Mononuclear Dysprosium Alkoxide and Aryloxide Single-Molecule Magnets

Recent studies have shown that mononuclear lanthanide (Ln) complexes can be high-performing single-molecule magnets (SMMs). Recently, there has been an influx of mononuclear Ln alkoxide and aryloxide SMMs, which have provided the necessary geometrical control to improve SMM properties and to allow the intricate relaxation dynamics of Ln SMMs to be studied in detail. Here non-aqueous Ln alkoxide and aryloxide chemistry applied to the synthesis of low-coordinate mononuclear Ln SMMs are reviewed. The focus is on mononuclear Dy^III alkoxide and aryloxide SMMs with coordination numbers up to eight, covering synthesis, solid-state structures and magnetic attributes. Brief overviews are also provided of mononuclear Tb^III, Ho^III, Er^III and Yb^III alkoxide and aryloxide SMMs.     

Chiral discrimination by hydrolytic enzymes in the synthesis of optically pure materials

Enantioselection effected by commercially available hydrolytic enzymes reported in recent years from our own laboratory and those published by other groups is described. The discussion is confined to enantioselection in symmetric diols, amino acids and benzopyran derivatives only. The paper describes a variety of substrates accepted by these hydrolytic enzymes to produce compounds in high enantiomeric excess which can be used as chiral building blocks for the synthesis of compounds of pharmaceutical and synthetic interest.     

Two-dimensional electrophoresis of cereal prolamins: applications to biochemical and genetic analyses

Three complementary two-dimensional systems for the analysis of cereal prolamins are described. These are electrophoresis at pH 3.1 followed by electrophoresis at pH 9.2, isoelectric focusing (IEF) followed by sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) and SDS-PAGE under non-reducing conditions followed by SDS-PAGE with reduction. They together give information on the pIs, Mrs and charge properties of the individual prolamin components, and on their interactions to form oligomers stabilized by inter-chain disulphide bonds. The three systems are then compared for their effectiveness in analysing unreduced prolamin I fractions from wheat and rye, and the IEF/SDS-PAGE system for analysing reduced and pyridylethylated prolamin fractions from all the major cereals. Finally, applications of the systems in biochemical and genetic studies are discussed and illustrated with three examples: analysis of the structural relationships of the S-rich prolamins (B hordeins and gamma-type hordeins) of barley, determination of the interactions of wheat and rye prolamin subunits in a 2RS/2BL translocation line, and the mapping of genes for alpha-type prolamins in the wild grass Haynaldia villosa.     

Ruthenium(VI)-catalysed oxidation of diols by alkaline hexacyanoferrate(III) ion. A kinetic study

The kinetics of Ru^VI-catalysed oxidation of ethane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butane-1,4-diol and 2-butoxyethanol by hexacyanoferrate(III) ion in an aqueous alkaline medium at constant ionic strength shows zeroth order dependence on hexacyanoferrate(III) and first order dependence on Ru^VI and substrate. The results suggest that a complex is formed, between Ru^VI and the diol, which slowly decomposes to a reduced form of ruthenium, which is reoxidized to Ru^VI in a fast step by alkaline hexacyanoferrate(III). A plausible reaction mechanism is proposed.     

Synthesis of l-(N-acelylpiperidino)-4-aryl semicarbazides as possible anticonvulsants

Six 1-(N-acetylpiperidino)-4-aryl semicarbazides were synthesized from ethyl-N-piperidino-aeetatc which on treatment with hydrazine hydrate was converted into N-piperidinoacethydrazide. The resulting hydrazide on treatment with the appropriate arylisoeyanales formed l -(N-acelyl-piperidino)-4-aryl semicarbazides. Amongst these piperidinosemicarbazides, three compound possessed low anticonvulsanl activity and provided 20-40% protection against pentylenetetrazol-induced convulsions in mice. All piperidino semicarbazides (0.1 mM) possessed antihemolytic activity (13-35%) and caused 40-72% inhibition of monoamine oxidase activity of rat brain homogenates at a final concentration of 0.3 mM.     

Substituted thiosemicarbazido/semicarbazido quinolines as possible antimalarials

Several 2-aryl substituted thiosemicarbazido-4-methyl-6-methoxyquinolines and 2-aryl substituted semi-carbazido 4-methyl-6-methoxyquinolines were synthesized and evaluated for their antimalarial activity in mice infected with Plasmodium berghei. Two of these substituted quinolines were found to exhibit 50% clearance in a dose of 500 mg./kg. administered intraperitoneally for 5 days.