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61.
We consider dimensional crossover for anO(N) Landau-Ginzburg-Wilson model on ad-dimensional film geometry of thicknessL in the large-N limit. We calculate the full universal crossover scaling forms for the free energy and the equation of state. We compare the results obtained using environmentally friendly renormalization with those found using a direct, non-renormalization-group approach. A set of effective critical exponents are calculated and scaling laws for these exponents are shown to hold exactly, thereby yielding nontrivial relations between the various thermodynamic scaling functions. 相似文献
62.
The suggestion that hydroxide is coordinated to the oxidised molybdenum site in xanthine oxidase (XnO) is tested theoretically by computing the structures of a range of four-, five-, and six-coordinate active site models. The local density approximation of density functional theory has been used with the two experimentally verified singly bonded sulfur ligands modeled by both dithiolene, [SRCCRS](2-) (R = H and CH(3)), and thiolate, [CH(3)S](-) groups. Both ligand types give virtually identical results for analogous species. Based on a comparison of the computed M-L distances and those reported in recent EXAFS studies, it is concluded that both four- and six-coordination are unlikely since the optimized Mo-S contacts are too short or too long respectively. Of the five-coordinate MoOS(SR)(2)X models, the ones with X = [OH](-) give computed M-L bond lengths in excellent agreement with the reported EXAFS data while X = H(2)O, NH(3), [CH(3)S](-), and O(2-) give relatively poor agreement. The theoretical results imply that the active site represents a stable, preferred geometry rather than some imposed entatic state. 相似文献
63.
64.
We formulate scattering theory in the framework of a surface-integral approach utilizing analytically known asymptotic forms of the two-body and three-body scattering wavefunctions. This formulation is valid for both short-range and long-range Coulombic interactions. New general definitions for the potential scattering amplitude are presented. For the Coulombic potentials, the generalized amplitude gives the physical on-shell amplitude without recourse to a renormalization procedure. New post and prior forms for the Coulomb three-body breakup amplitude are derived. This resolves the problem of the inability of the conventional scattering theory to define the post form of the breakup amplitude for charged particles. The new definitions can be written as surface-integrals convenient for practical calculations. The surface-integral representations are extended to amplitudes of direct and rearrangement scattering processes taking place in an arbitrary three-body system. General definitions for the wave operators are given that unify the currently used channel-dependent definitions. 相似文献
65.
PaulA. Stocks PatrickG. Bray VictoriaE. Barton Mohammed Al‐Helal Michael Jones NunaC. Araujo Peter Gibbons StephenA. Ward RuthH. Hughes GiancarloA. Biagini Jill Davies Richard Amewu AmyE. Mercer Gemma Ellis PaulM. O'Neill 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2007,119(33):6394-6399
66.
67.
Bence Paul Dominic J. Hare David P. Bishop Chad Paton Van Tran Nguyen Nerida Cole Megan M. Niedwiecki Erica Andreozzi Angela Vais Jessica L. Billings Lisa Bray Ashley I. Bush Gawain McColl Blaine R. Roberts Paul A. Adlard David I. Finkelstein John Hellstrom Janet M. Hergt Jon D. Woodhead Philip A. Doble 《Chemical science》2015,6(10):5383-5393
Metals have a number of important roles within the brain. We used laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to map the three-dimensional concentrations and distributions of transition metals, in particular iron (Fe), copper (Cu) and zinc (Zn) within the murine brain. LA-ICP-MS is one of the leading analytical tools for measuring metals in tissue samples. Here, we present a complete data reduction protocol for measuring metals in biological samples, including the application of a pyramidal voxel registration technique to reproducibly align tissue sections. We used gold (Au) nanoparticle and ytterbium (Yb)-tagged tyrosine hydroxylase antibodies to assess the co-localisation of Fe and dopamine throughout the entire mouse brain. We also examined the natural clustering of metal concentrations within the murine brain to elucidate areas of similar composition. This clustering technique uses a mathematical approach to identify multiple ‘elemental clusters’, avoiding user bias and showing that metal composition follows a hierarchical organisation of neuroanatomical structures. This work provides new insight into the distinct compartmentalisation of metals in the brain, and presents new avenues of exploration with regard to region-specific, metal-associated neurodegeneration observed in several chronic neurodegenerative diseases. 相似文献
68.
Christopher D. Bray 《Tetrahedron letters》2006,47(23):3937-3939
Irradiation of a solution of α,β-unsaturated aldehyde 10 in benzene leads to the methylenecyclobutanol 11 by way of a novel intramolecular C-H insertion reaction. The conversion of 10 into 11 has relevance to the possible origin of the cyclobutane ring-based furanocembrane providencin 1 found in gorgonian octocorals. 相似文献
69.
Na2[UO2(IO3)4(H2O)] has been synthesized under mild hydrothermal conditions. Its structure consists of Na+ cations and [UO2(IO3)4(H2O)](2-) anions. The [UO2(IO3)4(H2O)](2-) anions are formed from the coordination of a nearly linear uranyl, UO2(2+), cation by four monodentate IO(3-) anions and a coordinating water molecule to yield a pentagonal bipyramidal environment around the uranium center. The water molecules form intermolecular hydrogen bonds with the terminal oxo atoms of neighboring [UO2(IO3)4(H2O)](2-) anions to yield one-dimensional chains that extend down the b axis. There are two crystallographically unique iodate anions in the structure of Na2[UO2(IO3)4(H2O)]. One of these anions is aligned so that the lone-pair of electrons is also directed along the b axis. The overall structure is therefore polar, owing to the cooperative alignment of both the hydrogen bonds and the lone-pair of electrons on iodate. The polarity of the monoclinic space group C2 (a = 11.3810(12) A, b = 8.0547(8) A, c = 7.6515(8) A, beta = 90.102(2) degrees , Z = 2, T = 193 K) found for this compound is consistent with the structure. Second-harmonic generation of 532 nm light from a 1064 nm laser source yields a response of approximately 16x alpha-SiO2. 相似文献
70.
The catalytic transformations of functional alkynes with diazoalkanes in the presence of the catalyst precursor RuCl(COD)Cp* are presented. They show the unique role played by the Ru(X)Cp* moiety in catalysis and that the nature of the formed products strongly depends on the alkyne functionality. Simple alkynes generate dienes via double diazoalkane carbene addition to the triple bond. Enynes with terminal triple bond lead to alkenyl bicyclo[x.1.0]alkanes, including bicyclic aminoacid derivatives. 1,6-enynes with disubstituted propargylic carbon produce in priority alkenyl alkylidene cyclopentanes. 1,6-Allenynes offer the direct access to alkenyl alkylidene bicyclo[3.1.0]hexanes. Propargylic carboxylates lead to conjugated dienes by coupling of the diazoalkane carbene with the alkyne terminal carbon and 1,2-shift of the carboxylate. All catalytic reactions can be explained by the initial formation of the 16 electron RuCl(CHR)Cp* moiety giving first a 2+2 cycloaddition with the alkyne triple bond. 相似文献