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161.
A Cu2N2 diamond core structure, {(PNP)CuI}2 (2), supported by a [PNP]- ligand (1) ([PNP]- = bis(2-(diisobutylphosphino)phenyl)amide) has been prepared. 2 is highly emissive at ambient temperature in both the solid and solution states and is characterized by a relatively long-lived excited state (tau > 10 mus) and an unusually high quantum yield (phi > 0.65). These observations are consistent with a low degree of structural reorganization between the ground state of 2 and its excited state *2, and also with a high degree of steric protection of the two copper centers of 2 afforded by the bulky [PNP]- ligand. An estimate for the excited-state reduction potential of *2 (ca. -3.2 V vs Fc+/Fc), and the availability of two well-separated and reversible ground-state redox processes, suggests that bimetallic copper systems of these types may be interesting candidates to consider for photochemically driving multielectron redox transformations. 相似文献
162.
A new high-performance liquid chromatographic/electrospray ionization tandem mass spectrometric (HPLC/ESI-MS/MS) method was developed for the simultaneous quantification of 5-fluorouracil (5FU), methotrexate (MTX) and cyclophosphamide (CP) in environmental samples. These compounds, commonly used in the treatment of cancer, are recognized as genotoxic. In order to estimate the occupational exposure of hospital personnel handling these drugs, wipe samples were taken from the working surfaces and directly analyzed (with trophosphamide as internal standard) using a reversed-phase capillary column and MS/MS detection. This is the first HPLC/MS/MS method for the simultaneous determination of 5FU, MTX and CP. The present method offers high sensitivity, with detection limits of 1.1 microg l(-1) for MTX and CP and 33.3 microg l(-1) for 5FU, avoiding any sample preconcentration procedure. Rapidity, specificity, high accuracy (mean values between 92.4 and 99.9%) and precision (mean RSD values between 3.4 and 12.1%) make the method suitable for the routine determination of these three antineoplastic drugs. 相似文献
163.
Attilio Citterio Anna Gentile Francesco Minisci Marco Serravalle Susanna Ventura 《Tetrahedron》1985,41(3):617-620
The homolytic decomposition of hydroxylamine-O-sulphonic acid in alcoholic solvents was investigated in the presence or absence of protonated heteroaromatic bases and Fe(II) salt. The addition of the α-hydroxyalkyl radicals to the base and their oxidation by Fe(III) salt to the corresponding alkyl cyanide were competitive processes. A redox chain process involving the amino radical cation, NH3t., is suggested and the factors affecting the yields of the homolytic substitution are discussed. 相似文献
164.
165.
A method for calculating the various components of the magnetically induced current-density tensor using gauge-including atomic orbitals is described. The method is formulated in the framework of analytical derivative theory, thus enabling implementation at the Hartree-Fock self-consistent-field (HF-SCF) as well as at electron-correlated levels. First-order induced current densities have been computed up to the coupled-cluster singles and doubles level (CCSD) augmented by a perturbative treatment of triple excitations [CCSD(T)] for carbon dioxide and benzene and up to the full coupled-cluster singles, doubles, and triples (CCSDT) level in the case of ozone. The applicability of the gauge including magnetically induced current method to larger molecules is demonstrated by computing first-order current densities for porphin and hexabenzocoronene at the HF-SCF and density-functional theory level. Furthermore, a scheme for obtaining quantitative values for the induced currents in a molecule via numerical integration over the current flow is presented. For benzene, a perpendicular magnetic field induces a (field dependent) ring current of 12.8 nA T(-1) at the HF-SCF level using a triple-zeta basis set augmented with polarization functions (TZP). At the CCSD(T)/TZP level the induced current was found to be 11.4 nA T(-1). Gauge invariance and its relation to charge-current conservation is discussed. 相似文献
166.
