Stereoselective synthesis of internal allylic fluorides

Ru-based catalysts can be used in E-selective cross metathesis (CM) reactions to synthesise various functionalised internal allylic monofluorides.     

Sorption of nonionic organic solutes from water to tetraalkylammonium bentonites: Mechanistic considerations and application of the Polanyi-Manes potential theory

This work describes the role of quaternary alkylammonium amendment length on sorption mechanisms of modified bentonites for four nonionic organic compounds; benzene, carbon tetrachloride, TCE, and 1,2-DCB. Tetramethyl to tetrabutyl alkyl amendments were studied and an important mechanistic shift occurred at the propyl chain length for all four solutes studied. Three- and four-carbon-chain functional groups on the ammonium cation resulted in a linear, rather than a curvilinear isotherm. The uptake on tetrapropyl and tetrabutylammonium clays was noncompetitive in binary systems and showed negligible sensitivity to temperature variations, indicating the linear isotherms describe a partitioning uptake mechanism for these organoclays. The adsorptive organoclays (tetramethyl and tetraethylammonium clays) were fit with the Dubinin-Radushkevich equation to investigate the application of the Polanyi-Manes potential theory to organoclay adsorption. It was found that TCE and carbon tetrachloride, with similar physical and chemical characteristics, behaved according to the Polanyi-Manes theory. Benzene showed an anomalously high adsorption volume limit, possibly due to dense packing in the adsorption space or chemisorption to the short chain alkyl groups.     

Cis→Trans Isomerization of Pro<Superscript>7</Superscript> in Oxytocin Regulates Zn<Superscript>2+</Superscript> Binding

Ion mobility/mass spectrometry techniques are employed to investigate the binding of Zn²⁺ to the nine-residue peptide hormone oxytocin (OT, Cys¹-Tyr²-Ile³-Gln⁴-Asn⁵-Cys⁶-Pro⁷-Leu⁸-Gly⁹-NH₂, having a disulfide bond between Cys¹ and Cys⁶ residues). Zn²⁺ binding to OT is known to increase the affinity of OT for its receptor [Pearlmutter, A. F., Soloff, M. S.: Characterization of the metal ion requirement for oxytocin-receptor interaction in rat mammary gland membranes. J. Biol. Chem. 254, 3899–3906 (1979)]. In the absence of Zn²⁺, we find evidence for two primary OT conformations, which arise because the Cys⁶–Pro⁷ peptide bond exists in both the trans- and cis-configurations. Upon addition of Zn²⁺, we determine binding constants in water of K_A = 1.43 ± 0.24 and 0.42 ± 0.12 μM^?1, for the trans- and cis-configured populations, respectively. The Zn²⁺ bound form of OT, having a cross section of Ω = 235 Ų, has Pro⁷ in the trans-configuration, which agrees with a prior report [Wyttenbach, T., Liu, D., Bowers, M. T.: Interactions of the hormone oxytocin with divalent metal ions. J. Am. Chem. Soc. 130, 5993–6000 (2008)], in which it was proposed that Zn²⁺ binds to the peptide ring and is further coordinated by interaction of the C-terminal, Pro⁷-Leu⁸-Gly⁹-NH₂, tail. The present work shows that the cis-configuration of OT isomerizes to the trans-configuration upon binding Zn²⁺. In this way, the proline residue regulates Zn²⁺ binding to OT and, hence, is important in receptor binding.

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Pickering emulsions with controllable stability

We prepare solid-stabilized emulsions using paramagnetic particles at an oil/water interface that can undergo macroscopic phase separation upon application of an external magnetic field. A critical field strength is found for which emulsion droplets begin to translate into the continuous-phase fluid. At higher fields, the emulsions destabilize, leading to a fully phase-separated system. This effect is reversible, and long-term stability can be recovered by remixing the components with mechanical agitation.     

An integrated microfluidic device for influenza and other genetic analyses

An integrated microfluidic device capable of performing a variety of genetic assays has been developed as a step towards building systems for widespread dissemination. The device integrates fluidic and thermal components such as heaters, temperature sensors, and addressable valves to control two nanoliter reactors in series followed by an electrophoretic separation. This combination of components is suitable for a variety of genetic analyses. As an example, we have successfully identified sequence-specific hemagglutinin A subtype for the A/LA/1/87 strain of influenza virus. The device uses a compact design and mass production technologies, making it an attractive platform for a variety of widely disseminated applications.     

Benders decomposition for a class of variational inequalities

This paper examines Benders decomposition for a useful class of variational inequality (VI) problems that can model, e.g., economic equilibrium, games or traffic equilibrium. The dual of the given VI is defined. Benders decomposition of the original VI is derived by applying a Dantzig–Wolfe decomposition procedure to the dual of the given VI, and converting the dual forms of the Dantzig–Wolfe master and subproblems to their primal forms. The master problem VI includes a new cut at each iteration, with information from the latest subproblem VI, which is solved by fixing the “difficult” variables at values determined by the previous master problem. A scalar parameter called the convergence gap is calculated at each iteration; a negative value is equivalent to the algorithm making progress in that the last master problem solution is made infeasible by the new cut. Under mild conditions, the convergence gap approaches zero in the limit of many iterations. With a more restrictive condition that still admits many useful models, a zero value of the convergence gap implies that the master problem has found a solution of the VI. A small model of competitive equilibrium of three commodities in two regions serves as an illustration.     

Two-color rotary modulated flow birefringence

A method is described that solves the problem of determining the correct birefringence and orientation angle of samples having multiple orders of retardation. The approach simultaneously uses two wavelengths of light combined with modulation of the polarization vector using a high-speed rotating half waveplate. The simultaneous application of two wavelengths is possible with the use of an achromatic waveplate. The technique is demonstrated by performing start-up Couette flow experiments on a concentrated polystyrene solution that produced multiple orders in retardation.