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81.
Reingold JA Uk Son S Bok Kim S Dullaghan CA Oh M Frake PC Carpenter GB Sweigart DA 《Dalton transactions (Cambridge, England : 2003)》2006,(20):2385-2398
Coordination of the carbocyclic ring of hydroquinones to electrophilic transition-metal fragments such as Mn(CO)3+ and Rh(COD)+ produces stable pi-bonded eta6-complexes that are activated to facile reversible deprotonation of the -OH groups. The deprotonations are accompanied by electron transfer to the transition metal, which acts as an internal oxidizing agent or electron sink. With manganese as the metal, the resulting eta5-semiquinone and eta4-quinone complexes have been used to synthesize one- two- and three-dimensional polymeric metal-organometallic coordination networks. With rhodium as the metal, the pi-quinonoid complexes have been demonstrated to play a unique role in multifunctional C-C coupling catalysis and in the synthesis of new organolithium reagents. Both classes of pi-quinonoid complexes appear to have significant applications in nanochemistry by providing an excellent vehicle for templating the directed self-assembly of nanoparticles into functional materials. 相似文献
82.
Son SU Reingold JA Carpenter GB Sweigart DA 《Chemical communications (Cambridge, England)》2006,(7):708-710
The ionic complexes [(1,4- and 1,3-hydroquinone)Rh(P(OPh)3)2]BF4 form porous organometallic structures dictated by charge assisted hydrogen bonding. 相似文献
83.
Huang T. Zeng D. Petit L. O’Brien D. Read E.R. Lewis R.P. Cowburn 《Journal of magnetism and magnetic materials》2010,322(14):2010-2014
We present here a numerical study of the magnetostatic charge distribution of transverse Néel type domain wall in permalloy nanowires. The calculations indicate that not only is the distribution highly non-uniform within a given transverse wall but it also varies dramatically with respect to the wire width. The implications of this for magnetostatic domain wall pinning are analyzed by considering the stray field interaction between a wall and another extended magnetic body for a particular domain wall chirality, where two distinct depinning mechanisms are observed depending on the wire width. 相似文献
84.
A. Graham G.A. Read V. King 《International Journal of Mathematical Education in Science & Technology》2013,44(2):149-159
In this paper we discuss three ways of introducing calculus all based on concepts which students would either already know or which can be introduced without much difficulty at this stage of their mathematical training. The aim of this paper is to persuade teachers of mathematics that topics in ‘higher mathematics’, specifically calculus, can and should be presented to students in terms of concepts with which they are familiar. 相似文献
85.
Richard P. Dwight 《Journal of computational physics》2008,227(5):2845-2863
A heuristic method is proposed to estimate a posteriori that part of the total discretization error which is attributable to the smoothing effect of added dissipation, for finite volume discretizations of the Euler equations. This is achieved by observing variation in a functional of the solution as the level of dissipation is varied, and it is deduced for certain test-cases that the dissipation alone accounts for the majority of the functional error. Based on this result an error estimator and mesh adaptation indicator is proposed for functionals, relying on the solution of an adjoint problem. The scheme is considerably implementationally simpler and computationally cheaper than other recently proposed a posteriori error estimators for finite volume schemes, but does not account for all sources of error. In mind of this, emphasis is placed on numerical evaluation of the performance of the indicator, and it is shown to be extremely effective in both estimating and reducing error for a range of 2d and 3d flows. 相似文献
86.
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Trammell SA Seferos DS Moore M Lowy DA Bazan GC Kushmerick JG Lebedev N 《Langmuir : the ACS journal of surfaces and colloids》2007,23(2):942-948
We describe the synthesis of two oligo(phenylene vinylene)s (OPVs) with a hydroquinone moiety and a thiol anchor group: 4-(2',5'-dihydroxystyryl)benzyl thioacetate and 4-[4'-(2' ',5' '-dihydroxystyryl)styryl]benzyl thioacetate. Monolayers on gold of these molecules were examined by electrochemical techniques to determine the electron transfer kinetics of the hydroquinone functionality (H2Q) through these delocalized tethers ("molecular wires") as a function of pH. Between pH 4 and 9, rate constants were ca. 100-fold faster than for the same H2Q functionality confined to the surface via alkane tethers. Also, in this same pH range rate constants were independent of the length of the OPV bridge. These new electroactive molecules in which the hydroquinone functionality is wired to the gold surface by means of OPV tethers should be useful platforms for constructing bioelectronic devices such as biosensors, biofuel cells, and biophotovoltaic cells with a fast response time. 相似文献
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90.
When kinetics are studied for a catalyzed reaction, the active catalyst surface available affects the results. This article illustrates the effect of a progressively decreasing available surface on the heterogeneous kinetics of a gas‐phase reaction in a closed system. The present contribution focuses on the effect of simple mth order surface deactivation on a simple nth order kinetic expression. The basic analysis and general results are unchanged if more complex equations are used. It is shown that there are certain common anomalous characteristics of kinetic expressions involving deactivation. In particular, the apparent rate constant and the apparent order are usually dependent on both the actual and initial pressures of the reactant, and the reaction may not go to completion. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 7–16, 2000 相似文献