Sensitivity analysis in chemical kinetics: Recent developments and computational comparisons

The advantages and disadvantages of various methods of parametric sensitivity analysis in chemical kinetic modeling are discussed. Particular attention is given to estimates of computational labor for realistic problems, and quantitative comparisons are made utilizing a 52-reaction, 11-species CO oxidation mechanism. The authors′ CHEMSEN/AIM program compares favorably to other techniques in many circumstances, and provides the additional convenience of accepting input information in familiar chemical notation. This paper also reviews recent developments in theory of sensitivity analysis, relevant to chemical kinetic modeling.     

Novel route to a finite center-of-mass momentum pairing state for superconductors: A current-driven Fulde-Ferrell-Larkin-Ovchinnikov state

The previously studied Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state is stabilized by a magnetic field via the Zeeman coupling in spin-singlet superconductors. Here we suggest a novel route to achieve nonzero center-of-mass momentum pairing states in superconductors with Fermi surface nesting. We investigate two-dimensional superconductors under a uniform external current, proportional to a finite pair momentum of q(e). We find that an FFLO state with a spontaneous pair momentum of q(s) is stabilized above a certain critical current that depends on the direction of the external current. A finite q(s) arises in order to make the total pair-momentum of q(t)(=q(s) + q(e)) perpendicular to the nesting vector, which is independent of spin states of Cooper pairs. We also discuss experimental signatures of the FFLO state.     

Studies on oxidopyrylium [5+2] cycloadditions: toward a general synthetic route to the C12-hydroxydaphnetoxins

[Structure: see text] 12-hydroxydaphnetoxins, members of the structurally fascinating daphnane diterpene family, exhibit a wide range of significant biological activities. A general route to the BC-ring system of 12-hydroxy daphnetoxins is reported based on D-ribose. Depending on the choice of protecting groups and solvent, the oxidopyrylium-alkene [5+2] cycloaddition originating from A provides cycloadduct diastereomer B or C with good to excellent selectivity.     

Resonant amplification of frustrated evanescent waves by single dielectric coating

Resonant amplification and enhancement of evanescent wave’s frustration across an optical barrier by using single dielectric coating is numerically demonstrated in this article. With further tuning of the thickness values of the second and the third medium (optical barrier) of the proposed stratified four-media configuration, it is shown that it may be possible to achieve unity transmittance at discrete, but closely spaced incident angles within the full range defined by the theoretical cut-off limit. The designed configuration may have other potential applications than lithography and waveguide design is one such example.     

Material functions generated by the complex viscosity

Based on the complex viscosity model various steady-state and transient material functions have been completed. The model is investigated in terms of a corotational frame reference. Also, BKZ-type integral constitutive equations have been studied. Some relations between material functions have been derived. C ^–1 Finger tensor - F[], (F ^–1[]) Fourier (inverse) transform - rate of deformation tensor in corotating frame - h(I, II) Wagner's damping function - J (x) Bessel function - m parameter inh (I, II) - m(s) memory function - m _k, n_k integers (powers in complex viscosity model) - P principal value of the integral - parameter in the complex viscosity model - rate of deformation tensor - shear rates - [], [] incomplete gamma function - (a) gamma function - steady-shear viscosity - ^* complex viscosity - , real and imaginary parts of ^* - ₀ zero shear viscosity - ⁺, ₁ ⁺ stress growth functions - ^–, ₁ ^- stress relaxation functions - (s) relaxation modulus - ₁(s) primary normal-stress coefficient - ø(a, b; z) degenerate hypergeometric function - ₁, ₂ time constants (parameters of ^*) - frequency - extra stress tensor     

Extraction of lead ions by electromembrane isolation

A new microextraction approach namely electromembrane isolation (EMI) coupled with capillary electrophoresis (CE) and ultraviolet (UV) detection for determining lead (Pb) ions was developed. The EMI technique involved the use of a polypropylene hollow fiber whose channel was filled with a sodium dihydrogen phosphate/sodium tetraborate buffer solution of pH 8.1, immersed in 10 mL of an aqueous sample solution. A voltage of 300 V was applied across the hollow fiber wall for 15 min to extract Pb ions. The extract was then complexed with ethylenediamminetetracetic acid (20 mM EDTA solution, at pH 3.4) for CE analysis. Satisfactory linear dynamic ranges (0.1-10 mg L(-1)), limits of detection (0.019 mg L(-1)) and good repeatability (ranging from 4.9 to 15.6%, n=3) were obtained. EMI exhibits good linearity with a correlation coefficient of 0.9935. The optimized EMI procedure was applied to determine the concentration of Pb(2+) in various matrices, such as amniotic fluid, blood serum, lipstick and urine samples.     

The deposition of osmium carbonyl clusters onto inorganic oxide surfaces: a ToF-SIMS and IR spectroscopic study of the surface species

The interaction between the osmium clusters [Os3(CO)12], [Os3(CO)10(mu-H)2], [Os3(CO)10(mu-H)(mu-OH)], and a series containing a free functional group, viz., [Os3(CO)10(mu-H)(mu-S--EH)] (where -- =alkylwedge chain or an aromatic ring, E=COO, S or O), with SiO2, ZnO and In2O3, was examined by ToF-SIMS and IR spectroscopy. While the interaction with the silica surface is mostly via an O atom or the functional group, the interaction with the ZnO and In2O3 surfaces is more complex.     

Thermolysis of polymeric [Ru(CO)4]infinity to metallic ruthenium: molecular shape of the precursor affects the nanoparticle shape

Pyrolysis of the organometallic polymer [Ru(CO) 4] infinity affords metallic ruthenium nanofibers. The molecular structure, especially the presence of metal-metal bonds, appears to direct the aggregation of the metal atom chains upon loss of the carbonyl ligands.