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71.
Gräwert T Kaiser J Zepeck F Laupitz R Hecht S Amslinger S Schramek N Schleicher E Weber S Haslbeck M Buchner J Rieder C Arigoni D Bacher A Eisenreich W Rohdich F 《Journal of the American Chemical Society》2004,126(40):12847-12855
The ispH gene of Escherichia coli specifies an enzyme catalyzing the conversion of 1-hydroxy-2-methyl-2-(E)-butenyl diphosphate into a mixture of isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP) in the nonmevalonate isoprenoid biosynthesis pathway. The implementation of a gene cassette directing the overexpression of the isc operon involved in the assembly of iron-sulfur clusters into an Escherichia coli strain engineered for ispH gene expression increased the catalytic activity of IspH protein anaerobically purified from this strain by a factor of at least 200. For maximum catalytic activity, flavodoxin and flavodoxin reductase were required in molar concentrations of 40 and 12 microM, respectively. EPR experiments as well as optical absorbance indicate the presence of a [3Fe-4S](+) cluster in IspH protein. Among 4 cysteines in total, the 36 kDa protein carries 3 absolutely conserved cysteine residues at the amino acid positions 12, 96, and 197. Replacement of any of the conserved cysteine residues reduced the catalytic activity by a factor of more than 70 000. 相似文献
72.
M. Schneider R. Bacher P. Blüm D. Gotta K. Heitlinger W. Kunold D. Rohmann J. Egger L. M. Simons K. Elsener 《Zeitschrift für Physik A Hadrons and Nuclei》1991,338(2):217-222
Antiprotonic X-rays from the helium isotopes have been observed at pressures of 36, 72, 375 and 600 mbar. The antiproton beam from LEAR with momenta of 309 and 202 MeV/c has been stopped at these pressures using the cyclotron trap. The X-rays were detected with Si (Li) and intrinsic Ge semiconductor detectors. Absolute X-ray yields were determined and the strong-interaction 2p shifts and the 2p and 3d broadenings measured to be 2p=(–17±4) eV, 2p=(25±9) eV and 3d=(2.14 ±0.18) meV for ¯p3He and 2p=(-18±2) eV, 2p =(45±5) eV and 3d=(2.36±0.10) meV for ¯p4He.The efforts of the LEAR staff and the help of P. Gauss from the CERN Cryogenic Group as well as the technical assistance of M. Dröge and M. Stoll are gratefully acknowledged. This work is part of the Ph.D. of one of us (M.S.), University of Karlsruhe (1987), KfK report no. 4222. 相似文献
73.
Illarionov B Lee CY Bacher A Fischer M Eisenreich W 《The Journal of organic chemistry》2005,70(24):9947-9954
[graph: see text] Lumazine proteins of luminescent bacteria are paralogs of riboflavin synthase which are devoid of catalytic activity but bind the riboflavin synthase substrate, 6,7-dimethyl-8-ribityllumazine, with high affinity and are believed to serve as optical transponders for bioluminescence emission. Lumazine protein of Photobacterium leiognathi was expressed in a recombinant Escherichia coli host and was reconstituted with mixtures (random libraries) of 13C-labeled isotopologs of 6,7-dimethyl-8-ribityllumazine or riboflavin that had been prepared by biotransformation of [U-(13)C6]-, [1-(13)C1]-, [2-(13)C1]-, and [3-(13)C1]glucose. 13C NMR analysis of the protein/ligand complexes afforded the assignments of the 13C NMR chemical shifts for all carbon atoms of the protein-bound ligands by isotopolog abundance editing. The carbon atoms of the ribityl groups of both ligands studied were shifted up to 6 ppm upon binding to the protein. Chemical shift modulation of the side chain and chromophore carbon atoms due to protein/ligand interaction is discussed on the basis of the sequence similarity between lumazine protein and riboflavin synthase. 相似文献
74.
Fabio Zappa Dr. Manuel Beikircher Andreas Mauracher Stephan Denifl Dr. Michael Probst Prof. Dr. Natcha Injan Jumras Limtrakul Arntraud Bacher Dr. Olof Echt Prof. Dr. Tilmann D. Märk Prof. Dr. Paul Scheier Prof. Dr. Thomas A. Field Prof. Dr. Karola Graupner 《Chemphyschem》2008,9(4):607-611
A comprehensive analysis of metastable dissociation of 2,4‐dinitrotoluene (DNT) parent anions formed by attachment of electrons of controlled energy is presented. We characterize the energy dependence and kinetic energy release of the reaction which competes with autodetachment. A surprising finding is a highly exothermic metastable reaction triggered by the attachment of thermal electrons which we relate to the well‐known electrostatic ignition hazards of DNT and other explosives. Quantum chemical calculations are performed for dinitrobenzene in order to elucidate the process of NO abstraction. 相似文献
75.
