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421.
Morton D Dick AR Ghosh D Davies HM 《Chemical communications (Cambridge, England)》2012,48(47):5838-5840
The preparation and reactivity of steroidal vinyldiazo compounds is reported, providing a convenient, substituent tolerant, chemo- and stereoselective entry into 4- and 6-substituted androgen analogues from a common precursor. Under dirhodium catalysis, O-H insertion occurs at the carbenoid site, leading to 4-substituted steroids, but under silver catalysis, O-H insertion occurs at the vinylogous position, leading to 6-substituted steroids. 相似文献
422.
Wu B Szymański W Wybenga GG Heberling MM Bartsch S de Wildeman S Poelarends GJ Feringa BL Dijkstra BW Janssen DB 《Angewandte Chemie (International ed. in English)》2012,51(2):482-486
Turn to switch: A mutant of phenylalanine aminomutase was engineered that can catalyze the regioselective amination of cinnamate derivatives (see scheme, red) to, for example, β-amino acids. This regioselectivity, along with the X-ray crystal structures, suggests two distinct carboxylate binding modes differentiated by C(β)-C(ipso) bond rotation, which determines if β- (see scheme) or α-addition takes place. 相似文献
423.
Mirjam Kretzschmar Johannes C. Jager Dick P. Reinking Gertjan van Zessen Henk Brouwers 《The Journal of mathematical sociology》2013,37(4):351-374
Survey data and a simulation model based on a stochastic pair formation process are used to construct networks of sexual contacts. We model heterosexual partnerships which can be steady or casual depending on their average duration. Transmission of an infectious disease can take place in pairs of a susceptible and an infected individual. We study networks of sexual contacts accumulated during 1 year for different types of mixing patterns. The networks are constructed on the basis of data from a survey in The Netherlands. We analyze the network structure for different mixing patterns and investigate the relationship between network structure and disease spread; furthermore we study the effect of prevention measures on the structure of the network. 相似文献
424.
Vonhof HB van Breukelen MR Postma O Rowe PJ Atkinson TC Kroon D 《Rapid communications in mass spectrometry : RCM》2006,20(17):2553-2558
A method for the isotope analysis of fluid inclusion water in speleothem calcite is presented. The technique is based on a commercially available continuous-flow pyrolysis furnace (ThermoFinnigan TC-EA). The main adaptation made to the standard TC-EA configuration is the addition of a crusher and cold trap unit, which is connected to the carrier gas inlet at the top of the TC-EA reactor tube. A series of tests conducted with this device shows that: (1) standard waters, injected in the crusher, and passed through a cryogenic trapping routine, yield accurate delta(2)H values; (2) crushed cubes of speleothem calcite from two Peruvian caves with rather dissimilar seepage water delta(2)H values yield fluid inclusion delta(2)H values in good accordance with these drip waters. The clear advantage of this continuous-flow technique for fluid inclusion isotope analysis is that it is relatively quick compared with other techniques. Since the conditions of water sample introduction into the TC-EA are identical for delta(2)H and delta(18)O analysis, we expect that only limited adaptations to the extraction procedure are required to provide delta(18)O analysis of fluid inclusion samples with the same device. 相似文献
425.
Protein structural class describes the overall folding type of a protein or its domain. A number of methods were developed to predict protein structural class based on its primary sequence. The homology of the predicted sequences with respect to the training sequences is a key attribute for the prediction performance. In this article we investigated the FDOD method developed by Jin et al. [Jin, L., Fang, W., Tang, H., 2003. Prediction of protein structural classes by a new measure of information discrepancy. Comput. Biol. Chem. 27, 373-380], which gave high prediction accuracy on a low homology dataset, and we empirically confirmed that the reported results were an artifact of improper implementation. 相似文献
426.
Jan Baldeaux Josef Dick Gunther Leobacher Dirk Nuyens Friedrich Pillichshammer 《Numerical Algorithms》2012,59(3):403-431
We show how to obtain a fast component-by-component construction algorithm for higher order polynomial lattice rules. Such
rules are useful for multivariate quadrature of high-dimensional smooth functions over the unit cube as they achieve the near
optimal order of convergence. The main problem addressed in this paper is to find an efficient way of computing the worst-case
error. A general algorithm is presented and explicit expressions for base 2 are given. To obtain an efficient component-by-component
construction algorithm we exploit the structure of the underlying cyclic group. We compare our new higher order multivariate
quadrature rules to existing quadrature rules based on higher order digital nets by computing their worst-case error. These
numerical results show that the higher order polynomial lattice rules improve upon the known constructions of quasi-Monte
Carlo rules based on higher order digital nets. 相似文献
427.
