Ruthenium tetraoxide oxidations of alkanes: DFT calculations of barrier heights and kinetic isotope effects

The oxidation of C-H and C-C bonds by metal-oxo compounds is of general interest. We studied the RuO4-mediated catalytic oxidation of several cycloalkanes such as adamantane and cis- and trans-decalin as well as methane. B3LYP/6-31G(d) calculations on the experimentally proposed (3+2) mechanism are in good agreement with known experimental results. Comparison of experimental and theoretical kinetic isotope effects confirms the proposed mechanism. Besides RuO4, we also looked at RuO4(OH)- as a potential active species to account for ruthenium tetraoxide oxidations under strong basic conditions.     

Brewster-angled chirped mirrors for broadband pulse compression without dispersion oscillations

We use Brewster-angled chirped mirrors for dispersion compensation of a noncollinear optical parametric amplifier. This novel mirror design virtually eliminates spurious surface reflections and resultant dispersion ripple. The absence of compression artifacts is demonstrated by the generation of clean 5.6 fs pulses, with what is believed to be an unprecedented low ripple-induced satellite content for a nonadaptive scheme. In addition, the 270 THz spectral coverage allows generation of widely tunable visible pulses of 8 to 15 fs duration.     

Combined coherent anti-Stokes Raman spectroscopy and linear Raman spectroscopy for simultaneous temperature and multiple species measurements

The simultaneous application of pure rotational coherent anti-Stokes Raman spectroscopy (CARS) and vibrational linear Raman spectroscopy (LRS) for the measurement of temperature and species concentrations in combustion systems is demonstrated. In addition to the standard rotational CARS experimental setup, only one detection system (spectrometer and intensified CCD camera) for the collection of the LRS signals was applied. The emission of the broadband dye laser used for CARS was shifted to the deep red to avoid interferences with the LRS signals located in the visible region. First experimental results from a vaporizing propane spray using an engine injection system are shown.     

The 15N chemical shifts in mixed NB2Si and NBSi2 environments of Si3B3N7--a theoretical investigation

Nuclear magnetic resonance (NMR) chemical shifts in solids may be calculated by ab initio methods approximating the solid state by molecular clusters. We employed this technique to obtain estimates of (15)N chemical shifts in NB(2)Si and NBSi(2) environments in the solid state. Such nitrogen environments are found in amorphous (Si/B/N-)ceramics which exhibit very interesting features such as high thermal and mechanical stability. We based our calculations on cutouts of hypothetical Si(3)B(3)N(7) crystals suggested by Kroll and Hoffmann [Silicon boron nitrides: hypothetical polymorphs of Si(3)B(3)N(7), Angew. Chem. Int. Ed. 37 (1998) 2527]. Taking the systematic errors of our calculations into account we expect the chemical shifts in NBSi(2) environments around -293+/-5ppm. Chemical shifts in NB(2)Si environments are expected at -272+/-6ppm. The range of the calculated chemical shifts in NBSi(2) environments coincides with experimental chemical shifts in molecular compounds. Experimental chemical shifts of NB(2)Si nitrogen in molecules appear at lower field than our calculated chemical shifts in the solid state.     

Performance of cryogenic probes as a function of ionic strength and sample tube geometry

The pursuit for more sensitive NMR probes culminated with development of the cryogenic cooled NMR probe. A key factor for the sensitivity is the overall resistance of RF circuitry and sample. Lowering the coil temperature to approximately 25 K and the use of superconducting coil material has greatly reduced the resistance contribution of the hardware. However, the resistance of a salty sample remains the same and evolves as the major factor determining the signal-to-noise ratio. Several approaches have been proposed to reduce the resistance contribution of the sample. These range from encapsulating proteins in a water cavity formed by reverse micelles in low viscosity fluids to the optimal selection of low mobility, low conductivity buffer ions. Here we demonstrate that changing the sample diameter has a pronounced effect on the sample resistance and this results in dramatic improvements of the signal-to-noise ratio and shorter pi/2 pulses. We determined these parameters for common 5 mm NMR tubes under different experimental conditions and compared them to the 2, 3 and 4 mm tubes, in addition, 5mm Shigemi tubes were included since these are widely used. We demonstrate benefits and applicability of studying NMR samples with up to 4M salt concentrations in cryogenic probes. Under high salt conditions, best results in terms of short pi/2 pulses and high signal-to-noise ratios are obtained using 2 or 3mm NMR tubes, especially when limited sample is available. The 4 mm tube is preferred when sample amounts are abundant at intermediate salt conditions.     

