The preparation and properties of dicarbonyl-h5-cyclopentadienyliron h2-vinyl ether and h2-ketene acetal complexes

Metallation of >-haloacetals wth sodium dicarbonyl-h⁵-cyclopentadienyl- ferrate (Fp^-) provides a convenient point of departure for the synthesis of alhyde -iron complexes (FpCHRCHO) and of h²-vinyl alcohol and vinyl ether cations [Fp(CH₂=CHOR)]⁺. These latter complexes are shown to be best described as distorted dihapto cation. Treatment of FpCOCH₂OMe with strong acid leads to the ketene hemiacetal cation [Fp(CH₂=C(OH)OMe)]⁺ rather than to the expected ketene complex. This substance, as well as the acetal cation [Fp(CH₂=C(OMe)OEt)]⁺ prepared by alkylation of FpCH₂COOMe, may possess the structure of an h¹-metal complex incorporating a carboxonium ion. A correlation is shown to exist between the chemical shift of cyclopentadienyl protons and the average infrared carbonyl stretching frequency in a variety of Fp(olefin)⁺ FpR complexes.     

Rapid extraction of abscisic acid and its metabolites for liquid chromatography-tandem mass spectrometry

We have described a simple, reliable and rapid method of extracting and partially purifying the phytohormone (+)-abscisic acid and its catabolites for liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS) analysis. Lyophilized tissue samples were powdered by high-speed agitation with ceramic beads for 5 s. Metabolites were extracted from the tissue powder using acetone-water-acetic acid (80:19:1, v/v) with the addition of deuterated internal standards for quantification. Essentially all endogenous hormones were recovered by three successive tissue extractions. However we demonstrated that, with the use of internal standards, one extraction with vigorous vortexing was sufficient to obtain accurate results (recovery 65-90%). Solvents were optimized for partial purification of abscisic acid and related compounds by solid-phase extraction using Oasis HLB cartridges. The eluted metabolites were then analyzed by LC-MS-MS. To illustrate the applicability of these techniques, we analyzed the levels of abscisic acid and metabolites in seeds and valves of Brassica napus siliques at two stages of development. We detected abscisic acid, phaseic acid, 7'-hydroxyabscisic acid, dihydrophaseic acid and abscisic acid glucose ester. In both tissues, dihydrophaseic acid was the major accumulating product, reaching 97300 pmol/g dry mass in valves at 24 days after anthesis. The amount of abscisic acid in seeds was high at 24 days after anthesis (23300 pmol/g dry mass), but low in the other samples (292-447 pmol/g dry mass).     

Surfactant-sensitive polymeric membrane electrodes

The development and testing is described of surfactant-sensitive electrodes in which the active element is a plasticised polymeric membrane containing a dissolved complex of a cationic and anionic surfactant. Electrodes made with poly(vinyl chloride) membranes plasticised with 40–60% tricresyl phosphate and containing cetyl trimethylammonium dodecyl sulphate are reasonably satisfactory for determining sodium dodecyl sulphate activities below and above the critical micelle concentration. A new class of membrane electrodes has been introduced in which ion-exchange groups are chemically bound to the ends of the poly(vinyl chloride) chains either through the use of an amine as chain transfer agent during polymerisation or by using the SO₃^? radical-anion as polymerisation initiator. The resulting electrodes are specific to anionic or to cationic surfactants but selectivity between different surfactants of the same charge sign is not high. The electrode lifetimes in micellar solutions are much higher than those of previously described electrodes because the electroactive material cannot be lost by solubilisation.     

Kinetic determination of the metalmetal bond dissociation energy in bis(dicarbonyl η5-cyclopentadienyliron)

The ironiron bond energy in [C₅H₅Fe(CO)₂]₂ (I) has been determined by measuring the rate of disproportionation of the monoacetyl complex (AcC₅H₄)(C₅H₅)Fe₂(CO)₄ (II) to I and [AcC₅H₄Fe(CO)₂]₂ (III). The reaction follows first order kinetics in benzene solution in the temperature range of 60–100°C with activation parameters calculated as: ΔH^≠ = 26.9 ± 2.7 kcal mol^?1 and ▽s^≠ = 2.0 ± 3.2 cal mol^?1 deg^?1.     

Effect of minor alloying additions on the solidification of single-crystal Ni-base superalloys

Grain boundary elements, such as carbon and boron, were initially removed from single-crystal alloys, but more recently they have been added back into single-crystal alloys for increased castability and defect tolerance. The mechanism(s) for the increased castability is not completely understood. In this study, carbon was added to the second generation, single crystal, Ni-base superalloy and CMSX-4, to form MC-type carbides. Then either nitrogen or boron was added to the carbon-containing alloy to alter the carbide morphology and the castability of the alloy. The segregation coefficients of the alloying elements in CMSX-4 were measured with varying techniques, but no changes in partitioning were observed. The addition of carbon to CMSX-4 did reduce the number of solidification defects observed in the samples. The addition of carbon and boron to CMSX-4 did not significantly change the number of solidification defects compared to the carbon-only alloy. However, the addition of nitrogen and carbon resulted in an increase in the number of solidification defects in the CMSX-4 samples compared to the baseline CMSX-4 and carbon-containing CMSX-4 samples. The effects of these alloy additions on the carbide morphology and solidification defects are discussed.