Enantioselective synthesis of cyclic, quaternary oxonitriles

Quaternary oxonitriles are stereoselectively generated from the union of five-, six-, and seven-membered 2-chloroalkenecarbonitriles with chiral alcohols via a Claisen rearrangement. The strategy rests on a new conjugate addition-elimination of allylic alkoxides to 2-chlorocycloalkenecarbonitriles to afford substituted 2-alkoxyalkenenitriles. Subsequent thermolysis unmasks a cyclic oxonitrile while selectively forming a new quaternary center with enantiomeric ratios typically greater than 9:1. The overall alkylation strategy addresses the challenge of enantioselectively generating hindered, quaternary centers while simultaneously installing ketone, nitrile, and olefin functionalities.     

Some inequalities of majorization type

We show some majorization inequalities and apply them to derive norm, eigenvalue, singular value, and trace inequalities of matrices. We also present a generalization and a different proof of a recent result on majorization concerning partitioned Hermitian positive semidefinite matrices.     

Dielectrophoretic assembly of grain-boundary-free 2D colloidal single crystals

Dielectrophoresis (DEP) force-assisted assembly of a colloidal single photonic-crystal monolayer in a microfluidic chamber was demonstrated. Negative DEP force with a high-frequency AC electric field induced the compression of colloidal microspheres to form a colloidal crystal domain at the center of a hexapolar-shaped electrode. While typical assembly by monotonic DEP force forms multicrystalline domains containing crystal defects, repetitions of the DEP/relaxation cycle significantly facilitated crystal growth of 10μm monodispersed polystyrene microspheres, allowing a grain-boundary-free single-crystal monolayer domain of ca. 200μm in size. Microsphere size as well as size distribution affected the formation of the single-crystal domain. A simple method was used to immobilize the single-crystal domain on the glass substrate without losing its crystallinity.     

Thermal and kinetic analysis of uranium salts

The thermal decomposition kinetics of UO₂C₂O₄·3H₂O were studied by TG method in a flowing nitrogen, air, and oxygen atmospheres. It is found that UO₂C₂O₄·3H₂O decomposes to uranium oxides in four stages in all atmosphere. The first two stages are the same in the whole atmosphere that correspond to dehydration reactions. The last two stages correspond to decomposition reactions. Final decomposition products are determined with X-Ray powder diffraction method. Decomposition mechanisms are different in nitrogen atmosphere from air and oxygen atmosphere. The activation energies of all reactions were calculated by model-free (KAS and FWO) methods. For investigation of reaction models, 13 kinetic model equations were tested and correct models, giving the highest linear regression, lowest standard deviation, and agreement of activation energy value to those obtained from KAS and FWO equations were found. The optimized value of activation energy and Arrhenius factor were calculated with the best model equation. Using these values, thermodynamic functions (??H ^*, ??S ^*, and ??G ^*) were calculated.     

Bound state energies for the exponential cosine screened Coulomb potential

The energy eigenvalues of bound states of an electron in the general exponential cosine screened Coulomb potential are obtained using the shifted 1/N expansion method. The energies for the states from 1s to 8k are calculated from six to eight significant figures. The energy eigenvalues for the 1s, 2s – 2p, 3s – 3d, and 4s – 4f states are also presented as a function of the screening parameter λ. Results are compared with the ones obtained by other workers. The agreement reduces roughly for large λ. It is also observed that the convergence of the expansion series increases remarkably asl increases.     

Interactive Compromise Programming

The purpose of this paper is to introduce a solution method for multiple objective linear programming (MOLP) problems. The method, called interactive compromise programming (ICP), offers a practical solution to MOLP problems by combining judgement with an automatic optimization technique in decision-making. This is realised by using the method of compromise programming and the method of a two-person zero-sum game in an iterative way. The method is illustrated by a numerical example.     

New experimental and theoretical approach to the heterogeneous hydrolysis of NO2: key role of molecular nitric acid and its complexes

Although heterogeneous chemistry on surfaces in the troposphere is known to be important, there are currently only a few techniques available for studying the nature of surface-adsorbed species as well as their chemistry and photochemistry under atmospheric conditions of 1 atm pressure and in the presence of water vapor. We report here a new laboratory approach using a combination of long path Fourier transform infrared spectroscopy (FTIR) and attenuated total reflectance (ATR) FTIR that allows the simultaneous observation and measurement of gases and surface species. Theory is used to identify the surface-adsorbed intermediates and products, and to estimate their relative concentrations. At intermediate relative humidities typical of the tropospheric boundary layer, the nitric acid formed during NO2 heterogeneous hydrolysis is shown to exist both as nitrate ions from the dissociation of nitric acid formed on the surface and as molecular nitric acid. In both cases, the ions and HNO3 are complexed to water molecules. Upon pumping, water is selectively removed, shifting the NO(3-)-HNO3(H2O)y equilibria toward more dehydrated forms of HNO3 and ultimately to nitric acid dimers. Irradiation of the nitric acid-water film using 300-400 nm radiation generates gaseous NO, while irradiation at 254 nm generates both NO and HONO, resulting in conversion of surface-adsorbed nitrogen oxides into photochemically active NO(x). These studies suggest that the assumption that deposition or formation of nitric acid provides a permanent removal mechanism from the atmosphere may not be correct. Furthermore, a potential role of surface-adsorbed nitric acid and other species formed during the heterogeneous hydrolysis of NO2 in the oxidation of organics on surfaces, and in the generation of gas-phase HONO on local to global scales, should be considered.     

Exact Pseudospin Symmetric Solution of the Dirac Equation for Pseudoharmonic Potential in the Presence of Tensor Potential

Under the pseudospin symmetry, we obtain exact solution of the Dirac equation for the pseudoharmonic potential in the presence of the tensor potential with arbitrary spin–orbit coupling quantum number κ. The energy eigenvalue equation of the Dirac particles is found and the corresponding radial wave functions are presented in terms of confluent hypergeometric functions. We investigate the tensor potential dependence of the energy of the each state in the pseudospin doublet. It is shown that degeneracy between members of the pseudospin doublet is removed by tensor interaction. Furthermore, the radial node structure of the Dirac spinor is discussed.     

Tractability of convex vector optimization problems in the sense of polyhedral approximations

There are different solution concepts for convex vector optimization problems (CVOPs) and a recent one, which is motivated from a set optimization point of view, consists of finitely many efficient solutions that generate polyhedral inner and outer approximations to the Pareto frontier. A CVOP with compact feasible region is known to be bounded and there exists a solution of this sense to it. However, it is not known if it is possible to generate polyhedral inner and outer approximations to the Pareto frontier of a CVOP if the feasible region is not compact. This study shows that not all CVOPs are tractable in that sense and gives a characterization of tractable problems in terms of the well known weighted sum scalarization problems.