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71.
A series of five cyanoximes (compounds having the general formula NC-C(=NOH)-R, where R is an amide or carboxylic ester group) have been synthesized and spectroscopically and structurally characterized. These are 2-cyano-2-isonitrosoacetamide (later HACO), 2-cyano-2-isonitrosothioacetamide (HTCO), 2-cyano-2-isonitrosoethylacetate (HECO), 2-cyano-2-isonitroso-N-piperidinylacetamide (HPiPCO), and 2-cyano-2-isonitroso-N-morpholinylacetamide (HMCO). A high yield method of synthesis was developed for the last two previously unknown amidocyanoximes. Variable temperature (13)C NMR studies in DMSO-d(6) solutions allowed the determination of rotational energy barriers for these two new cyanoximes. The HPiPCO and HMCO oxime molecules adopt a trans-anti configuration in the solid state according to X-ray analysis. Reactions between aqueous solutions of K(+)L(-) (L = cyanoximate anions: TCO(-), PiPCO(-), and MCO(-)) and K(2)[MCl(4)] (M = Pd, Pt) resulted in the formation of ML(2) complexes. The crystal structure of Pd(MCO)(2).DMSO was determined and showed the formation of coplanar dimeric [Pd(MCO)](2) units with 3.13 A Pd...Pd separation. The complex adopts cis geometry with anions being in the nitroso form. In the presence of bivalent Pd and Pt, ACO(-) and ECO(-) anions completely or partially hydrolyze in aqueous solutions to the dianion of 2-cyano-2-isonitrosoacetic acid (AACO(2-)). The crystal structure of the product of the hydrolysis reaction, K(2)[Pd(AACO)(2)].4H(2)O, was determined. Data revealed planar and cis geometry of the [Pd(AACO)(2)](2)(-) anion where cyanoximes are in the nitroso form and adopt a cis-anti configuration. All synthesized cyanoxime ligands and nine of their Pd(II) and Pt(II) complexes were tested in vitro on antiproliferating activity using human cervical cancer HeLa cell lines, and cisplatin as a positive control substance. Two out of the nine studied complexes, Pd(MCO)(2) and Pt(MCO), were found to be active compounds inflicting death on 28% and 16% of the cells, respectively, with 55% value for the cisplatin under the same conditions. 相似文献
72.
Zhou SZ Sey M De Clercq PJ Milanesio M Viterbo D 《Angewandte Chemie (International ed. in English)》2000,39(16):2861-2863
73.
Gunter S Wolf RC Leuterer F Gruber O Kaufmann M Lackner K Maraschek M Mc Carthy PJ Meister H Peeters A Pereverzev G Salzmann H Schade S Schweinzer J Suttrop W 《Physical review letters》2000,84(14):3097-3100
Internal transport barriers have been demonstrated to exist also under conditions with T(e) approximately T(i) approximately 10 keV and predominant electron heating of the tokamak core region. Central electron cyclotron heating was added to neutral beam injection-heated ASDEX Upgrade discharges with a preexisting internal transport barrier, established through programmed current ramping leading to shear reversal. Compared to a reference internal transport barrier discharge without electron cyclotron resonance heating, the electron heat conductivity in the barrier region was found not to increase, in spite of a fivefold increase in electron heat flux, and also angular momentum and ion energy transport did not deteriorate. 相似文献
74.
Angle-resolved photoemission (ARPES) studies of the (100) face of clean copper using He I radiation reveal two distinct peaks with binding energies between 0 and 2 eV. These peaks have the opposite dispersion with emission angle and have very different widths, one peak in particular being unusually sharp. We show that both of these peaks are associated with the upper part of the s-p band and that their behaviour can be qualitatively explained by an examination of the bulk band structure for finite values of k∥ away from the Δ-symmetry direction. We also show that rather good quantitative agreement with the experimental spectra can be obtained by performing realistic photocurrent calculations which include a proper treatment of the surface electronic structure, matrix elements and lifetime effects. Finally, the significance of a sharp peak arising from the s-p band for ARPES studies of random alloys and chemisorption systems is briefly discussed. 相似文献
75.
