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941.
Dimitrov S Dimitrova N Parkerton T Comber M Bonnell M Mekenyan O 《SAR and QSAR in environmental research》2005,16(6):531-554
The base-line modeling concept presented in this work is based on the assumption of a maximum bioconcentration factor (BCF) with mitigating factors that reduce the BCF. The maximum bioconcentration potential was described by the multi-compartment partitioning model for passive diffusion. The significance of different mitigating factors associated either with interactions with an organism or bioavailability were investigated. The most important mitigating factor was found to be metabolism. Accordingly, a simulator for fish liver was used in the model, which has been trained to reproduce fish metabolism based on related mammalian metabolic pathways. Other significant mitigating factors, depending on the chemical structure, e.g. molecular size and ionization were also taken into account in the model. The results (r(2)=0.84) obtained for a training set of 511 chemicals demonstrate the usefulness of the BCF base line concept. The predictability of the model was evaluated on the basis of 176 chemicals not used in the model building. The correctness of predictions (abs(logBSF(Obs)-logBCF(Calc))=0.75)) for 59 chemicals included within the model applicability domain was 80%. 相似文献
942.
Björn O. Roos Valera Veryazov Per-Olof Widmark 《Theoretical chemistry accounts》2004,111(2-6):345-351
New basis sets of the atomic natural orbital (ANO) type have been developed for the atoms Li–Fr and Be–Ra. The ANOs have been obtained from the average density matrix of the ground states and the lowest excited states of the atom, the positive ion, and the dimer at its equilibirium geometry. Scalar realtivisitc effects are included through the use of a Douglas–Kroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of the ground-state potentials for the dimers. Computed bond energies are accurate to within 0.05 eV for the alkaline dimers and 0.02 eV for the alkaline-earth dimers (except for Be2).Acknowledgments.ensp;B.O.R. would like to express his gratitude to Prof. Jacopo Tomasi for all the inspiration that his scientific work has given him through the years and continues to do in particular through the work on solvent effects on molecular properties. This work has been supported by a grant from the Swedish Science Research Council, VR.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
943.
Lapidus A. L. Eliseev O. L. Stepin N. N. Bondarenko T. N. 《Russian Chemical Bulletin》2004,53(11):2564-2567
The carboxylation of styrene into carboxylic acids in the N(C4H9)4Br—heptane system in the presence of phosphine complexes and palladium acetate was studied. In the absence of phosphine, the Pd catalyst seems to be stabilized in solution by forming anionic complexes with NBu4Br; the stabilization depends on the acidity of the reaction medium. The catalytic system can be used repeatedly, its activity being reduced only slightly.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2458–2461, November, 2004. 相似文献
944.
Yarovaya O. I. Korchagina D. V. Salomatina O. V. Polovinka M. P. Barkhash V. A. 《Russian Journal of Organic Chemistry》2003,39(7):985-991
Acid-catalyzed reactions of 2,3-epoxy derivatives of citral (which is a widely spread naturally occurring unsaturated aldehyde) with alcohols were studied under conditions of heterogeneous catalysis and in fluorosulfonic acid. A number of new products were obtained, and possible mechanisms of their formation were proposed. 相似文献
945.
Martin L. Bennink Dessy N. Nikova Kees O. van der Werf Jan Greve 《Analytica chimica acta》2003,479(1):3-15
Atomic force microscopy (AFM) imaging of static DNA-protein complexes, in air and in liquid, can be used to directly obtain quantitative and qualitative information on the structure of different complexes. For example, DNA length, the location of preferential binding sites for proteins and bending of DNA as a result of the complexation can all be measured. Recording consecutive AFM images of DNA and protein molecules under conditions that they are still able to move and interact, or dynamic AFM imaging, however, can reveal information on the dynamic aspects of the interactions between these molecules. Here, an overview is given of the technical challenges that need to be considered for successful dynamic AFM imaging studies of individual DNA-protein interactions. Necessary technical improvements to the AFM set-up and the development of new sample preparation methods are described in this paper. 相似文献
946.
