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991.
Cianetti S Négrerie M Vos MH Martin JL Kruglik SG 《Journal of the American Chemical Society》2004,126(43):13932-13933
Cytochrome c (cyt c) is an electron-transfer heme protein that also binds nitric oxide (NO). In resting cyt c, two endogenous ligands of the heme iron are histidine-18 (His) and methionine-80 (Met) side chains, and NO binding requires the cleavage of one of the axial bonds. Previous femtosecond transient absorption studies suggested the photolysis of either Fe-His or Fe-Met bonds. We aimed at unequivocally identifying the internal side chain that is photodissociated in ferrous cyt c and at monitoring heme structural dynamics, by means of time-resolved resonance Raman (TR3) spectroscopy with approximately 0.6 ps time resolution. The Fe-His stretching mode at 216 cm-1 has been observed in photoproduct TR3 spectra for the first time for a c-type heme. The same transient mode was observed for a model ferrous cyt c N-fragment (residues 1-56) ligated with two His in the resting state. Our TR3 data reveal that upon ferrous cyt c photoexcitation, (i) distal Met side chain is instantly released, producing a five-coordinated domed heme structure, (ii) proximal His side chain, coupled to the heme, exhibits distortion due to strain exerted by the protein, and (iii) alteration in heme-cysteine coupling takes place along with the relaxation of the protein-induced deformations of the heme macrocycle. 相似文献
992.
Sibrina N. Collins Constance M. Brett Bruce E. Bursten 《Journal of Cluster Science》2004,15(4):469-487
The photochemical CO-loss products of the diruthenium complexes [CpRu(CO) 2]2 (5; Cp = 5-C5H5), [Cp*Ru(CO)2]2 (5*; Cp* = 5-C5(CH3)5) and CpCp*[Ru(CO)2]2 (5) have been studied experimentally in low-temperature (96 K) matrices in 3-methylpentane by using IR spectroscopy. It is proposed that all three complexes undergo single-CO-loss chemistry but that the products have different structures. The single-CO-loss product from 5 is proposed to have one bridging and two terminal carbonyl ligands, whereas 5* and 5 generate triply bridged CO-loss products similar to that observed from [CpFe(CO)2]2 and [Cp*Fe(CO)2]2. Double-CO-loss from 5* and 5*
9 is also apparently observed. Relativistic DFT calculations have been carried out on various isomers of the starting materials and on potential CO-loss products from 5. The calculations suggest that the triply bridged product Cp2Ru2(-CO)3 (6) might have a singlet ground state in contrast to the corresponding diiron complex Cp2Fe2(-CO)3 (3), which has a triplet ground state. 相似文献
993.
Martin Gruebele 《Theoretical chemistry accounts》2003,109(2):53-63
Vibrational energy flow in organic molecules occurs by a multiple-time-scale mechanism that can be modeled by a single exponential
only in its initial stages. The mechanism is a consequence of the hierarchical structure of the vibrational Hamiltonian, which
leads to diffusion of vibrational wavepackets on a manifold with far fewer than the 3N−6 dimensions of the full vibrational state space. The dynamics are controlled by a local density of states, which does not
keep increasing with molecular size. In addition, the number of vibrational coordinates severely perturbed during chemical
reaction is small, leading to preservation of the hierarchical structure at chemically interesting energies. This regularity
opens up the possibility of controlling chemical reactions by controlling the vibrational energy flow. Computationally, laser
control of intramolecular vibrational energy redistribution can be modeled by quantum-classical, or by purely quantum-mechanical
models of the molecule and control field.
Received: 26 July 2002 / Accepted: 30 September 2002 / Published online: 2 December 2002
Electronic Supplementary Material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00214-002-0394-2.
Acknowledgements. This work was supported by NSF grant CHE 9986670.
Correspondence to: M. Gruebele e-mail: gruebele@scs.uiuc.edu 相似文献
994.
In situ polarized Fourier transform IR external reflection spectra of Langmuir monolayers of zinc stearate and zinc 12-hydroxystearate
on a water surface were recorded for various surface areas, and their molecular structures were estimated. In the zinc stearate
monolayer, the wavenumbers and the absorbances of the antisymmetric and symmetric methylene stretching bands did not change
during monolayer compression, which means that orientational and conformational changes of the hydrocarbon chain did not occur.
However, wavenumber changes of the antisymmetric and symmetric carboxylate stretching bands were observed during surface compression.
The change in the binding nature of the zinc cation to the carboxylate group was speculated. Moreover, it was elucidated that
the structure of the hydrocarbon chain in the zinc 12-hydroxystearate monolayer was different from that in the zinc stearate
monolayer.
Received: 21 March 2001 Accepted: 6 July 2001 相似文献
995.
996.
Ivan Gutman 《Monatshefte für Chemie / Chemical Monthly》2005,136(6):1055-1069
Summary. The fact that cyclic arrangements of double bonds have a dramatic effect on the behavior of conjugated organic molecules is known since the 19th century. The fact that in monocyclic conjugated systems the size of the cycle and the number of -electrons involved is decisive for their stability (aromaticity) or lack of stability (antiaromaticity) is known since the 1930s. In polycyclic -electron systems several cyclic effects are present simultaneously and their separation became possible only recently. A molecular orbital method has been elaborated, by means of which the energy effects of individual cycles in polycyclic -electron systems can be estimated. This method is briefly outlined and illustrated by pertinent examples. An exhaustive bibliography of the topic considered is given. 相似文献
997.
Claudia Mureşanu Lucian Copolovici Florina Pogącean 《Central European Journal of Chemistry》2005,3(4):592-604
The inhibitory effect of para-nitrophenol on the catalytic reaction of catalase was investigated. Michaelis-Menten kinetic parameters were determined from
Lineweaver-Burk plots obtained in the absence or in the presence of the inhibitor. The inhibitor pattern, revealed by the
Lineweaver-Burk plots, suggested a fully mixed inhibition mechanism. Spectrophotometric monitoring of the indicator reaction:
in conjunction with initial rate measurements was employed for the kinetic determination of the inhibitor. Calibration plots
of initial rate vs. para-nitrophenol concentration were linear in the concentration range 0.9·10−5–2.5·10−5 mol/L and the detection limit was 3·10−6 mol/L (417 μg/L) para-nitrophenol. Interferences from other phenolic compounds like orto-cresole, meta-and orto-nitrophenol were observed. 相似文献
998.
[reaction: see text] A short synthesis of intermediates possessing the tricyclic core of natural madangamines, bioactive alkaloids found in marine sponges, is described. The key reaction entails the condensation of the sodium salt of diethylacetonedicarboxylate with a dihydropyridinium salt derivative. This new approach is modeled on a biogenetic proposal linking madangamines to ircinals, related alkaloids occurring in sponges of the same order. 相似文献
999.
M. Alami R. Brochu J. L. SoubeyrouxP. Gravereau G. Le FlemP. Hagenmuller 《Journal of solid state chemistry》1991,90(2)
LiGe2(PO4)3 belongs to the Nasicon-type family. Room-temperature structure has been determined on a single crystal from 3D X-ray data. Thermal evolution of this structure has been established from neutron powder diffraction data between 300 and 1000 K using the Rietveld method. The thermal expansion is positive along the c-axis, whereas shrinking is observed along the a-axis below 900 K, followed by dilatation. The atomic displacements noted with increasing temperature are consistent with a model proposed for NaZr2(PO4)3. 相似文献
1000.