Rudolf Schmid Marco Cereghetti Bernd Heiser Peter Schnholzer Hans-Jürgen Hansen 《Helvetica chimica acta》1988,71(4):897-929
The axially dissymmetric diphosphines (?)-(R)- and (+)-(S)-(6-6′-dimethylbiphenyl-2,2′-diyl)bis(diphenyl-phosphine) ((?)-(R)- 10 and (+)-(S)- 10 ; ‘BIPHEMP’) have been synthesized, starting from (R)- and (S)-6,6′-dimethylbiphenyl-2,2′-diamine ((R)- and(S)- 16 ), respectively, via Sandmeyer reaction, liathiation, and phosphinylation. Moreover, racemic 4,4′- dimethyl- and 4,4′-bis(dimethylamino)-substituted analogues 11 and 12 respectively, and the 6,6′-bridged analogues 1,11-bis(diphenylphosphino)-5,7-dihydrodibenz[c,e]oxepin (13) were synthesized and resolved into optically pure (R)- and(S)-enantiomers via complexation with di-μ-chlorob is {(R)-2-[1-(dimethylamino)ethyl]pheny-C? N}dipalladium(II) ((R)- 18 ). The molecular structures of the diphosphines (S)- 10 and (R)- 13 and of two derived cationic Rh(I) complexes,[Rh((S)- 10 )(nbd)]BF4 and [Rh((R)- 13 )(nbd)]BF 4 were determined by x-ray analyses. Absolute configurations were established for (+)-(S)- 10 by X-ray analyses of both the free diphosphine and of the derived Rh(I) complex, and for (?)-(R)- 13 by X-ray analysis of the derived Rh(I) complex. Configurational assignments for the substituted BIPHEMP analogues 11 12 were achieved by means of 1H-NMR comparisons. The BIPHEMP ligand 10 and analogues 11 , 12 and 13 are the first examples of optically active bis(triaylphosphines) containing the axially dissymmetric biphenyl moiety. All these new diphosphines proved to be excellent asymmetry-inducing ligands in Rh(I)-catalyzed isomerizations of N,N-diethylnerylamine affording citronellat enamine of 98-99% ee. 相似文献
167.
A new optimization based adaptive control strategy for simulated moving beds (SMBs) is proposed. A linearized reduced order model, which accounts for the periodic nature of the SMB process, is used for online optimization and control. The manipulated variables are the four inlet flow rates, the outputs are the raffinate and extract concentrations. Concentration measurements at the raffinate and extract outlets are used as the feedback information. The state estimate from the periodic Kalman filter is used for the prediction of the outlet concentrations over a chosen horizon. Predicted outlet concentrations are the basis for the calculation of the optimal input adjustments, which maximize the productivity and minimize the desorbent consumption subject to constraints on product purities. The realization of this concept is discussed and the implementation on a virtual eight column SMB platform is assessed, in the case of binary linear systems. For a whole series of typical plant disturbances it is shown that the proposed approach is effective in minimizing off-spec products and in achieving optimal SMB operation, also in the case where there are significant model uncertainties. 相似文献
168.
Marco Biddau Marcella Massacesi Rosalba Pinna Gustavo Ponticelli 《Transition Metal Chemistry》1977,2(1):5-9
Summary Complexes of cobalt(II) and copper(II) with 5-amino-3,4-dimethylisoxazole (5-ADI) have been prepared and studied by means of magnetic susceptibility measurements, near and far i.r. spectra, electronic spectroscopy and, when possible, conductivity measurements. The 5-ADI generally behaves as bridging (Nring-, O- or Nring-, -NH2) ligand. All the complexes have an octahedral sterochemistry, except Co(5-ADI)2X2 (X = Cl, Br), Co2(5-ADI)7I4 which are tetrahedral and Cu(5-ADI)2 (ClO4)2 · 4 H2O which is square planar. 相似文献
169.
By a comparison between Maxwell's electrodynamics classically interpreted (MT) and relativistic electrodynamics (RED), this paper discusses whether the asymmetries in MT mentioned by A. Einstein in his 1905 relativity paper are only of a conceptual nature or rather involve specific empirical claims. It is shown that in fact MT predicts strongly asymmetric behaviour for very simple interactions, and an analysis is made of the extent of the symmetry achieved by means of relativistic postulates. A low velocity experiment is suggested which could provide another test of the accuracy of RED with respect to MT. 相似文献
170.
Marco Arfelli Giovanni Cossu Giulia Mattogno Carla Ferragina Maria Antonietta Massucci 《Journal of inclusion phenomena and macrocyclic chemistry》1990,9(2):161-170
X-ray photoelectron spectroscopy provides evidence that when [Cu(phen)2]2+(phen = 1,10-phenanthroline) is diffused between the layers of -zirconium phosphate, the complex species does not remain intact after intercalation, but some Cu-N bonds are broken, replaced with Cu-O bonds and the released nitrogen atoms can now interact with the PO3-OH groups of the host. XPS also provides evidence for coordination of the Cu2+ ions when they are diffused by ion exchange in the phenanthroline--zirconium phosphate intercalation compound. Although Cu2+ and phen are in a 1 : 1 molar ratio in the interlayer region of the host, so that a 1 : 1 coordination could be expected between the two species, the characteristic peaks of the uncoordinated phenanthroline, even though at a low intensity, are still present. The differences between the two Cu(II)-intercalation compounds are discussed. 相似文献