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81.
Ribas X Dias JC Morgado J Wurst K Santos IC Almeida M Vidal-Gancedo J Veciana J Rovira C 《Inorganic chemistry》2004,43(12):3631-3641
The deprotonated form of the pyrazine-2,3-diselenol (pds) ligand, pds(2-), reacts with Ni(II) inorganic salts to form the nickel compounds [Ni(II)(pds)(2)](nBu(4)N)(2) (1), [Ni(II)(pds)(2)]Na(2).2H(2)O (2), and [Ni(III)(pds)(2)](2)Na(2).4H(2)O (3), depending on the reaction conditions. They are characterized by NMR, EPR, UV-vis, and IR spectroscopies, elemental analysis, cyclic voltammetry, and X-ray crystallography. The crystal structure of compound 3 shows the formation of segregated stacks of Ni(pds)(2-) units, with a strong dimerization along the stacks. The stacked fashion of the crystal packing was expected since the supramolecular forces of the alkaline side coordination to the pyrazine moieties dominate, as happens in the recently reported analogous copper system [Cu(III)(pds)(2)]Na.2H(2)O. The structure of 2 further emphasizes the alkaline coordination as the dominating supramolecular event, and an orthogonal array of 2D layers is observed. The absence of alkaline cations in complex 1 is reflected in a crystal packing with isolated complex Ni(pds)(2)(2-) units. The dimerization found in the paramagnetic Ni(III) complex 3 promotes a very strong antiferromagnetic interaction, leading to a singlet ground state. 相似文献
82.
The kinetics of exoglucanase (Cel7A) from Trichoderma reesei was investigated in the presence of cellobiose and 24 different enzyme/Avicel ratios for 47 h, in order to establish which of the eight available kinetic models best explained the factors involved. The heterogeneous catalysis was studied and the kinetic parameters were estimated employing integrated forms of Michaelis-Menten equations through the use of nonlinear least squares. It was found that cellulose hydrolysis follows a model that takes into account competitive inhibition by cellobiose (final product) with the following parameters: Km = 3.8 mM, Kic = 0.041 mM, kcat = 2 h-1 (5.6 x 10-4 s-1). Other models, such as mixed type inhibition and those incorporating improvements concerning inhibition by substrate and parabolic inhibition, increased the modulation performance very slightly. The results support the hypothesis that nonproductive enzyme substrate complexes, parabolic inhibition, and enzyme inactivation (Selwyn test) are not the principal constraints in enzymatic cellulose hydrolysis. Under our conditions, the increment in hydrolysis was not significant for substrate/enzyme ratios <6.5. 相似文献
83.
The solvation parameter model is used to identify suitable chromatographic models for estimating the octanol-water partition coefficient for neutral compounds of varied structure by reversed-phase liquid chromatography. The stationary phase Supelcosil LC-ABZ with methanol-water mobile phases affords a series of suitable correlation models for estimating the octanol-water partition coefficient (log KOW) under isocratic and gradient elution conditions. Isocratic separations with mobile phase compositions containing from about 25 to 40% (v/v) methanol provide the most accurate results for log KOW values in the range -0.1 to 4.0. Gradient separations programmed from 5 to 100% (v/v) methanol are suitable for faster separations of compounds with large log KOW values. The standard error in the estimate for the regression models of the predicted log KOW values against literature values are 0.135 log units for the 30% (v/v) methanol-water isocratic system and 0.263 log units for the methanol-water gradient system. Isocratic retention factors predicted from two gradient separations with gradient times of 15 and 45 min afford a poorer fit for the correlation models between log KOW and the estimated retention factors than that of either the above isocratic and gradient models. Plots of the retention factor (log k) as a function of mobile phase composition are generally non-linear. Values of log kw obtained by non-linear extrapolation to a volume fraction of 0% (v/v) methanol do not afford a useful model for estimating log KOW. 相似文献
84.
Measurements of the electronic energy loss are presented for (4)He and (7)Li ions channeling along the Si main axial directions at intermediate to high projectile energies. The Barkas effect, an energy-loss enhancement proportional to the third power of the projectile charge at high energies, is clearly separated from other processes. It reaches about 50% for Li ions channeling along the Si [110] direction. The observed Barkas contribution from the valence-electron gas is in fair agreement with the Lindhard model. 相似文献
85.
86.
