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51.
Milway VA Niel V Abedin TS Xu Z Thompson LK Grove H Miller DO Parsons SR 《Inorganic chemistry》2004,43(6):1874-1884
The structures and magnetic properties of self-assembled copper(II) clusters and grids with the "tritopic" ligands 2poap (a), Cl2poap (b), m2poap (c), Cl2pomp (d), and 2pomp (e) are described [ligands derived by reaction of 4-R-2,6-pyridinedicarboxylic hydrazide (R = H, Cl, MeO) with 2-pyridinemethylimidate (a-c, respectively) or 2-acetylpyridine (d, R = Cl; e, R = H)]. Cl2poap and Cl2pomp self-assemble with Cu(NO(3))(2) to form octanuclear "pinwheel" cluster complexes [Cu(8)(Cl2poap-2H)(4)(NO(3))(8)].20H(2)O (1) and [Cu(8)(Cl2pomp-2H)(4)(NO(3))(8)].15H(2)O (2), built on a square [2 x 2] grid with four pendant copper arms, using "mild" reaction conditions. Similar reactions of Cl2pomp and 2pomp with Cu(ClO(4))(2) produce pinwheel clusters [Cu(8)(Cl2pomp-2H)(4)(H(2)O)(8)](ClO(4))(8).7H(2)O (3) and [Cu(8)(2pomp-2H)(4)(H(2)O)(8)](ClO(4))(8) (4), respectively. Heating a solution of 1 in MeOH/H(2)O produces a [3 x 3] nonanuclear square grid complex, [Cu(9)(Cl2poap-H)(3)(Cl2poap-2H)(3)](NO(3))(9).18H(2)O (5), which is also produced by direct reaction of the ligand and metal salt under similar conditions. Reaction of m2poap with Cu(NO(3))(2) produces only the [3 x 3] grid [Cu(9)(m2poap-H)(2)(m2poap-2H)(4)](NO(3))(8).17H(2)O (6) under similar conditions. Mixing the tritopic ligand 2poap with pyridine-2,6-dicarboxylic acid (picd) in the presence of Cu(NO(3))(2) produces a remarkable mixed ligand, nonanuclear grid complex [Cu(9)(2poap-H)(4)(picd-H)(3)(picd-2H)](NO(3))(9).9H(2)O (7), in which aromatic pi-stacking interactions are important in stabilizing the structure. Complexes 1-3 and 5-7 involve single oxygen atom (alkoxide) bridging connections between adjacent copper centers, while complex 4 has an unprecedented mixed micro-(N-N) and micro-O metal ion connectivity. Compound 1 (C(76)H(92)N(44)Cu(8)O(50)Cl(4)) crystallizes in the tetragonal system, space group I, with a = 21.645(1) A, c = 12.950(1) A, and Z = 2. Compound 2 (C(84)H(88)N(36)O(44)Cl(4)Cu(8)) crystallizes in the tetragonal system, space group I, with a = 21.2562(8) A, c = 12.7583(9) A, and Z = 2. Compound 4 (C(84)H(120)N(28)O(66)Cl(8)Cu(8)) crystallizes in the tetragonal system, space group I4(1)/a, with a = 20.7790(4) A, c = 32.561(1) A, and Z = 4. Compound 7(C(104)H(104)N(46)O(56)Cu(9)) crystallizes in the triclinic system, space group P, with a = 15.473(1) A, b = 19.869(2) A, c = 23.083(2) A, alpha = 88.890(2) degrees, beta = 81.511(2) degrees, gamma = 68.607(1) degrees, and Z = 2. All complexes exhibit dominant intramolecular ferromagnetic exchange coupling, resulting from an orthogonal bridging arrangement within each polynuclear structure. 相似文献
52.
Semi-empirical model potential calculations have been performed for bound and continuum properties of Li? and Na?. The calculated electron affinities of the 2s21S state of Li? and the 3s21S and 3p23Pe states of Na? are in agreement with the calculations of Norcross and with experimental data. Positions of possible autoionizing states are calculated using projection and root stabilization methods. The Stieltjes imaging method of Langhoff is employed to compute the photodetachment cross sections of Li? and Na? and the results are in excellent agreement with the close-coupling calculations of Moores and Norcross. A comparison of variational and numerical results for the coupled time-dependent Hartree-Fock photoionization of helium shows that good Stieltjes imaging results can be obtained with a very small basis set for the variational calculation. The continuous photoemission profile for the 3p23Pe state of Na? is also obtained. 相似文献
53.
An HPLC post column chemical derivatization procedure based on the interaction between an acridinium triflate and amines to form highly colored derivatives on-line is described for the determination of aromatic amines. Benzocaine and butesin, local anesthetic agents that contain the aromatic amine group, were used as model compounds. Reversed-phase HPLC conditions were developed for both the separation of analytes and the reaction between analytes and the acridinium triflate in the system. Three-dimensional knitted teflon shape coils and the internal diameter and length of the coils were important parameters in reducing band broadening and background noise.N-Methyl-9-chloroacridinium triflate was shown to be applicable to the determination of primary aromatic amines, selected secondary aromatic amines, hydrazides, and hydrazines. Application of the on-line chemical derivatization procedure to the analysis of pharmaceutical dosage forms containing procainamide (primary aromatic amine), isoniazid (hydrazide), and hydralazine (hydrazine) is also described. 相似文献
54.
