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111.
《Electroanalysis》2004,16(16):1311-1317
The determination of some toxic metals by stripping chronopotentiometry with a supporting solution having an unconventional composition has been investigated with the aim of using such components in disposable measuring cells preservable in dry state and quite ready for use, only needing addition of a small volume of sample. The new supporting solution is prepared with a solid strong acid, p‐toluenesulfonic acid, in the place of the inorganic acids commonly used to improve the cation availability. The other components are, as usual, sodium chloride, which fixes the potential of the screen‐printed silver – silver chloride reference electrode, and mercury(II) chloride as the plating agent. This supporting solution has been tested in batch measurements with the mercury film glassy carbon electrode as well as with screen‐printed carbon‐ink electrodes, either with mercury film or bare. The physical shape of the mercury layer electrolytically deposited on screen‐printed carbon‐ink electrodes from a supporting solution containing 0.1 M p‐toluenesulfonic acid and 0.1 M sodium chloride has been investigated by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) microanalysis. In chronopotentiometric stripping p‐toluenesulfonic acid performs as well as the usual inorganic strong acids, particularly in terms of sensitivity. At 0.1 mol dm?3 it proved very suitable for the determination of toxic metals, in particular lead(II), at levels down to a few μg dm?3. The overall results appear promising and can open new avenues for preparing disposable cells for on‐field stripping chronopotentiometric determination of toxic metals. 相似文献
112.
Partial molar volumes for a homologous series of amino acids and peptides have been measured in aqueous 1M sodium acetate, sodium thiocyanate, and sodium sulfate at 25°C. These data have been utilized in conjunction with the data in water to deduce partial molar volumes of transfer V
2,m
0(tr) from water to these aqueous salt solutions. The volumes of transfer for the amino acids and peptides are found to be positive. The interpretation is that this result arises from the dominant interaction of the sodium salts with the charged centers of amino acids and peptides. Thermal denaturation of the structurally homologous proteins lysozyme and -lactalbumin has been studied in the presence of these salts. Significant thermal stabilization of hen egg-white lysozyme has been observed in the presence of sodium acetate and sodium sulfate. However, the thermal stabilization observed for -lactalbumin is very small in the presence of these salts and sodium thiocyanate leads to a lowering of its thermal denaturation temperature. The rise in the surface tension of aqueous salt solutions with salt concentration has been correlated with the calorimetric and volumetric measurements. The results show that V
2,m
0(tr) depends less on the type of electrolyte than on the ionic strength of the solution. The V
2,m
0(tr) values correlate very well with the increase in the surface tension of aqueous salt solutions, indicating significant role of surface tension in interactions of amino acids, peptides, or protein with the salts. 相似文献
113.
Pogliani L 《Journal of computational chemistry》2003,24(9):1097-1109
The complete graph conjecture that encodes the inner-core electrons of atoms with principal quantum number n >or= 2 with complete graphs, and especially with odd complete graphs, is discussed. This conjecture is used to derive new values for the molecular connectivity and pseudoconnectivity basis indices of hydrogen-suppressed chemical pseudographs. For atoms with n = 2 the new values derived with this conjecture are coincident with the old ones. The modeling ability of the new homogeneous basis indices, and of the higher-order terms, is tested and compared with previous modeling studies, which are centered on basis indices that are either based on quantum concepts or partially based on this new conjecture for the inner-core electrons. Two similar algorithms have been proposed with this conjecture, and they parallel the two "quantum" algorithms put forward by molecular connectivity for atoms with n > 2. Nine properties of five classes of compounds have been tested: the molecular polarizabilities of a class of organic compounds, the dipole moment, molar refraction, boiling points, ionization energies, and parachor of a series of halomethanes, the lattice enthalpy of metal halides, the rates of hydrogen abstraction of chlorofluorocarbons, and the pED(50) of phenylalkylamines. The two tested algorithms based on the odd complete graph conjecture give rise to a highly interesting model of the nine properties, and three of them can even be modeled by the same set of basis indices. Interesting is the role of some basis indices all along the model. 相似文献
114.
