Enynones in organic synthesis. I. Spiroannulation by tandem oxy-cope rearrangement-electrocyclic ring closure

Bis-acetylenic alcohols of proper design undergo a facile oxy-Cope rearrangement to afford mixtures of E- and Z-enynones. These latter compounds afford methylenecyclopentenones upon enolization and electrocyclic ring closure.     

Enynones in organic synthesis. III. A novel synthesis of phenols

Enynones are converted to phenols by an acid catalyzed process which can be controlled to give either of two regioisomeric series of products.     

On the Couette-Taylor instability in ferrohydrodynamics

A theory for the stabilizing influence of an axial external magnetic field on a magnetic colloid engaged in cylindrical Couette flow is presented. For the case of a narrow gap, analytical expressions which predict the magnetic field dependences of the critical wavelength and the critical Taylor number at the onset of cellular Taylor flow are obtained.     

Nonequilibrium Thermodynamics of Polymeric Liquids via Atomistic Simulation

The challenge of calculating nonequilibrium entropy in polymeric liquids undergoing flow was addressed from the perspective of extending equilibrium thermodynamics to include internal variables that quantify the internal microstructure of chain-like macromolecules and then applying these principles to nonequilibrium conditions under the presumption of an evolution of quasie equilibrium states in which the requisite internal variables relax on different time scales. The nonequilibrium entropy can be determined at various levels of coarse-graining of the polymer chains by statistical expressions involving nonequilibrium distribution functions that depend on the type of flow and the flow strength. Using nonequilibrium molecular dynamics simulations of a linear, monodisperse, entangled C₁₀₀₀H₂₀₀₂ polyethylene melt, nonequilibrium entropy was calculated directly from the nonequilibrium distribution functions, as well as from their second moments, and also using the radial distribution function at various levels of coarse-graining of the constituent macromolecular chains. Surprisingly, all these different methods of calculating the nonequilibrium entropy provide consistent values under both planar Couette and planar elongational flows. Combining the nonequilibrium entropy with the internal energy allows determination of the Helmholtz free energy, which is used as a generating function of flow dynamics in nonequilibrium thermodynamic theory.     

A comparison of selective saturation and selective echo chemical shift imaging techniques

We report on a comparative study of two methods of chemical shift imaging which can be used to selectively image fat and water in vivo. Both methods require a B0 field sufficiently homogenous to resolve the methylene and water spectral lines. One method, called CHESS, uses a chemically selective pulse to saturate the unwanted spectral line. The other method, called SECSI, achieves chemical selectivity by using a soft 180 degree RF pulse in forming a spin echo image. Both methods require that the strength of the B1 RF field be accurately calibrated and homogenous. We show by theoretical analysis that the suppression of unwanted spectral lines is sensitive to the first power of B1 errors in the CHESS method but to the second power of B1 errors in the SECSI method. Experiments with phantoms confirmed the expected non linearity of the SECSI method, and showed superior water suppression factors in phantoms with it. Experiments with a large phantom and a living rabbit showed superior results using the SECSI method, and the best results were obtained using a combination of the two techniques.     

Optimization of Biocompatibility for a Hydrophilic Biological Molecule Encapsulation System

Despite considerable advances in recent years, challenges in delivery and storage of biological drugs persist and may delay or prohibit their clinical application. Though nanoparticle-based approaches for small molecule drug encapsulation are mature, encapsulation of proteins remains problematic due to destabilization of the protein. Reverse micelles composed of decylmonoacyl glycerol (10MAG) and lauryldimethylamino-N-oxide (LDAO) in low-viscosity alkanes have been shown to preserve the structure and stability of a wide range of biological macromolecules. Here, we present a first step on developing this system as a future platform for storage and delivery of biological drugs by replacing the non-biocompatible alkane solvent with solvents currently used in small molecule delivery systems. Using a novel screening approach, we performed a comprehensive evaluation of the 10MAG/LDAO system using two preparation methods across seven biocompatible solvents with analysis of toxicity and encapsulation efficiency for each solvent. By using an inexpensive hydrophilic small molecule to test a wide range of conditions, we identify optimal solvent properties for further development. We validate the predictions from this screen with preliminary protein encapsulation tests. The insight provided lays the foundation for further development of this system toward long-term room-temperature storage of biologics or toward water-in-oil-in-water biologic delivery systems.     

All-optical logic AND-NOR gate with three inputs based on cross-gain modulation in a semiconductor optical amplifier

We report the realization of a novel all-optical logic AND-NOR gate based on cross-gain modulation (XGM). The used scheme requires only one SOA to perform the logic gate with three input signals. A 8.5 dB dynamic extinction ratio with a switching time of about 650 ps for the rise time and 100 ps for the fall time.