Graupner K Field TA Mauracher A Scheier P Bacher A Denifl S Zappa F Märk TD 《The Journal of chemical physics》2008,128(10):104304
Fragmentation of metastable SF(6)(-*) ions formed in low energy electron attachment to SF(6) has been investigated. The dissociation reaction SF(6)(-*)-->SF(5) (-)+F has been observed approximately 1.5-3.4 micros and approximately 17-32 micros after electron attachment in a time-of-flight and a double focusing two sector field mass spectrometer, respectively. Metastable dissociation is observed with maximum intensity at approximately 0.3 eV between the SF(6)(-*) peak at zero and the SF(5)(-) peak at approximately 0.4 eV. The kinetic energy released in dissociation is low, with a most probable value of 18 meV. The lifetime of SF(6)(-*) decreases as the electron energy increases, but it is not possible to fit this decrease with statistical Rice-Ramsperger-Kassel/quasiequilibrium theory. Metastable dissociation of SF(6)(-*) appears to compete with autodetachment of the electron at all electron energies. 相似文献
76.
Reduction of 5-nitro-6-D-ribitylaminouracil (9) afforded 5-amino-6-D-ribitylaminouracil (1), which reacted with ethyl chloroformate to yield 5-ethylcarbamoyl-6-D-ribitylaminouracil (12). The latter compound was cyclized to 9-D-ribityl-1,3,7-trihydropurine-2,6,8-trione (13), which was found to be a relatively potent inhibitor of both Escherichia coli riboflavin synthase (K(i) 0.61 microM) and Bacillus subtilis lumazine synthase (K(i) 46 microM). Molecular modeling of the lumazine synthase-inhibitor complex indicated the possibility for hydrogen bonding between the Lys135 epsilon-amino group of the enzyme and both the 8-keto group and the 4'-hydroxyl group of the ligand. A bisubstrate analogue of the riboflavin synthase-catalyzed reaction, 1,4-bis[1-(9-D-ribityl-1,3,7-trihydropurine-2,6,8-trionyl)]butane (18), was also synthesized using a similar route and was found to be inactive as an inhibitor of both riboflavin synthase and lumazine synthase. 相似文献
77.
78.
Wang W Wang K Span I Jauch J Bacher A Groll M Oldfield E 《Journal of the American Chemical Society》2012,134(27):11225-11234
The [4Fe-4S] protein IspH in the methylerythritol phosphate isoprenoid biosynthesis pathway is an important anti-infective drug target, but its mechanism of action is still the subject of debate. Here, by using electron paramagnetic resonance (EPR) spectroscopy and (2)H, (17)O, and (57)Fe isotopic labeling, we have characterized and assigned two key reaction intermediates in IspH catalysis. The results are consistent with the bioorganometallic mechanism proposed earlier, and the mechanism is proposed to have similarities to that of ferredoxin, thioredoxin reductase, in that one electron is transferred to the [4Fe-4S](2+) cluster, which then performs a formal two-electron reduction of its substrate, generating an oxidized high potential iron-sulfur protein (HiPIP)-like intermediate. The two paramagnetic reaction intermediates observed correspond to the two intermediates proposed in the bioorganometallic mechanism: the early π-complex in which the substrate's 3-CH(2)OH group has rotated away from the reduced iron-sulfur cluster, and the next, η(3)-allyl complex formed after dehydroxylation. No free radical intermediates are observed, and the two paramagnetic intermediates observed do not fit in a Birch reduction-like or ferraoxetane mechanism. Additionally, we show by using EPR spectroscopy and X-ray crystallography that two substrate analogues (4 and 5) follow the same reaction mechanism. 相似文献
79.
N. Endstrasser F. Zappa A. Mauracher A. Bacher S. Feil D.K. Bohme P. Scheier M. Probst T.D. Mrk 《International journal of mass spectrometry》2009,280(1-3):65
We present absolute partial electron impact ionization cross sections for ethylene in the electron energy range between threshold and 1000 eV measured with a two sector field double focusing mass spectrometer. Ion kinetic energy distribution functions have been measured at all electron energies by applying a deflection field method. Multiplication of the measured relative cross sections by the appropriately determined discrimination factors lead to accurate relative partial cross sections. Normalization of the sum of the relative partial cross sections to an absolute total cross section gives absolute partial cross section values. The initial kinetic energy distributions of several fragment ions show the presence of two or more contributions that exhibit different electron energy dependencies. Differential cross sections with respect to the initial kinetic energy of the ions are provided and are related to specific ion production channels. The electron threshold energies for the direct and numerous other dissociative ionization channels are determined by quantum chemical calculation and these allow the determination of the total kinetic energy release and the electron energy loss for the most prominent dissociative ionization channels. 相似文献
80.
We studied in details the recombination dynamics and its temperature dependence in epitaxially grown neutral CdSe/ZnSSe quantum
dots with additional wide-band gap MgS barriers. Such design allows to preserve a very high quantum yield and track the radiative
recombination dynamics up to room temperature. A fast initial decay of ∼0.6 ns followed by a slow decay with a time constant
∼30–50 ns is observed at low temperature T < 50 K. The fast decay gradually disappears with increasing temperature while the slow decay shortens and above 100 K predominantly
a single-exponential decay is observed with a time constant ∼1.3 ns, which is weekly temperature dependent up to 300 K. To
explain the experimental findings, a two-level model which includes bright and dark exciton states and a temperature dependent
spin-flip between them is considered. According to the model, it is a thermal activation of the dark exciton to the bright
state and its consequent radiative recombination that results in the long decay tail at low temperature. The doubling of the
decay time at high temperatures manifests a thermal equilibrium between the dark and bright excitons. 相似文献