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21.
In order to investigate the relative effects of the differences between the structures and lipophilicities of 1, 10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TA-18-crown-6) and the tetrabenzyl derivative of 1,10-dioxa-4, 7, 13, 16-tetra-azacyclo-octadecane (TBTA-18-crown-6) on their extraction-abilities and -selectivities for transition metal cations, constants of the overall extraction (logK
ex) of 1:1 (M:L) complexes, the distribution (K
D) for two diluents (CH2Cl2 and CHCl3) with different dielectric constants have been determined at 25 ± 0.1 °C. The magnitude of logK
ex is largely determined by that of K
D. The equilibrium constants of TA-18-crown-6 have been compared with those of TBTA-18-crown-6. It is found that:(i) logK
ex sequences of TA-18-crown-6 and TBTA-18-crown-6 for transition metals in CH2Cl2 lie in order: Fe3+ > Cu2+ > Mn2+ > Co2+ > Cd2+ > Ni2+ > Zn2+ and Fe3+ > Cu2+ > Co2+ > Mn2+ > Ni2+ > Cd2+ > Zn2+ respectively; (ii) the stability sequences of two types of tetra-aza-crown ethers with the transition metal cations in CHCl3 are the same as follows: Fe3+ > Ni2+ > Cu2+ > Co2+ > Zn2+ > Cd2+ > Mn2+, and (iii) unusual selectivities are observed for transition metal-tetra-aza-crowns, e.g. the high Fe3+/M
n+ selectivity factors (Sf) of TA-18-crown-6, except for the competitive-extractions for the special case in CHCl3 of TBTA-18-crown-6, it was found that the Mn2+/M
n+ values were relatively higher according to the other transition metal cations. A systematic sequence in these two types of solvents is not found for a given transition metal cation in terms of the variation of selectivity with the tetra-aza-crown ethers. The results provide alternatives for the rational design of other specific ligands on the transition metal cations. 相似文献
22.
The vibrational dynamics of protein folding is analyzed in the framework of Tsallis statistics. We employ exact expressions
for classical harmonic oscillators by considering the unnormalized constraints. As q→1, we show that these approximations agree with the result of Gaussian network model. 相似文献
23.
Ana Luísa Daniel‐da‐Silva João Carlos Moura Bordado José Miguel Martín‐Martínez 《Journal of Polymer Science.Polymer Physics》2007,45(22):3034-3045
The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007 相似文献
24.
In order to reduce infant mortality in the municipality of Rio de Janeiro it is desired to encourage all mothers-to-be to attend the appropriate health care facilities. A 3-level hierarchical prenatal–neonatal health care system is described together with a basic model for optimising accessibility to facilities. A genetic algorithm to solve the basic model is developed and some numerical experience reported. Extensions to the basic model and planned future research are briefly indicated. 相似文献
25.
A preconditioning approach based on the artificial compressibility formulation is extended to solve the governing equations for unsteady turbulent reactive flows with heat release, at low Mach numbers, on an unstructured hybrid grid context. Premixed reactants are considered and a flamelet approach for combustion modelling is adopted using a continuous quenched mean reaction rate. An overlapped cell‐vertex finite volume method is adopted as a discretisation scheme. Artificial dissipation terms for hybrid grids are explicitly added to ensure a stable, discretised set of equations. A second‐order, explicit, hybrid Runge–Kutta scheme is applied for the time marching in pseudo‐time. A time derivative of the dependent variable is added to recover the time accuracy of the preconditioned set of equations. This derivative is discretised by an implicit, second‐order scheme. The resulting scheme is applied to the calculation of an infinite planar (one‐dimensional) turbulent premixed flame propagating freely in reactants whose turbulence is supposed to be frozen, homogeneous and isotropic. The accuracy of the results obtained with the proposed method proves to be excellent when compared to the data available in the literature. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
26.
The paper presents a new formulation of the integral boundary element method (BEM) using subdomain technique. A continuous approximation of the function and the function derivative in the direction normal to the boundary element (further ‘normal flux’) is introduced for solving the general form of a parabolic diffusion‐convective equation. Double nodes for normal flux approximation are used. The gradient continuity is required at the interior subdomain corners where compatibility and equilibrium interface conditions are prescribed. The obtained system matrix with more equations than unknowns is solved using the fast iterative linear least squares based solver. The robustness and stability of the developed formulation is shown on the cases of a backward‐facing step flow and a square‐driven cavity flow up to the Reynolds number value 50 000. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
27.
Christophe Roussel Loc Dayon Henrik Jensen Hubert H. Girault 《Journal of Electroanalytical Chemistry》2004,570(2):187-199
A series of electrogenerated selective electrophiles based on substituted benzoquinones has been characterized as tags for l-cysteine and cysteine residues in proteins. The electrophiles are generated electrochemically from the corresponding hydroquinones. It is shown from mass spectrometry analysis that the electrogenerated benzoquinone can tag the biomolecules. The rate constants pertaining to the addition of l-cysteine onto the electrogenerated benzoquinones have been determined using electrochemical techniques. The substitution patterns have been unraveled leading to the assessment of site-specific rate constants. It is shown that the rate constants are primarily dependent on the electronic nature of the substituents as expressed by the Hammett substitution constant. The apparent tagging yields observed for l-cysteine in nanospray mass spectrometry experiments do not correspond to the yields expected from the electrochemical study, as the ionisation efficiencies are highly dependent on the tag. Finally, the on-line tagging has been tested using β-lactoglobulin A and myoglobin. Based on these results, it is concluded that the tagging reaction is selective towards cysteine when it takes place in the nanospray interface. The results show that the methodology presented can be used for a rapid characterization and identification of reactive sites in biomolecules. 相似文献
28.
H. William Bosch Sre
o D. kapin Egon Matijevi 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):43-50
Controlled precipitation of the diagnostic imaging agent ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate has been used to produce fine particles of various sizes, morphologies, and degrees of crystallinity, which depended on experimental conditions. In addition, two distinct polymorphic forms of the drug have been fully characterized by single crystal X-ray diffraction studies, and evidence for a third polymorph was also observed. Some of the so prepared dry particles were coated with a thin layer of silica. 相似文献
29.
Inequalities satisfied by the zeros of the solutions of second-order hypergeometric equations are derived through a systematic use of Liouville transformations together with the application of classical Sturm theorems. This systematic study allows us to improve previously known inequalities and to extend their range of validity as well as to discover inequalities which appear to be new. Among other properties obtained, Szegő's bounds on the zeros of Jacobi polynomials for , are completed with results for the rest of parameter values, Grosjean's inequality (J. Approx. Theory 50 (1987) 84) on the zeros of Legendre polynomials is shown to be valid for Jacobi polynomials with |β|1, bounds on ratios of consecutive zeros of Gauss and confluent hypergeometric functions are derived as well as an inequality involving the geometric mean of zeros of Bessel functions. 相似文献
30.