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61.
62.
An ion-exchange method was used to determine complexation constants for the Ni-oxalate and Ni-carbonate systems in a NaClO4 background electrolyte. The Ni-oxalate data were interpreted in terms of a single Niox(aq) complex having log K
1 values for Ni2+ + ox2– Niox(aq) of 3.9 ± 0.1 (I.S. = 0.5 mol-L–1 p[H] = 7.1) and 4.4 ± 0.1 (I.S. = 0.1 mol-L–1 p[H] = 8.6) at 22 ± 1C. Specific ion-interaction theory (SIT) was used to obtain log K
1
= 5.17 ± 0.05 (95% confidence level and = –0.23 ± 0.15) at I.S. = 0. The Ni-carbonate studies were carried out at p[H] values of 7.5, 8.5, and 9.6 in 0.5 mol-L–1 NaClO4/NaHCO3 solutions. The NiCO3(aq) species was the dominant complex in the [CO3
2–] concentration ranges studied at all three p[H] values. A log K
1 value for Ni2+ + CO3
2– NiCO3(aq) of 2.9 ± 0.3 was deduced at I.S. = 0.5 mol-L–1. Extrapolating this value to zero ionic strength using the SIT approach yielded log K
1
= 4.2 ± 0.3 (95% confidence level and = –0.26 ± 0.04). The data allowed upper bound values for the complexation constants for NiHCO3
+ and Ni(CO3)2
2– to be estimated, i.e., log K
< 1.4 for Ni2+ + HCO3
– NiHCO3
+, and log K
2
< 2 for NiCO3(aq) + CO3
2– Ni(CO3)2
2–, respectively. 相似文献
63.
Summary Gas chromatographic unified retention indices for 43 hydrocarbons (alkanes and cycloalkanes) are given for squalane and OV-101. Comparison of these values and unified retention index increments are presented as linear regression equations with high correlation coefficients and acceptable standard deviations. 相似文献
64.
In environmental chemistry studies, it may be necessary to analyze data sets constituted by different blocks of variables, possibly of different types, measured on the same samples. Multiple factor analysis (MFA) is presented as a tool for exploring such data. The most important features of MFA are shown on a real environmental data set, consisting of two blocks of data, namely heavy metals and polycyclic aromatic hydrocarbons, measured for sediment samples. They are discussed and compared to principal component analysis (PCA). The usefulness of the weighting scheme used in MFA as a preprocessing step for other chemometric methods, such as clustering, is also highlighted. 相似文献
65.
The linearity of the relationship between σT,t2 and (1 + k)2 is studied with the view of using it for the evaluation of GC equipment. Based on appropriate analytical expressions it is concluded that in general this relationship is not linear and that practical procedures for column evaluation should be developed that take this non-linearity into account. 相似文献
66.
Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at temperatures 0–60°C up to a molality of 2.0 mol-kg–1. The data obtained by Harned and Ehlers(2,3) on galvanic cells without a liquid junction were used in the parameter estimations of these equations. These data consist of sets of measurements at the temperature intervals of 5°C. It was observed that all estimated parameters follow very simple equations with respect to temperature. They are either constant or depend linearly on the temperature. The values for the activity coefficient parameters calculated by these simple equations are recommended here. The recommended parameter values were tested by predicting the data of Gupta, Hills, and Ives,(5) consisting of cell measurements from 5 to 45°C and molalities up to 1.0 mol-kg–1, and the data of Bates and Bower,(4) which extend to 95°C but measurements were only made on molalities less than about 0.1 mol-kg–1. The activity coefficients obtained by the new equations were also compared to those calculated by the Pitzer equations with the parameter values determined by Saluja, Pitzer, and Phutela(6) from calorimetric data. The agreement observed was excellent up to a molality of 1.5 mol-kg–1 at temperatures from 0 to 60°C. 相似文献
67.
Czakis-Sulikowska D. Malinowska A. Łuczak A. 《Journal of Thermal Analysis and Calorimetry》2004,78(2):461-471
Two lactates and four new mixed ligand complexes with formulae Co(lact)2·2H2O, Ni(lact)2·3H2O, Co(4-bpy)(lact)2, Co(2,4'-bpy)2(lact)2, Ni(4-bpy)(lact)2·2H2O and Ni(2,4'-bpy)2(lact)2 (where 4-bpy=4,4'-bipyridine, 2,4'-bpy=2,4'-bipyridine, lact=CH3CH(OH)COO-) were isolated and investigated. The thermal behaviour of compounds was studied by thermal analysis (TG, DTG, DTA). In the
case of hydrated complexes thermal decomposition starts with the release of water molecules. The compounds decompose at high
temperature to metal(II) oxides in air. A coupled TG-MS system was used to analyse the principal volatile products of thermolysis
and fragmentation processes of obtained complexes.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
68.
