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991.
Reetz MT Peyralans JJ Maichele A Fu Y Maywald M 《Chemical communications (Cambridge, England)》2006,(41):4318-4320
The concept of utilizing the methods of directed evolution for tuning the enantioselectivity of synthetic achiral metal-ligand centers anchored to proteins has been implemented experimentally for the first time. 相似文献
992.
Chin KK Chuang SC Hernandez B Selke M Foote CS Garcia-Garibay MA 《The journal of physical chemistry. A》2006,110(51):13662-13666
The photophysical properties of a novel 1,2,3,4,5,6-hexasubstituted fullerene derivative (1) are examined in this study. In addition to the ground state absorption spectrum of 1, we report its triplet-triplet absorption spectrum and molar extinction coefficient (Deltae(T-T)), as well as the triplet quantum yield (PhiT), lifetime (tauT), and energy (ET). The saturation of a single six-member ring on the fullerene cage results in significant changes in the triplet state properties as compared to that of pristine C60. The triplet-triplet absorption spectrum shows a hypsochromic shift in long wavelength absorption, and both the triplet state lifetime and the triplet quantum yield are decreased. The triplet energy was found to be similar to that of C60. In addition, the quantum yield (PHI(delta)) of singlet oxygen generated by 1 was calculated and is found to be significantly less than in the case of C60. 相似文献
993.
Hoyermann K Nothdurft J Olzmann M Wehmeyer J Zeuch T 《The journal of physical chemistry. A》2006,110(9):3165-3173
The formation and the decomposition of chemically activated cyclopentoxy radicals from the c-C5H9 + O reaction have been studied in the gas phase at room temperature. Two different experimental arrangements have been used. Arrangement A consisted of a laser-flash photolysis set up combined with quantitative Fourier transform infrared spectroscopy and allowed the determination of the stable products at 4 mbar. The c-C5H9 radicals were produced via the reaction c-C5H10 + Cl with chlorine atoms from the photolysis of CFCl3; the O atoms were generated by photolysis of SO2. Arrangement B, a conventional discharge flow-reactor with molecular beam sampling, was used to determine the rate coefficient. Here, the hydrocarbon radicals (c-C5H9, C2H5, CH2OCH3) were produced via the reaction of atomic fluorine with c-C5H10, C2H6, and CH3OCH3, respectively, and detected by mass spectrometry after laser photoionization. For the c-C5H9 + O reaction, the relative contributions of intermediate formation (c-C5H9O) and direct abstraction (c-C5H8 + OH) were found to be 68 +/- 5 and 32 +/- 4%, respectively. The decomposition products of the chemically activated intermediate could be identified, and the following relative branching fractions were obtained: c-C5H8O + H (31 +/- 2%), CH2CH(CH2)2CHO + H (40 +/- 5%), 2 C2H4 + H + CO (17 +/- 5%), and C3H4O + C2H4 + H (12 +/- 5%). Additionally, the product formation of the c-C5H8 + O reaction was studied, and the following relative yields were obtained (mol %): C2H4, 24%; C3H4O, 18%; c-C5H8O, 30%; c-C5H8O, 23%; 4-pentenal, 5%. The rate coefficient of the c-C5H9 + O reaction was determined relative to the reactions C2H5 + O and CH3OCH2 + O leading to k = (1.73 +/- 0.05) x 10(14) cm3 mol(-1) s(-1). The experimental branching fractions are analyzed in terms of statistical rate theory with molecular and transition-state data from quantum chemical calculations, and high-pressure limiting Arrhenius parameters for the unimolecular decomposition reactions of C5H9O species are derived. 相似文献
994.
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997.
Weiss ME Fischer DF Xin ZQ Jautze S Schweizer WB Peters R 《Angewandte Chemie (International ed. in English)》2006,45(34):5694-5698
998.
Reconstruction of dynamic contrast enhanced magnetic resonance imaging of the breast with temporal constraints 总被引:1,自引:0,他引:1
A number of methods using temporal and spatial constraints have been proposed for reconstruction of undersampled dynamic magnetic resonance imaging (MRI) data. The complex data can be constrained or regularized in a number of different ways, for example, the time derivative of the magnitude and phase image voxels can be constrained separately or jointly. Intuitively, the performance of different regularizations will depend on both the data and the chosen temporal constraints. Here, a complex temporal total variation (TV) constraint was compared to the use of separate real and imaginary constraints, and to a magnitude constraint alone. Projection onto Convex Sets (POCS) with a gradient descent method was used to implement the diverse temporal constraints in reconstructions of DCE MRI data. For breast DCE data, serial POCS with separate real and imaginary TV constraints was found to give relatively poor results while serial/parallel POCS with a complex temporal TV constraint and serial POCS with a magnitude-only temporal TV constraint performed well with an acceleration factor as large as R=6. In the tumor area, the best method was found to be parallel POCS with complex temporal TV constraint. This method resulted in estimates for the pharmacokinetic parameters that were linearly correlated to those estimated from the fully-sampled data, with Ktrans,R=6=0.97 Ktrans,R=1+0.00 with correlation coefficient r=0.98, kep,R=6=0.95 kep,R=1+0.00 (r=0.85). These results suggest that it is possible to acquire highly undersampled breast DCE-MRI data with improved spatial and/or temporal resolution with minimal loss of image quality. 相似文献
999.
Daniel Hartmann Matthias Meinke Wolfgang Schr?der 《Journal of computational physics》2010,229(5):1514-1535
Based on the constrained reinitialization scheme [D. Hartmann, M. Meinke, W. Schröder, Differential equation based constrained reinitialization for level set methods, J. Comput. Phys. 227 (2008) 6821–6845] a new constrained reinitialization equation incorporating a forcing term is introduced. Two formulations for high-order constrained reinitialization (HCR) are presented combining the simplicity and generality of the original reinitialization equation [M. Sussman, P. Smereka, S. Osher, A level set approach for computing solutions to incompressible two-phase flow, J. Comput. Phys. 114 (1994) 146–159] in terms of high-order standard discretization and the accuracy of the constrained reinitialization scheme in terms of interface displacement. The novel HCR schemes represent simple extensions of standard implementations of the original reinitialization equation. The results evidence the significantly increased accuracy and robustness of the novel schemes. 相似文献
1000.
The purpose of this paper is to extend classical modal analysis to decouple any viscously damped linear system in non-oscillatory free vibration or in forced vibration. Based upon an exposition of how exponential decay in a system can be regarded as imaginary oscillations, the concept of damped modes of imaginary vibration is introduced. By phase synchronization of these real and physically excitable modes, a time-varying transformation is constructed to decouple non-oscillatory free vibration. When time drifts caused by viscous damping and by external excitation are both accounted for, a time-varying decoupling transformation for forced vibration is derived. The decoupling procedure devised herein reduces to classical modal analysis for systems that are undamped or classically damped. This paper constitutes the second and final part of a solution to the “classical decoupling problem.” Together with an earlier paper, a general methodology that requires only the solution of a quadratic eigenvalue problem is developed to decouple any damped linear system. 相似文献