Electrochemical perfluoroalkoxylation of aromatic compounds

New approaches to the electrochemical synthesis of aryl perfluoroalkyl ethers based on a) the electrooxidation of perfluorocarboxylic acid on a consumable PbO₂ anode and b) the simultaneous anodic oxidation of the “aromatic compound-alkaline perfluoroalkoholate” system on a platinum electrode were proposed.     

A temperature-controlled graphite tube furnace for the determination of trace metals in solid biological tissue

A temperature-controlled graphite furnace for atomic-absorption analysis has been built and tested. The temperature of the graphite tube was monitored with an infrared-sensitive detector. Samples were introduced directly or via a separately heated graphite cup. Micro-samples of solid biological tissue were analysed directly for Zn, Mn and Co and the sensitivities for 1% absorption were 0.05,2 and 10 pg respectively. The salt content of the tissue limits the sample sizes, owing to non-specific absorption. The ashing conditions were investigated and found to be especially critical for Zn.     

Recent advances in surface x-ray diffraction and the potential for determining structure-sensitivity relations in single-crystal electrocatalysis

Determining how electrode structure governs the performance of an electrocatalyst requires techniques capable of probing structure at the atomic scale, often in situ and operando. In recent years, there have been numerous advances in the main experimental techniques for determining the structure of the electrochemical interface. In situ/operando synchrotron surface x-ray diffraction measurements are key to investigate the atomic structure of the electrode surfaces as well as understand the structure-reactivity relations in electrocatalysis. Here we discuss some recent improvements that have taken place in surface x-ray diffraction and how we expect them to lead to an enhanced understanding of electrocatalysis.     

Interaction of phospholipids with rhodamine 6G in toluene.

Upon interaction of various glycerophospholipids with Rhodamine 6G in toluene, a typical difference spectrum with an absorption maximum at approximately 515 nm is obtained . This spectrum is obtained with phosphatidylcholine only after treatment with NaCl, which presumably weakens intra- and/or inter-molecular electrostatic binding between the negatively charged phosphate moiety and the protonated nitrogen in this molecule. Absorption at 515 nm was linear for all of the phospholipids investigated from a concentration of approximately 1.2 microM up to at least 50 microM. The highest extinction coefficient was obtained for diphosphatidylglycerol (251 mM-1 cm-1) and all of the compounds tested, with the exception of phosphatidylethanolamine, demonstrated extinction coefficients higher than that of palmitic acid. Thus, the absorption spectrum which results from the interaction of purified glycerophospholipids with Rhodamine 6G in organic solvent is a sensitive measure of the amount of phospholipid present.     

Polymer-supported pyridine-bis(oxazoline). Application to ytterbium-catalyzed silylcyanation of benzaldehyde

[reaction: see text] Terminal acetylenes containing hydroxy and carboxylic acid groups were subjected to Sonogashira coupling with 4-bromo-2,6-bis[(R)-4-phenyloxazolin-2-yl]pyridine and the resulting pybox derivatives were immobilized on Tentagel resins. Ytterbium(III) chloride complexes of the polymeric ligands catalyzed the addition of trimethylsilyl cyanide to benzaldehyde with 80-81% ee. The ligands were reused more than 30 times without any loss in selectivity or activity, and the metal complexes could be recovered and reused at least four times, although with slightly decreasing activity.