Combinatorial Chemistry for Ligand Development in Catalysis: Synthesis and Catalysis Screening of Peptidosulfonamide Tweezers on the Solid Phase

On the basis of a pyrrolidine tweezer 1, a library of peptidosulfonamide tweezers (15a-e, 16a-e) was synthesized on the solid phase. This library was screened in a simultaneous substrate screening procedure for the ability to enantioselectively catalyze the Ti(O-i-Pr)(4)-mediated addition of diethylzinc to aldehydes. One of the best solid-phase tweezer catalyst (i.e., 16d, giving an ee of 32% in solid-phase catalysis) was resynthesized in solution (compounds 20 and 21). The now homogeneous solution-phase catalysis showed even better enantioselectivity (i.e., up to 66%).     

The determination of ethanol by alternating current tensammetry

A method for the determination of ethanol in vodka by phase-sensitive a.c. tensammetry is described; the only prior treatment of the sample is dilution with water and addition of KCl The positive wave of the tensammetric response was used. Ethanol concentrations in the range 2–10% can be determined with a relative imprecision of 0.5%. Other species having surfactant properties, such as the fusel oils found in most distilled liquors, interfere.     

CHEMILUMINESCENCE QUENCHING TERMS

Abstract— A methodology for the determination of chemiluminescence quenching terms is given. By using the oxidation of tetrakis(dimethylamino)ethylene as an example, it is shown how the nature and magnitude of the quenching terms help to elucidate the reaction mechanism, or how ignoring them can lead to false impressions. It is shown that chemiluminescence quenching effects need not be the same as those for photoluminescence of the same electronically excited species.     

The cochlear amplifier as a standing wave: "squirting" waves between rows of outer hair cells?

This paper draws attention to symmetric Lloyd-Redwood (SLR) waves-known in ultrasonics as "squirting" waves-and points out that their distinctive properties make them well-suited for carrying positive feedback between rows of outer hair cells. This could result in standing-wave resonance-in essence a narrow-band cochlear amplifier. Based on known physical properties of the cochlea, such an amplifier can be readily tuned to match the full 10-octave range of human hearing. SLR waves propagate in a thin liquid layer enclosed between two thin compliant plates or a single such plate and a rigid wall, conditions found in the subtectorial space of the cochlea, and rely on the mass of the inter-plate fluid interacting with the stiffness of the plates to provide low phase velocity and high dispersion. The first property means SLR wavelengths can be as short as the distance between rows of outer hair cells, allowing standing wave formation; the second permits wide-range tuning using only an order-of-magnitude variation in cochlear physical properties, most importantly the inter-row spacing. Viscous drag at the two surfaces potentially limits SLR wave propagation at low frequencies, but this can perhaps be overcome by invoking hydrophobic effects.     

Multiphonon vibrations at high angular momentum in 182 Os

Evidence is presented for multiphonon excitations based on a high-spin (25 Planck) intrinsic state in the deformed nucleus 182 Os. Angular momentum generation by this mode competes with collective rotation. The experimental data are compared with tilted-axis cranking calculations, supporting the vibrational interpretation. However, the lower experimental energies provide evidence that more complex interactions of states are playing a role.     

Electrical currents and liquid flow rates in micro-reactors

For micro-reactor devices in which liquids are pumped by electro-osmotic flow (EOF), in situ monitoring of the electrical currents in the channel networks provides a valuable diagnostic tool. We demonstrate here that the voltage-current characteristics of a micro-reactor channel network can be accurately modelled using measurements of the full 3-D geometry of the channel network, the liquid conductivity and the channel wall-liquid surface conductivity. It is shown that surface conductivity provides a significant contribution to the overall measured electrical currents in channel networks for which the ratio of surface area to volume is high. Following correction for surface conductivity, the electrical currents are proportional to the liquid volumetric flow rates measured in the different branches of the channel network. The constant of proportionality is related to the zeta potential of the channel wall-liquid surface. Measurements of the variation of electrical currents and volumetric flow rates as a function of the applied voltages allows the determination of the surface conductivity and zeta potential within the micro-reactor which enables the prediction of the voltages required to produce the desired flow rates in any channel section. In situ logging of the electrical currents, incorporated within the control system, allows continuous monitoring of the liquid flow rates during micro-reactor operation.