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41.
In the title compound, germanium is penta‐coordinated and adopts a trigonal bipyramidal geometry. The (2‐thienyl)phenyl group and the nitrogen atom each occupy an apical position with a transannular N→Ge bond distances of 2.247(4) and 2.219(4) Å for the two independent molecules. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
42.
Tatjana Nahtman 《Linear algebra and its applications》2006,417(1):183-210
The goal of the present paper is to perform a comprehensive study of the covariance structures in balanced linear models containing random factors which are invariant with respect to marginal permutations of the random factors. We shall focus on model formulation and interpretation rather than the estimation of parameters. It is proven that permutation invariance implies a specific structure for the covariance matrices. Useful results are obtained for the spectra of permutation invariant covariance matrices. In particular, the reparameterization of random effects, i.e., imposing certain constraints, will be considered. There are many possibilities to choose reparameterization constraints in a linear model, however not every reparameterization keeps permutation invariance. The question is if there are natural restrictions on the random effects in a given model, i.e., such reparameterizations which are defined by the covariance structure of the corresponding factor. Examining relationships between the reparameterization conditions applied to the random factors of the models and the spectrum of the corresponding covariance matrices when permutation invariance is assumed, restrictions on the spectrum of the covariance matrix are obtained which lead to “sum-to-zero” reparameterization of the corresponding factor. 相似文献
43.
Solitary Wave Transformation Due to a Change in Polarity 总被引:1,自引:0,他引:1
Roger Grimshaw Efim Pelinovsky & Tatjana Talipova 《Studies in Applied Mathematics》1998,101(4):357-388
Solitary wave transformation in a zone with sign-variable coefficient for the quadratic nonlinear term is studied for the variable-coefficient Korteweg–de Vries equation. Such a change of sign implies a change in polarity for the solitary wave solutions of this equation. This situation can be realized for internal waves in a stratified ocean, when the pycnocline lies halfway between the seabed and the sea surface. The width of the transition zone of the variable nonlinear coefficient is allowed to vary over a wide range. In the case of a short transition zone it is shown using asymptotic theory that there is no solitary wave generation after passage through the turning point, where the coefficient of the quadratic nonlinear term goes to zero. In the case of a very wide transition zone it is shown that one or more solitary waves of the opposite polarity are generated after passage through the turning point. Here, asymptotic methods are effective only for the first (adiabatic) stage when the solitary wave is approaching the turning point. The results from the asymptotic theories are confirmed by direct numerical simulation. The hypothesis that the pedestal behind the solitary wave approaching the turning point has a significant role on the generation of the terminal solitary wave after the transition zone is examined. It is shown that the pedestal is not the sole contributor to the amplitude of the terminal solitary wave. A negative disturbance at the turning point due to the transformation in the zone of the variable nonlinear coefficient contributes as much to the process of the generation of the terminal solitary waves. 相似文献
44.
Nardis S Paolesse R Licoccia S Fronczek FR Vicente MG Shokhireva TK Cai S Walker FA 《Inorganic chemistry》2005,44(20):7030-7046
An undecasubstituted chloroiron corrolate, octamethyltriphenylcorrolatoiron chloride, (OMTPCorr)FeCl, has been synthesized and studied by X-ray crystallography and (1)H and (13)C NMR spectroscopy. It is found that, although the structure is slightly saddled, the average methyl out-of-plane distance is only 0.63 Angstroms, while it is much greater for the dodecasubstituted porphyrinate analogue (OMTPP)FeCl (1.19 Angstroms) (Cheng, R.-J.; Chen, P.-Y.; Gau, P.-R.; Chen, C.-C.; Peng, S.-M. J. Am. Chem. Soc. 1997, 119, 2563-2569). In addition, the distance of iron from the mean plane of the four macrocycle nitrogens is also smaller for (OMTPCorr)FeCl (0.387 Angstroms) than for (OMTPP)FeCl (0.46 Angstroms). The (1)H and (13)C NMR spectra of (OMTPCorr)FeCl, as well as the chloroiron complexes of triphenylcorrolate, (TPCorr)FeCl; 7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolate, (DMHECorr)FeCl; 7,8,12,13-tetramethyl-2,3,17,18-tetraethylcorrolate, (TMTECorr)FeCl; and the phenyliron complex of 7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolate, (DMHECorr)FePh, have been assigned, and the spin densities at the carbons that are part of the aromatic ring of the corrole macrocycle have been divided into the part due to spin delocalization by corrole --> Fe pi donation and the part due to the unpaired electron present on the corrole ring. It is found that although the spin density at the beta-pyrrole positions is fairly similar to that of (TPCorr)FeCl, the meso-phenyl-carbon shift differences delta(m) - delta(p) are opposite in sign of those of (TPCorr)FeCl. This finding suggests that the radical electron is ferromagnetically coupled to the unpaired electrons on iron, rather than antiferromagnetically coupled, as in all of the other chloroiron corrolates. The solution magnetic moment was measured for (OMTPCorr)FeCl and found to be mu(eff) = 4.7 +/- 0.5 micro(B), consistent with S = 2 and ferromagnetic coupling. From this study, two conclusions may be reached about iron corrolates: (1) the spin states of chloroiron corrolates are extremely sensitive to the out-of-plane distance of iron, and (2) pyrrole-H or -C shifts are not useful in delineating the spin state and electron configuration of (anion)iron corrolates. 相似文献
45.
