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111.
Dunsmore CJ Carr R Fleming T Turner NJ 《Journal of the American Chemical Society》2006,128(7):2224-2225
Deracemization of racemic chiral tertiary amines has been achieved by combination of an enantioselective amine oxidase, obtained through directed evolution, and ammonia borane in a one-pot process. 相似文献
112.
Triplet-triplet (TT) energy transfer requires two molecular fragments to exchange electrons that carry different spin and energy. In this paper, we analyze and report values of the electronic coupling strengths for TT energy transfer. Two different methods were proposed and tested: (1) Directly calculating the off-diagonal Hamiltonian matrix element. This direct coupling scheme was generalized from the one used for electron transfer coupling, where two spin-localized unrestricted Hartree-Fock wave functions are used as the zero-order reactant and product states, and the off-diagonal Hamiltonian matrix elements are calculated directly. (2) From energy gaps derived from configuration-interaction-singles (CIS) scheme. Both methods yielded very similar results for the systems tested. For TT coupling between a pair of face-to-face ethylene molecules, the exponential attenuation factor is 2.59 A(-1)(CIS6-311+G(**)), which is about twice as large as typical values for electron transfer. With a series of fully stacked polyene pairs, we found that the TT coupling magnitudes and attenuation rates are very similar irrespective of their molecular size. If the polyenes were partially stacked, TT couplings were much reduced, and they decay more rapidly with distance than those of full-stacked systems. Our results showed that the TT coupling arises mainly from the region of close contact between the donor and acceptor frontier orbitals, and the exponential decay of the coupling with separation depends on the details of the molecular contacts. With our calculated results, nanosecond or picosecond time scales for TT energy-transfer rates are possible. 相似文献
113.
Using the nonperturbative approach to the calculation of nonlinear optical spectra developed in a foregoing paper [Mancal et al., J. Chem. Phys. 124, 234504 (2006), preceding paper], calculations of two-dimensional electronic spectra of an excitonically coupled dimer model system are presented. The dissipative exciton transfer dynamics is treated within the Redfield theory and energetic disorder within the molecular ensemble is taken into account. The manner in which the two-dimensional spectra reveal electronic couplings in the aggregate system and the evolution of the spectra in time is studied in detail. Changes in the intensity and shape of the peaks in the two-dimensional relaxation spectra are related to the coherent and dissipative dynamics of the system. It is shown that coherent electronic motion, an electronic analog of a vibrational wave packet, can manifest itself in two-dimensional optical spectra of molecular aggregate systems as a periodic modulation of both the diagonal and off-diagonal peaks. 相似文献
114.
Optimization of L‐shell X‐ray fluorescence detection of lead in bone phantoms using synchrotron radiation
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Closely related toxicity and retention mechanisms of lead (Pb) in the human body involve the bone tissues where Pb can accumulate and reside on a time scale ranging from years to tens of years. In vivo measurements of bone Pb can, therefore, play an important role in a comprehensive health risk assessment of Pb exposure. In vivo L‐shell X‐ray fluorescence (LXRF) measurement of bone Pb was first demonstrated over 4 decades ago. Implementation of the method, however, encountered challenges associated with low sensitivity and calibration procedure. In this study, the LXRF measurement was optimized by varying the incident photon energy and the excitation‐detection geometry. The Canadian Light Source synchrotron radiation was used to compare 2 different excitation‐detection geometries of 90° and 135° using 3 different X‐ray photon energies: 15.8, 16.6, and 17.5 keV. These energies optimized excitation of the L3 subshell of Pb and simulated the most intense K‐shell emissions of zirconium, niobium, and molybdenum, respectively. Five rectangular plaster‐of‐Paris bone phantoms with Pb concentrations of 0, 7, 17, 26, and 34 μg/g, and one rectangular 3.1‐mm‐thick resin phantom mimicked the X‐ray attenuation properties of human bone and soft tissue, respectively. Optimal LXRF detection was obtained by the 15.8‐keV energy and the 90° and 135° geometries for the bare bone and the bone and soft tissue phantoms, respectively. 相似文献
115.
