Chromatographic study of adsorption from binary and ternary solutions

Adsorption of benzene, anisole, and nitrobenzene on hydroxylated silica gel from binary and ternary solutions (adsorbate--n-hexane and adsorbate--n-hexane--terahydrofuran) was studied by HPLC. The equation that describes the adsorbate retention as a function of its concentration in binary and ternary solutions was proposed. The equation makes it possible to calculate the adsorption isotherms and adsorption equilibrium constants directly from chromatograms using the retention parameters and equilibrium concentrations of the adsorbate in the mobile phase.     

Aluminum Nitride Oxidation by Simultaneous TG and DTA

This work is a study, by simultaneous thermogravimetry (TG) and differential thermal analysis (DTA), of the oxidation of a water resistant aluminum nitride powder which has a special protective coating, and an uncoated AlN powder which has become partially hydrated during its use. The activation energy for oxidation is estimated by the Kissinger and isoconversional methods. In the former method, the temperatures of the oxidation peaks were obtained from DTA and DTG curves. The activation energies for oxidation of the water resistant AlN, obtained by the Kissinger method, are 357±10 kJ mol^–1, 392±12 kJ mol^–1 using respectively DTG and DTA data. For the uncoated AlN, the values are 243±7 and 257±8 kJ mol^–1, respectively. By the isoconversional method, the average values obtained for coated and uncoated samples are, respectively, 323±10 and 224±7 kJ mol^–1. Therefore, the special coating, which protects the aluminum nitride from humidity action, also provides a higher resistance to oxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

荧光猝灭法测定痕量砷（Ⅲ）

根据在稀盐酸介质中,碘酸钾可与As(Ⅲ）发生氧化还原反应生成I2,I2与荧光试剂吡咯红Y作用,使其荧光猝灭,提出了一种新的测定痕量As(Ⅲ）的荧光分析法。该方法的线性范围为24.0-248μg/L,检出限为14.1μg/L,方法用于自来水、尿液、血清及合成样中痕量As(Ⅲ）的测定,均获得满意结果。     

“Comment” on the Reply to the Paper “On the Elber–Karplus Reaction Path-Following Method and Related Procedures”

The flaws in the Reply [1] to our paper [2] have been pointed out. Elber and Karplus (EK) have not disproved our irrefutable global statement that the energy average cannot be minimized which rebuts the theoretical background of EK-type calculations. Another statement of ours has shown that even a curve for which the average energy is locally minimal for all directional perturbations in the sense of classical variational calculus cannot be identical with the reaction path (RP) defined as a steepest descent path (SDP). EK found an error in the early preprint of our theoretical paper [3] and because of this error they qualified our correct variational statement as false for all the SDPs consisting of a straight line each. Mixing global and variational arguments, EK refuted our criticism in a logically incorrect manner. In this Comment we prove that both of our earlier statements invariably remain in force and the criticism included in those has been as well-established and solid as was before.     

Simultaneous long‐chain branching and random scission: I. Monte Carlo simulation

In free‐radical olefin polymerizations, the polymer transfer reactions could lead to chain scission as well as forming long‐chain branches. For the random scission of branched polymers, it is virtually impossible to apply usual differential population balance equations because the number of possible scission points is dependent on the complex molecular architecture. On the other hand, the present problem can be solved on the basis of the probability theory by considering the history of each primary polymer molecule in a straightforward manner. The random sampling technique is used to solve this problem and a Monte Carlo simulation method is proposed. In this simulation method, one can observe the structure of each polymer molecule formed in this complex reaction system, and virtually any structural information can be obtained. In the illustrative calculations, the full molecular weight distribution development, the gel point determination, and examples of two‐ and three‐dimensional polymer structure are shown. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 391–403, 2001     

Comparison of the sequential simplex method and linear solvent strength theory in HPLC gradient elution optimization of multicomponent flavonoid mixtures

Summary Using a camomile flavonoid extract as the sample and four different reversed-phase partition systems, the ability of the Simplex procedure to produce optimum gradient separation of unknown multicomponent mixtures was checked against the linear solvent strength (LSS) gradient elution theory. On the same partition systems the mean solvent strenghts were measured by experimentally determined logk vs. mobile phase composition plots. These mean solvent strengths are compared to those inferred from the optimum gradients and the usefulness of LSS theory in multicomponent mixture gradient elution optimization is discussed.Dadicated to Prof. Dr. A Liberti on the occasion of his 70th birthday.     

