Oxidative coupling polymerization of 4‐methyltriphenylamine

4‐Methyltriphenylamine was oxidatively polymerized in chloroform (CL) or propylene carbonate (PC) in the presence of ferric chloride (FeCl₃) at 50°C. Polymerization proceeded more rapidly and the molecular weight of the resulting polymer was higher in CL than in PC due to the higher oxidation potential of the solution. The linear structure was confirmed by ¹³C NMR, and the resulting polymer exhibited high thermal stability and electrochemical activity.     

Determination of various inorganic anions and organic acids in the atmospheric particulate matter using capillary zone electrophoresis with indirect UV detection

Capillary zone electrophoresis with indirect UV detection was developed for the simultaneous analysis of inorganic anions and organic acids using a mixed solution of 2,6-pyridinedicarboxylic acid and cetyltrimethylammonium hydroxide as the background electrolyte (BGE). The parameters which influence the separation, such as indirect UV detection wavelength, BGE conditions, applied voltage and extraction conditions were investigated. Thirteen inorganic anions and organic acids were detected within 20 min. The calibration curves of each analyte were linear with correlation coefficients greater than 0.991. The relative standard deviations (n = 10) of the peak areas ranged from 0.6% to 3.3%. The detection limits for these species ranged from 0.4 to 1.4 mg/L at a signal-to-noise ratio of 3. The recovery rate of each analyte was more than 80% under optimised extraction conditions, except for nitrite. The proposed method was applied towards the analysis of inorganic anions and organic acids in the atmospheric particulate matter using an Andersen sampler. The particle size of the particulate matter was determined, but not the size of the anions.     

Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment

A combination of nuclear resonance vibrational spectroscopy (NRVS), FTIR spectroscopy, and DFT calculations was used to observe and characterize Fe?H/D bending modes in CrHydA1 [FeFe]‐hydrogenase Cys‐to‐Ser variant C169S. Mutagenesis of cysteine to serine at position 169 changes the functional group adjacent to the H‐cluster from a ‐SH to ‐OH, thus altering the proton transfer pathway. The catalytic activity of C169S is significantly reduced compared to that of native CrHydA1, presumably owing to less efficient proton transfer to the H‐cluster. This mutation enabled effective capture of a hydride/deuteride intermediate and facilitated direct detection of the Fe?H/D normal modes. We observed a significant shift to higher frequency in an Fe?H bending mode of the C169S variant, as compared to previous findings with reconstituted native and oxadithiolate (ODT)‐substituted CrHydA1. On the basis of DFT calculations, we propose that this shift is caused by the stronger interaction of the ‐OH group of C169S with the bridgehead ‐NH‐ moiety of the active site, as compared to that of the ‐SH group of C169 in the native enzyme.     

Author Index

Authors Index

Author Index     

Synthesis and properties of poly(arylene ether)s bearing sulfonic acid groups on pendant phenyl rings

Two kinds of new aromatic poly(arylene ether)s containing sulfonic acid groups were synthesized. Polymer 1 composed of tetraphenylphenylene ether and perfluorobiphenylene units was sulfonated with chlorosulfonic acid. Sulfonation took place only at the para position of the pendant phenyl rings. The average degree of sulfonation per repeating unit (m) was controlled from 1 to 4. Sulfonated polymer 2 with m = 3 was soluble in methanol and dimethyl sulfoxide and swelled in water. Incorporating bis(3,5‐dimethylphenyl)sulfone moieties into the sulfonated polymer imparts less methanol affinity. Polymers 4 with 30–65 mol % tetrakis(sulfophenyl)phenylene ether units has high decomposition temperatures above 300 °C, hydrophilicity, and good hydrolytic stability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3211–3217, 2001     

Amphiphilic block and statistical copolymers with pendant glucose residues: Controlled synthesis by living cationic polymerization and the effect of copolymer architecture on their properties

Amphiphilic block and statistical copolymers of vinyl ethers (VEs) with pendant glucose residues were synthesized by the living cationic polymerization of isobutyl VE (IBVE) and a VE carrying 1,2:5,6‐di‐O‐isopropylidene‐D ‐glucose (IpGlcVE), followed by deprotection. The block copolymer was prepared by a two‐stage sequential block copolymerization, whereas the statistical copolymer was obtained by the copolymerization of a mixture of the two monomers. The monomer reactivity ratios estimated with the statistical copolymerization were r₁ (IBVE) = 1.65 and r₂ (IpGlcVE) = 1.15. The obtained statistical copolymers were nearly uniform with the comonomer composition along the main chain. Both the block and statistical copolymers had narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight ∼ 1.1). Gel permeation chromatography, static light scattering, and spin–lattice relaxation time measurements in a selective solvent revealed that the block copolymer formed multimolecular micelles, possibly with a hydrophobic poly(IBVE) core and a glucose‐carrying poly(VE) shell, whereas the statistical copolymer with nearly the same molecular weight and segment composition was molecularly dispersed in solution. The surface properties of the solvent‐cast films of the block and statistical copolymer were also investigated with the contact‐angle measurement. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 459–467, 2001     

Diatomic interactions in momentum space. The effect of polarization and floating functions

The method of momentum density for interatomic interactions is used to investigate the pictures and roles of the polarization and floating functions in momentum (p-) space. Referring to the previous results from the minimal LCAO (Finkelstein-Horowitz) momentum density, we quantitatively discuss the effect of these functions for the bonding process in the ground state of H ₂ ⁺ system. The essence of the polarization and floating effects is found to be a modulation of the oscillation in the two-center part of the momentum density. The polarization function introduces a term with a phase and the floating function enlarges the period of the oscillation. An increased migration of the density from the one-center to the two-center part is also important. As a result, both the functions contribute to emphasize the contraction and expansion of momentum density observed previously. However, the floating function disturbs the density distribution in high momentum region, reflecting the destruction of cusps in position (r-) space. We point out an error in the pioneer work of Duncanson.     

A stereoselective synthesis of “natural” (4S,6S,7S)-serricornin,the sex pheromone of cigarette bettle,from levoglucosenone

The natural stereoisomer of serricornin was synthesized stereoselectively from levoglucosenone. This firmly established the absolute stereochemistry of serricornin to be 4S,6S,7S. A short synthesis of (?)-δ-multistriatin was also reported.