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41.
42.
Single crystals of two liquid crystal compounds, 5‐{[4′‐(((pentyl)oxy)‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO5) and 5‐{[(4′‐nonyloxy‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO9), have been prepared by solution growth technique. The morphologies and structures of A3EO5 and A3EO9 crystals were investigated by wide angle X‐ray diffraction (WXRD), atom force microscope (AFM) and transmission electron microscope (TEM). In contrast to the same series of compounds which have a longer alkyl tail, 5‐{[(4′‐heptoxy‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO7), 5‐{[(4′‐heptoxy‐4‐biphenylyl)oxy]carbonyl}‐1‐pentyne (A3E′O7) and A3EO9, A3EO5 shows strikingly different crystalline behavior. The former three compounds have only one crystal form, whereas A3EO5 exhibits polymorphism. Specifically, A3EO5 crystals grown from toluene solution show two crystal forms. The first one is crystal I which adopts a monoclinic P112/m space group with unit cell parameters of a?5.79 Å, b?8.34 Å, c?43.92 Å, γ?96°, and the other one is crystal II which adopts a monoclinic P112 space group with unit cell parameters of a?5.55 Å, b?7.38 Å, c?31.75 Å, γ?94°. When using dioxane as the solvent to grow A3EO5 crystal, we can selectively obtain crystal I. A3EO5 melt‐grown crystals also have two crystal forms which derive from crystal I and crystal II, respectively. The different crystalline behavior of the compounds should correlate with their different electron dipole moment resulting from the different length of alkyl tail. 相似文献
43.
Ruthenium complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane for atom and group transfer reactions
Sharon Lai-Fung Chan Yu-He Kan Ka-Lai Yip Jie-Sheng Huang Chi-Ming Che 《Coordination chemistry reviews》2011,255(7-8):899-919
With support by macrocyclic tertiary amine ligand 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3tacn), a number of mononuclear metal–ligand multiple bonded complexes have been isolated. Starting with a brief summary of these complexes, the present review focuses on ruthenium-oxo and -imido complexes of Me3tacn. A family of monooxoruthenium(IV) complexes [RuIV(Me3tacn)O(N–N)]2+ (N–N = 2,2′-bipyridines) and a cis-dioxoruthenium(VI) complex cis-[RuVI(Me3tacn)O2(CF3CO2)]+ have been isolated, and the structures of [RuIV(Me3tacn)O(bpy)](ClO4)2 (bpy = 2,2′-bipyridine) and cis-[RuVI(Me3tacn)O2(CF3CO2)]ClO4 have been determined by X-ray crystallography. Oxidation of [RuIII(Me3tacn)(NHTs)2(OH)] (Ts = p-toluenesulfonyl) with Ag+ and electrochemical oxidation of [RuIII(Me3tacn)(H2L)](ClO4)2 (H3L = α-(1-amino-1-methylethyl)-2-pyridinemethanol) are likely to generate ruthenium-imido complexes supported by Me3tacn. DFT calculations on cis-[RuVI(Me3tacn)O2(CF3CO2)]+ and proposed ruthenium-imido complexes have been performed. Complexes [RuIV(Me3tacn)O(N–N)]2+ are reactive toward alkene epoxidation, and cis-[RuVI(Me3tacn)O2(CF3CO2)]+ efficiently oxidizes various organic substrates including concerted [3+2] cycloaddition reactions with alkynes and alkenes to selectively afford α,β-diketones, cis-diols, or CC bond cleavage products. Related oxidation reactions catalyzed by ruthenium Me3tacn complexes include epoxidation of alkenes, cis-dihydroxylation of alkenes, oxidation of alkanes, alcohols, aldehydes, and arenes, and oxidative cleavage of CC, CC, and C–C bonds, all of which exhibit high selectivity. Ruthenium Me3tacn complexes are also active catalysts for amination of saturated C–H bonds. 相似文献
44.
Gates AJ Kemp GL To CY Mann J Marritt SJ Mayes AG Richardson DJ Butt JN 《Physical chemistry chemical physics : PCCP》2011,13(17):7720-7731
In protein film electrochemistry a redox protein of interest is studied as an electroactive film adsorbed on an electrode surface. For redox enzymes this configuration allows quantification of the relationship between catalytic activity and electrochemical potential. Considered as a function of enzyme environment, i.e., pH, substrate concentration etc., the activity-potential relationship provides a fingerprint of activity unique to a given enzyme. Here we consider the nature of the activity-potential relationship in terms of both its cellular impact and its origin in the structure and catalytic mechanism of the enzyme. We propose that the activity-potential relationship of a redox enzyme is tuned to facilitate cellular function and highlight opportunities to test this hypothesis through computational, structural, biochemical and cellular studies. 相似文献
45.
In this paper we use the combinatorics of alcove walks to give uniform combinatorial formulas for Macdonald polynomials for all Lie types. These formulas resemble the formulas of Haglund, Haiman and Loehr for Macdonald polynomials of type GLn. At q=0 these formulas specialize to the formula of Schwer for the Macdonald spherical function in terms of positively folded alcove walks and at q=t=0 these formulas specialize to the formula for the Weyl character in terms of the Littelmann path model (in the positively folded gallery form of Gaussent and Littelmann). 相似文献
46.
The ray tracing method was applied to study etched tracks from α-particles in CR-39 solid-state nuclear track detectors. The transmission mode of a microscope operation was simulated. A track was considered as a set of small triangular elements, and the brightness of all elements was calculated systematically through the entire track to create the final image. Preliminary results are given for α-particle tracks in the CR-39 detector for initial energies of 4 and 4.5 MeV, and incident angles of 40 and 90°, respectively. Total reflection, as well as the slope of a surface element in the track wall, were identified as the main factors that affect the brightness of that element. At this stage, comparisons with experimental results can be made in terms of the average grey levels for the entire tracks. 相似文献
47.
