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101.
Goldsmith RH Wasielewski MR Ratner MA 《The journal of physical chemistry. B》2006,110(41):20258-20262
We present a simple theoretical treatment of nonadiabatic electron transfer in multiply bridged donor-bridge-acceptor molecules using the density matrix formalism. Destructive interference can result from different signed couplings between bridge sites, with the simplest system being a four-site Joachim-type molecular interferometer. Previous work has shown that deposition of energy on the bridge sites erases the interference and recovers transport. We show that pure local dephasing, a completely elastic process, is also capable of eliminating destructive interference and regaining transport. Destructive interference as a result of system connectivity can explain the familiar ortho-meta-para reactivity of benzene bridges. We also show that pure dephasing can yield a coalescence of ortho, meta, and para effective coupling strengths and suggest a system to observe this effect experimentally. 相似文献
102.
R. Kanthack J. S. Goldsmith und Max Bottler 《Fresenius' Journal of Analytical Chemistry》1922,61(1-2):87-88
Ohne Zusammenfassung 相似文献
103.
A. Gérard J. Marcusson v. Reibnitz J. Scheiber und Goldsmith 《Fresenius' Journal of Analytical Chemistry》1931,84(1-2):67-68
Ohne Zusammenfassung 相似文献
104.
Microwave synthesis of polymer-embedded Pt-Ru catalyst for direct methanol fuel cell 总被引:2,自引:0,他引:2
Bensebaa F Farah AA Wang D Bock C Du X Kung J Le Page Y 《The journal of physical chemistry. B》2005,109(32):15339-15344
Platinum-ruthenium nanoparticles stabilized within a conductive polymer matrix are prepared using microwave heating. Polypyrrole di(2-ethylhexyl) sulfosuccinate, or PPyDEHS, has been chosen for its known electrical conductivity, thermal stability, and solubility in polar organic solvents. A scalable and quick two-step process is proposed to fabricate alloyed nanoparticles dispersed in PPyDEHS. First a mixture of PPyDEHS and metallic precursors is heated in a microwave under reflux conditions. Then the nanoparticles are extracted by centrifugation. Physical characterization by TEM shows that crystalline and monodisperse alloyed nanoparticles with an average size of 2.8 nm are obtained. Diffraction data show that crystallite size is around 2.0 nm. Methanol electro-oxidation data allow us to propose these novel materials as potential candidates for direct methanol fuel cells (DMFC) application. The observed decrease in sulfur content in the polymer upon incorporation of PtRu nanoparticles may have adversely affected the measured catalytic activity by decreasing the conductivity of PPyDEHS. Higher concentration of polymer leads to lower catalyst activity. Design and synthesis of novel conductive polymers is needed at this point to enhance the catalytic properties of these hybrid materials. 相似文献
105.
Tuan P. Tran Edmund L. Ellsworth Brian M. Watson Joseph P. Sanchez H. D. Hollis Showalter John R. Rubin Michael A. Stier Judy Yip Dai Q. Nguyen Paul Bird Rajeshwar Singh 《Journal of heterocyclic chemistry》2005,42(4):669-674
A new synthesis of a series of 3‐amino‐1H‐quinazoline‐2,4‐diones is described. The 1H‐quinazoline‐2,4‐dione 10 was made starting with fluorobenzoic acid in three high yielding steps. The key step of this synthesis involved the generation of the dianion of urea 7 and the subsequent intramolecular nucleophilic displacement of the 2‐fluoro to form the quinazolinedione ring. The 3‐amino moiety was incorporated using (2,4‐dinitro‐phenyl)‐hydroxylamine as the aminating reagent. 相似文献
106.
P. F. Goldsmith H. R. Fetterman B. J. Clifton C. D. Parker N. R. Erickson 《International Journal of Infrared and Millimeter Waves》1981,2(5):915-924
We report here the first results obtained by cooling a submillimeter quasioptical mixer, utilizing a Schottky diode in a corner reflector mixer structure. Measurements have been carried out at a wavelength of 434 microns. The diode inverse slope parameter Vo at low current decreases by a factor of 3 upon cooling to 50 K while the minimum system noise temperature of 5600 K (SSB), including the IF contribution, demonstrates a reduction of approximately 40% from the ambient temperature value. We also report improved system noise temperatures at 184 m and 119 m wavelengths of 38000 K and 64000 K (SSB), respectively.This work was supported by the Army Research Office and the Air Force Office of Scientific Research 相似文献
107.