Molecularly Imprinted Nanospheres by Nonaqueous Emulsion Polymerization

The preparation of nanosized, molecularly imprinted polymer particles by nonaqueous emulsion polymerization is presented. Monodisperse cross‐linked polymer nanospheres with a diameter of around 100 nm were synthesized using a standard monomer mixture of methacrylic acid and ethylene dimethacrylate, containing (±)‐propranolol as a template. The rebinding efficiency of the resulting particles was determined by batch rebinding tests and isothermal titration calorimetry (ITC). The results indicate that the proposed imprinting process under nonaqueous conditions lead to particles with an enhanced capacity of template rebinding compared to both nonimprinted ones and to particles obtained by more conventional emulsion polymerization in water.

     

On retardation,radiation and Liénard–Wiechert type potentials in electrodynamics and elastodynamics

The aim of this paper is to investigate the fundamental problems of retardation and radiation caused by non-uniformly moving point sources using the theories of electrodynamics and elastodynamics. This paper investigates and compares the retarded electromagnetic fields and the retarded elastodynamic fields. For the non-uniform motion of a general point source, the Liénard–Wiechert type potentials and the radiation and nonradiation fields are derived for a point charge and for a point force.     

Simultaneous Measurements of Temperature and CO Concentration in Stagnation Stabilized Flames

An impinging jet burner was developed to investigate flame-wall interactions (FWI) using laser based diagnostics. CO concentrations were measured with two-photon laser-induced fluorescence (LIF) in combination with coherent anti-Stokes Raman spectroscopy (CARS) gas phase temperature measurements. Besides being the principal factor in chemical kinetics, temperature data is required to correct the CO LIF data for various factors like density variation, quenching and variation in the Boltzmann population. Phosphor thermometry was used to determine surface temperatures of the wall and to estimate the heat flux. In an parameter study Reynolds numbers and fuel equivalence ratio were varied.     

Thermodynamic model formulation for viscoplastic solids as general equations for non-equilibrium reversible–irreversible coupling

Thermodynamic models for viscoplastic solids are often formulated in the context of continuum thermodynamics and the dissipation principle. The purpose of the current work is to show that models for such material behavior can also be formulated in the form of a General Equation for Non-Equilibrium Reversible–Irreversible Coupling (GENERIC), see, e.g., Grmela and Öttinger (Phys Rev E, 56:6620–6632, 1997), Öttinger and Grmela (Phys Rev E, 56:6633–6655, 1997), Grmela (J Non-Newtonian Fluid Mech, 165:980–986, 2010). A GENERIC combines Hamiltonian-dynamics-based modeling of time-reversible processes with Onsager–Casimir-based modeling of time-irreversible processes. The result is a model for the approach of non-equilibrium systems to thermodynamic equilibrium. Originally developed to model complex fluids, it has recently been applied to anisotropic inelastic solids in Eulerian (Hütter and Tervoort, in J Non-Newtonian Fluid Mech, 152:45–52, 2008; Hütter and Tervoort, in J Non-Newtonian Fluid Mech, 152:53–65, 2008; Hütter and Tervoort, in Adv Appl Mech, 42:254–317, 2008) and Lagrangian (Hütter and Svendsen, in J Elast 104:357–368, 2011) settings, as well as to damage mechanics. For simplicity, attention is focused in the current work on the case of thermoelastic viscoplasticity. Central to this formulation is a GENERIC-based form for the viscoplastic flow rule. A detailed comparison with the formulation based on continuum thermodynamics and the dissipation principle is given.