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31.
32.
K. D. Sen T. V. Gayatri R. Krishnaveni M. Kakkar Helge Toufar Geert O. A. Janssens Bart G. Baekelandt Robert A. Schoonheydt Wilfried J. Mortier 《International journal of quantum chemistry》1995,56(4):399-408
The average local electrostatic potential function, V(r)/ ρ(r), is calculated for 87 atoms, Li-Ac, in the ground state using the nonrelativistic average-over-configuration numerical Hartree-Fock density. It is found empirically that in a given atom the shell boundaries are expressed as the successively increasing maxima in V(r)/ ρ(r) and the outermost maximum presents good approximate estimates of the core-valence separation in atoms. The likeness in behavior of V(r)/ ρ(r) at each shell boundary with the maximum hardness principle is discussed. The single-exponent-fit parameters for the electron density in the valency region are provided for all atoms. © 1995 John Wiley & Sons, Inc. 相似文献
33.
The reaction of peri-substituted anthracenediones with sodium dithionite in dimethylformamide and water has been investigated. The system selectively reduces the carbonyl group flanked by the peri substituents of the anthracenediones to give the corresponding 4,5-disubstituted 9(10H)-anthracenones and thus provides a route to anthracenones which are otherwise difficult to obtain. Many functional groups can be tolerated, the reaction is compatible with the presence of peri alkoxy groups and unsaturated side chains of the starting anthracenediones, and the reduction does not go beyond the anthracenone stage. However, the formation of anthracenones depends on the nature of the peri substituents. No products were obtained from the 1,8-dimethyl-substituted anthracenedione and the parent compound with no substituents. 相似文献
34.
The introduction of selected fractions from a liquid chromatograph into a gas chromatograph has been described; however, analyses were performed by off-line experiments requiring collection and reinjection of the separate fractions or by on-line procedures where disadvantageously, only a fraction of the separated peak or a well resolved component in a mixture could be introduced into a gas chromatograph. This disadvantage is overcome by the apparatus and method described in this paper, which utilizes a multidimensional chromatography system employing a high efficiency, packed capillary LC column coupled on-line to a capillary gas chromatograph. The liquid chromatograph (so designed) can act as a highly efficient clean-up or chemical class fractionation step prior to introduction into the gas chromatograph, significantly reducing sample preparation times in many applications. Thus minor components in a complex matrix can be determined without prior sample clean-up, an example of which is the determination of polychlorinated biphenyls in a complex hydrocarbon matrix. 相似文献
35.
Quaternary pyridinium salts were investigated by field desorption, field ionization and electron impact mass spectrometry. Thermal decomposition of the salts under field desorption conditions was found to give very abundant volatile products, identified as the dihydro analogues and the ‘methides’ of the cations. The formation of the volatile compounds, especially those with molecular weights corresponding to those of the (cation ?1), (cation +1) and (cation +13) was studied in detail by deuterium and 13C labelling experiments. 相似文献
36.
Ingo Hartenbach Falk Lissner Tanja Nikelski Steffen F. Meier Helge Müller‐Bunz Thomas Schleid 《无机化学与普通化学杂志》2005,631(12):2377-2382
About Lanthanide Oxotantalates with the Formula MTaO4 (M = La – Nd, Sm – Lu) Besides being a by‐product of solid state syntheses in tantalum ampoules the lanthanide(III) oxotantalates of the formula MTaO4 can be easily prepared by sintering lanthanide sesquioxide M2O3 and tantalum(V) oxide Ta2O5 with sodium chloride as flux. Under these conditions two structure types emerge depending upon the M3+ cationic radius. For M = La – Pr the MTaO4‐type tantalates crystallize in the space group P21/c with lattice constants of a = 762(±1), b = 553(±4), c = 777(±4) pm, β = 101(±1)° and four formula units per unit cell. With M = Nd, Sm – Lu, the monoclinic cell dimensions (space group P2/c) shrink to the lattice constants like a = 516(±9), b = 551(±9), c = 534(±9) pm, β = 96.5(±0.3)° and there are only two formula units present. Both structures show a coordination sphere of eight oxygen atoms for the lanthanide trications shaped as distorted square antiprism for the structure with the larger lanthanides (in the following referred to as A‐type) and as trigonal dodecahedron for the structure with the smaller ones (called as B‐type in the following). The coordination environment about the Ta5+ cations can be described as a slightly distorted octahedron (CN = 6) for the A‐type structure of MTaO4 and a heavily distorted one (CN = 6) for the B‐type. The difference between the two types results from the interconnection of these [TaO6]7? octahedra. Whereas they are connected via four vertices to form corrugated layers according to parallel the bc‐plane in the A‐type, the octahedra of the B‐type MTaO4 structure share edges to built up zig‐zag chains along the c axis. 相似文献
37.
