Reversal of stability on metalation of pentagonal-bipyramidal (1-MB6H7(2-) 1-M-2-CB5H7(1-) and 1-M-2,4-C2B4H7) and Icosahedral (1-MB11H12(2-) 1-M-2-CB10H12(1-) and 1-M-2,4-C2B9H12) boranes (M = Al, Ga, In, and Tl): energetics of condensation and relationship to binuclear metallocenes

The usual assumption of the extra stability of icosahedral boranes (2) over pentagonal-bipyramidal boranes (1) is reversed by substitution of a vertex by a group 13 metal. This preference is a result of the geometrical requirements for optimum overlap between the five-membered face of the ligand and the metal fragment. Isodesmic equations calculated at the B3LYP/LANL2DZ level indicate that the extra stability of 1-M-2,4-C(2)B(4)H(7) varies from 14.44 kcal/mol (M = Al) to 15.30 kcal/mol (M = Tl). Similarly, M(2,4-C(2)B(4)H(6))(2)(1-) is more stable than M(2,4-C(2)B(9)H(11))(2)(1-) by 9.26 kcal/mol (M = Al) and by 6.75 kcal/mol (M = Tl). The preference for (MC(2)B(4)H(6))(2) over (MC(2)B(9)H(11))(2) at the same level is 30.54 kcal/mol (M = Al), 33.16 kcal/ mol (M = Ga) and 37.77 kcal/mol (M = In). The metal-metal bonding here is comparable to those in CpZn-ZnCp and H(2)M-MH(2) (M= Al, Ga, and In).     

Effect of additional hydrogen peroxide to H2O2...(H2O)n, n=1 and 2 complexes: quantum chemical study

Hydrogen peroxide, H2O2, acts as a particularly strong reactant in aqueous environment. It has been demonstrated earlier that agglomerates with a single peroxide interacting with one and two water molecules manifest in several stable conformers within a narrow energy range. In the present study we seek structural changes brought out by adding an extra H2O2 to these systems at molecular level employing ab initio quantum chemical methods, viz., restricted Hartree-Fock and the second order Moller-Plesset perturbation theory. These clusters exhibit consistent trends in energy hierarchy at both the levels. Further, a many body interaction energy analysis quantifies the strength and cooperativity of hydrogen bonding in the (H2O2)2...(H2O)n, (n=1 and 2) clusters, bringing out structuring/destructuring effects attributed to attachment of water and hydrogen peroxide molecules.     

Effect of Cd1−xZnxS/ZnS core/shell quantum dot on the optical response and relaxation behaviour of ferroelectric liquid crystal

Dielectrics, polarizing optical microscopic and electro-optical measurements have been carried out on a core/shell quantum dot Cd_1?xZn_xS/ZnS dispersed ferroelectric liquid crystal (FLC). In the present study, quantum dots were dispersed into two different concentrations of 0.1 and 0.25 wt./wt.% in pure FLC. The electro-optical parameters of pure and QDs dispersed FLC were carried out as a function of applied voltage. A significant improvement in optical response time of QDs dispersed FLC system is one of the major finding of the present study which may be useful for fabrication of faster liquid crystal system.     

Magneto-hydrodynamic stability of plane Poiseuille flow with flexible boundaries

MHD stability of plane Poiseuille flow between parallel flexible walls with coplaner magnetic field is analysed. The study is restricted to sufficiently low values of magnetic Reynolds number. The eigen-value problem so posed is then solved graphically and neutral curves are obtained for various sets of magnetic parameter and flexible wall parameters. The nature of influence on flow stability depends on the values of these parameters.     

The synthesis of 3-methyl- and 3,4-dimethyltetrahydroisoquinolines by intramolecular hydroamination with n-butyllithium

The synthesis of 3-methyltetrahydroisoquinolines and 3,4-dimethyltetrahydroisoquinolines from aromatic aminoalkenes using intramolecular hydroamination reactions, mediated by sub-stoichiometric amounts of n-butyllithium, is described.     

A sum rule for the transverse current correlation function in an electron liquid

An exact expression for the first frequency moment sum rule of the transverse current correlation function in an electron liquid is obtained and discussed.     

Elastic flow instability in nanotube suspensions

We report an elastic instability associated with flow-induced clustering in semidilute non-Brownian colloidal nanotubes. Rheo-optical measurements are compared with simulations of mechanical flocculation in sheared fiber suspensions, and the evolving structure is characterized as a function of confinement and shear stress. The transient rheology is correlated with the evolution of highly elastic vorticity-aligned aggregates, with the underlying instability being somewhat ubiquitous in complex fluids.     

Dendrimer-activated surfaces for high density and high activity protein chip applications

Highly functional Si and glass surfaces for protein immobilization have been prepared by a facile activation of native surface silanol groups. Poly(propyleneimine) dendrimers of generations 1-5 were immobilized onto the surface using a facile room-temperature coupling procedure that involved activation of native silanol groups of glass using 1,1'-carbonyldiimidazole under anhydrous conditions. The dendrimer-coated surfaces were used to immobilize proteins and were characterized with respect to surface loading and activity. A number of different chemical, physical, and biochemical techniques including contact angle measurement, ellipsometry, and fluorescence microscopy were used to characterize the resulting surfaces. Increasing the dendrimer generation past G-3 led to increased surface amine content, immobilized protein concentration, and the activity of immobilized alkaline phosphatase (used as a test system). Very high activity of the immobilized proteins in the case of higher generation (G-4 and G-5) dendrimers led us to conclude that such an approach has true potential for creating highly functional surfaces for protein chip applications.     

Momentum-space properties from coordinate-space electron density

Electron density and electron momentum density, while independently tractable experimentally, bear no direct connection without going through the many-electron wave function. However, invoking a variant of the constrained-search formulation of density-functional theory, we develop a general scheme (valid for arbitrary external potentials) yielding decent momentum-space properties, starting exclusively from the coordinate-space electron density. A numerical illustration of the scheme is provided for the closed-shell atomic systems He, Be, and Ne in their ground state and for 1s(1) 2s(1) singlet electronic excited state for helium by calculating the Compton profiles and the expectation values derived from given coordinate-space electron densities.