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101.
Suitably functionalized vinylheptafulvenes (VHFs) act as thermoswitches undergoing ring closure to the corresponding dihydroazulenes (DHAs). Here we present the synthesis of a new such thermoswitch incorporating two heptafulvene rings on a dicyanoethylene unit. The synthetic protocol explores both the tropylium species as an electrophile and as a leaving group in the generation of the heptafulvene units. The thermally induced ring closure was enhanced as a result of two accessible sites for the reaction to occur. 相似文献
102.
Kirchmair J Williamson MJ Tyzack JD Tan L Bond PJ Bender A Glen RC 《Journal of chemical information and modeling》2012,52(3):617-648
Metabolism of xenobiotics remains a central challenge for the discovery and development of drugs, cosmetics, nutritional supplements, and agrochemicals. Metabolic transformations are frequently related to the incidence of toxic effects that may result from the emergence of reactive species, the systemic accumulation of metabolites, or by induction of metabolic pathways. Experimental investigation of the metabolism of small organic molecules is particularly resource demanding; hence, computational methods are of considerable interest to complement experimental approaches. This review provides a broad overview of structure- and ligand-based computational methods for the prediction of xenobiotic metabolism. Current computational approaches to address xenobiotic metabolism are discussed from three major perspectives: (i) prediction of sites of metabolism (SOMs), (ii) elucidation of potential metabolites and their chemical structures, and (iii) prediction of direct and indirect effects of xenobiotics on metabolizing enzymes, where the focus is on the cytochrome P450 (CYP) superfamily of enzymes, the cardinal xenobiotics metabolizing enzymes. For each of these domains, a variety of approaches and their applications are systematically reviewed, including expert systems, data mining approaches, quantitative structure-activity relationships (QSARs), and machine learning-based methods, pharmacophore-based algorithms, shape-focused techniques, molecular interaction fields (MIFs), reactivity-focused techniques, protein-ligand docking, molecular dynamics (MD) simulations, and combinations of methods. Predictive metabolism is a developing area, and there is still enormous potential for improvement. However, it is clear that the combination of rapidly increasing amounts of available ligand- and structure-related experimental data (in particular, quantitative data) with novel and diverse simulation and modeling approaches is accelerating the development of effective tools for prediction of in vivo metabolism, which is reflected by the diverse and comprehensive data sources and methods for metabolism prediction reviewed here. This review attempts to survey the range and scope of computational methods applied to metabolism prediction and also to compare and contrast their applicability and performance. 相似文献
103.
Stevenson GP Lee CY Kennedy GF Parkin A Baker RE Gillow K Armstrong FA Gavaghan DJ Bond AM 《Langmuir : the ACS journal of surfaces and colloids》2012,28(25):9864-9877
A detailed analysis of the cooperative two-electron transfer of surface-confined cytochrome c peroxidase (CcP) in contact with pH 6.0 phosphate buffer solution has been undertaken. This investigation is prompted by the prospect of achieving a richer understanding of this biologically important system via the employment of kinetically sensitive, but background devoid, higher harmonic components available in the large-amplitude Fourier transform ac voltammetric method. Data obtained from the conventional dc cyclic voltammetric method are also provided for comparison. Theoretical considerations based on both ac and dc approaches are presented for cases where reversible or quasi-reversible cooperative two-electron transfer involves variation in the separation of their reversible potentials, including potential inversion (as described previously for solution phase studies), and reversibility of the electrode processes. Comparison is also made with respect to the case of a simultaneous two-electron transfer process that is unlikely to occur in the physiological situation. Theoretical analysis confirms that the ac higher harmonic components provide greater sensitivity to the various mechanistic nuances that can arise in two-electron surface-confined processes. Experimentally, the ac perturbation with amplitude and frequency of 200 mV and 3.88 Hz, respectively, was employed to detect the electron transfer when CcP is confined to the surface of a graphite electrode. Simulations based on cooperative two-electron transfer with the employment of reversible potentials of 0.745 ± 0.010 V, heterogeneous electron transfer rate constants of between 3 and 10 s(-1) and charge transfer coefficients of 0.5 for both processes fitted experimental data for the fifth to eighth ac harmonics. Imperfections in theory-experiment comparison are consistent with kinetic and thermodynamic dispersion and other nonidealities not included in the theory used to model the voltammetry of surface-confined CcP. 相似文献
104.
M. Cavallaro F. Cappuzzello D. Carbone A. Cunsolo A. Foti A. Khouaja M. R. D. Rodrigues J. S. Winfield M. Bondì 《The European Physical Journal A - Hadrons and Nuclei》2012,48(5):59
The focal plane detector of the MAGNEX large acceptance magnetic spectrometer is presented. It is based on a large low-pressure
gas-filled tracker followed by a wall of silicon detectors to stop the particles. It has been designed for the stringent requirements
from the ion optics and the foreseen use with heavy ions. The performances of the device are demonstrated using 4MeV/u oxygen beams. The results of the tests are described and discussed in view of the application of the particle identification
and trajectory reconstruction techniques to recover the kinematic properties of the reaction products. They demonstrate the
suitability of such detector in a wide range of experiments where low-energy thresholds, large-accepted solid angle, precise
momentum measurement and good particle identification are needed. 相似文献
105.
Walsh JJ Mallon CT Bond AM Keyes TE Forster RJ 《Chemical communications (Cambridge, England)》2012,48(30):3593-3595
Thin films of polyoxometalates that are sensitized with a Ru(II) metallopolymer generate significant photocurrents in the presence of benzyl alcohol and visible light. Significantly, the photocurrent generated by the tungstate based adduct, α-[P(2)W(18)O(62)](6-), is approximately seven fold larger than that found for the Dawson polyoxomolybdate α-[S(2)Mo(18)O(62)](4-). 相似文献
106.