This paper presents a versatile solution-scheme for the convective-diffusion equation. A small-time, asymptotic, solution for an instantaneous point source of scalar contaminant is expressed as a three-dimensional, Hermite polynomial expansion and manipulated, using superposition, to generate the contaminant concentration field that results at larger times and for arbitrary, continuous or instantaneous, source contaminant distribution. This equation is commonly used to model contaminant dispersion in complex environmental flows so that the considerable degree of generality, flexibility and efficiency of this solution-scheme highly commends it to this application. The off-diagonal terms in the diffusivity tensor and the non-zero gradient of this term and the mean-velocity field are shown to make a significant contribution to the evolution of the contaminant concentration field resulting from the instantaneous release of contaminant from a point source.
Zusammenfassung Die vorliegende Arbeit gibt eine vielseitig brauchbare Lösungsmethode für die konvektive Diffusionsgleichung. Die für kurze Zeiten gültige asymptotische Lösung für eine plötzlich wirkende Punktquelle der diffundierenden Skalargröße wird als dreidimensionale Entwicklung in Hermite'schen Polynomen dargestellt. Dies wird benützt um das Feld für größere Zeiten darzustellen, für beliebige, kontinuierliche oder diskontinuierliche Quellverteilungen. Diese Gleichung wird allgemein benützt als Modell für Dispersion von Schadstoffen in komplizierten Strömungen bei natürlichen Umgebungsverhältnissen; die Allgemeingültigkeit, Anpassungsfähigkeit und Wirksamkeit der Lösung machen die Methode für diese Anwendungen besonders geeignet. Es wird gezeigt, daß die Nichtdiagonalterme des Diffusionstensors sowie die nichtverschwindenden Gradienten dieses Termes und der mittleren Geschwindigkeit wesentliche Beiträge zur Entwicklung des Feldes leisten, die von der Punktquelle erzeugt wurde.相似文献
48.
A combined OH/acetone planar laser-induced fluorescence (PLIF) imaging technique that provides simultaneous visualizations of regions of unburned fuel and of combustion in a reacting flow is described. OH marks the location of chemical reaction and of combustion products, and acetone vapor, which is seeded into the fuel stream, marks unburned fuel. A single pulse from an ultraviolet laser is used to simultaneously excite both the OH and acetone, and the fluorescence from each is detected on separate cameras. Acetone spectroscopy and chemistry are reviewed to provide a basis for interpreting acetone fluorescence signals in high-temperature combusting environments. The imaging technique is applied to two nonpremixed turbulent reacting flows to assess the utility of the technique for visualizing the instantaneous flow structure and to illustrate the dependence of the interpretation of the acetone PLIF images on the flow conditions.Support was provided for this work by the Air Force Office of Scientific Research, Aerospace Sciences Directorate, with Julian Tishkoff as Technical Monitor, and is gratefully acknowledged. The contributions of Mr. T. C. Island in operating the supersonic flow facility are also greatly appreciated. 相似文献
49.
Kenneth Man-Kam Yip 《Theoretical and Computational Fluid Dynamics》1996,8(2):145-167
A new kind of symbolic program to aid the heuristic simplification of fluid models is presented. The program, AOM, employs order of magnitude analysis and method of dominant balance to generate simplified models. It has two novel features: (1) it uses heuristic techniques to decide what equations to solve and what algebra to do, and (2) it explains its deduction steps. The basic operation of AOM consists of five steps: (1) assign order of magnitude estimates to terms in the equations, (2) find maximal terms of each equation, i.e., terms that are not dominated by any other terms in the same equation, (3) consider all possible n-term dominant balance assumptions, (4) propagate the effects of the balance assumptions, and (5) remove partial models based on inconsistent balance assumptions. AOM also exploits constraints among equations and submodels to simplify complicated fluid models such as the triple-deck equations. Three annotated examples are presented to explain the operations of AOM. The implications for the development of computer-aided analysis programs for fluid dynamics and education are discussed.This research was funded in part by NSF NYI Award ECS-9357773 and CCR-9109567. 相似文献
50.
D.F. Zheng P.M. Hui K.F. Yip N.F. Johnson 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,27(2):213-218
We present generalized dynamical models describing the sharing of information, and the corresponding herd behavior, in a population
based on the recent model proposed by Eguıluz and Zimmermann (EZ) [Phys. Rev. Lett. 85, 5659 (2000)]. The EZ model, which is a dynamical version of the herd formation model of Cont and Bouchaud (CB), gives a
reasonable model for the formation of clusters of agents and for actions taken by clusters of agents. Both the EZ and CB models
give a cluster size distribution characterized by a power law with an exponent -5/2. By introducing a size-dependent probability
for dissociation of a cluster of agents, we show that the exponent characterizing the cluster size distribution becomes model-dependent
and non-universal, with an exponential cutoff for large cluster sizes. The actions taken by the clusters of agents generate
the price returns, the distribution of which is also characterized by a model-dependent exponent. When a size-dependent transaction
rate is introduced instead of a size-dependent dissociation rate, it is found that the distribution of price returns is characterized
by a model-dependent exponent while the exponent for the cluster-size distribution remains unchanged. The resulting systems
provide simplified models of a financial market and yield power law behaviour with an easily tunable exponent.
Received 31 December 2001 相似文献