Extraction and spectrophotometric determination of zinc in coal fly ash and pond sediments with 2-[2-(3,5-dibromopyridyl)azo]-5-dimethylaminobenzoic acid

An extraction-spectrophotometric method is described for the determination of traces of zinc with 2-[2-(3,5-dibromopyridyl)azo]-5-dimethylaminobenzoic acid. The reagent forms a stable, blue 1:2 zinc/reagent complex that can be extracted into chloroform. The apparent molar absorptivity of the zinc(II) complex is 1.26 × 10⁵ l mol^?1 cm^?1 at 610 nm in chloroform. The reagent is relatively selective; interferences from cobalt, copper and nickel can be masked with dimethylglyoxime and aluminium and iron with a mixture of sodium fluoride and triethanolamine. The method is applied to the determination of zinc in coal fly ash and pond sediments with good precision and accuracy.     

Evaluation of molecular structure in Langmuir monolayers of zinc stearate and zinc 12-hydroxystearate by IR external reflection spectroscopy

 In situ polarized Fourier transform IR external reflection spectra of Langmuir monolayers of zinc stearate and zinc 12-hydroxystearate on a water surface were recorded for various surface areas, and their molecular structures were estimated. In the zinc stearate monolayer, the wavenumbers and the absorbances of the antisymmetric and symmetric methylene stretching bands did not change during monolayer compression, which means that orientational and conformational changes of the hydrocarbon chain did not occur. However, wavenumber changes of the antisymmetric and symmetric carboxylate stretching bands were observed during surface compression. The change in the binding nature of the zinc cation to the carboxylate group was speculated. Moreover, it was elucidated that the structure of the hydrocarbon chain in the zinc 12-hydroxystearate monolayer was different from that in the zinc stearate monolayer. Received: 21 March 2001 Accepted: 6 July 2001     

Effects of poly(ethylene glycol) (PEG) concentration on the permeability of PEG-grafted liposomes

Poly(ethylene glycol)-grafted liposomes (PEG-liposomes) were prepared from dipalmitoylphosphatidylcholine (DPPC) with various amounts of distearoyl-N-monomethoxy poly(ethylene glycol)-succinyl-phosphatidylethanolamines (DSPE-PEG) with PEG molecular weights of 1000, 2000, 3000 and 5000. The effects of DSPE-PEG concentration on the permeability of PEG-liposomes were investigated using carboxyfluorescein (CF). In the gel state, the CF leakage from PEG-liposomes was decreased with increasing mole fractions of DSPE-PEG for all PEG molecular weights. In the liquid-crystalline state, the CF leakage from PEG-liposomes containing DSPE-PEG1000 gradually increased with increasing mole fractions of DSPE-PEG, while that of PEG-liposomes whose molecular weight in PEG units was above 2000 rapidly decreased by the addition of DSPE-PEG. Furthermore, no effect of PEG molecular weight on CF leakage was observed. The relationship between the fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) (or 1-(4-trimethylammoniumphenyl)-6-phenyl-1,3,5-hexatriene (TMA-DPH)) and the mole fraction of DSPE-PEG for PEG-liposomes was also investigated. No significant changes in fluorescence polarization of DPH for liposomal bilayer membranes was observed in the gel and liquid-crystalline states due to the addition of DSPE-PEG, while that of TMA-DPH was decreased compared with that of liposomes without DSPE-PEG in both states.     

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.     

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.     

Preparation of multisubstituted allenes from allylsilanes

[reaction: see text] A three-step route of converting allylsilanes to functionalized allenes was developed. Thermal decomposition of 1,1-dibromo-2-(silylmethyl)cyclopropanes, which were quantitatively prepared by treatment of allylsilane derivatives with CHBr3/KO(t)Bu, afforded substituted 2-bromo-1,3-butadienes with elimination of bromosilanes. The Pd-catalyzed reaction of the bromodienes with soft nucleophiles gave the allene derivatives. Previously inaccessible tri- and tetrasubstituted allenes can be prepared by this method as well.