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991.
Miller BJ Du L Steel TJ Paul AJ Södergren AH Lane JR Henry BR Kjaergaard HG 《The journal of physical chemistry. A》2012,116(1):290-296
Vibrational spectra of vapor-phase dimethylamine (DMA) and pyrrole have been recorded in the 1000 to 13000 cm(-1) region using long path conventional spectroscopy techniques. We have focused on the absolute intensities of the NH-stretching fundamental and overtone transitions; Δν(NH) = 1-4 regions for DMA and the Δν(NH) = 1-3 regions for pyrrole. In the Δν(NH) = 1-3 regions for DMA, evidence of tunneling splitting associated with the NH-wagging mode is observed. For DMA, the fundamental NH-stretching transition intensity is weaker than the first NH-stretching overtone. Also, the fundamental NH-stretching transition in DMA is much weaker than the fundamental transition in pyrrole. We have used an anharmonic oscillator local mode model with ab initio calculated local mode parameters and dipole moment functions at the CCSD(T)/aug-cc-pVTZ level to calculate the NH-stretching intensities and explain this intensity anomaly in DMA. 相似文献
992.
993.
Smith BA O'Neil EJ Lampkins AJ Johnson JR Lee JJ Cole EL Smith BD 《Journal of fluorescence》2012,22(1):93-101
A series of fluorescent phosphatidylserine and phosphatidylcholine derivatives were prepared and evaluated by cell microscopy
for ability to translocate across mammalian plasma membranes via the putative aminophospholipid flippase. Phosphatidylserine
derivatives, with either a neutral 7-nitrobenz-2-oxa-1,3-diazol-4-yl (NBD) or a coumarin fluorophore appended to the 2-acyl
chain, entered the cytosol of all three cell lines tested and control experiments showed that the translocation was due to
flippase activity. In contrast, a phosphatidylserine conjugate containing a charged and polar carboxyfluorescein was not translocated
and remained in the cell plasma membrane. The phosphatidylserine-coumarin derivative exhibits bright fluorescence and higher
photostability than the NBD analogues, and thus is a promising new fluorescent probe for extended-imaging studies of flippase
action in living cells using laser confocal microscopes. 相似文献
994.
Realizing the theoretical promise of quantum computers will require overcoming decoherence. Here we demonstrate numerically that high fidelity quantum gates are possible within a framework of quantum dynamical decoupling. Orders of magnitude improvement in the fidelities of a universal set of quantum gates, relative to unprotected evolution, is achieved over a broad range of system-environment coupling strengths, using recursively constructed (concatenated) dynamical decoupling pulse sequences. 相似文献
995.
Gick B Ikegami Y Derrick D 《The Journal of the Acoustical Society of America》2010,128(5):EL342-EL346
Asynchronous cross-modal information is integrated asymmetrically in audio-visual perception. To test whether this asymmetry generalizes across modalities, auditory (aspirated "pa" and unaspirated "ba" stops) and tactile (slight, inaudible, cutaneous air puffs) signals were presented synchronously and asynchronously. Results were similar to previous AV studies: the temporal window of integration for the enhancement effect (but not the interference effect) was asymmetrical, allowing up to 200 ms of asynchrony when the puff followed the audio signal, but only up to 50 ms when the puff preceded the audio signal. These findings suggest that perceivers accommodate differences in physical transmission speed of different multimodal signals. 相似文献
996.
E.G. Yukihara Luiz G. Jacobsohn Michael W. Blair Bryan L. Bennett Stephanie C. Tornga Ross E. Muenchausen 《Journal of luminescence》2010,130(12):2309-2316
In this work we investigate and compare the thermoluminescence (TL) and related luminescent properties of cerium-doped Lu2SiO5 (LSO), Gd2SiO5 (GSO), and Y2SiO5 (YSO) nanophosphors prepared by solution combustion synthesis (SCS) to the properties of their single crystal counterparts. Photoluminescence emission and excitation spectra were obtained for comparison with TL and radioluminescence (RL) emission bands. We then compared the structure and intensity of TL curves, RL intensity, and afterglow at room temperature and investigated the trapped charge stability (revealed by TL). The results showed that the SCS technique is capable of producing scintillating materials with less afterglow and RL output comparable to single crystals. The nanophosphor samples also showed lower TL intensities than their single crystal counterparts, which points to a lower concentration of trapping centers. These results demonstrate the potential of nanophosphors produced by SCS for use as scintillators. 相似文献
997.
Francesco Barioli H. Tracy Hall Leslie Hogben Bryan Shader Hein van der Holst 《Linear algebra and its applications》2010,433(2):401-536
The zero forcing number Z(G), which is the minimum number of vertices in a zero forcing set of a graph G, is used to study the maximum nullity/minimum rank of the family of symmetric matrices described by G. It is shown that for a connected graph of order at least two, no vertex is in every zero forcing set. The positive semidefinite zero forcing number Z+(G) is introduced, and shown to be equal to |G|-OS(G), where OS(G) is the recently defined ordered set number that is a lower bound for minimum positive semidefinite rank. The positive semidefinite zero forcing number is applied to the computation of positive semidefinite minimum rank of certain graphs. An example of a graph for which the real positive symmetric semidefinite minimum rank is greater than the complex Hermitian positive semidefinite minimum rank is presented. 相似文献
998.
