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381.
Penkett CS Sims RO French R Dray L Roome SJ Hitchcock PB 《Chemical communications (Cambridge, England)》2004,(17):1932-1933
We describe the first application of a Heck arylation reaction being performed on a meta photocycloadduct. The resulting arylation/fragmentation process leads to the formation of a bridged bicyclic ketone and constitutes a dramatic increase in molecular complexity after just two synthetic operations. 相似文献
382.
An indirect method is described for effecting radical cyclization onto a benzene ring. Cross-conjugated dienones 6, which are readily prepared from phenols, undergo radical cyclization (6 --> 7 --> 8), and the products (8) are easily aromatized. The method has been applied to the synthesis of ent-nocardione A (21). 相似文献
383.
Metcalfe CL Ott M Patel N Singh K Mistry SC Goff HM Raven EL 《Journal of the American Chemical Society》2004,126(49):16242-16248
The mammalian heme peroxidases are distinguished from their plant and fungal counterparts by the fact that the heme group is covalently bound to the protein through ester links from glutamate and aspartate residues to the heme 1- and 5-methyl groups and, in the case of myeloperoxidase, through an additional sulfonium link from the Cbeta of the 2-vinyl group to a methionine residue. To duplicate the sulfonium link in myeloperoxidase and to obtain information on its mechanism of formation, we have engineered a methionine residue close to the 2-vinyl group in recombinant pea cytosolic ascorbate peroxidase (rpAPX) by replacement of Ser160 by Met (S160M variant). The S160M variant is isolated from Escherichia coli as apo-protein. Reconstitution of apo-S160M with exogenous heme gives a red protein (S160M(R)) which has UV-visible (lambda(max)/nm = 407, 511, 633) and steady-state kinetic (kcat = 156 +/- 7 s(-1), KM = 102 +/- 15 microM) properties that are analogous to those of rpAPX. The reaction of S160M(R) with H2O2 gives a green protein (S160M(G)). Electronic spectroscopy, mass spectrometry, and HPLC analyses are consistent with the formation of a covalent linkage between the methionine residue and the heme vinyl group in S160M(G). Single-wavelength and photodiode array stopped-flow kinetic analyses identify a transient Compound I species as a reaction intermediate. The results provide the first direct evidence that covalent heme linkage formation occurs as an H2O2-dependent process that involves Compound I formation. A mechanism that is consistent with the data is presented. 相似文献
384.
Periodic ab initio HF calculations using the CRYSTAL code have been used to calculate (23)Na NMR quadrupole parameters for a wide range of crystalline sodium compounds including Na(3)OCl. An approach is developed that can be used routinely as an alternative to point-charge modelling schemes for the assignment of distinct lines in (23)Na NMR spectra to specific crystallographic sodium sites. The calculations are based on standard 3-21 G and 6-21 G molecular basis sets and in each case the same modified basis set for sodium is used for all compounds. The general approach is extendable to other quadrupolar nuclei. For the 3-21 G calculations a 1:1 linear correlation between experimental and calculated values of C(Q)((23)Na) is obtained. The 6-21 G calculations, including the addition of d-polarisation functions, give better accuracy in the calculation of eta((23)Na). The sensitivity of eta((23)Na) to hydrogen atom location is shown to be useful in testing the reported hydrogen-bonded structure of Na(2)HPO(4). 相似文献
385.
Weidmann D Roller CB Oppenheimer C Fried A Tittel FK 《Isotopes in environmental and health studies》2005,41(4):293-302
Recent developments of two mid-infrared tunable laser spectrometers dedicated to carbon isotope ratio determination are presented. First, a field deployable quantum cascade laser-based sensor is described, along with line selection strategy for (13/12)CO(2) ratio measurements. Secondly, an instrument architecture based on difference frequency generation is presented. The analyses of fundamental limitations, specifically temperature and pressure stability, and water vapor collision broadening, are detailed. 相似文献
386.
Cross-conjugated dienones of type 5 (X = I), which are readily available from phenols, undergo radical cyclization (5 --> 6 --> 7), and the products are easily aromatized (7 --> 8), giving substances that are formally derived by radical cyclization onto a benzene ring (cf. eqn. (1)). 相似文献
387.
388.
Mohammadreza Estilaei Alex MacKay Clive Roberts John Mayo 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1997,124(2):410-419
Proton-magnetic-resonance measurements have been carried out on juvenile porcine peripheral lung parenchyma. The free-induction-decay signal contained a motionally restricted component which decayed in a few tens of microseconds and a mobile component with aT2time greater than 1 ms. The average second moment,M2, for the motionally restricted signal was found to be 3.42 ± (0.25) × 109s−2. TheT2distribution for the mobile signal consistently showed four resolvable components ofT2range: 2–6, 10–40, 80–110, and 190–400 ms. The 2–6 ms component was present in a fully dehydrated preparation and was therefore assigned to a nonaqueous lung constituent. The motionally restricted FID component had aT1= 0.772 ± 0.11 s and the mobile component had aT1= 0.967 ± 0.02 s. The hydrogen content per unit mass for lung parenchyma and water were estimated in two ways: (1) on the basis of chemical content and (2) on the basis of comparison of restricted and mobile signals to the gravimetric (G) water content for a lung sample studied at a wide range of water contents. Lung wet/dry weight ratios were estimated from the free-induction decays and compared with gravimetric measurement. The ratio of (wet/dry)NMR/(wet/dry)Gwas 1.00 ± 0.08 and 1.00 ± 0.05 for the two methods of estimation. 相似文献
389.
G. V. Iyengar W. B. Clarke R. G. Downing 《Fresenius' Journal of Analytical Chemistry》1990,338(4):562-566
Summary Essential features of the neutron activation-mass Spectrometry (NA-MS) technique are described. Applicability of this technique for the simultaneous determination of boron and lithium is demonstrated for a diverse group of biomaterials. NA-MS is a nondestructive analytical technique, and dynamic in nature since its coverage extends to a broad range of concentration levels. Contamination after the irradiation step, extraneous by natural lithium or boron is inconsequential, since only the activation products are the analyted assayed. Coupling the nuclear activation phenomenon which generates 4He and 3He (from 10B and 6Li, respectively), with the high precision potential of mass spectrometry forms the bases of this technique. Under ideal conditions the detection limit is extendable to pg g–1 concentration ranges and therefore, it is extremely well suited to investigate the natural concentration levels of boron and lithium in biomaterials. The potential of this method for the determination of lithium in biomedical trace element research is of special significance since determination of sub-ppb levels of lithium by other analytical techniques faces serious analytical difficulties mainly due to contamination control and in some cases to insufficiently low detection limits. 相似文献
390.
John Dalton William McFarlane Clive R. Wickens George W. Fraser James B. Millar 《Magnetic resonance in chemistry : MRC》1976,8(10):522-524
The spectra of A2BC spin systems provided by the 19F nuclei in cis (RO) (MeO)TeF4 and (RO) (Me2N)TeF4 (R = Me, Et, Pr, i-Pr) have been recorded and analysed. The geminal coupling constants 2J(F,F) range from 137–174 Hz and trends in the 19F chemical shifts permit complete assignment of the resonances. Stereospecific coupling between 19F and the protons of the N-methylamino groups is also observed. 相似文献