T E Keyes R J Forster A M Bond W Miao 《Journal of the American Chemical Society》2001,123(12):2877-2884
Solid-state voltammetry, spectroscopy, and microscopy studies have been used to probe the proton and electron conductivity within a self-assembled cocrystal, HQBpt. This crystallographically defined material contains 3,5-bis(pyridin-2-yl)-1,2,4-triazole, HBpt, dimers that are pi-stacked and hydrogen bonded to 1,4-hydroquinone, H(2)Q, in a herringbone arrangement. When deposited onto platinum microelectrodes, the cocrystal exhibits a well-defined voltammetric response corresponding to oxidation of H(2)Q to the quinone, Q, across a wide range of voltammetric time scales, electrolyte compositions, and pH values. Scanning electron microscopy reveals that redox cycling in aqueous perchlorate solutions in which the pH is systematically varied from 1 to 7 triggers electrocrystallization and the extensive formation of rodlike crystals. Fast scan rate voltammetry reveals that the homogeneous charge transport diffusion coefficient, D(app), is independent of the perchlorate concentration for 0.1 < [ClO(4)(-)] < 1.0 M (pH 6.6) at 3.14 +/- 0.11 x 10(-)(9) cm(2) s(-)(1). Moreover, D(app) is independent of the perchloric acid concentration for concentrations greater than approximately 2.0 M, maintaining a value of 4.81 +/- 0.07 x 10(-)(8) cm(2) s(-)(1). The observation that D(app) is independent of the supporting electrolyte suggests that the rate-determining step for homogeneous charge transport is not the availability of charge-compensating counterions or protons, but the dynamics of electron self-exchange between H(2)Q and Q. We have used the Dahms-Ruff formalism to determine electron self-exchange rate constants which are 2.84 +/- 0.22 x 10(9) and 9.69 +/- 0.73 x 10(10) M(-)(1) s(-)(1) for pH values greater than approximately 2.0 and less than -0.3, respectively. Significantly, these values are more than 2 orders of magnitude larger that those found for benzoquinone self-exchange reactions in aqueous solution. These results indicate that hydrogen bonds play an important role in supporting rapid electron transfer. The increase in D(app) between pH 1.0 and -0.3 is associated with protonation of the HBpt moieties, which triggers a reversible change in the material's structure. 相似文献
107.
The millennium being celebrated this year coincides with the 200th anniversary of the birth of practical electrochemistry made possible via Volta’s publication of the battery in the year 1800. The analytical chemists at the beginning of the 19th century were very quick to take advantage of this newly reported device and the first qualitative electrochemical determination of copper rapidly followed this pioneering discovery. In the last 200 years, electrochemical analysis, in its various forms, has been undertaken routinely in countless laboratories all over the world. However, in view of the long and distinguished history of the discipline, and some limitations that have been identified at the time of the celebration of the millennium, electrochemical analysis is regarded in some quarters as being a mature and conservative discipline whose importance in the future, when faced with severe competition from newly emerging alternative analytical techniques, is somewhat unclear. In this paper, an overview of past and present developments in electroanalytical chemistry and the possible future status of the technique is presented. In particular, emphasis is given to describing applications relevant to the also very mature field of electrowinning of zinc from plant electrolyte. This overview encompasses the author’s 25 years’ experience in developing polarographic, stripping voltammetric, adsorptive stripping voltammetric and ion-selective electrode (ISE) methods of analysis in on-line, on-stream and off-line modes for the determination of elements such as Cd, Pb, Ge, Sb (oxidation states (III) and (V)), Co, Ni, Zn, Fe, (oxidation states (II) and (III)), Tl, As (total) and Cu in zinc plant electrolyte. Developments that may contribute to an important future for analytical voltammetry are also considered as are limitations that could inhibit the extent of practical use of these electroanalytical techniques in the 21st century. 相似文献
108.
109.
Significant increase of the a.c. conductivity of Laponite is achieved when the sodium form is totally exchanged with potassium ions; however, the rheological properties alter, e.g. the clay will no longer form a gel with water. Exchange with Li+, Rb+, Cs+ or Cu2+ produces no increase in the a.c. conductivity over that of the sodium form. The synthesis of fluoro-laponites, with increased sodium contents, via a sol-gel method, gives materials of enhanced a.c. conductivity, which retain similar rheological properties to those of commercial Laponite. Some 29Si and 6Li MAS NMR data are reported for the new materials. 相似文献
110.
Dennis C. Johnson Stephen G. Weber Alan M. Bond R.Mark Wightman Ronald E. Shoup Ira S. Krull 《Analytica chimica acta》1986
A review is given of the principles, key developments and representative applications of small electrodes in flow-through electrochemical (ec) detectors having very low effective dead volume (<10 μl) for voltammetric and amperometric detection in flowing solutions. Emphasis is placed on factors contributing to high sensitivity, reliability and selectivity of ec detection as an integral part of larger analytical systems utilizing continuously flowing, unsegmented streams, e.g., flow-injection and liquid chromatographic analyses. Solid and mercury electrodes are considered under potentiostatic and potentiodynamic control. A review is given also of auxiliary chemical and photolytic derivatizations coupled to ec detection. The majority of the literature on the subject relates to liquid chromatography with electrochemical detection (l.c./ec); however, applications to these concepts to specific examples in flow-injection systems, as well as for on-line process control, should be obvious. Details of chromatographic separations and design of total analytical systems are not reviewed. 相似文献