Ricks AB Brown KE Wenninger M Karlen SD Berlin YA Co DT Wasielewski MR 《Journal of the American Chemical Society》2012,134(10):4581-4588
Donor-bridge-acceptor (D-B-A) systems in which a 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An) chromophore and a naphthalene-1,8:4,5-bis(dicarboximide) (NI) acceptor are linked by oligomeric 2,7-fluorenone (FN(n)) bridges (n = 1-3) have been synthesized. Selective photoexcitation of DMJ-An quantitatively produces DMJ(+?)-An(-?), and An(-?) acts as a high-potential electron donor. Femtosecond transient absorption spectroscopy in the visible and mid-IR regions showed that electron transfer occurs quantitatively in the sequence: DMJ(+?)-An(-?)-FN(n)-NI → DMJ(+?)-An-FN(n)(-?)-NI → DMJ(+?)-An-FN(n)-NI(-?). The charge-shift reaction from An(-?) to NI(-?) exhibits an exponential distance dependence in the nonpolar solvent toluene with an attenuation factor (β) of 0.34 ?(-1), which would normally be attributed to electron tunneling by the superexchange mechanism. However, the FN(n)(-?) radical anion was directly observed spectroscopically as an intermediate in the charge-separation mechanism, thereby demonstrating conclusively that the overall charge separation involves the incoherent hopping (stepwise) mechanism. Kinetic modeling of the data showed that the observed exponential distance dependence is largely due to electron injection onto the first FN unit followed by charge hopping between the FN units of the bridge biased by the distance-dependent electrostatic attraction of the two charges in D(+?)-B(-?)-A. This work shows that wirelike behavior does not necessarily result from building a stepwise, energetically downhill redox gradient into a D-B-A molecule. 相似文献
428.
Signal proteins are able to adapt their response to a change in the environment, governing in this way a broad variety of important cellular processes in living systems. While conventional molecular-dynamics (MD) techniques can be used to explore the early signaling pathway of these protein systems at atomistic resolution, the high computational costs limit their usefulness for the elucidation of the multiscale transduction dynamics of most signaling processes, occurring on experimental timescales. To cope with the problem, we present in this paper a novel multiscale-modeling method, based on a combination of the kinetic Monte-Carlo- and MD-technique, and demonstrate its suitability for investigating the signaling behavior of the photoswitch light-oxygen-voltage-2-Jα domain from Avena Sativa (AsLOV2-Jα) and an AsLOV2-Jα-regulated photoactivable Rac1-GTPase (PA-Rac1), recently employed to control the motility of cancer cells through light stimulus. More specifically, we show that their signaling pathways begin with a residual re-arrangement and subsequent H-bond formation of amino acids near to the flavin-mononucleotide chromophore, causing a coupling between β-strands and subsequent detachment of a peripheral α-helix from the AsLOV2-domain. In the case of the PA-Rac1 system we find that this latter process induces the release of the AsLOV2-inhibitor from the switchII-activation site of the GTPase, enabling signal activation through effector-protein binding. These applications demonstrate that our approach reliably reproduces the signaling pathways of complex signal proteins, ranging from nanoseconds up to seconds at affordable computational costs. 相似文献
429.
Gubbels KB Ma Q Alexander MH Dagdigian PJ Tanis D Groenenboom GC van der Avoird A van de Meerakker SY 《The Journal of chemical physics》2012,136(14):144308
We present detailed calculations on resonances in rotationally and spin-orbit inelastic scattering of OH (X(2)Π, j = 3/2, F(1), f) radicals with He and Ne atoms. We calculate new ab initio potential energy surfaces for OH-He, and the cross sections derived from these surfaces compare well with the recent crossed beam scattering experiment of Kirste et al. [Phys. Rev. A 82, 042717 (2010)]. We identify both shape and Feshbach resonances in the integral and differential state-to-state scattering cross sections, and we discuss the prospects for experimentally observing scattering resonances using Stark decelerated beams of OH radicals. 相似文献
430.
Yann Moguen Tarik Kousksou Pascal Bruel Jan Vierendeels Erik Dick 《Journal of computational physics》2012,231(16):5522-5541
Low Mach number flow computation in co-located grid arrangement requires pressure–velocity coupling in order to prevent the checkerboard phenomenon. Two broad categories of pressure–velocity coupling methods for unsteady flows can be distinguished based on the time-step dependency of the coupling coefficient in the definition of the transporting velocity on a face of a control volume. As an example of the time-step independent category, the AUSM+-up scheme is studied. As an example of the second category, Rhie–Chow momentum interpolation methods are studied. Within the momentum interpolation techniques, again two broad categories can be distinguished based on the time-step dependency of the coupling coefficient used for unsteady flow computations, but when a steady state is reached. Variants of Rhie–Chow interpolation methods in each subcategory are studied on critical test cases. The result of the study is that for a good representation of unsteady flows containing acoustic information, the pressure–velocity coupling coefficient must explicitly depend on the time-step, but that the transporting velocity must become independent of the time-step when a steady state is reached. 相似文献