Shivaiah Vaddypally Vitaly G. Kiselev Alex N. Byrne C. Franklin Goldsmith Michael J. Zdilla 《Chemical science》2021,12(6):2268
Cyanuric triazide reacts with several transition metal precursors, extruding one equivalent of N2 and reducing the putative diazidotriazeneylnitrene species by two electrons, which rearranges to N-(1′H-[1,5′-bitetrazol]-5-yl)methanediiminate (biTzI2−) dianionic ligand, which ligates the metal and dimerizes, and is isolated from pyridine as [M(biTzI)]2Py6 (M = Mn, Fe, Zn, Cu, Ni). Reagent scope, product analysis, and quantum chemical calculations were combined to elucidate the mechanism of formation as a two-electron reduction preceding ligand rearrangement.Cyanuric triazide reacts with transition metal precursors, extruding N2 and reducing the ligand by two electrons, which breaks an aromatic ring and rearranges to a bitetrazolylmethanediiminate (biTzI2−) ligand, forming two new aromatic rings. 相似文献
108.
Tiago de Oliveira F Bominaar EL Hirst J Fee JA Münck E 《Journal of the American Chemical Society》2004,126(17):5338-5339
[2Fe-2S] clusters found in the xanthine oxidase family of proteins exhibit an S = 1/2 EPR feature, called signal II, for which one g-value is significantly above g = 2.0. The g-values of signal II cannot be explained with the standard spin coupling model that has been so successful in describing the g = 1.94 signals of [2Fe-2S] ferredoxins. We have studied the EPR spectra of the Rieske protein from Thermus thermophilus at pH 14 and observed a signal II-type EPR spectrum, with g-values at 1.81, 1.94, and 2.14. It is shown that the g-values of signal II can be explained by including an antisymmetric exchange term, d.S1xS2, in the spin Hamiltonian. The presence of this term is sensed by EPR if the isotropic exchange coupling constant J is sufficiently small. For the Rieske protein we determined J = 43 cm-1 which is at least 4 times smaller than the J values reported for [2Fe-2S] clusters that yield standard g = 1.94 signals. 相似文献
109.
Iskender Yilgor Warren P. Steckle Emel Yilgor R. Gary Freelin Judy S. Riffle 《Journal of polymer science. Part A, Polymer chemistry》1989,27(11):3673-3690
Synthesis of novel triblock, polycaprolactone-b-polydimethylsiloxane (PDMS) and poly(2-ethyl-oxazoline)-b-PDMS copolymers were demonstrated. These materials were obtained via the ring-opening polymerization of ?-caprolactone or 2-ethyl-2-oxazoline monomers by using organofunctionally terminated PDMS oligomers as initiators and comonomers. Segment molecular weights in these copolymers were varied over a wide range between 1000 and 2000 g/mol and the formation of copolymers with desired backbone compositions were monitored by 1H-NMR spectroscopy and GPC. DSC and TMA studies showed the formation of two phase morphologies with PDMS (Tg, ?120°C) and polycaprolactone (Tm, 50–60°C) or poly(2-ethyl-2-oxazoline) (Tg, 40-60°C) transitions respectively. The use of polycaprolactone-b-PDMS copolymers as surface modifying additives in polymer blends were also investigated. When these copolymers were blended at low levels (0.25–10.0% by weight) with various commercial resins such as, polyurethanes, PVC, PMMA, and PET, the resulting systems displayed silicone-like, hydrophobic surface properties, as determined by critical surface tension measurements or water contact angles. The effect of siloxane content, block length, base polymer type and morphology on the resulting surfaces are discussed. 相似文献
110.
Tin oxide (SnO2) thin films were deposited on UV fused silica (UVFS) substrates using filtered vacuum arc deposition (FVAD). During deposition, the substrates were at room temperature (RT). As-deposited films were annealed at 400 and 600 °C in Ar for 30 min. The film structure, composition, and surface morphology were determined as function of the annealing temperature using X-ray diffraction (XRD), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The XRD patterns of the SnO2 thin films deposited on substrates at RT indicated that the films were amorphous, however, after the annealing the film structure became polycrystalline. The grain size of the annealed films, obtained from the XRD analysis, increased with the annealing temperature, and it was in the range 8-34 nm. The AFM analysis of the surface revealed an increase in the film surface average grain size from 15 nm to 46 nm, and the surface roughness from 0.2 to 1.8 nm, as function of the annealing temperature. The average optical transmission of the films in the visible spectrum was >80%, and increased by the annealing ∼10%. The films’ optical constants in the 250-989 nm wavelength range were determined by variable angle spectroscopic ellipsometry (VASE). The refractive indexes of as-deposited and annealed films were in the range 1.83-2.23 and 1.85-2.3, respectively. The extinction coefficients, k(λ), of as-deposited and annealed films were in the range same range ∼0-0.5. The optical energy band gap (Eg), as determined by the dependence of the absorption coefficient on the photon energy at short wavelengths, increased with the annealing temperature from 3.90 to 4.35 eV. The lowest electrical resistivity of the as-deposited tin oxide films was 7.8 × 10−3 Ω cm, however, film annealing resulted in highly resistive films. 相似文献