RJ Mycka S Duez S Bernhardt J Heppekausen P Knochel FF Fleming 《The Journal of organic chemistry》2012,77(17):7671-7676
Deprotonating substituted cyclohexanecarbonitriles with TMPZnCl·LiCl affords zincated nitriles that diastereoselectively couple with aryl bromides in the presence of catalytic Pd(OAc)(2) and S-Phos. Steric and electronic effects influence the diastereoselectivity; 4-t-butyl-, 4-TBSO-, and 2-Me-cyclohexanecarbonitriles exert virtually complete diastereocontrol whereas modest diastereoselectivity is observed with 4-i-Pr-, 4-Me-, and 3-Me-cyclohexanecarbonitriles. The unusual diastereoselectivity trends should prove useful for synthesizing substituted cyclohexanecarbonitrile-containing pharmaceuticals. 相似文献
116.
Richard A. Fleming 《Macromolecular Symposia》1992,57(1):75-93
The technology of separating plastics from the municipal waste stream for reuse is reviewed, with emphasis on the key role played by the bottle sorting step. Experience gained in the first year's operation of two large commercial recycling plants provides a better understanding of practical problems encountered, their relative importance, and technical advances needed for improved operation. It is concluded that purity of feedstock and processing rate are two critical independent variables requiring technical and business understanding and management. Hypothetical examples illustrate the interplay of these with dependent variables of yield and sorting cost. 相似文献
117.
L.F. Schneemeyer F.J. DiSalvo R.M. Fleming J.V. Waszczak 《Journal of solid state chemistry》1984,54(3):358-364
The monoclinic blue-bronze, K0.30MoO3, is an anisotropic metal that undergoes a charge density wave (CDW)-driven phase transition at 180 K, below which nonlinear current-voltage characteristics are observed. In this paper, we examine the anisotropy of the electric and magnetic properties of K0.30MoO3 and their relationship to observed CDW phenomena. We show that the conductivity is highest along the monoclinic b axis and 10 and 100 times lower in two directions perpendicular to b (in the ( plane and perpendicular to these planes, respectively). In the CDW state, the conductivity along the b axis is nonlinear when the applied electric field exceeds a small threshold on the order of 50 mV/cm, but is field-independent in perpendicular directions. A periodic response to a dc bias was observed in one small K0.30MoO3 sample, however, the observation of an NbSe3-like response in K0.30MoO3 may depend on sample size or the quality of the electrical contacts to the sample. 相似文献
118.
P. M. Beckett A. R. Fleming R. J. Foster J. M. Gilbert D. G. Whitehead 《Optical and Quantum Electronics》1995,27(12):1303-1311
Work being carried out at the University of Hull into the application of high power laser diodes to the soldering process is described. The commercial availability of semiconductor diode lasers has brought an exciting new soldering tool to the manufacturers of electronics assemblies: trends in electronics assembly are to increasingly high-density interconnections and increasing device functionality. Packages are reducing in size and pin-out counts are increasing. Currently 0.010–0.016 inch lead pitch devices are being introduced by many manufacturers. Lasers can be used with advantage in the soldering of such fine and precise devices and high-power semiconductor laser diodes can be used to build compact, flexible and controllable soldering units. With computer control of the power and duration of the laser energy it is possible to ensure consistent and reliable soldering. To achieve this, however, the various parameters involved in the laser beam-solder assembly interaction need to be carefully defined. This paper reports on our identification of these parameters and the salient design features of an automated diode laser soldering system. 相似文献
119.
M. Senba R. E. Turner D. J. Arseneau D. M. Garner L. Y. Lee I. D. Reid D. G. Fleming 《Hyperfine Interactions》1986,32(1-4):795-799
The spin polarization of positive muons thermalized in Xe has been measured as a function of pressure up to 4660 Torr (6.1
atm) by the muon spin rotation (MSR) technique. At 4660 Torr, triplet muonium (F=1, M=1) accounts for about 40% of the initial
muon polarization and no significant signal from diamagnetic muons has been observed. The unexpectedly slow recovery of the
polarization in Xe at high pressures is discussed in conjunction with similar results seen in CCl4 and CHCl3 vapors. 相似文献
120.