On heating, ammonium metavanadate (AMV) decomposes in several atmospheredependent stages. An important decomposition intermediate, ammonium hexavanadate (AHV), may also be prepared by wet-chemical methods and the kinetic parameters for the thermal decomposition of AMV and of the AHV preparation have been obtained. The kinetic study has been supplemented by surface-area measurements and by electron microscopic examination of the surfaces of reactant, intermediate and product crystallites. On the basis of the type of decomposition curve, the measured activation energies, and the effects of oxygen and water vapour on the decomposition rate, it has been concluded that in vacuum and in inert atmospheres the evolution of ammonia is the rate-determining step, while in oxidizing atmospheres evolution of water is rate determining. Comparison of the kinetic parameters with thermodynamic data for the decomposi. tion has led to suggestions as to the nature of the activated complexes involved. 相似文献
55.
Charles W. Stewart C. A. Von Frankenberg 《Journal of Polymer Science.Polymer Physics》1967,5(3):623-631
The thermodynamic properties of amorphous polyethylene are calculated from a model based on the method of significant structures. The motion of a molecule as a whole is described by the motion of segments, each segment moving independently of all others. It is assumed that on melting, holes appear in the solid lattice and the segments can move into these vacancies, obtaining some gaslike degrees of freedom. The complete frequency distribution for polyethylene is used for the solidlike degrees of freedom, while a corrected classical partition function is used for the gaslike degrees of freedom. The calculated thermodynamic properties are in reasonable agreement with experimentally determined values, assuming each gaslike segment to consist of 20 CH2 groups. 相似文献
56.
Miklos Kertesz Yong S. Lee James J. P. Stewart 《International journal of quantum chemistry》1989,35(2):305-313
It is shown that infinite long polyacene chains may have three energetically close but structurally distinct isomers (a symmetrical, sym, form and two lower symmetry forms: one with double bonds in a trans and another isomer with double bonds in a cis pattern). The energetics is based on solid state MNDO theory. We discuss that the symmetrical form has a substantial energy gap Eg in the Hartree–Fock approach owing to exact exchange terms, which are nonlocal. Broken symmetry Hartree–Fock (HF ) solutions for polyacene are also described. An angularly distorted structure suggested earlier on Jahn–Teller grounds is found to be energetically not favorable. 相似文献
57.
James J. P. Stewart 《Journal of computational chemistry》1991,12(3):320-341
Using a recently developed procedure for optimizing parameters for semiempirical methods,1 PM3 has been extended to a total of 28 elements. Average ΔHf errors for the newly parameterized elements are Be: 8.6, Mg: 8.4, Zn: 5.8, Ga: 14.9, Ge: 11.4, As: 8.5, Se: 11.1, Cd: 2.6, In: 11.3, Sn: 9.0, Sb: 13.7, Te: 11.3, Hg: 6.8, Tl: 6.5, Pb: 7.4, and Bi: 10.9 kcal/mol. For some elements the paucity of data has resulted in a method, which, while highly accurate, is likely to be only poorly predictive. 相似文献
58.
4-(4-Hydroxyphenyl)-2-phenylamino-1,8-naphthyridine was prepared via cyclisation of N-phenyl-N′-3-(4-hydroxyphenethen-1-yl)pyridin-2-ylthiourea in the presence of mercuric oxide. Derivatives of 4-methyl-2-aminoquinolines were prepared in a similar manner from 2-vinylphenylthioureas. 相似文献
59.
Determination of capsaicinoids in salsa by liquid chromatography and enzyme immunoassay 总被引:2,自引:0,他引:2
Perkins B Bushway R Guthrie K Fan T Stewart B Prince A Williams M 《Journal of AOAC International》2002,85(1):82-85
Two simple and rapid methods were developed to monitor pungency of salsa in production. Capsaicin (C) and dihydrocapsaicin (DHC) were quantitated in 17 commercially available tomato-based salsas by enzyme immunoassay (EIA) and liquid chromatography (LC) with fluorescent detection. Samples were extracted with methanol and the extracts were subjected to solid-phase extraction (SPE) using polystyrene-divinylbenzene columns. Analysis of SPE eluates showed good correlation (r2 = 0.953) between LC and EIA, with a slightly high bias for EIA. Salsa fortified with C and DHC from 0.118 to 103.2 microg/g resulted in recoveries of 90-112% (C) and 76-97% (DHC). Limits of detection by LC were 0.1 microg/g for each capsaicinoid and 0.1 microg/g by EIA for total capsaicinoids. The LC on-column response was linear from 0.2 to 100 ng for both C and DHC, whereas the working range for EIA was 0.1-2.0 ppm. Pungency varied between different salsa brands labeled mild, medium, and hot. 相似文献
60.
Aalders MC Sterenborg HJ Stewart FA van der Vange N 《Photochemistry and photobiology》2000,72(4):521-525
In 75% of cases, ovarian carcinoma has already metastasized in the abdominal cavity at the time of diagnosis. For determination of the necessity for a supplementary therapy, in addition to surgical resection, it is important to localize and stage microscopical intraperitoneal metastases of the tumor. Intraperitoneal photodetection of tumor metastases is based on preferential tumor distribution of a fluorescent tumor marker. The time-dependent differences in drug concentration between tumor and normal (T/N) tissues can be used to visualize small tumors. We performed fluorescence measurements on abdominal organs and tumor in the peritoneal cavity of rats. 5-Aminolevulinic acid (ALA)-induced protoporphyrin IX (PpIX) was used as the fluorescent marker. Three different drug doses (100, 25 and 5 mg/kg) were used and PpIX fluorescence profiles were followed up to 24 h after intravenous administration. Maximum T/N ratios were found 2-3 h after administration of ALA with all drug doses. A significant T/N tissue contrast was obtained for all abdominal organs tested after administration of 5 mg/kg. 相似文献