Reduced Clusters with Remarkable Topological and Electronic Properties of the Type of [V18O42(X)]n? (X = SO4, VO4) with Td-Symmetry and Related Clusters [V(18—p)As2pO42(X)]m? (X = SO3, SO4, H2O; p = 3, 4) The novel cluster-compounds Na6[V18O42H9(VO4)] · 21 H2O, (NH4)8[V18O42(SO4)] · 25 H2O, K6[V15As6O42(H2O)] · 8 H2O, (NH4)6[V14As8O42(SO3)], (NH4)6[V14As8O42(SO4)] and [N(CH3)3]4[4V14As8042(H20)] were prepared and characterized by IR- and UV/Vis/NIR-spectroscopy, magnetic measurements and complete crystal structure analysis. For structural data see Inhaltsübersicht. Topological relations to the rhombicuboctahedron spanned by 24 0-atoms of the genuine hypothetical a-Keggin ion, at which the square planes are capped by V?O or As2O groups, are discussed. Of particular interest are the ?extended”? Keggin ions [V18O42(X)]n- (X = SO4 VO4), (formaly derived from the hypothetical genuine a-Keggin ion by addition of six V?O groups) which have quite different electron populations in spite of the same structure of their cluster shells. 相似文献
69.
Mordvintsev DY Polyak YL Levtsova OV Tourleigh YV Kasheverov IE Shaitan KV Utkin YN Tsetlin VI 《Computational Biology and Chemistry》2005,29(6):398-411
Short-chain alpha-neurotoxins from snakes are highly selective antagonists of the muscle-type nicotinic acetylcholine receptors (nAChR). Although their spatial structures are known and abundant information on topology of binding to nAChR is obtained by labeling and mutagenesis studies, the accurate structure of the complex is not yet known. Here, we present a model for a short alpha-neurotoxin, neurotoxin II from Naja oxiana (NTII), bound to Torpedo californica nAChR. It was built by comparative modeling, docking and molecular dynamics using 1H NMR structure of NTII, cross-linking and mutagenesis data, cryoelectron microscopy structure of Torpedo marmorata nAChR [Unwin, N., 2005. Refined structure of the nicotinic acetylcholine receptor at 4A resolution. J. Mol. Biol. 346, 967-989] and X-ray structures of acetylcholine-binding protein (AChBP) with agonists [Celie, P.H., van Rossum-Fikkert, S.E., van Dijk, W.J., Brejc, K., Smit, A.B., Sixma, T.K., 2004. Nicotine and carbamylcholine binding to nicotinic acetylcholine receptors as studied in AChBP crystal structures. Neuron 41 (6), 907-914] and antagonists: alpha-cobratoxin, a long-chain alpha-neurotoxin [Bourne, Y., Talley, T.T., Hansen, S.B., Taylor, P., Marchot, P., 2005. Crystal structure of Cbtx-AChBP complex reveals essential interactions between snake alpha-neurotoxins and nicotinic receptors. EMBO J. 24 (8), 1512-1522] and alpha-conotoxin [Celie, P.H., Kasheverov, I.E., Mordvintsev, D.Y., Hogg, R.C., van Nierop, P., van Elk, R., van Rossum-Fikkert, S.E., Zhmak, M.N., Bertrand, D., Tsetlin, V., Sixma, T.K., Smit, A.B., 2005. Crystal structure of nicotinic acetylcholine receptor homolog AChBP in complex with an alpha-conotoxin PnIA variant. Nat. Struct. Mol. Biol. 12 (7), 582-588]. In complex with the receptor, NTII was located at about 30 A from the membrane surface, the tip of its loop II plunges into the ligand-binding pocket between the alpha/gamma or alpha/delta nAChR subunits, while the loops I and III contact nAChR by their tips only in a 'surface-touch' manner. The toxin structure undergoes some changes during the final complex formation (for 1.45 rmsd in 15-25 ps according to AMBER'99 molecular dynamics simulation), which correlates with NMR data. The data on the mobility and accessibility of spin- and fluorescence labels in free and bound NTII were used in MD simulations. The binding process is dependent on spontaneous outward movement of the C-loop earlier found in the AChBP complexes with alpha-cobratoxin and alpha-conotoxin. Among common features in binding of short- and long alpha-neurotoxins is the rearrangement of aromatic residues in the binding pocket not observed for alpha-conotoxin binding. Being in general very similar, the binding modes of short- and long alpha-neurotoxins differ in the ways of loop II entry into nAChR. 相似文献
70.
Schultz J Gottlieb DM Petersen M Nesic L Jacobsen S Søndergaard I 《Electrophoresis》2004,25(3):502-511
Methods for classification of two-dimensional (2-DE) electrophoresis gels based on multivariate data analysis are demonstrated. Two-dimensional gels of ten wheat varieties are analyzed and it is demonstrated how to classify the wheat varieties in two qualities and a method for initial screening of gels is presented. First, an approach is demonstrated in which no prior knowledge of the separated proteins is used. Alignment of the gels followed by a simple transformation of data makes it possible to analyze the gels in an automated explorative manner by principal component analysis, to determine if the gels should be further analyzed. A more detailed approach is done by analyzing spot volume lists by principal components analysis and partial least square regression. The use of spot volume data offers a mean to investigate the spot pattern and link the classified protein patterns to distinct spots on the gels for further investigation. The explorative approach in analysis of 2-D gels makes it possible, in a fast and convenient way, to screen many gels in order to determine the protein patterns that form clusters and could be selected for further examination. 相似文献