排序方式: 共有51条查询结果,搜索用时 31 毫秒
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Linder DP Rodgers KR Banister J Wyllie GR Ellison MK Scheidt WR 《Journal of the American Chemical Society》2004,126(43):14136-14148
Recent years have seen dramatic growth in our understanding of the biological roles of nitric oxide (NO). Yet, the fundamental underpinnings of its reactivities with transition metal centers in proteins and enzymes, the stabilities of their structures, and the relationships between structure and reactivity remains, to a significant extent, elusive. This is especially true for the so-called ferric heme nitrosyls ([FeNO](6) in the Enemark-Feltham scheme). The Fe-CO and C-O bond strengths in the isoelectronic ferrous carbonyl complexes are widely recognized to be inversely correlated and sensitive to structural, environmental, and electronic factors. On the other hand, the Fe-NO and N-O bonds in [FeNO](6) heme complexes exhibit seemingly inconsistent behavior in response to varying structure and environment. This report contains resonance Raman and density functional theory results that suggest a new model for FeNO bonding in five-coordinate [FeNO](6) complexes. On the basis of resonance Raman and FTIR data, a direct correlation between the nu(Fe)(-)(NO) and nu(N)(-)(O) frequencies of [Fe(OEP)NO](ClO(4)) and [Fe(OEP)NO](ClO(4)).CHCl(3) (two crystal forms of the same complex) has been established. Density functional theory calculations show that the relationship between Fe-NO and N-O bond strengths is responsive to FeNO electron density in three molecular orbitals. The highest energy orbital of the three is sigma-antibonding with respect to the entire FeNO unit. The other two comprise a lower-energy, degenerate, or nearly degenerate pair that is pi-bonding with respect to Fe-NO and pi-antibonding with respect to N-O. The relative sensitivities of the electron density distributions in these orbitals are shown to be consistent with all published indicators of Fe-N-O bond strengths and angles, including the examples reported here. 相似文献
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A new, vectorial approach to fast correlation attacks on binary memoryless combiners is proposed. Instead of individual input sequences or their linear combinations, the new attack is targeting subsets of input sequences as a whole thus exploiting the full correlation between the chosen subset and the output sequence. In particular, the set of all the input sequences can be chosen as the target. The attack is based on a novel iterative probabilistic algorithm which is also applicable to general memoryless combiners over finite fields or finite rings. To illustrate the effectiveness of the introduced approach, experimental results obtained for random balanced combining functions are presentedMost of this work was done while he was with Rome CryptoDesign Center, Gemplus, Italy 相似文献
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The motion of a holonomic scleronomic non-conservative mechanicalsystem with minimal dissipation is considered. As applicationsof the theory several problems are studied in detail. 相似文献
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Starovoitova V Budarz TE Wyllie GR Scheidt WR Sturhahn W Alp EE Prohofsky EW Durbin SM 《The journal of physical chemistry. B》2006,110(26):13277-13282
The normal-mode spectrum for the four-coordinated heme compound Fe(II) octaethylporphyrin, Fe(OEP), has been determined by refining force constants to the experimental Fe vibrational density of states measured with nuclear resonance vibrational spectroscopy (NRVS). Convergence of the calculated spectrum to the data was achieved by first imposing D4 symmetry on the model structure as well as the force constants, progressively including different internal coordinates of motion, then allowing the true Ci (or S2) point group symmetry of the C(i)1 Fe(OEP) crystal structure. The NRVS-refined normal modes are in good agreement with Raman and IR spectra at high frequencies. Prior density functional theory predictions for a model porphyrin are similar to the core modes computed with the best-fit force field, but significant differences between D4 and Ci modes underline the sensitivity of porphyrin Fe normal modes to structural details. Some differences between the Ci best fit and the NRVS data can be attributed to intermolecular contacts not included in the normal-mode analysis. 相似文献
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Chia PW Livesey MR Slawin AM van Mourik T Wyllie DJ O'Hagan D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(28):8813-8819
N-Methyl-D-aspartate (NMDA) is the prototypical agonist of the NMDA receptor subtype of ionotropic glutamate receptors. Stereogenic placement of a C-F bond at the 3-position of (S)-NMDA generates either the (2S,3S)- or (2S,3R)- diastereoisomers of 3F-NMDA. The individual diastereoisomers were prepared by synthesis in enantiomerically pure forms and it was found that (2S,3S)-3F-NMDA is an agonist with a comparable potency to NMDA itself, whereas the (2S,3R)-diastereoisomer has negligible potency. The difference in potency of these stereoisomers is attributed to a preference of the C-F bond (2S,3S)-3F-NMDA to adopt a gauche conformation to the C-N(+) bond in the binding conformation, whereas the (2S,3R)-3F-NMDA forces these bonds anti, losing electrostatic stabilisation, to achieve the required binding conformation. These observations illustrate the utility of stereoselective fluorination in influencing the molecular conformation of β-fluorinated amino acids and thus probing the active conformations of bioactive compounds at receptors. 相似文献
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A Mukherjee M Dasgupta DJ Hinde CR Morton AC Berriman RD Butt JO Newton H Timmers 《Pramana》2001,57(1):195-198
Fusion cross-sections for the 7Li + 12C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy
evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their
contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections
due to the breakup of 7Li may not be significant for 7Li + 12C reaction at energies around the barrier. 相似文献
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The alternating step generator is a well-known keystream generator consisting of two stop/go clocked LFSRs, LFSR1 and LFSR2, whose clocks are controlled by another LFSR, LFSR3, which is clocked regularly. A probabilistic analysis of this generator is conducted which shows that the posterior probabilites of individual bits of the first derivatives of the regularly clocked LFSR1 and LFSR2 sequences, when conditioned on a given segment of the first derivative of the keystream sequence, can be computed efficiently in a number of probabilistic models of interest. The expected values of these probabilities, for a random keystream sequence, are derived by an approximate theoretical analysis and are also verified by systematic computer experiments. It is pointed out that these posterior probabilities can be enhanced in a resynchronization scenario and thus used for a low-complexity fast correlation attack on the two LFSRs. More generally, it is argued that even without resynchronization these probabilities may be significantly different from one half for fast correlation attacks based on iterative decoding algorithms to be successful, although with incresead complexity. A related method for computing the posterior probabilities of individual bits of the LFSR3 sequence, when conditioned on both the keystream sequence and the LFSR1 and LFSR2 sequences, is also developed. As these posterior probabilities are much more different from one half, they can be used for a low-complexity fast correlation attack on LFSR3, provided that the initial states of LFSR1 and LFSR2 are previously reconstructed. 相似文献
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