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61.
62.
The silicon KLL Auger spectrum from a range of stainless steel-silicon thin films was studied to provide information on changes in the silicon-silicon to silicon-metal bond ratio. This work complements earlier Auger spectroscopic studies of stainless steel-carbon films. Unlike the carbon KLL spectrum, the silicon KLL spectrum contains little chemical information. Changes in the principal plasmon loss peak associated with the silicon KLL spectrum may however prove useful in identifying the silicon phases. 相似文献
63.
Abstract— Single-strand breaks are produced in the phosphodiester backbone of ultraviolet-light-irradiated 5–bromodeoxyuridine-containing DNA (BU-DNA) after treatment with alkali. No radiation dependent breakage is observed in thymine-containing DNA (thy-DNA). The relative yields of breaks terminated by 5'-hydroxyl and 5'-phosphate groups was determined by measuring the rate of phosphorylation achieved with polynucleotide kinase in BU-DNA single strands before and after treatment with alkaline phosphatase. The ratio of 5'-phosphate to 5' hydroxyl groups ranged from 2.3 to 2.9 in different experiments. When cysteamine was present during irradiation no new end groups were produced.
In order to identify the nucleoside(s) at the 5'-termini, phosphate groups were removed with alkaline phosphatase and the 5'-hydroxyl groups were phosphorylated with polynucleotide kinase. Electrophoresis of enzymatic digests showed a single32 P-labeled component migrating more rapidly than any of the four usual 5'-mononucleotides. Upon column chromatography this component resolved into a major peak coincident with 5'-dUMP and a lesser unidentified constituent. No 5'-dBUM32 P was observed among these nucleotides. 相似文献
In order to identify the nucleoside(s) at the 5'-termini, phosphate groups were removed with alkaline phosphatase and the 5'-hydroxyl groups were phosphorylated with polynucleotide kinase. Electrophoresis of enzymatic digests showed a single
64.
Mai Gehrke John Harding Yde Venema 《Transactions of the American Mathematical Society》2006,358(2):573-590
Let be a variety of monotone bounded lattice expansions, that is, bounded lattices endowed with additional operations, each of which is order preserving or reversing in each coordinate. We prove that if is closed under MacNeille completions, then it is also closed under canonical extensions. As a corollary we show that in the case of Boolean algebras with operators, any such variety is generated by an elementary class of relational structures.
Our main technical construction reveals that the canonical extension of a monotone bounded lattice expansion can be embedded in the MacNeille completion of any sufficiently saturated elementary extension of the original structure.
65.
Argent SP Adams H Riis-Johannessen T Jeffery JC Harding LP Clegg W Harrington RW Ward MD 《Dalton transactions (Cambridge, England : 2003)》2006,(42):4996-5013
The coordination chemistry of a series of di- and tri-nucleating ligands with Ag(I), Hg(I) and Hg(II) has been investigated. Most of the ligands contain two or three N,N'-bidentate chelating pyrazolyl-pyridine units pendant from a central aromatic spacer; one contains three binding sites (2 + 3 + 2-dentate) in a linear sequence. A series of thirteen complexes has been structurally characterised displaying a wide range of structural types. Bis-bidentate bridging ligands react with Ag(I) to give complexes in which Ag(I) is four-coordinate from two bidentate donors, but the complexes can take the form of one-dimensional coordination polymers, or dinuclear complexes (mesocate or helicate). A tris-bidentate triangular ligand forms a complicated two-dimensional coordination network with Ag(I) in which Ag...Ag contacts, as well as metal-ligand coordination bonds, play a significant role. Three dinuclear Hg(I) complexes were isolated which contain an {Hg2}2+ metal-metal bonded core bound to a single bis-bidentate ligand which can span both metal ions. Also characterised were a series of Hg(II) complexes comprising a simple mononuclear four-coordinate Hg(II) complex, a tetrahedral Hg(II)4 cage which incorporates a counter-ion in its central cavity, a trinuclear double helicate, and a trinuclear catenated structure in which two long ligands have spontaneously formed interlocked metallomacrocyclic rings thanks to cyclometallation of two of the Hg(II) centres. 相似文献
66.
