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41.
A copper(I) complex with new N2S thiol ligand transforms to a multicopper(I) cluster, [(L(S-))6Cu(I)13(S2-)2]3+ (1); its X-ray structure exhibiting mu4-sulfido and mu3-thiolato coordination is presented and compared to other cuprous thiolato/sulfido clusters including that observed in the copper enzyme nitrous oxide reductase. 相似文献
42.
Efficient, nonlinearly stable entropic lattice Boltzmann models for computational fluid dynamics are presented. A new method of fast evaluation of equilibria to machine precision is proposed. Analytical solution is found for the collision step which guarantees stability and thermodynamic consistency of the scheme. As an example, a novel 15-velocity lattice Boltzmann model is derived and validated with a simulation of a three-dimensional backward-facing step flow. 相似文献
43.
Biased random walks 总被引:1,自引:0,他引:1
Yossi Azar Andrei Z. Broder Anna R. Karlin Nathan Linial Steven Phillips 《Combinatorica》1996,16(1):1-18
How much can an imperfect source of randomness affect an algorithm? We examine several simple questions of this type concerning the long-term behavior of a random walk on a finite graph. In our setup, at each step of the random walk a “controller” can, with a certain small probability, fix the next step, thus introducing a bias. We analyze the extent to which the bias can affect the limit behavior of the walk. The controller is assumed to associate a real, nonnegative, “benefit” with each state, and to strive to maximize the long-term expected benefit. We derive tight bounds on the maximum of this objective function over all controller's strategies, and present polynomial time algorithms for computing the optimal controller strategy. 相似文献
44.
Abdolrahman Razani Valdimir Rakočević Zahraa Goodarzi 《Central European Journal of Mathematics》2010,8(2):357-366
The aim of this paper, is to introduce the convex structure (specially, Takahashi convex structure) on modular spaces. Moreover, we are interested in proving some common fixed point theorems for non-self mappings in modular space. 相似文献
45.
Conclusions It has been established that patrinoside D1 is the -D-glucopyranosido(13) -D-xylopyranosido(12) -L-rhamnosido(14)--D-xylopyranoside (13) of oleanolic acidKhimiya Prirodnykh Soedinenii, Vol. 5, No. 2, pp. 84–89, 1969 相似文献
46.
V. G. Bukharov V. V. Karlin I. L. Bukharova L. N. Surkova 《Chemistry of Natural Compounds》1976,10(5):612-615
Summary The structure of philoside B — a gypsogenin nonaoside isolated from the roots ofGypsophila patrinii — has been established.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan'Branch, Academy of Sciences of the USSR. Correspondence Institute of Soviet Commerce. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 603–607, September–October, 1974. 相似文献
47.
Hatcher LQ Lee DH Vance MA Milligan AE Sarangi R Hodgson KO Hedman B Solomon EI Karlin KD 《Inorganic chemistry》2006,45(25):10055-10057
Employing a tetradentate N3S(thioether) ligand, LN3S, dioxygen reactivity of a copper(I) complex, [(LN3S)CuI]+ (1) was examined. In CH2Cl2, acetone (at -80 degrees C), or 2-methyltetrahydrofuran (at -128 degrees C), 1 reacts with O2 producing the end-on bound peroxodicopper(II) complex [{(LN3S)CuII}2(mu-1,2-O2(2-))]2+ (2), the first reported copper-dioxygen adduct with sulfur (thioether) ligation. Its absorption spectrum contains an additional low-energy feature (but not a Cu-S CT band) compared to the previously well-characterized N4 ligand complex, [{(TMPA)CuII}2(mu-1,2-O2(2-))]2+ (3) (TMPA = tris(2-pyridylmethyl)amine). Resonance Raman spectroscopy confirms the peroxo formulation {nu(O-O) = 817 cm-1 (16-18O2 Delta = 46 cm-1) and nu(Cu-O) = 545 cm-1 (16-18O2 Delta = 26 cm-1), in close analogy to that known for 3 {nu(O-O) = 827 cm-1 and nu(Cu-O) = 561 cm-1}. Direct evidence for thioether ligation comes from EXAFS spectroscopy {Cu K-edge; Cu-S = 2.4 A}. 相似文献
48.