A detailed study of the role of solution pH and ionic strength on the swelling behavior of capsules composed of the weak polyelectrolytes poly(4-vinylpyridine) (P4VP) and poly(methacrylic acid) (PMA) with different numbers of layers was carried out. The polyelectrolyte layers were assembled onto silicon oxide particles and multilayer formation was followed by zeta-potential measurements. Hollow capsules were investigated by scanning electron microscopy and atomic force microscopy. The pH-dependent behavior of P4VP/PMA capsules was probed in aqueous media using confocal laser scanning microscopy. All systems exhibited a pronounced swelling at the edges of stability, at pHs of 2 and 8.1. The swelling degree increased when more polymer material was adsorbed. The swollen state can be attributed to uncompensated positive and negative charges within the multilayers, and it is stabilized by counteracting hydrophobic interactions. The swelling was related to the electrostatic interactions by infrared spectroscopy and zeta-potential measurements. The stability of the capsules as well as the swelling degree at a given pH could be tuned, when the ionic strength of the medium was altered. 相似文献
46.
Tatjana Souza Lima Keesen Larisse Virgolino da Silva Juliana da Câmara Rocha Luciana Nalone Andrade Tamires Cardoso Lima 《Natural product research》2019,33(17):2536-2540
Leishmaniasis belongs to a complex of zoonotic disease caused by protozoa of the genus Leishmania and is considered a major public health problem. Several essential oil chemical components have inhibitory effect against protozoa, including Leishmania donovani. Thus, the aim of this study was to evaluate for the first time the anti-Leishmania activity of two p-menthane monoterpene isomers (EPER-1: perillaldehyde 1,2-epoxide and EPER-2: perillaldehyde 8,9-epoxide) against L. donovani promastigotes as well as evaluating cytotoxic effect on mononuclear peripheral blood cells. Results of anti-Leishmania assay revealed that EPER-2 (IC50 = 3.8 μg.mL?1) was 16-fold more potent than its isomer EPER-1 (IC50 = 64.6 μg.mL?1). In contrast to PBMC cells, EPER-2 was not cytotoxic (IC50 > 400 μg.mL?1) when compared to positive control. These data suggest that the disposition of epoxide group into the p-menthane skeleton affects the anti-Leishmania activity, being that the presence of the exocyclic epoxide group considerably increased potency. Thus, it was possible to observe that the location of the epoxide group into the p-menthane skeleton resulted in different potencies. 相似文献
47.
48.
Straksys Antanas Kavleiskaja Tatjana Gruskiene Ruta Badokas Kazimieras Sereikaite Jolanta 《Cellulose (London, England)》2022,29(16):8705-8718
Cellulose - The study aimed to propose a new system based on xylan for β-carotene delivery into aqueous environments. The xylan fraction of low molecular weight of... 相似文献
49.
50.
Ozalp-Yaman S de Hoog P Amadei G Pitié M Gamez P Dewelle J Mijatovic T Meunier B Kiss R Reedijk J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(11):3418-3426
The synthesis and biological activity of three heteronuclear platinum-copper complexes based on 3-Clip-Phen are reported. These rigid complexes have been designed to alter the intrinsic mechanism of action of both the platinum moiety and the Cu(3-Clip-Phen) unit. The platinum centers of two of these complexes are coordinated to a 3-Clip-Phen moiety, an ammine ligand and two chlorides, which are either cis or trans to each other. The third complex comprises two 3-Clip-Phen units and two chloride ligands bound in a trans fashion to the platinum ion. DNA-cleavage experiments show that the complexes are highly efficient nuclease agents. In addition, a markedly difference in their aptitude to perform direct double-strand cleavage is observed, which appears to be strongly related to the ability of the platinum unit to coordinate to DNA. Indeed, complex 6 is unable to coordinate to DNA, which is reflected by its incapability to carry out double-strand breaks. Nonetheless, this complex exhibits efficient DNA-cleavage activity, and its cytotoxicity is high for several cell lines. Complex 6 shows better antiproliferate activity than both cisplatin and Cu(3-Clip-Phen) toward most cancer cell lines. Furthermore, the cytotoxicity observed for 1 is for most cell lines close to that of cisplatin, or even better. Cu(3-Clip-Phen) induces very low cytotoxic effects, but a marked migratory activity. Complex 6 presents DNA-cleavage properties comparable to the one of Cu(3-Clip-Phen), but it does not show any migratory activity. Interestingly, both Cu(3-Clip-Phen) and 6 induces vacuolisation processes in the cell in contrast to complex 1 and cisplatin. Thus, the four complexes cisplatin tested, Cu(3-Clip-Phen), 1 and 6 stimulate different cellular responses. 相似文献