Positive muons in [Co(NH3)6]Cl3 and [Co(ND3)6]Cl3

We have carried out SR experiments on [Co(NH₃)₆]Cl₃ and [Co(ND₃)₆]Cl₃. At 293 K, all the muons implanted into the complexes were in the diamagnetic state. The observed Gaussian-type muon spin relaxation function proved that the internal magnetic field was caused by nuclear dipole moments of the atoms in the complexes. In addition, another exponential-type muon spin relaxation function was observed in [Co(ND₃)₆]Cl₃ below 50 K.     

Remarkably Selective Ag(+) Extraction and Transport by Thiolariat Ethers

Synthesis and metal binding properties of thiolariat ethers, where a sulfide side chain is introduced into a framework of a crown ether, have been performed. Remarkably high Ag(+) selectivity among heavy metal ions was observed in solvent extraction and transport across a liquid membrane using thiolariat ethers with a 15-crown-5 ring as carriers. Thiolariat ethers with a 12-crown-4 or a 18-crown-6 do not exhibit such a high Ag(+) selectivity. The former binds metal ions weakly, and the latter recognizes Pb(2+) as well as Ag(+). The corresponding oxygen analogs, i.e. lariat ethers, do not show Ag(+) selectivity. The Ag(+) binding strength of the sulfoxide and sulfone analogs is much lower than that of thiolariat ethers. Thiolariat ethers with a benzocrown framework containing a sulfide chain at the 4 position of the benzene nucleus showed very low affinity to Ag(+). Extractability and transport ability using various thiolariat ether derivatives strongly suggested that this high Ag(+) selectivity is a result of the synergistic coordination of the ring oxygen and the sulfur atom of the thiolariat ether. NMR chemical shifts of protons and carbons in the proximity of the sulfur atom of the thiolariat ether were changed significantly in accordance with the synergistic coordination described above. 1:1 Complexation between a thiolariat ether and Ag(+) were supported by a Job plot using the chemical shift of the methylene protons adjacent to the sulfur atom.     

Conformation of poly(<Emphasis Type="SmallCaps">l</Emphasis>-glutamic acid) in bipolar amphiphiles with alkyl ammonium cations of different hydrophobicity

The conformation of the sodium salt of poly(l-glutamic acid) (P(Glu)) in solutions of the cationic bipolar amphiphile 1, 20-isosanediylbis(alkylammonium chloride) (C ₂₀(RA) ₂) with different alkyl head groups as a function of amphiphile concentration was investigated using circular dichroism (CD). RA included methylammonium (MA), ethylammonium (EA), propylammonium (PA), butylammonium (BA), and pentylammonium (PeA) cationic groups. The CD spectrum of each C ₂₀(RA) ₂ had a double minima corresponding to the a-helix of P(Glu), which was replaced by CD spectra with a single minimum at wavelengths larger than 222 nm as concentration increased. These changes in the CD spectrum were ascribed to the conformational change from random coil to a-helix and to aggregates of helices. In C ₂₀(EA) ₂ solutions, a step-like change in the CD intensity was observed at 222 nm as a function of the ratio of C ₂₀(RA) ₂ to P(Glu). At the step, the CD spectrum of the complete a-helix was observed. At 10–35 °C, an a-helix was induced in P(Glu) in the order: C ₂₀(EA) ₂>C ₂₀(MA) ₂>C ₂₀(PA) ₂>C ₂₀(BA) ₂>C ₂₀(PeA) ₂. This order was ascribed to the best fit of ethylammonium to the P(Glu) side chain.     

Nickel-catalyzed addition of P(O)-H bonds to propargyl alcohols: one-pot generation of phosphinoyl 1,3-butadienes

[reaction: see text] Diphenylphosphine oxide and related P(O)H compounds react with propargyl alcohols at room temperature in the presence of a catalytic amount of Ni(0) complex and Ph(2)P(O)OH to produce high yields of phosphinoyl 1,3-dienes though an efficient in situ dehydration process.     

Transformation of indole alkaloids—I : Conversion of oxindole alkaloids into indole alkaloids

Chemical conversion of some natural oxindoles (pteropodine, isopteropodine and isorhynchophylline) into the corresponding indole alkaloids has been made by way of a sequence of reactions which include formation of iminoethers of the natural oxindoles with Meerwein's reagent, reduction of the iminoethers to 2,3-seco-indoles and cyclization of 2,3-seco-indoles to the desired natural indole alkaloids. Sodium borohydride in acetic acid was found to be a specific reagent for the reduction of oxindole-iminoethers to 2,3-seco-indoles which were the key intermediates in these transformations. Yohimbine-oxindole iminoether was similarly converted to yohimbine and pseudoyohimbine. A number of by-products were obtained and their structures were elucidated.     

Electrostatics of cell membrane recognition: structure and activity of neutral and cationic rigid push-pull rods in isoelectric, anionic, and polarized lipid bilayer membranes.

Design, synthesis, and structural and functional studies of rigid-rod ionophores of different axial electrostatic asymmetry are reported. The employed design strategy emphasized presence of (a) a rigid scaffold to minimize the conformational complexity, (b) a unimolecular ion-conducting pathway to minimize the suprastructural complexity and monitor the function, (c) an extended fluorophore to monitor structure, (d) variable axial rod dipole, and (e) variable terminal charges to create axial asymmetry. Studies in isoelectric, anionic, and polarized bilayer membranes confirmed a general increase in activity of uncharged rigid push-pull rods in polarized bilayers. The similarly increased activity of cationic rigid push-pull rods with an electrostatic asymmetry comparable to that of alpha-helical bee toxin melittin (positive charge near negative axial dipole terminus) is shown by fluorescence-depth quenching experiments to originate from the stabilization of transmembrane rod orientation by the membrane potential. The reduced activity of rigid push-pull rods having an electrostatic asymmetry comparable to that in alpha-helical natural antibiotics (a positive charge near the positive axial dipole terminus) is shown by structural studies to originate from rod "ejection" by membrane potentials comparable to that found in mammalian plasma membranes. This structural evidence for cell membrane recognition by asymmetric rods is unprecedented and of possible practical importance with regard to antibiotic resistance.