Li L Murthy NN Telser J Zakharov LN Yap GP Rheingold AL Karlin KD Rokita SE 《Inorganic chemistry》2006,45(18):7144-7159
A dinuclear copper(II) complex [Cu(II)2(PD'O-)(H2O)2](ClO4)3 (5) with terminal Cu(II)-H(2)O moieties and a Cu...Cu distance of 4.13 A (X-ray structure) has been synthesized and characterized by EPR spectroscopy (ferromagnetic coupling observed) and cyclic voltammetry. Dizinc(II) and mononuclear copper(II) analogues [Zn(II)2(PD'O-)(H2O)2]3+ (7) and [Cu(II)(mPD'OH)(H2O)]2+ (6), respectively, have also been synthesized and structurally characterized. Reacting 5/MPA/O(2) (MPA = 3-mercaptopropionic acid) with DNA leads to a highly specific oxidation of guanine (G) at a junction between single- and double-stranded DNA. Mass spectrometric analysis of the major products indicates a gain of +18 and +34 amu relative to initial DNA strands. The most efficient reaction requires G at the first and second unpaired positions of each strand extending from the junction. Less reaction is observed for analogous targets in which the G cluster is farther from the junction or contains less than four Gs. Consistent with our previous systems, the multinuclear copper center is required for selective reaction; mononuclear complex 6 is not effective. Hydrogen peroxide as a substitute for MPA/O2 also does not lead to activity. Structural analysis of a [Cu(II)2(PD'O-)(G)]3+ complex (8) and dizinc analogue [Zn(II)(2)(PD'O-)(G)](ClO4)3 (9) (G = guanosine) reveals coordination of the G O6 and N7 atoms with the two copper (or zinc) centers and suggests that copper-G coordination likely plays a role in recognition of the DNA target. The Cu2-O2 intermediate responsible for guanine oxidation appears to be different from that responsible for direct-strand scission induced by other multinuclear copper complexes; the likely course of reaction is discussed. 相似文献
49.
Zhu Q Lian Y Thyagarajan S Rokita SE Karlin KD Blough NV 《Journal of the American Chemical Society》2008,130(20):6304-6305
Dinuclear Cu(II) complexes, CuII2Nn (n = 4 or 5), were recently found to specifically cleave DNA in the presence of a reducing thiol and O2 or in the presence of H2O2 alone. However, CuII2N3 and a closely related mononuclear Cu(II) complex exhibited no selective reaction under either condition. Spectroscopic studies indicate an intermediate is generated from CuII2Nn (n = 4 or 5) and mononuclear Cu(II) solutions in the presence of H2O2 or from CuI2Nn (n = 4 or 5) in the presence of O2. This intermediate decays to generate OH radicals and ligand degradation products at room temperature. The lack of reactivity of the intermediate with a series of added electron donors suggests the intermediate discharges through a rate-limiting intramolecular electron transfer from the ligand to the metal peroxo center to produce an OH radical and a ligand-based radical. These results imply that DNA cleavage does not result from direct reaction with a metal-peroxo intermediate but instead arises from reaction with either OH radicals or ligand-based radicals. 相似文献
50.
Li L Narducci Sarjeant AA Vance MA Zakharov LN Rheingold AL Solomon EI Karlin KD 《Journal of the American Chemical Society》2005,127(44):15360-15361
A dicopper(I)/phenol-ligand complex in RCN solvents reacts with O2 producing a mu-1,1-hydroperoxo dicopper(II) species. Subsequent thermal transformation results in nitrile hydroxylation and elimination of cyanide, as revealed by the isolation in comparable yields of (i) a cyanide-bridged tetranuclear cluster complex and (ii) benzaldehyde (for R = PhCH2); 18O labeling confirms that the PhC(O)H oxygen atom derives from O2. 相似文献