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1.
2.
The use of temporary tethers in facilitating meta photocycloaddition reactions between phenol and allyl alcohol derivatives has been investigated. The merits of silicon, carbonate and methylene acetal tethers were assessed, whilst considering strategies for the preparation of the natural products gymnomitrol and gelsemine. The photoadducts were epoxidised, and then subjected to acid catalysed fragmentation with concomitant cleavage of the tether. Depending on whether water or methanol was used during the fragmentation stage of the methylene tethers, the methylene group was either removed altogether or transformed into a MOM group. 相似文献
3.
Five lead fragments from bullet cores from the assassination of American President John F. Kennedy in 1963 were analyzed twice
by NAA, first by the FBI in 1964 and then by Vincent P. Guinn in 1977. Their concentrations of Sb have provided invaluable information about the number and origin of bullets that hit
Kennedy and Texas Governor John B. Connally. While both analyses appeared to group the fragments into a body shot and a head shot, the FBI set contained a systematic
error and Guinn's results from quarters of test bullets showed that the indicator element Sb varied enough over quarters to potentially merge
the groups. The latter problem was resolved by the FBI replicate analyses, which showed that antimony was nearly homogeneos
on the small scales of the fragments, and by the mechanism by which jacketed bullets break when hitting bone, which generates
tiny fragments from a single break near the middle of the lead core. They collectively meant that the fragments within each
group were formed on the scale of subfragments. The two groups were just as they appear because the larger quarter-bullet
heterogeneities did not apply. This result substantiates Guinn's original conclusion that two and only two bullets from Lee Harvey Oswald's rifle struck the two men.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
4.
Jim Bashkin Clive E. Briant D. Michael P. Mingos Robert W. M. Wardle 《Transition Metal Chemistry》1985,10(3):113-114
Summary [(Ph3P)AuCo(CO)3(PPh3)] has been synthesised from [(Ph3P)AuCo(CO)4], PPh3v and Me3NO in acetonitrile. Its molecular structure, determined by single-crystal x-ray crystallography, consists of an almost linear
P-Au-Co-P arrangement in which the Co atom is in a slightly distorted trigonalbipyramidal geometry, with the Au and P atoms
occupying the apical sites. The Au-Co bond length of 2.450(1) ? is shorter than that reported for [(Ph3P)AuCo(CO)4]. The carbonyl ligands are bent towards the Au atom and the mean Au-Co-C angle is 81(1)°. 相似文献
5.
Transition metal complexes that reversibly bind to DNA have been studied for almost 30 years. In the last few years a variety of new systems have been developed, employing a range of metal ions and ligand architectures. In many cases, high affinity binding and specific selectivities have been observed. These complexes display properties that make them attractive as probes of DNA structure and function, suggesting that they may find a r?le as prototypical tools for a spectrum of applications, from basic molecular biology to medicine. This review presents an overview of some of the structures and properties of such complexes. 相似文献
6.
Griffith GA Percy JM Pintat S Smith CA Spencer N Uneyama E 《Organic & biomolecular chemistry》2005,3(15):2701-2712
Highly-functionalised difluorinated cyclooctenones were synthesised from trifluoroethanol using either metallated difluoroenol acetal or carbamate chemistry, followed by a [2,3]-Wittig rearrangement or aldol reaction. Efficient RCM reactions afforded the title compounds which showed rather restricted fluxional behaviour by VT (19)F NMR. Topological characterisation by molecular modelling and NOESY/ROESY experiments offered a number of challenges, but allowed the identification of two favoured boat-chair conformers which interconverted by pseudorotation with relatively large activation barriers. 相似文献
7.
Potassium Iodide as a Chemical Actinometer for 254 nm Radiation: Use of lodate as an Electron Scavenger 总被引:2,自引:0,他引:2
Ronald O. Rahn 《Photochemistry and photobiology》1997,66(4):450-455
Abstract— A solution of 0.6 M iodide and 0.1 M iodate in 0.01 M borate buffer (pH 9.25) can be used as a chemical actinometer to measure the incident fluence from a low-pressure mercury lamp that puts out more than 85% of its energy at 254 nm. The actinometric solution is optically opaque to light below 290 nm and is optically transparent to wavelengths greater than 330 nm. Hence, the solution absorbs all of the germicidal wavelengths but little if any of the ambient light normally present in the laboratory. Iodate acts as an electron scavenger and prevents the back reaction of the free electron with the iodine atom following UV excitation of KI. Irradiation results in the linear formation of triiodide, which is quantitated by measuring its absorbance at 352 nm. The quantum yield for this system is approximately 0.75 0.03 at 20.7Ao C or approximately three times greater than that obtained previously using nitrous oxide as an electron scavenger. A model is proposed to account for this difference. A precise expression to account for the concentration and temperature dependence of the quantum yield is given by pH = 0.75(1 + 0.23[C - 0.577])(1 + 0.02[T - 20.7]) where C is the concentration of iodide and T is the temperature. The concentration of iodide can be obtained from the absorbance at 300 nm prior to irradiation using 1.061 MJ cm−1 as the molar extinction coefficient. This actinometric system meets the quality criteria established by the International Union of Pure and Applied Chemistry with the caveat that it is designed to measure only germicidal radiation (i.e. wavelengths less than 290 nm). 相似文献
8.