Synthesis and electrochemical performanceof cobalt disulfide

The anode material cobalt disulfide for lithium-ion batteries was synthesized using the hydrothermal method at a lower temperature. The microstructure and surface morphology of the powders were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Electrochemical tests showed that this sample had superior electrochemical properties. The first discharge capacity is up to 1313.9 mAh/g in the voltage range of 3.00–0.02 V at a current density of 50 mA/g. Adjusting the voltage range to 3.00–0.50 V, the first discharge capacity decreases, but the 20th discharge capacity is 435.5 mAh/g, which is better than what has been reported in the literature.     

DFT-calculated structures based on 1H NMR chemical shifts in solution vs. structures solved by single-crystal X-ray and crystalline-sponge methods: Assessing specific sources of discrepancies

DFT calculations of ¹H NMR chemical shifts, using various functionals and basis sets, the conductor-like polarizable continuum model and discrete solute-solvent hydrogen bond interactions have been used to derive the solution structures of methyl salicylate and methyl 2,5-dihydroxybenzoate. We demonstrate that very good agreement between experimental and computed ¹H NMR chemical shifts can be obtained for various basis sets. The DFT structures in solution were compared with the recently reported X-ray structure, solved by the crystalline-sponge method, of the methyl salicylate and the single-crystal X-ray structure of methyl 2,5-dihydroxybenzoate. It is demonstrated that the information provided by ¹H NMR chemical shifts about the solution structure is significantly more precise than that obtained by the single-crystal X-ray and the crystalline-sponge methods.     

A non-conforming monolithic finite element method for problems of coupled mechanics

In this study, a Lagrange multiplier technique is developed to solve problems of coupled mechanics and is applied to the case of a Newtonian fluid coupled to a quasi-static hyperelastic solid. Based on theoretical developments in [57], an additional Lagrange multiplier is used to weakly impose displacement/velocity continuity as well as equal, but opposite, force. Through this approach, both mesh conformity and kinematic variable interpolation may be selected independently within each mechanical body, allowing for the selection of grid size and interpolation most appropriate for the underlying physics. In addition, the transfer of mechanical energy in the coupled system is proven to be conserved. The fidelity of the technique for coupled fluid–solid mechanics is demonstrated through a series of numerical experiments which examine the construction of the Lagrange multiplier space, stability of the scheme, and show optimal convergence rates. The benefits of non-conformity in multi-physics problems is also highlighted. Finally, the method is applied to a simplified elliptical model of the cardiac left ventricle.     

From a point-like to an arbitrarily shaped sample: A survey of equations for electron paramagnetic resonance signal intensity calculations

A set of original, analytical equations useful for theoretical calculation of the electron paramagnetic resonance (EPR) signal intensity are presented for the multitude of sample shapes, which range from point-like, line-like, planar, rectangular, cubical, circular, cylindrical, spherical to an irregularly shaped sample. The samples can be situated at any available position within the prescribed part of the microwave cavity (a central cylinder of diameter 11 mm and length 23.5 mm, in either a Bruker single TE₁₀₂ or double TE₁₀₄ rectangular cavity, with the modulation coils situated in the left and right side cavity walls, which is connected to a X-band, field-modulated CW Bruker EPR spectrometer). The theoretical computations of EPR signal intensity can be used in the computer simulations in which: (i) the EPR signal intensity profiles are constructed; (ii) the optimal sample positions in the cavity to give a maximum value of signal intensity are found; (iii) the errors associated with sample positioning within the cavity when compared to a second sample of a different size, shape or position are studied.