This paper describes a new multiobjective interactive memetic algorithm applied to dynamic location problems. The memetic
algorithm integrates genetic procedures and local search. It is able to solve capacitated and uncapacitated multi-objective
single or multi-level dynamic location problems. These problems are characterized by explicitly considering the possibility
of a facility being open, closed and reopen more than once during the planning horizon. It is possible to distinguish the
opening and reopening periods, assigning them different coefficient values in the objective functions. The algorithm is part
of an interactive procedure that asks the decision maker to define interesting search areas by establishing limits to the
objective function values or by indicating reference points. The procedure will be applied to some illustrative location problems. 相似文献
87.
A new National Science Foundation supported curriculum, Interactions in Physical Science?, was evaluated on students’ conceptual change in the twelve concept areas of the national physical science content standard (B) for grades 5–8. Eighth grade students (N=66) were evaluated pre and post on a 31‐item multiple‐choice test of conceptual understanding developed by the Harvard ‐Smithsonian Center for Astrophysics. Significant student gains (p<. 05, t‐test, two‐tailed) occurred in all concept areas in the category of properties and changes in properties of matter; for the force concept areas in the category motions and forces; and for the heat transfer and light interactions areas in the category of transfer of energy. Two of the six concept areas in the category of transfer of energy, chemical and nuclear reactions and the sun as a major source of energy, were not addressed in this study. Significant learning gains as item percent correct were typically close to 20%, though effect sizes were small to medium in magnitude (d = 0.3–0.6). Implications of the study for conceptual change curriculum and teaching are discussed. 相似文献
88.
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90.
G.M.N. Costa T. Dias M. Cardoso Y. Guerrieri F.L.P. Pessoa S.A.B. Vieira de Melo M. Embiruu 《Fluid Phase Equilibria》2008,267(2):140-149
A large number of equations of state and activity coefficient models capable of describing phase equilibria in polymer solutions are available today, but only a few of these models have been applied to different systems. It is therefore useful to investigate the performance of existing thermodynamic models for complex polymer solutions which have not yet been widely studied. The present work studies the application of several activity coefficient models [P.J. Flory, Principles of Polymer Chemistry, Cornell University Press, New York, NY, 1953; T. Oishi, J.M. Prausnitz, Estimation of solvent activities in polymer solutions using a group-contribution method, Ind. Eng. Chem. Process Design Dev. 17 (1978) 333; H.S. Elbro, A. Fredenslund, P. Rasmussen, A new simple equation for the prediction of solvent activities in polymer solutions, Macromolecules 23 (1990) 4707; G.M. Kontogeorgis, A. Fredenslund, D. Tassios, Simple activity coefficient model for the prediction of solvent activities in polymer solutions, Ind. Eng. Chem. Res. 32 (1993) 362; C. Chen, A segment-based local composition model for the Gibbs energy of polymer solutions, Fluid Phase Equilib. 83 (1993) 301; A. Vetere, Rules for predicting vapor–liquid equilibria of amorphous polymer solutions using a modified Flory–Huggins equation, Fluid Phase Equilib. 97 (1994) 43; C. Qian, S.J. Mumby, B.E. Eichinger, Phase diagrams of binary polymer solutions and blends, Macromolecules 24 (1991) 1655; Y.C. Bae, J.J. Shim, D.S. Soane, J.M. Prausnitz, Representation of vapor–liquid and liquid–liquid equilibria for binary systems containing polymers: applicability of an extended Flory–Huggins equation, J. Appl. Polym. Sci. 47 (1993) 1193; G. Bogdanic, J. Vidal, A segmental interaction model for liquid–liquid equilibrium calculations for polymer solutions, Fluid Phase Equilibria 173 (2000) 241] and activity coefficient from equations of state [F. Chen, A. Fredenslund, P. Rasmussen, Group-contribution Flory equation of state for vapor–liquid equilibria en mixtures with polymers, Ind. Eng. Chem. Res. 29 (1990) 875; M.S. High, R.P. Danner, Application of the group contribution lattice—fluids EOS to polymer solutions, AIChE J. 36 (1990) 1625]. The evaluation of these models was carried out both at infinite dilution and at finite concentrations and the results compared to experimental data. Furthermore, liquid–liquid equilibrium predictions for binary polymer solutions using six activity coefficient models are compared in this work. The parameters were estimated for all the models to achieve the best possible representation of the reported experimental equilibrium behavior. 相似文献