In contrast to conventional single-scattering probes, X-ray absorption near edge structure (XANES) is sensitive, through multiple scattering of the excited electron, not only to pairwise atomic correlations but also to higher order correlations, including bond angles. We present a flexible theory, based on a full multiple scattering cluster calculation, which can be used to extract such information in ordered, disordered and other complex systems now being studied using synchrotron radiation. 相似文献
76.
Calderbank AR; Cameron PJ; Kantor WM; Seidel JJ 《Proceedings London Mathematical Society》1997,75(2):436-480
When m is odd, spreads in an orthogonal vector space of type+(2m + 2,2) are related to binary Kerdock codes and extremalline-sets in 2m + 1 with prescribed angles. Spreads in a 2m-dimensionalbinary symplectic vector space are related to Kerdock codesover Z4 and extremal line-sets in with prescribed angles. These connections involve binary, realand complex geometry associated with extraspecial 2-groups.A geometric map from symplectic to orthogonal spreads is shownto induce the Gray map from a corresponding Z4-Kerdock codeto its binary image. These geometric considerations lead tothe construction, for any odd composite m, of large numbersof Z4-Kerdock codes. They also produce new Z4-linear Kerdockand Preparata codes. 1991 Mathematics Subject Classification:primary 94B60; secondary 51M15, 20C99. 相似文献
77.
J. -C. Roy J. -E. Côté R. W. Durham S. R. Joshi 《Journal of Radioanalytical and Nuclear Chemistry》1989,130(1):221-230
Cosmic ray neutron interactions with indium, used as electrical contact within a Ge diode, the diode itself and the surrounding materials can give rise to a large number of photopeaks in the 50 to 1300 keV region of background spectra of Ge spectrometers with a passive shield. The nuclear processes and decays involved in the production of these photopeaks are discussed. These cosmic ray produced photopeaks are compared with those due to primordial radionuclides. Some useful information can be drawn from these measurements on the contribution of the cosmic rays on the background of Ge detectors with a passive shield. 相似文献
78.
79.
Methods are described for the extraction and preparation of total nuclear proteins for high resolution two-dimensional polyacrylamide gel electrophoresis (2-D PAGE). The conditions for protein extraction and preparation limit both protease and phosphatase activity, allowing application of this technique to the reliable analysis of changes in nuclear protein composition and nuclear protein phosphorylation as well as other forms of post-translational modifications. Unlike other procedures for 2-D PAGE analysis of nuclear proteins the technique allows solubilization and extraction of all nuclear proteins along with removal of nucleic acids which interfere with isoelectric focusing and autoradiography of 32Pi-labeled proteins. It avoids lengthy dialysis in which precipitation of nuclear proteins often occurs and does not require precipitation and resolubilization of nuclear proteins to obtain sufficient protein concentrations for 2-D PAGE analysis; often impractical steps in which complete resolubilization of all proteins is not possible. It produces high resolution 2-D PAGE analysis in which identification of even low abundance proteins can be made, based on isoelectric point and molecular weight, allowing comparison with other studies. 相似文献
80.
Philip J. Cox David G. Durham Xiaojun Liu R. Michael E. Richards 《Journal of chemical crystallography》1993,23(10):779-783
A triterpenoid glycoside has been isolated from the roots of a herb used in traditional Chinese medicine. The molecular structure of this compound and its derivatives have been determined by spectroscopic studies and an X-ray analysis of the 2,3,23-triacetoxy-28-methyl ester of the aglycone. This aglycone belongs to the ursene structure series. The hydroxy group on ring E of these triterpenoids is orientated and the side chains at C(2), C(3), C(4) and C(17) are .,, and orientated, respectively. The C ring, which has a double bond at C(12)=C(13), adopts a sofa conformation. 相似文献