Evaluation of Multicenter Electronic Attraction, Electric Field and Electric Field Gradient Integrals with Screened and Nonscreened Coulomb Potentials over Integer and Noninteger n Slater Orbitals

By the use of complete orthonormal sets of -exponential-type orbitals, where ( = 1, 0, –1, –2,...) the multicenter electronic attraction (EA), electric field (EF) and electric field gradient (EFG) integrals of nonscreened and Yukawa-like screened Coulomb potentials are expressed through the two-center overlap integrals with the same screening constants and the auxiliary functions introduced in our previous paper (I.I. Guseinov, J. Phys. B, 3 (1970) 1399). The recurrence relations for auxiliary functions are useful for the calculation of multicenter EA, EF and EFG integrals for arbitrary integer and noninteger values of principal quantum numbers, screening constants, and location of slater-type orbitals. The convergence of the series is tested by calculating concrete cases.     

The optimization of silica gel synthesis from chemical bottle waste using response surface methodology

To reduce the amount of hazardous chemical bottle waste in the environment, we report the optimization research of silica extraction in chemical bottle waste into silica gel. Alkali fusion and sol–gel process were utilised to prepare silica gel effectively. The alkali fusion process was carried out by adding sodium hydroxide to produce sodium silicate. Afterwards, silica gel was prepared by the sol–gel method using hydrochloric acid. Box-Behnken Design (BBD) was applied to Optimisation factors the poptimiseactors affecting the silica recovery. The factors that optimised mass ratio, particle size, and temperature. The optimum recovery of silica gel was obtained by SiO₂: NaOH mass ratio of 1:3, the particle size of 63–74 µm, and a temperature of 800 °C. The purity of silica gel optimum is 63.74% characterised using X-ray fluorescence. The structure of silica gel is the appearance of amorphous peaks at 2θ 20-30° characterised using an x-ray diffractogram. The silica gel surface was characterises using scanning electron microscopy-energy dispersive x-ray. It showed an irregular surface and characteristic showed that silica gel had a radius of 15.74 nm and a specific surface area of 297.08 m².     

Electrophoresis simulations using Chebyshev pseudo-spectral method on a moving mesh

We present the implementation and demonstration of the Chebyshev pseudo-spectral method coupled with an adaptive mesh method for performing fast and highly accurate electrophoresis simulations. The Chebyshev pseudo-spectral method offers higher numerical accuracy than all other finite difference methods and is applicable for simulating all electrophoresis techniques in channels with open or closed boundaries. To improve the computational efficiency, we use a novel moving mesh scheme that clusters the grid points in the regions with poor numerical resolution. We demonstrate the application of the Chebyshev pseudo-spectral method on a moving mesh for simulating nonlinear electrophoretic processes through examples of isotachophoresis (ITP), isoelectric focusing (IEF), and electromigration-dispersion in capillary zone electrophoresis (CZE) at current densities as high as 1000 A/m. We also show the efficacy of our moving mesh method over existing methods that cluster the grid points in the regions with large concentration gradients. We have integrated the adaptive Chebyshev pseudo-spectral method in the open-source SPYCE simulator and verified its implementation with other electrophoresis simulators.     

Synthesis and absolute configuration of (1S,8S)-as-hydrindacene-1,8-diol as determined by the circular dichroism exciton chirality method

2,3,6,7-Tetrahydro-as-indacene-1,8-dione 4 was prepared in 4 steps starting from 2-methyl-furan by modification of a literature procedure. Appliance of Noyori’s asymmetric transfer hydrogenation, resulted in (1S,8S)-1,2,3,6,7,8-hexahydro-as-indacene-1,8-diol 5 in high yield (81%) and excellent enantioselectivity (>99% ee) or (8S)-8-hydroxy-3,6,7,8-tetrahydro-2H-as-indacen-1-one 6 in moderate yield (58%) and equally high enantioselectivity (98.5% ee), depending on the conditions. The asymmetric reduction was expected to yield the (S)-alcohols using the (S,S)-Ts-DPEN ligand, which was confirmed by the appliance of the exciton chirality method on the corresponding bis(p-dimethylamino)benzoate 7.     

