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91.
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93.
A key contact in the active site of an aminoglycoside phosphotransferase enzyme (APH(3')-IIIa) is a pi-pi stacking interaction between Tyr42 and the adenine ring of bound nucleotides. We investigated the prevalence of similar Tyr-adenine contacts and found that many different protein systems employ Tyr residues in the recognition of the adenine ring. The geometry of these stacking interactions suggests that electrostatics play a role in the attraction between these aromatic systems. Kinetic and calorimetric experiments on wild-type and mutant forms of APH(3')-IIIa yielded further experimental evidence of the importance of electrostatics in the adenine binding region and suggested that the stacking interaction contributes approximately 2 kcal/mol of binding energy. This type of information concerning the forces that govern nucleotide binding in APH(3')-IIIa will facilitate inhibitor design strategies that target the nucleotide binding site of APH-type enzymes. 相似文献
94.
Dallera C Grioni M Shukla A Vankó G Sarrao JL Rueff JP Cox DL 《Physical review letters》2002,88(19):196403
Resonant inelastic x-ray scattering (RIXS) yields clear evidence of spectroscopic Kondo scales in heavy fermions. In YbInCu4 and YbAgCu4 RIXS probes the Yb2+ component of the hybrid ground state and the temperature dependence of the Yb 4f occupation. We report a sudden valence change at a phase transition in YbInCu4, but a continuous temperature dependence in YbAgCu4, consistent with the predictions of the Anderson impurity model, for a Kondo temperature T(K) = 70 K. These results solve a long-standing controversy and establish RIXS as a quantitative probe of the electronic structure of strongly correlated electron systems. 相似文献
95.
Intelligibility ratings of continuous discourse: application to hearing aid selection 总被引:1,自引:0,他引:1
Twelve normal-hearing subjects rated the intelligibility of 35-s, hearing-aid-processed continuous discourse (CD) passages. Three talkers (two male, one female), four hearing aids, and two signal-to-babble (S/B) ratios were used in a completely crossed design. Research questions concerned: (1) ability of listeners to rate intelligibility, (2) sensitivity of hearing aid rankings were based on intelligibility ratings for three CD passages per instrument, and (3) dependence of hearing aid rankings on (a) S/B ratio, and (b) talker characteristics. Results were: (1) listeners were able to rate intelligibility, (2) rankings based on intelligibility ratings of three CD passages per hearing aid were capable of identifying two superior instruments within a group of four hearing aids that were similar in frequency/gain function, (3) listening in a more difficult S/B ratio substantially decreased the sensitivity of the hearing aid rankings for the female talker but had only minor effects on the rankings for the male talkers, and (4) hearing aid intelligibility rankings were found to be different for different talkers. Applications to hearing aid selection are discussed. 相似文献
96.
The 13C? 13C spin coupling constants have been determined in substituted [1-13C]tetrahydronaphthylenes, [5-13C]hexahydrobenzanthracenes and [5-13C]benzanthracene. In addition, the 13C? 13C spin coupling constants for 7-hydroxy[7-13C]benzopyrene, trans-7,8-dihydro[7-13C]benzopyrene-7,8-diol and trans-7,8-dihydro[10-13C]benzopyrene-7,8-diol are reported, together with the one-bond carbon-carbon coupling constants between C-4 and C-5 in selected 4,5-disubstituted benzopyrenes. Values for the directly bonded coupling constants and long-range coupling constants are similar to those reported previously for other aromatic and aliphatic systems. Substituent effects on carbon-carbon coupling are compared for similarly substituted cyclic and acyclic systems. 相似文献
97.
Let Z = {Z0, Z1, Z2,…} be a martingale, with difference sequence X0 = Z0, Xi = Zi ? Zi ? 1, i ≥ 1. The principal purpose of this paper is to prove that the best constant in the inequality λP(supi |Xi| ≥ λ) ≤ C supiE |Zi|, for λ > 0, is C = (log 2)?1. If Z is finite of length n, it is proved that the best constant is . The analogous best constant Cn(z) when Z0 ≡ z is also determined. For these finite cases, examples of martingales attaining equality are constructed. The results follow from an explicit determination of the quantity Gn(z, E) = supzP(maxi=1,…,n |Xi| ≥ 1), the supremum being taken over all martingales Z with Z0 ≡ z and E|Zn| = E. The expression for Gn(z,E) is derived by induction, using methods from the theory of moments. 相似文献
98.
The UV absorption spectrum of acetylperoxy radicals, produced in several photochemical systems, has been investigated using the molecular modulation technique. Rate coefficients were determined at 28 and 715 Torr for the reaction CH3COO2 + NO2(+M) → CH3COO2NO2(+M), which exhibits a pressure dependence. 相似文献
99.
100.
Electron spin resonance has been observed for Fe3+ and Mn2+ ions occupying sites with trigonal symmetry in undoped and doped Verneuil-grown crystals of the ilmenite type compound MgTiO3. At 300 K, the fine structure parameters in the spin Hamiltonian are (in 10?4cm?1) D = +844 (± 1), (a? F) = +118 (± 1), a = 69 (± 7) for Fe3+ and D = +164 (± 1), (a ? F) = +10.2 (± l), a = 7.0 (± 1) for Mn2+. These values are compared with literature data for Fe3+ and Mn2+ in other oxides, especially Al2o3, with particular reference to the recent “superposition” theory of the effect of a trigonal distortion. From the orientation of the axes of cubic pseudosymmetry of the spin Hamiltonian, and with the assumption that a has the same sign for both ions, it is proposed that Fe3+ and Mn2+ occupy the same octahedral site, namely the Mg2+ site. Anomalous line splittings observed for one sample were attributed to twinning on (0001) or {1120} planes. 相似文献