W.John Albery David Clark Humphrey J.J. Drummond Anthony J.M. Coombs William K. Young Clive E.W. Hahn 《Journal of Electroanalytical Chemistry》1992,340(1-2)
A novel electrochemical sensor for the determination of CO2 in expired breath is described. The sensor works by generating
from the reduction of O2 in dimethyl sulphoxide (DMSO) in a generating pulse. There is a rapid titration reaction between the
and any CO2 present. In the recovery pulse the amount of unreacted
is determined. The larger the concentration of CO2 the less
is found in the recovery pulse. The solubilities and diffusion coefficients of O2 and CO2 in DMSO have been determined using rotating disc voltammetry and rotation speed step experiments. The stoichiometry, the product, and the rate constant of the titration reaction have been determined using ring—disc voltammetry and laser Raman spectroscopy. The operation and the effect of adventitious water on the sensor are described. Results are presented which show that the sensor can indeed measure the breath-by-breath rhythm of expired CO2 from a human subject. 相似文献
9.
Abstract— A variety of polynucleotides containing 5-iodouracil residues were irradiated in aqueous solution with wavelengths between 240 and 313 nm. From the rate of deiodination the photochemical cross sections (aB) were determined as a function of the irradiation wavelength (A). The expression was used to relate the observed values of B to the intrinsic quantum yield, φINT, and to the absorption cross sections, and for the iodinated and noniodinated residues, respectively. φINT is the probability an excited iodouracil residue will deiodinate, while the parameter b is a measure of the number of noniodinated bases which contribute their excitation energy to the deiodination process. For IdUrd and poly(5-iodouridylic acid), the average values of φINT calculated from the experimental B values were 0.0202 and 0.0188, respectively, for irradiation in air. In native, denatured, and depurinated DNA in which IdUrd was substituted for 10% of the Thd, the average φINT values were 0.0069, 0.0088, and 0.0153, respectively, indicating an enhancement in φINT upon decreasing the order of the polynucleotide. In contrast, the average values of b bor the same set of compounds were found to be 4 , 2 and 0.4, respectively, indicating a decrease in b with decreasing polynucleotide order, i.e. a loss of base stacking decreases the extent of energy transfer. A value of b= 4 for native DNA is assumed to mean that the extent of energy transfer in native DNA is limited to four base donors per iodouracil residue serving as an energy trap. 相似文献
10.
Abstract— –Irradiation at 313 nm of compounds containing iodinated cytosine moieties results in the photolysis of iodine. Photolysis occurs with a quantum yield of 0·0224·024 for 5-iododeoxycytidine and 5-iododeoxycytidine monophosphate, and 0·004–0·008 for iodinated DNA as well as for iodinated polycytidylate. Photodegradation of the cytosine moiety occurs when air is present during irradiation, presumably due to the reaction of oxygen with the cytosyl radical formed when iodine is lost. This oxygen promoted photodegradation destroys the cytosine chromophore and is complete in the monomers but occurs to only a limited extent in the polymers. In the absence of oxygen or in the presence of ethanol, photodegradation is prevented and the loss of iodine leads exclusively to the formation of the cytosine chromophore. In DNA, the loss of iodine is accompanied by the formation of sugar damage and/or chain breaks. As measured by sedimentation in alkaline sucrose gradients, approximately one break is made for every six iodinqs lost in denatured DNA. The frequency of chain breakage per iodine photolyzed is reduced 2-fold in renatured DNA. Analysis in neutral gradients suggests that half of the breaks observed in alkali are alkali-labile bonds. Both ethanol and cysteamine reduce the number of chain breaks observed in alkali by ˜ 3-fold. 相似文献