Synthesis of Novel C/D Ring Modified Bile Acids

Bile acid receptors have been identified as important targets for the development of new therapeutics to treat various metabolic and inflammatory diseases. The synthesis of new bile acid analogues can help elucidate structure–activity relationships and define compounds that activate these receptors selectively. Towards this, access to large quantities of a chenodeoxycholic acid derivative bearing a C-12 methyl and a C-13 to C-14 double bond provided an interesting scaffold to investigate the chemical manipulation of the C/D ring junction in bile acids. The reactivity of this alkene substrate with various zinc carbenoid species showed that those generated using the Furukawa methodology achieved selective α-cyclopropanation, whereas those generated using the Shi methodology reacted in an unexpected manner giving rise to a rearranged skeleton whereby the C ring has undergone contraction to form a novel spiro–furan ring system. Further derivatization of the cyclopropanated steroid included O-7 oxidation and epimerization to afford new bile acid derivatives for biological evaluation.     

Electro-oxidation of amino-functionalized multiwalled carbon nanotubes

We report the electrochemistry of amino-functionalized multiwalled carbon nanotubes (MWCNTs-NH₂) in the pH range from 0.3 to 6.4 using quantitative cyclic voltammetry (CV) and single entity electrochemistry measurements, making comparison with non-functionalized MWCNTs. CV showed the latter to both catalyze the solvent (water) decomposition and to undergo irreversible electro-oxidation forming oxygen containing surface functionality. The MWCNTs-NH₂ additionally undergo an irreversible oxidation to an extent which is dependent on the pH of the solution, reflecting the variable amount of deprotonated amino groups present as a function of pH. Nano-impact experiments conducted at the single particle level confirmed the oxidation of both types of MWCNTs, showing agreement with the CV. The pK_a of the amino groups in MWCNTs was determined via both electrochemical methods giving consistent values of ca. 2.5.

A new and generic approach to the study of the oxidation of different forms of CNTs is found by using quantitative single entity and ensemble electrochemistry measurements.     

Separation technology of used polymers

The technology of separating plastics from the municipal waste stream for reuse is reviewed, with emphasis on the key role played by the bottle sorting step. Experience gained in the first year's operation of two large commercial recycling plants provides a better understanding of practical problems encountered, their relative importance, and technical advances needed for improved operation. It is concluded that purity of feedstock and processing rate are two critical independent variables requiring technical and business understanding and management. Hypothetical examples illustrate the interplay of these with dependent variables of yield and sorting cost.     

On-line determination of organochlorine pesticides in water by solid-phase microextraction and gas chromatography with electron capture detection

This paper describes the extraction of 20 organochlorine pesticides (OCPs) from water samples using solid-phase microextraction (SPME). Three fused-silica fibers coated or bonded with polydimethylsiloxane (PDMS) of different film thicknesses (20-, 30-, and 100-μm) were evaluated. The extraction time, the effects of stirring and addition of NaCl to the aqueous sample, the linear range and the precision of this technique, and the effect of carryover were examined for 20 analytes and are presented here. A comparison with results using conventional liquid-liquid extraction demonstrate that the SPME technique is well suited as a fast screening technique for OCPs in water samples.     

Effect of molecular architecture on DBS-induced block copolymer gels: A rheological study

Dibenzylidene sorbitol (DBS) is capable of gelling a variety of organic solvents and polymeric materials by forming a rigid, 3-D hydrogen-bonded network. In this work, two poly(siloxane)/poly(propylene oxide) segmented copolymers of equal composition and molecular weight, but different architectures (endblocked vs. pendant), as well as a pure poly(propylene oxide), have been gelled with DBS. We have investigated the dynamic rheological properties of these gels to ascertain the effect of copolymer architecture, PDMS comonomer and DBS concentration on network formation.     

Reductive allylation of poly(chlorotrifluoroethylene)

Treatment of poly(chlorotrifluoroethylene) with allyltin reagents results in the clean replacement of chlorine by the allyl group under free-radical–chain conditions (AIBN, allyltributyltin), affording about a 10% degree of functionalization. An improved method using one-electron reduction of the polymer with cobalt(II) (generated by reduction of chloro(pyridine)bis(dimethylglyoximato)cobalt(III) with Mg) and allyltributyltin gives 50% functionalization. Further modification of the allyl group is realized through hydroboration-oxidation to the alcohol and subsequent Cr(VI) oxidation to the acid. A mechanistic discussion is provided. © John Wiley & Sons, Inc.