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531.
KM Clapham T Rennison G Jones F Craven J Bardos BT Golding RJ Griffin K Haggerty IR Hardcastle P Thommes A Ting C Cano 《Organic & biomolecular chemistry》2012,10(33):6747-6757
Substitution at the 7-position of the chromen-4-one pharmacophore of 8-(dibenzo[b,d]thiophen-4-yl)-2-morpholino-4H-chromen-4-one NU7441, a potent and selective DNA-dependent protein kinase (DNA-PK) inhibitor, with allyl, n-propyl or methyl enabled the resolution by chiral HPLC of atropisomers. Biological evaluation against DNA-PK of each pair of atropisomers showed a marked difference in potency, with biological activity residing exclusively in the laevorotatory enantiomer. 相似文献
532.
Reid GD Whittaker DJ Day MA Turton DA Kayser V Kelly JM Beddard GS 《Journal of the American Chemical Society》2002,124(19):5518-5527
Quenching of redox active, intercalating dyes by guanine bases in DNA can occur on a femtosecond time scale both in DNA and in nucleotide complexes. Notwithstanding the ultrafast rate coefficients, we find that a classical, nonadiabatic Marcus model for electron transfer explains the experimental observations, which allows us to estimate the electronic coupling (330 cm(-1)) and reorganization (8070 cm(-1)) energies involved for thionine-[poly(dG-dC)](2) complexes. Making the simplifying assumption that other charged, pi-stacked DNA intercalators also have approximately these same values, the electron-transfer rate coefficients as a function of the driving force, DeltaG, are derived for similar molecules. The rate of electron transfer is found to be independent of the speed of molecular reorientation. Electron transfer to the thionine singlet excited state from DNA obtained from calf thymus, salmon testes, and the bacterium, micrococcus luteus (lysodeikticus) containing different fractions of G-C pairs, has also been studied. Using a Monte Carlo model for electron transfer in DNA and allowing for reaction of the dye with the nearest 10 bases in the chain, the distance dependence scaling parameter, beta, is found to be 0.8 +/- 0.1 A(-1). The model also predicts the redox potential for guanine dimers, and we find this to be close to the value for isolated guanine bases. Additionally, we find that the pyrimidine bases are barriers to efficient electron transfer within the superexchange limit, and we also infer from this model that the electrons do not cross between strands on the picosecond time scale; that is, the electronic coupling occurs predominantly through the pi-stack and is not increased substantially by the presence of hydrogen bonding within the duplex. We conclude that long-range electron transfer in DNA is not exceptionally fast as would be expected if DNA behaved as a "molecular wire" but nor is it as slow as is seen in proteins, which do not benefit from pi-stacking. 相似文献
533.
Gavin R. Hedwig Geoffrey B. Jameson Harald Høiland 《Journal of solution chemistry》2014,43(4):804-820
Sound speeds have been measured for aqueous solutions of the nucleoside thymidine at T = 298.15 K and at the pressures p = (10, 20, 40, 60, 80, and 100) MPa. The partial molar volumes at infinite dilution, $ V_{2}^{\text{o}} $ , the partial molar isentropic compressions at infinite dilution, $ K_{S,2}^{\text{o}} $ , and the partial molar isothermal compressions at infinite dilution, $ K_{T,2}^{\text{o}} $ $ \{ K_{T,2}^{\text{o}} = - (\partial V_{2}^{\text{o}} /\partial p)_{T} \} $ , have been derived from the sound speeds at elevated pressures using methods described in our previous work. The $ V_{2}^{\text{o}} $ and $ K_{T,2}^{\text{o}} $ results were rationalized in terms of the likely interactions between thymidine and the aqueous solvent. The $ V_{2}^{\text{o}} $ results were also compared with those calculated using the revised Helgeson–Kirkham–Flowers (HKF) equation of state. 相似文献
534.
A method has been developed, optimised and validated to analyse protein powder supplements on an inductively coupled plasma-sector field mass spectrometer (ICP-SFMS), with reference to ICH Guideline Q2 Validation of Analytical Procedures: Text and Methodology. This method was used in the assessment of twenty-one (n = 21) elements (Al, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Mn, Mo, Pb, Pt, Sn, Ti, Tl, V) to evaluate the safety of thirty-six (n = 36) protein powder samples that were commercially available in the Irish marketplace in 2016/2017. Using the determined concentrations of elements in samples (µg·kg−1), a human health risk assessment was carried out to evaluate the potential carcinogenic and other risks to consumers of these products. While the concentrations of potentially toxic elements were found to be at acceptable levels, the results suggest that excessive and prolonged use of some of these products may place consumers at a slightly elevated risk for developing cancer or other negative health impacts throughout their lifetimes. Thus, the excessive use of these products is to be cautioned, and consumers are encouraged to follow manufacturer serving recommendations. 相似文献
535.