experimental observations where available. In particular, the origin of the anomalous split Soret spectrum observed in low-spin ferric complexes with mercaptide but not a mercaptan is investigated. Finally, a two part hypothesis is presented which provides a general explanation for the origin of both the observed split Soret and the red-shifted normal Soret in various ferrous and ferric P450 complexes in terms of the ground state orbital characters and simple symmetry considerations. 相似文献
45.
Griffiths G. Keegan E. Young E. Wotherspoon A. Palmer T. Lu K. Davis J. Alexander J. Jolly L. Nevers N. Delaunay F. Collins J. M. Dimayuga I. Bergeron A. Samuleev P. Dai Z. Holliday K. Robel M. Knight K. 《Journal of Radioanalytical and Nuclear Chemistry》2018,315(2):365-378
Journal of Radioanalytical and Nuclear Chemistry - Physical characterization is one of the most broad and important categories of techniques to apply in a nuclear forensic examination. Physical... 相似文献
46.
L. Y. Tonge J. Hodgkin A. S. Blicblau P. J. Collins 《Journal of Thermal Analysis and Calorimetry》2001,64(2):721-730
Differential scanning calorimetry(DSC) was used to study the effects of varying NaOH concentrations on the thermochemical
curing properties of 2,4-dimethylol phenol (2,4-DMP), and 2,6-dimethylol phenol(2,6-DMP). Analysis of the DSC curves showed
significant differences in the thermochemical curing behavior of these compounds with increasing NaOH:DMP molar ratios, in
terms of the peak shape, position of the reaction peaks, (T
p), along the temperature scale and energy of activation, E. The curves consisted of either a single, two or three exothermic peaks which indicated the occurrence of multiple reactions.
One of these peaks was observed for the entire range of NaOH molar ratios, and is attributed to the self-condensation reaction.
For the 2,4-DMP, NaOH had the effect of lowering the T
p of curing from 212°C in the uncatalyzed state to135°C between 0.15–0.75 molar ratios. The lowest value of E, however, was 111 kJ mole−1, only through 0.45–0.60 molar ratios and this combined with the above, points to this concentration range as the optimum
NaOH level. Similarly, the T
p of curing for the 2,6-DMP was lowered from 211°C in the uncatalyzed state, to a minimum of 116°C at the NaOH:2,6-DMP molar
ratio of 0.45. At this ratio, Ealso had the lowest value of 117 kJ mole−1 and this suggests that 0.45 molar ratio is the optimum NaOH level.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
47.
In the United States, fractions are an important part of the middle school curriculum, yet many middle school students struggle with fraction concepts. Teachers also have difficulty with the conceptual understanding needed to teach fractions and rely on textbooks when making instructional decisions. This reliance on textbooks, the idea that teaching and learning of fractions is a complex process, and that fraction understanding is the foundation for later topics such as proportionality, algebra, and probability, makes it important to examine the variation in presentation of fraction concepts in U.S. textbooks, especially the difference between traditional and standards‐based curricula. The purpose of this study is to determine if differences exist in the presentation of fractions in conventional and standards‐based textbooks and how these differences align with the recommendations of National Council of Teachers of Mathematics, Common Core State Standards, and the research on the teaching and learning of fractions. 相似文献
48.
Edmund J Collins 《The Journal of the Operational Research Society》2015,66(10):1595-1604
We introduce a class of models for multidimensional control problems that we call skip-free Markov decision processes on trees. We describe and analyse an algorithm applicable to Markov decision processes of this type that are skip-free in the negative direction. Starting with the finite average cost case, we show that the algorithm combines the advantages of both value iteration and policy iteration—it is guaranteed to converge to an optimal policy and optimal value function after a finite number of iterations but the computational effort required for each iteration step is comparable with that for value iteration. We show that the algorithm can also be used to solve discounted cost models and continuous-time models, and that a suitably modified algorithm can be used to solve communicating models. 相似文献
49.
50.
In this paper we design and implement rigorous algorithms for computing symbolic dynamics for piecewise-monotone-continuous maps of the interval. The algorithms are based on computing forwards and backwards approximations of the boundary, discontinuity and critical points. We explain how to handle the discontinuities in the symbolic dynamics which occur when the computed partition element boundaries are not disjoint. The method is applied to compute the symbolic dynamics and entropy bounds for the return map of the singular limit of a switching system with hysteresis and the forced Van der Pol equation. 相似文献