A gas chromatograph/quadrupole mass spectrometer (GC/MS) system was used to supervise a test programme for evaluating the potential of a natural gas storage plant. The dispersion characteristics of a large nitrogen reservoir located in a tight sandstone formation 1600 m below sea level between claystones, was investigated by injection and withdrawal of 350 000 m3 nitrogen with argon as tracer gas. The GC/MS system was installed in a shed in an open field and operated under computer control continuously 24 h a day for three weeks; about 3000 analyses were done. The on-line results were in good agreement with those obtained from additional gas samples withdrawn every 4 h for independent quantitative gas analyses with a purpose-built mass spectrometer. 相似文献
38.
We consider a random Schrödinger operator onL
2(v) of the form
, {C
i} being a covering of
v
with unit cubes around the sites of
v
and {q
i} i.i.d. random variables with values in [0, 1]. We assume that theq
i's are continuously distributed with bounded densityf(q) and that 0<P(q
0<1/2)=<1. Then we show that an ergodic mean of the quantity dx|x|2|(exp(itH
))(x)|2t
–1 vanishes provided =g
E(H
), where is well-localized around the origin andg
E is a positiveC
-function with support in (0,E),EE*(, |f|). Our estimate ofE*(, |f|) is such that the set {x
v
|V
(x) E*(, |f|)} may contain with probability one an infinite cluster of cubes {C
i} which are nearest neighbours. The proof is based on the technique introduced by Fröhlich and Spencer for the analysis of the Anderson model.Work supported in part by C.N.R. (Italy) and NAVF (Norway)On leave of absence from Instituto di Fisica Università di Roma, Italia 相似文献
39.
Rose A Scheller FW Wollenberger U Pfeiffer D 《Fresenius' Journal of Analytical Chemistry》2001,369(2):145-152
The use of thick-film electrodes as basic transducers for highly sensitive amperometric biosensors using PQQ (pyrroloquinoline quinone) dependent glucose dehydrogenase (GDH) with short response times is described. The enzyme is embedded in a polyurethane matrix on top of a platinum based thick film electrode and its ability to reduce oxidized phenolic compounds is exploited. The electrochemical amplification is based on the oxidation of the analyte on the surface of the electrode followed by its enzymatic reduction. Different parameters of the glucose dehydrogenase electrode system using dopamine as a model analyte were optimized, e.g., membrane thickness, pH value, buffer system, flow rate and storage conditions. Using optimized parameters the sensitivity and detection limits for various phenolic compounds were evaluated. The comparison of electrodes from the identical as well as from different batches shows the ability to produce a number of well reproducible sensors showing remarkably small differences with respect to parameters as sensitivity, response times and measuring range. 相似文献
40.
Bongui JB Elomri A Seguin E Tillequin F Pfeiffer B Renard P Pierré A Atassi G 《Chemical & pharmaceutical bulletin》2001,49(9):1077-1080
Condensation of either 2-bromobenzoic acid (4) or 2-chloro-3-nitrobenzoic acid (5) with suitable aminoquinolines 6-8 afforded phenylquinolylamines 9-13. Acid mediated cyclization gave the corresponding 12H-benzo[b][1,7]phenanthrolin-7-ones 14 and 15, and 12H-benzo[b][1,10]phenanthrolin-7-ones 16-18. Compounds 14, 16, and 17 were subsequently N-methylated to 6-demethoxyacronycine and acronycine analogues 19-21, whereas reduction of the aromatic nitro group of 18 gave the amino derivative 22. Unsubstituted 12H-benzo[b][1,10]phenanthrolin-7-ones 16, 17, 20, and 21 were devoid of significant cytotoxic activity, whereas 18 and 22, bearing a nitrogen substituent at position 11, were significantly active. Unsubstituted 12H-benzo[b][1,7]phenanthrolin-7-ones 14 and 19, which include a pyridine nitrogen in the same 4-position as the pyran oxygen of acronycine exhibited cytotoxic activities within the same range of magnitude as acronycine itself. 相似文献