947.
A. I. Kovalev Yu. I. Lyakhovetskli M. M. Teplyakov A. L. Rusanov P. V. Petrovskii S. O. Yakushin 《Russian Chemical Bulletin》1993,42(9):1529-1535
The chemical heterogeneity of polyphenylenes obtained by trimerization poiycycio-condensation of acetylaromatic compounds has been investigated by GLC-MS analysis of the products of trimerization cyclocondensation of acetophenone. The mechanism for the formation of side products of the reaction is discussed. The presence of dypnone fragments in the polyphenylene structure results in a decrease in the thermal stability of these polymers.Deceased March, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1595–1601, September, 1993. 相似文献
948.
V. A. Glushkov I. V. Mashevskaya V. I. Sokol E. V. Feshina O. A. Maiorova 《Chemistry of Heterocyclic Compounds》1997,33(7):783-788
The reaction of arylhydrazides of -alkyl--chlorocarboxylic acids with thiocyanate ions gave intermediate thiocyanates which rearranged to isothiocyanates on heating and the latter cyclized to 5,5-dialkyl-3-arylamino-2-thiohydantoins.Institute of Technical Chemistry, Urals Branch, Russian Academy of Sciences, Perm' 614000. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 898–903, July, 1997. 相似文献
949.
Phanstiel O IV Price HL Wang L Juusola J Kline M Shah SM 《The Journal of organic chemistry》2000,65(18):5590-5599
An efficient five-step synthetic method was developed to access a homologous series of spermidine-acridine and spermidine-anthracene conjugates. The derivatives were comprised of a spermidine fragment covalently tethered at its N4 position to either an acridine or anthracene nucleus via an aliphatic chain (e.g., spermidine-[aliphatic tether]-acridine). The distance separating the spermidine and aromatic nucleus was altered by using different tethers comprised of four or five methylene units, respectively. These ligands (2-5) were shown to inhibit human DNA topoisomerase-II (TOPO-II) activity at 10 microM. Enzymatic activity was assessed as the ability to unknot (decatenate) and cleave kinetoplast DNA (kDNA). Polyamine conjugation did not disrupt the ability of the acridine-spermidine conjugates 2 and 3 to inhibit TOPO-II activity as compared with the 9-aminoacridine and 9-(N-butyl)aminoacridine controls (at 10 microM). In general, the acridine derivatives (2 and 3) showed higher TOPO-II inhibitory activity than their anthracene counterparts (4 and 5). However, this trend was reversed in a whole cell assay with L1210 (murine leukemia) cells, wherein the anthracene analogues were more potent than their acridine counterparts. In this regard the qualitative enzyme-based assay did not predict the trends in the corresponding IC(50) values. Within either series insertion of an additional methylene unit did not significantly alter activity. While the appended spermidine unit did not disrupt TOPO II inhibition by the tethered DNA intercalator, it did provide an alternative mode of entry into the cell as demonstrated by spermidine protection assays. These results were compared with a spermine-intercalator analogue. Of all the conjugates tested the N(4)-(4-(9-aminoacridinyl)butyl)spermine hexahydrochloride (conjugate 16)resulted in the highest degree of L1210 cell rescue upon cotreatment of the cells with exogenous spermidine. It was concluded that the monoalkylated spermine motif present in 16 holds promise as a better vector than its N4 monoalkylated spermidine counterpart. 相似文献
950.
Dependences of differential capacitance C on potential E of a stationary electrode (hanging mercury drop) in aqueous 0.1 M NaF solutions containing 4.6 × 10–4 to 3 × 10–3 M C9H6O2 are obtained using an automatic impedancemeter. At coumarin concentrations below 0.001 M and potential slowly scanned near –1.1 V (SCE) the capacitance is unstable, which results in differently-shaped C vs. E curves in this potential range. The obtained results are attributed to nonequilibrium phase transitions in the adsorption layer, during which the orientation of coumarin molecules at the electrode surface alters. These phenomena are explained semiquantitatively on the basis of a developed theory. 相似文献