GRECP/MRD‐CI calculations on the Hg atom and HgH molecule

Multireference single‐ and double‐excitation configuration interaction (MRD‐CI) calculations of transition energies for the Hg atom and spectroscopic constants for the HgH molecule are carried out with the generalized relativistic effective core potential (GRECP) method. A new selection criterium for the reference configurations is discussed. The calculated spectroscopic constants are compared with experimental data and results of calculations of other groups. Improvement of accuracy is mainly observed for bond lengths from the GRECP/MRD‐CI calculations (without applying the T = 0 correction) with respect to the results of other groups. Analysis of the quality of the approximations employed is carried out. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Influence of hydrophobe content on the solution rheology of hydrophobically modified terpolymer of SO2, N,N-diallyl-N-carboethoxymethylammonium chloride

Rheological properties of hydrophobically modified copolymer of SO₂, N,N-diallyl-N-carboethoxymethylammonium chloride and the hydrophobic monomer N,N-diallyl-N-octadecylammonium chloride were studied. The influence of hydrophobe content (HP) and polymer concentration was investigated. Polymers with HP content in the range 1.5-5% were examined and the concentration was varied in the range 2-5 wt%. Both dynamic and steady-shear experiments were performed in ARES rheometer. Copolymers were observed to exhibit typical viscoelastic behavior even with low HP content. Both the dynamic viscosity, η′ and storage modulus, G′, increase with the increase of both the polymer concentration and the HP content of the system. The viscosity of the high HP content polymer showed a strong shear dependency, while G′ was a weak function of frequency and gel-like behavior was observed. The zero-shear viscosity, η₀, showed a strong concentration dependency (η₀ ∼ ?^α; 1.1 < α < 5.9). The concentration dependency of η₀ suggests that intermolecular association is dominant in the high HP content polymer. Control of the HP content and polymer concentration of this class of polymers can lead to a wide range of interesting rheological properties.     

Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers

Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80 °C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (r_MMA = 0.62 ± 0.04; r_HEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, M_n = 475 g mol⁻¹) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (r_MMA = 0.75 ± 0.07; r_PEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr₂(PPh₃)₂) were observed by ¹H NMR spectroscopy.     

Adsorption of ionic surfactants on polar surfaces with a low content of chemically adsorbed alkyl chains

Colloidal silica and titanium dioxide were surface-modified by chemisorption of octadecyl dimethylmethoxy silane. The surface density of these alkyl silane groups was adjusted to less than 7% of the available surface hydroxyls, leaving the adsorbents hydrophilic and electrically charged in aqueous solution.Ionic surfactants (tetradecylpyridinium chloride and sodium lauryl sulfate) are adsorbed onto the surface-modified silica and titanium dioxide from aqueous solution, even in the case where the surface of the adsorbents exhibits the same sign of electrical charge as the surfactant ionic head groups. According to the adsorption model of Gu the chemiadsorbed alkyl chains are supposed to serve as anchors for small surface aggregates of the ionic surfactants.     

Kinetics of CO oxidation on the surface of heterophase catalysts. Modeling by the Monte Carlo method

The Monte Carlo method has been used to simulate CO oxidation on a lattice consisting of various alternating patches: M1, where s(CO)>s(O₂) and M2, where s(CO)2). The reaction is shown to proceed over all the surface at low temperature as CO_ads spillover from M1 to M2 and backwards.     

Electronic structure and conformational flexibility of 1,2-dihydropyridine, 1,2- and 1,6-dihydropyrimidines,and their ylide derivatives

Molecular and electronic structures of 1,2-dihydropyridine, 1,2- and 1,6-dihydropyrimidine, and their oxo, imino, and methylene derivatives were studied by the semiempirical quantum-chemical AM1 method. In all compounds, the heterocycle exhibits a high conformational flexibility. The transition from a planar equilibrium conformation to a distorted sofa conformation with the =C-NH-C-C(N)= torsion angle of ±20° causes an increase in the energy by less than 1.7 kcal mol^–1. All molecules have similar -electronic structures, which, apparently, determines the similarity in their conformational behavior. The bending strain and the nonaromatic character of the cyclic -system are the factors that stabilize the nonplanar conformation of the ring in unsubstituted dihydroazines and ylide derivatives, respectively.Translated fromIzvestiva Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1934–1937, August, 1996.