Bryan Petrak 《Journal of Geometry》2010,99(1-2):101-106
It has been conjectured that all non-desarguesian projective planes contain a Fano subplane. The Figueroa planes are a family of non-translation planes that are defined for both infinite orders and finite order q 3 for q > 2 a prime power. We will show that there is an embedded Fano subplane in the Figueroa plane of order q 3 for q any prime power. 相似文献
999.
The rotational spectra for six isotopologues of the complex formed between formamide and formic acid have been measured using a pulsed-beam Fourier transform microwave spectrometer and analyzed to obtain rotational constants and quadrupole coupling parameters. The rotational constants and quadrupole coupling strengths obtained for H (12)COOH-H(2) (14)NCOH are A = 5889.465(2), B = 2148.7409(7), 1575.1234(6), eQq(aa) = 1.014(5), eQq(bb) = 1.99(1), and eQq(cc) = -3.00(1)?MHz. Using the 15 rotational constants obtained for the H (13)COOH, HCOOD, DCOOH, and H(2) (15)NCHO isotopologues, key structural parameters were obtained from a least-squares structure fit. Hydrogen bond distances of 1.78 A? for R(O3?H1) and 1.79 A? for R(H4?O1) were obtained. The "best fit" value for the angle(C-O-H) of formic acid is significantly larger than the monomer value of 106.9° with an optimum value of 121.7(3)°. The complex is nearly planar with inertial defect Δ = -0.158?amu A?(2). The formamide proton is moved out of the molecular plane by 15(3)° for the best fit structure. Density functional theory using B3PW91, HCTH407, and TPSS as well as MP2 and CCSD calculations were performed using 6-311++G(d,p) and the results were compared to experimentally determined parameters. 相似文献
1000.
Wasylenko DJ Ganesamoorthy C Henderson MA Koivisto BD Osthoff HD Berlinguette CP 《Journal of the American Chemical Society》2010,132(45):16094-16106
The mechanistic details of the Ce(IV)-driven oxidation of water mediated by a series of structurally related catalysts formulated as [Ru(tpy)(L)(OH(2))](2+) [L = 2,2'-bipyridine (bpy), 1; 4,4'-dimethoxy-2,2'-bipyridine (bpy-OMe), 2; 4,4'-dicarboxy-2,2'-bipyridine (bpy-CO(2)H), 3; tpy = 2,2';6',2'-terpyridine] is reported. Cyclic voltammetry shows that each of these complexes undergo three successive (proton-coupled) electron-transfer reactions to generate the [Ru(V)(tpy)(L)O](3+) ([Ru(V)=O](3+)) motif; the relative positions of each of these redox couples reflects the nature of the electron-donating or withdrawing character of the substituents on the bpy ligands. The first two (proton-coupled) electron-transfer reaction steps (k(1) and k(2)) were determined by stopped-flow spectroscopic techniques to be faster for 3 than 1 and 2. The addition of one (or more) equivalents of the terminal electron-acceptor, (NH(4))(2)[Ce(NO(3))(6)] (CAN), to the [Ru(IV)(tpy)(L)O](2+) ([Ru(IV)=O](2+)) forms of each of the catalysts, however, leads to divergent reaction pathways. The addition of 1 eq of CAN to the [Ru(IV)=O](2+) form of 2 generates [Ru(V)=O](3+) (k(3) = 3.7 M(-1) s(-1)), which, in turn, undergoes slow O-O bond formation with the substrate (k(O-O) = 3 × 10(-5) s(-1)). The minimal (or negligible) thermodynamic driving force for the reaction between the [Ru(IV)=O](2+) form of 1 or 3 and 1 eq of CAN results in slow reactivity, but the rate-determining step is assigned as the liberation of dioxygen from the [Ru(IV)-OO](2+) level under catalytic conditions for each complex. Complex 2, however, passes through the [Ru(V)-OO](3+) level prior to the rapid loss of dioxygen. Evidence for a competing reaction pathway is provided for 3, where the [Ru(V)=O](3+) and [Ru(III)-OH](2+) redox levels can be generated by disproportionation of the [Ru(IV)=O](2+) form of the catalyst (k(d) = 1.2 M(-1) s(-1)). An auxiliary reaction pathway involving the abstraction of an O-atom from CAN is also implicated during catalysis. The variability of reactivity for 1-3, including the position of the RDS and potential for O-atom transfer from the terminal oxidant, is confirmed to be intimately sensitive to electron density at the metal site through extensive kinetic and isotopic labeling experiments. This study outlines the need to strike a balance between the reactivity of the [Ru═O](z) unit and the accessibility of higher redox levels in pursuit of robust and reactive water oxidation catalysts. 相似文献