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121.
Gopalakrishnan K Bodenhausen G 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,182(2):254-259
Singlet-states |S=(|alphabeta> - |betaalpha>)/sq.rt.2 can be excited in pairs of coupled spins I and S, first by preparing either a non-vanishing zero-quantum coherence I(+)S(-) or a state of longitudinal two-spin order I(z)S(z) and then by applying a coherent radio-frequency (RF) irradiation with a carrier frequency omega(rf) = (Omega(I) + Omega(S))/2 that lies half-way between the chemical shifts of the two spins involved. The life-times T(S) can be much longer than the spin-lattice relaxation time T(1) of longitudinal magnetization, but singlet-states are ultimately relaxed, not only by dipolar interactions between the active spins or with the external spins, but also as a result of a non-vanishing offset Deltaomega = omega(rf) - (Omega(I) + Omega(S))/2 or an insufficient amplitude of the RF irradiation that fails to fulfill the condition omega(1) > DeltaOmega = (Omega(I) - Omega(S)). In this work, the effect of off-resonance irradiation is explored and an approximate formula for the effective relaxation rate of the singlet population is provided on the basis of perturbation theory. The qualitative features of the dependence of the relaxation rate of the singlet population on the offset Deltaomega and on the difference DeltaOmega of the chemical shifts of the two spins are illustrated by comparison with numerical simulations. 相似文献
122.
BACKGROUND: Mitomycin C (MC), a DNA cross-linking and alkylating agent, targets guanines in the m5CpG sequence with 2-3-fold preference over guanines in unmethylated CpG. Benzo[a]pyrenediolepoxide (BPDE) and several other aromatic carcinogens form guanine adducts with an identical selectivity for m5CpG, and in certain cancers G to T transversion mutation 'hotspots' in the p53 tumor suppressor gene are more frequent at this sequence than at guanines in other sequences. MC appears suitable to probe the general mechanism of this selectivity. RESULTS: A 162-bp DNA fragment containing C, m5C or f5C (5-fluoro cytosine) at all cytosine positions was cross-linked by MC at guanines in CpG steps. The extent of cross-linking increased in the order f5C < C < m5C. Monoalkylation or cross-linking of duplex 12-mer oligonucleotides containing a single CpG, f5CpG or m5CpG step gave yields of adducts that increased in the same order. The rates showed a correlation with the Hammett sigma constant of the methyl and fluoro substituents of the cytosine. Only the base-pair cytosine substituent influenced reactivity of guanine. CONCLUSIONS: The 2-amino group of guanine in the m5CpG sequence of DNA has a greater nucleophilic reactivity with mitomycin than CpG. Evidence is presented for a novel mechanism: transmission of the electron-donating effect of the 5-methyl substituent of the cytosine to guanine through H-bonding of the m5C.G base pair. The results explain the enhanced reaction of BPDE at m5CpG in DNA and the origin of G-T mutational hotspots in the p53 gene in cancer. 相似文献
123.
The Homogenous Relaxation Model (HRM) is used to study thermal non-equilibrium, two-phase flows with flash-boiling and condensation. Typically, such non-equilibrium phase-change models have been studied in one-dimensional flow, but the goal of the present work is to create and utilize a multi-dimensional CFD implementation. The simulations are able to handle general polyhedral meshes, an important convenience for irregular channel or nozzle shapes. The model is applied to flash-boiling flow in short channels and validated against experimental measurements. The simulations predict the multi-dimensional features that have been observed in the past in experiments. Nozzle choking is also observed in the calculations. 相似文献
124.
R. Ramesh Babu K. Sethuraman N. Vijayan G. Bhagavannarayana R. Gopalakrishnan P. Ramasamy 《Crystal Research and Technology》2008,43(1):50-54
The bulk organic single crystal of phthalic anhydride (PA) was grown by vertical Bridgman technique. The structural perfection of the grown crystal was analysed by high resolution X‐ray diffraction (Multicrystal X‐ray diffractometry) studies. The thermal and mechanical properties have been studied. The second harmonic generation relative efficiency of Phthalic anhydride crystal is compared with KDP crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
125.
G. Srinivasan N. Gopalakrishnan Y.S. Yu R. Kesavamoorthy J. Kumar 《Superlattices and Microstructures》2008
Thin films of zinc oxide have been deposited onto (0001) sapphire substrate by sol–gel and spin-coating methods. The XRD pattern showed that the crystallinity of the annealed ZnO films had improved in comparison with that of the as-grown films. Photoluminescence spectra revealed a two-line structure, which is identified in terms of UV emission and defect-related emission. The emission intensity was found to be greatly dependent on heat treatment. Host phonons of ZnO and a shift of the E2 (high) peak from its position have been observed from Raman spectra. The surface morphologies of the film had been improved after annealing was observed from AFM images. 相似文献
126.
Sulaiman Cheruthazhakkat Gopalakrishnan Velliyur K. Balachandran Indira 《平面色谱法杂志一现代薄层色谱法》2014,27(2):88-92
JPC – Journal of Planar Chromatography – Modern TLC - Phytochemical studies were carried out in different parts of three Acacia species viz. A. catechu, A. nilotica and A. leucophloea,... 相似文献
127.
128.
Gyrgy Tarczay Sandhya Gopalakrishnan Terry A. Miller 《Journal of Molecular Spectroscopy》2003,220(2):276-290
Spectroscopic constants for the conformers of the 1-alkoxy radicals were computed by ab initio and density functional methods. These parameters include ground and excited state rotational constants, harmonic frequencies, and
and
excitation energies. Elements of the electronic spin–molecular rotation tensor have also been predicted for the ground electronic state utilizing a simple transformation. The transformation employed the experimentally observed spin-rotation tensor of the ethoxy radical as a reference and the calculated rotational constants of the ethoxy radical and the investigated 1-alkoxy radicals. The predicted spectroscopic parameters are in good agreement with the experimental ones where available, and found to be useful parameters for assigning the rotationally resolved spectral bands to given conformers. 相似文献
129.
130.