M. SenŌ H. Noritomi Y. Kuroyanagi K. Iwamoto G. Ebert 《Colloid and polymer science》1984,262(9):727-733
The conformation of various basic poly (-amino acid)s was investigated by CD measurements in aqueous solutions containing bis (2-ethylhexyl)sodium sulfosuccinate (AOT) as well as in the AOT reversed micelles. The addition of AOT into an aqueous solution of poly(L-lysine) induces the conformational transition from coil to ordered structure, followed by aggregation. On the other hand, poly(L-lysine) assumes-structure in the reversed micelles at low wovalue (wo=[H2O]/[AOT]). Similarly to poly(L-lysine), poly(L-ornithine) takes an ordered structure in the aqueous solution containing AOT and-structure in the reversed micelles. In this case, however, these ordered structures are not so stable, compared with that of poly(L-lysine). Poly(L-arginine) undergoes the conformational transition from coil to helix by addition of AOT into the aqueous solution. Further addition of AOT allows transformation into-structure. Copoly(L-lysyl-L-leucine) with 63% leucine residue was shown to take a stable helical conformation even in pure water. In the reversed micelles, however, this ordered structure is significantly changed probably because the hydrophobic interaction among the leucyl residues is lowered in the reversed micelles. 相似文献
115.
Two polyether bridged dihydroxamic acids and their mono-and binuclear manganese(Ⅱ), zinc(Ⅱ) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono-and binuclear metal, the pseudo-macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dthydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo-macrocyclic polyether might synergetically activate H20 coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP. 相似文献
116.
Romeiro NC Albuquerque MG de Alencastro RB Ravi M Hopfinger AJ 《Journal of computer-aided molecular design》2005,19(6):385-400
The p38-mitogen-activated protein kinase (p38-MAPK) plays a key role in lipopolysaccharide-induced tumor necrosis factor-alpha (TNF-alpha) and interleukin-1 (IL-1) release during the inflammatory process, emerging as an attractive target for new anti-inflammatory agents. Four-dimensional quantitative structure-activity relationship (4D-QSAR) analysis [Hopfinger et al., J. Am. Chem. Soc., 119 (1997) 10509] was applied to a series of 33 (a training set of 28 and a test set of 5) pyridinyl-imidazole and pyrimidinyl-imidazole inhibitors of p38-MAPK, with IC50 ranging from 0.11 to 2100 nM [Liverton et al., J. Med. Chem., 42 (1999) 2180]. Five thousand conformations of each analogue were sampled from a molecular dynamics simulation (MDS) during 50 ps at a constant temperature of 303 K. Each conformation was placed in a 2 angstroms grid cell lattice for each of three trial alignments. 4D-QSAR models were constructed by genetic algorithm (GA) optimization and partial least squares (PLS) fitting, and evaluated by leave-one-out cross-validation technique. In the best models, with three to six terms, the adjusted cross-validated squared correlation coefficients, Q2adj, ranged from 0.67 to 0.85. Model D (Q2adj = 0.84) was identified as the most robust model from alignment 1, and it is representative of the other best models. This model encompasses new molecular regions as containing pharmacophore sites, such as the amino-benzyl moiety of pyrimidine analogs and the N1-substituent in the imidazole ring. These regions of the ligands should be further explored to identify better anti-inflammatory inhibitors of p38-MAPK. 相似文献
117.
N. S. Papageorgiou 《Journal of Optimization Theory and Applications》1991,68(2):305-320
In this paper, we consider a sequence of abstract optimal control problems by allowing the cost integrand, the partial differential operator, and the control constraint set all to vary simultaneously. Using the notions of -convergence of functions,G-convergence of operators, and Kuratowski-Mosco convergence of sets, we show that the values of the approximating problems converge to that of the limit problem. Also we show that a convergent sequence of optimal pairs for the approximating problems has a limit which is optimal for the limit problem. A concrete example of parabolic optimal control problems is worked out in detail.This research was supported by NSF Grant No. DMS-88-02688. 相似文献
118.
El-B. Yallaoui 《Periodica Mathematica Hungarica》1991,23(2):109-120
Let X be an abstract set and L a lattice of subsets of X. To each lattice regular measure µ, we associate two induced measures
and
on suitable lattices of the Wallman space IR(L) and another measure µ on the spaceIR(L). We will investigate the reflection of smoothness properties of p onto
,
and µ; and try to set some new criterion for repleteness and measure repleteness. 相似文献
119.
R. E. Beverly III 《Applied physics. B, Lasers and optics》1991,53(3):187-193
Discharge behavior of large-aperture (10–70 cm) CO2 lasers is computed using a coupled particle kinetics-equivalent circuit model. Pulsed power systems that produce a single excitation pulse are only able to satisfy the preionization, ignition, and impedance matching conditions for interelectrode gaps 40–50 cm. Double-pulse systems are required for larger gaps, not only to optimize electrical efficiency, but to avoid oscillatory behavior which can lead to arc formation during the second cycle. 相似文献
120.
The reaction of the dimethoxyaminyl radical with functionally substituted nitrosoalkanes (2) in a 2:1 ratio at 20°C gives the corresponding N-alkyl-N-methoxydiazene N-oxides (3) as a single isomer in preparative yields.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2443–2445, October, 1992. 相似文献