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41.
Ratiometric fluorescent chemosensors based on the position of ring annulation of the naphthol–thiazole moiety for quantification of zinc ions in aqueous ethanol were synthesized and investigated. It was found that sensor 3 exhibited a remarkably large red shift of 140 nm in emission upon complexation with Zn2+. A TD-B3LYP/6-31G (d,p) calculation was performed to characterize the nature of the fluorescence behavior of sensor 3 upon Zn2+ complexation. The combination of experimental and computational analyses provides a more complete understanding of the molecular level origin of these unique photophysical properties of this type of chemosensor. 相似文献
42.
We comment on the paper [Song et al., J. Comput. Chem. 2009, 30, 399]. and discuss the efficiency of the orbital optimization and gradient evaluation in the Valence Bond Self Consistent Field (VBSCF) method. We note that Song et al. neglect to properly reference Broer et al., who published an algorithm [Broer and Nieuwpoort, Theor. Chim. Acta 1988, 73, 405] to use a Fock matrix to compute a matrix element between two different determinants, which can be used for an orbital optimization. Further, Song et al. publish a misleading comparison with our VBSCF algorithm [Dijkstra and van Lenthe, J. Chem. Phys. 2000, 113, 2100; van Lenthe et al., Mol. Phys. 1991, 73, 1159] to enable them to favorably compare their algorithm with ours. We give detail timings in terms of different orbital types in the calculation and actual timings for the example cases. © 2012 Wiley Periodicals, Inc. 相似文献
43.
Mubasher Jamil Muneer Ahmad Rashid 《The European Physical Journal C - Particles and Fields》2008,56(3):429-434
We have investigated the model of dark energy interacting with dark matter by choosing inhomogeneous equations of state for
the dark energy and a nonlinear interaction term for the underlying interaction. The equations of state have dependencies
either on the energy densities, the redshift, the Hubble parameter or the bulk viscosity. We have considered these possibilities
and have derived the effective equations of state for the dark energy in each case. 相似文献
44.
45.
Summary This paper deals with testing the hypothesis of independence of two attributes inr×c Markovian Contingency tables. Likelihood ratio test and χ2-test of the form used in contingency tables are proposed. It is observed that both likelihood ratio criterion and χ2-test lead to the same test statistic in the sense that −2 log λ and χ2-test have asymptotically the same distribution. 相似文献
46.
47.
Segmentation of diffusion-weighted echo-planar imaging (DW-EPI) is challenging because of concerns regarding spatial resolution and distortion. Methods commonly used require manual input and often need thresholding measures to segment white matter (WM), gray matter (GM) and cerebrospinal fluid (CSF). This may introduce operator bias and misclassification error. When comparing patients with a diffuse disease process-such as multiple sclerosis (MS)--with healthy controls, although information from all images may be biased due to disease effect, this is more so if the data set employed to perform segmentation is also used as a measured outcome for the study, for example, fractional anisotropy maps. Presented in this work is an unbiased method for segmenting DW-EPI data sets using the b=0 and single-shot inversion recovery EPI into WM, GM and CSF. The method employs an iterative clustering technique to account for partial volume effects and signal variation caused by radiofrequency inhomogeneity. The technique is evaluated with both real and synthetic brain data and results compared with statistical parametric mapping (SPM02). With synthetic brain data, where a gold standard of segmentation exists, the presented method showed less misclassification compared to SPM02. The unbiased method proposed may provide a more accurate methodology of segmentation in the analysis of DWI-EPI images in conditions such as MS. 相似文献
48.
We demonstrate the generation of up to the 63rd harmonic (lambda = 12.6 nm) of a Ti:sapphire laser pulse (150 fs, 10 mJ), using a prepulse- (210-ps,24-mJ) produced boron plasma as the nonlinear medium. The influence of various parameters on the harmonic conversion efficiency was analyzed. The steep decrease in intensity for low-order harmonics (up to 19th order) was followed by a plateau. Typical conversion efficiencies were evaluated to be 10(-4) (for a 3rd harmonic) to 10(-7) (within the plateau region). Harmonic generation appeared to be efficient for the plasma that comprised neutral atoms and singly ionized boron. 相似文献
49.
Kinetic and thermodynamic investigations were performed for a mixed aqueous-organic, 1:1 (v/v) water–1,4-dioxane medium, which was found to be an efficient solvent for the interaction of a neutral dichlorotris(triphenylphosphine) ruthenium(II), RuCl2(PPh3)3 complex with carbon monoxide at atmospheric pressure. During the interaction, RuCl2(PPh3)3 dissociates to a neutral complex dichlorobis(triphenylphosphine) ruthenium(II), RuCl2(PPh3)2, by losing a coordinated PPh3 ligand and RuCl2(PPh3)2 coordinates with CO to form an in situ carbonyl complex RuCl2(CO)(PPh3)2. The in situ formed carbonyl complex RuCl2(CO)(PPh3)2 was thoroughly characterized by equilibrium, spectrophotometric, IR, and electrochemical techniques. Under equilibrium conditions, the rate and dissociation constants for the dissociation of PPh3 from RuCl2(PPh3)3 were found to be favorable for the formation of the carbonyl complex RuCl2(CO)(PPh3)2. The rates of complexation for the formation of RuCl2(CO)(PPh3)2 were found to follow an overall second-order kinetics being first order in terms of the concentrations of both carbon monoxide and RuCl2(PPh3)2. The determined activation parameters corresponding to the rate constant (ΔH# = 35.9 ± 2.5 kJ mol−1 and ΔS# = −122 ± 6 J K−1 mol−1) and thermodynamic parameters corresponding to the formation constant (ΔH° = −33.5 ± 4.5 kJ mol−1, ΔS° = −25 ± 8 J K−1 mol−1, and ΔG° = −25.7 ± 2.0 kJ mol−1) were found to be highly favorable for the formation of the complex RuCl2(CO)(PPh3)2. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 359–369, 2008 相似文献
50.
Sufyan Ababneh Rashid Ansari Ashfaq Khokhar 《Journal of Visual Communication and Image Representation》2009,20(5):303-311
Multimedia content authentication can be achieved by deriving a fragile content-based signature from a media signal and embedding it robustly back into the signal. The perturbation due to embedding needs to be compensated with mechanisms that lead to producing the original signature. Closed form solutions for compensation are not always feasible. In this paper, we propose two iterative compensation schemes to address such scenarios. The first is based on a set-theoretic approach by using projections onto convex sets (POCS), where signature generation and signal fidelity are modeled as convex constraint sets. The other scheme uses an additive iterative approach used in the cases where the POCS approach is not applicable. Examples of successful image authentication are presented to demonstrate the effectiveness of the proposed schemes over a range of watermark-embedding robustness. A comparison with the closed-form compensation scheme, when feasible, is also presented. 相似文献