Klippenstein SJ Georgievskii Y Harding LB 《Physical chemistry chemical physics : PCCP》2006,8(10):1133-1147
An ab initio transition state theory based procedure for accurately predicting the combination kinetics of two alkyl radicals is described. This procedure employs direct evaluations of the orientation dependent interaction energies at the CASPT2/cc-pvdz level within variable reaction coordinate transition state theory (VRC-TST). One-dimensional corrections to these energies are obtained from CAS+1+2/aug-cc-pvtz calculations for CH3 + CH3 along its combination reaction path. Direct CAS+1+2/aug-cc-pvtz calculations demonstrate that, at least for the purpose of predicting the kinetics, the corrected CASPT2/cc-pvdz potential energy surface is an accurate approximation to the CAS+1+2/aug-cc-pvtz surface. Furthermore, direct trajectory simulations, performed at the B3LYP/6-31G* level, indicate that there is little local recrossing of the optimal VRC transition state dividing surface. The corrected CASPT2/cc-pvdz potential is employed in obtaining direct VRC-TST kinetic predictions for the self and cross combinations of methyl, ethyl, iso-propyl, and tert-butyl radicals. Comparisons with experiment suggest that the present dynamically corrected VRC-TST approach provides quantitatively accurate predictions for the capture rate. Each additional methyl substituent adjacent to a radical site is found to reduce the rate coefficient by about a factor of two. In each instance, the rate coefficients are predicted to decrease quite substantially with increasing temperature, with the more sterically hindered reactants having a more rapid decrease. The simple geometric mean rule, relating the capture rate for the cross reaction to those for the self-reactions, is in remarkably good agreement with the more detailed predictions. With suitable generalizations the present approach should be applicable to a wide array of radical-radical combination reactions. 相似文献
67.
Barry CS Elsworth JD Seden PT Bushby N Harding JR Alder RW Willis CL 《Organic letters》2006,8(15):3319-3322
[Structure: see text] The total synthesis of the marine metabolite clavosolide A is reported which confirms the structure and absolute configuration of the natural product as the symmetrical diolide glycosylated by permethylated D-xylose moieties, 2. 相似文献
68.
Richard P. Chartoff Thomas S.K Lo E. Ray Harrell JR Ryong Joon Roe 《Journal of Macromolecular Science: Physics》2013,52(3):287-303
The influence of crystallinity and stereoregularity on the infrared (IR) spectrum of atactic PVC in the solid state has been studied by many researchers [1-12]. Although the molecules in commercial PVC consist of both syndiotactic and isotactic sequences, the bulk polymer is not highly stereoregular, having approximately 50% syndiotacticity. Its infrared spectrum is different from that of highly syndiotactic PVC [3,5,7,9,10-12], particularly in the carbon-to-chlorine stretching region where there are three bands located at 610(615), 635, and 690 cm?1. These three bands are known to be of complex origin, since each band consists of more than one absorption frequency and its relative intensity depends on the physical state or history of the specimen [3,5,7,9,10-12]. The spectrum in this region is most rigorously interpreted in terms of chain conformational structure, the spatial arrangement of the atoms around the C-C1 bond. Thus, while changes in absorbance intensities for the bands with history do not necessarily reflect changes in crystallinity, their history dependence renders these bands potentially useful as crystallinity indicators. 相似文献
69.
INTRODUCTION The tensor associated with a Raman band plays an important role in determining the band intensity and its structural significance. Each Raman tensor interrelates two electric vectors, that of the exciting radiation (i.e. laser photon) and that of the Raman scattered radiation (i.e. the inelastically scattered photon which results from the exchange of a vibrational quantum between the exciting photon and the molecule). The Raman tensor is obtained formally as the first derivative of the molecular polarizability tensor, the derivative being taken with respect to the vibrational normal coordinate. In other words, the Raman tensor associated with a vibrational Raman band is an indicator of how the polarizability of the molecule oscillates with the molecular normal mode of vibration. 相似文献
70.
Recent research has shown that a phase transformation of diamond to a different form of carbon is involved when diamonds are polished in the traditional fashion. The question as to how this phase transformation is activated and maintained to produce high wear rates is of great technological interest since it may radically change the way we view the processing of diamond. This paper describes the use of Raman spectroscopy to examine debris produced on the diamond polishing wheel, both during its preparation and during polishing. In addition, polished diamond surfaces were examined for the possible existence of non-diamond surface layers in an attempt to identify material removal mechanisms. Raman spectroscopy proves ideal for these analyses because its relatively high spatial resolution is well suited to the analysis of small wear features and debris particles, and because of the wealth of information it reveals about chemical structure. This level of structural information has been lacking in previous analyses of diamond polishing debris. In addition to the non-diamond carbon found in the wear debris, significant quantities of two iron oxides, magnetite (Fe3O4) and haematite (α-Fe2O3), were also found. An interesting observation was that a transformation from magnetite to haematite could be induced either by using high power laser excitation or by frictional heating during polishing. It is suggested that some of the Raman peaks previously attributed to lonsdaleite might better be explained by the presence of these oxides. 相似文献