Microextraction of metal ions based on solidification of a floating drop: Basics and recent updates

This review provides a comprehensive evaluation of solidified floating organic drop microextraction (SFODME) procedures for metal ions preconcentration and their contributions to green chemistry. In this article we focused on the modifications that have been performed in the recent years to improve this environmentally friendly procedure. Among the most important of these modifications are the inclusion of ultrasonic energy, vortex and air agitation to enhance the dispersion process. The article also discussed new challenges in the procedure by using more ecofriendly solvents as extractants such as ionic liquids, deep eutectic. and supramolecular solvents. The coupling of SFODME with solid phase extraction increases selectivity and efficiency of the preconcentration procedure.     

Spray Freeze-drying – The Process of Choice for Low Water Soluble Drugs?

Most of the novel highly potent drugs, developed on the basis of modern molecular medicine, taking into account cell surface recognition techniques, show poor water solubility. A chemical modification of the drug substance enhancing the solubility often decreases the pharmacological activity. Thus, as an alternative an increase of the solubility can be obtained by the reduction of the size of the drug particles. Unfortunately, it is often difficult to obtain micro or nanosized drug particles by classical or more advanced crystallization using supercritical gases or by milling techniques. In addition, nanosized particles are often not physically stable and need to be stabilized in an appropriate matrix. Thus, it may be of interest to manufacture directly nanosized drug particles stabilized in an inert hydrophilic matrix, i.e. nanostructured and nanocomposite systems. Solid solutions and solid dispersions represent nanostructured and nanocomposite systems. In this context, the use of the vacuum-fluidized-bed technique for the spray-drying of a low water soluble drug cosolubilized with a hydrophilic excipient in a polar organic solvent is discussed. In order to avoid the use of organic solvents, a special spray-freeze-drying technique working at atmospheric pressure is presented. This process is very suitable for temperature and otherwise sensitive drugs such as pharmaproteins.     

Fast and efficient preparation of Baylis-Hillman-derived (E)-allylic azides and related compounds in aqueous medium

A practical access to alkyl- and aryl-substituted (E)-2-(azidomethyl)alkenoates and related azido compounds from the corresponding allylic bromides in aqueous acetone is described. An alternative method to obtain the starting bromides based on heterogeneous catalysis under mild conditions was also investigated.     

A Note on Geometric Structures of Linear Ordered Orthogonal Arrays and (T,M,S)-Nets of Low Strength

The equivalent geometrical configurations of linear ordered orthogonal arrays are determined when their strengths are 3 and 4. Existence of such geometrical configurations is investigated. They are also useful in the study of (T, M, S)-nets.     

On Extracting Maximum Stable Sets in Perfect Graphs Using Lovász's Theta Function

We study the maximum stable set problem. For a given graph, we establish several transformations among feasible solutions of different formulations of Lovász's theta function. We propose reductions from feasible solutions corresponding to a graph to those corresponding to its induced subgraphs. We develop an efficient, polynomial-time algorithm to extract a maximum stable set in a perfect graph using the theta function. Our algorithm iteratively transforms an approximate solution of the semidefinite formulation of the theta function into an approximate solution of another formulation, which is then used to identify a vertex that belongs to a maximum stable set. The subgraph induced by that vertex and its neighbors is removed and the same procedure is repeated on successively smaller graphs. We establish that solving the theta problem up to an adaptively chosen, fairly rough accuracy suffices in order for the algorithm to work properly. Furthermore, our algorithm successfully employs a warm-start strategy to recompute the theta function on smaller subgraphs. Computational results demonstrate that our algorithm can efficiently extract maximum stable sets in comparable time it takes to solve the theta problem on the original graph to optimality. This work was supported in part by NSF through CAREER Grant DMI-0237415. Part of this work was performed while the first author was at the Department of Applied Mathematics and Statisticsat Stony Brook University, Stony Brook, NY, USA.     

Chain length effect on dynamical structure of poly (vinyl pyrrolidone)-polar solvent mixtures in dilute solution of dioxane studied by microwave dielectric relaxation measurement

Dielectric relaxation study of the binary mixtures of poly(vinyl pyrrolidone) (PVP) (Mw=24000, 40000 and 360000 g mol⁻¹) with ethyl alcohol (EA) and poly(ethylene glycol)s (PEGs) (Mw=200 and 400 g mol⁻¹) in dilute solutions of dioxane were carried out at 10.1 GHz and 35°C. The relaxation time of PVP-EA mixtures was interpreted by the consideration of a wait-and-switch model in the local structure of self-associated ethyl alcohol molecules and also the PVP chain length as a geometric constraint for the reorientational motion of ethyl alcohol molecules. The formation of complexes and effect of PVP chain length on the molecular dynamics, chain flexibility and stretching of PEG molecules in PVP-PEG mixtures were explored from the comparative values of dielectric relaxation time. Further, relaxation time values in dioxane and benzene solvent confirm the viscosity independent molecular dynamics in PVP-EA mixtures but the values vary significantly with the non-polar solvent environment.     

Hydrolysis-condensation of tetraethoxysilane in nonparental solvents studied by GC-MS

Gas-chromatography coupled with mass spectrometry was used to investigate the hydrolysis and condensation of tetra-ethoxysilane (TEOS) in nonparental solvents (MeOH and nPrOH). In the presence of nonparental solvents, the reaction that advanced at highest rate is alkoxy group scrambling, that changes the precursor at the molecular level. Subsequent stages of hydrolysis-polycondensation process are essentially determined by the reactivity of the new molecular species formed.     

Influence of concentration on the activation energy for diffusion in polymer-solvent systems

The self-diffusion of benzene, toluene, and ethylbenzene in polystyrene have been analyzed using the Vrentas/Duda free-volume diffusion model. Diffusion coefficient predictions suggest an exponential concentration dependence of the activation energy required to overcome attractive forces, E. Without the use of any diffusion data approximating E as zero over the entire concentration range yields self-diffusion coefficient predictions which are in good agreement with experimental data. © 1992 John Wiley & Sons, Inc.     

A Theta Lift for Spin7

We establish an example of a functorial lift from generic cuspidal representations of a similitude group of the type A ₁×C ₂ to generic representations of Spin₇. Our construction uses the theta correspondence associated to the dual pair of the type (A ₁×C ₂ B ₃) inside E ₇. We also consider another theta correspondence associated to the dual pair of type (A ₁×C ₂ A ₁×A ₁) in D ₆ and show that these two pairs fit into a tower and the standard properties of a tower of theta correspondences hold.     

Reagent concentration effects in the REM resin solid phase synthesis of tertiary amines

The use of reagent concentration has resulted in increased rates for all stages of the REM resin synthesis of tertiary amines. These increases in rate translate into faster reaction times, higher yields and lower reagent consumption. Of the methods examined, the most successful was the use of perfluorous solvents, either alone or with a small amount of organic co-solvent.