Structural Analysis of Novel [60]Fullerene Bisadduct Regioisomers by DFT Calculation

The structural analysis of the first [60]fullerenyl 1,38-bisadduct having the almost perpendicular angle between two addends was performed based on the simulation of ¹³C-NMR spectral line patterns using the DFT calculation at the B3LYP/6-31G? level of the theory. Among seven closely related model regioisomers of C₆₀(CH₃)₂ applied in the calculation, we confirmed that the 1,38-bisadduct and 1,4-bisadduct, being the most plausible regioisomers in a structure showing an approximate consistency of spectral line profiles, match with that of the experimentally obtained spectrum.     

Synthesis and characterization of postsulfonated poly(arylene ether sulfone) diblock copolymers for proton exchange membranes

Sulfonated poly(arylene ether sulfone) diblock copolymers were studied through the postsulfonation process. Two kinds of hydrophobic oligomers with a molecular weight of 20 kDa were prepared in advance as block sequences and then coupled together to obtain diblock copolymers. One oligomer was synthesized from bis(4‐hydroxyphenyl) sulfone (BHPS) and 4,4′‐difluorodiphenyl sulfone (DFDPS), which was thought to be incapable of postsulfonation. The other oligomer was synthesized from hydroquinone (HQ) and 4,4′‐dichlorodiphenyl sulfone (DCDPS), which successfully proceeded to a hydrophilic sequence as a result of sulfonation onto the HQ moiety after the coupling reaction. Consequently, a diblock copolymer with high molecular weight was obtained; although its intrinsic viscosity was too low to form a tough membrane because of its high rigidity and high crystallinity. Therefore, the use of decafluorobiphenyl (10F) as a termination reagent was investigated with the aim of achieving higher coupling reactivity and a kinky property. As a result, a sulfonated diblock copolymer was successfully obtained with sufficient molecular weight and intrinsic viscosity to form the membrane, as well as with adequate thermal properties. It was observed that proton conductivity, water uptake, and the water diffusion coefficient increased with higher ion exchange capacity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 700–712, 2009     

Preconditioned GMRES methods with incomplete Givens orthogonalization method for large sparse least-squares problems

We propose to precondition the GMRES method by using the incomplete Givens orthogonalization (IGO) method for the solution of large sparse linear least-squares problems. Theoretical analysis shows that the preconditioner satisfies the sufficient condition that can guarantee that the preconditioned GMRES method will never break down and always give the least-squares solution of the original problem. Numerical experiments further confirm that the new preconditioner is efficient. We also find that the IGO preconditioned BA-GMRES method is superior to the corresponding CGLS method for ill-conditioned and singular least-squares problems.     

Ferromagnetic interaction between [Ni(bdt)2]− anions in [Mn2(Saloph)2(μ-OH)][Ni(bdt)2](CH3CN)2

A new molecule-based magnetic material [Mn₂(Saloph)₂(μ-OH)][Ni(bdt)₂](CH₃CN)₂ was prepared by the metathesis of [Mn(Saloph)(H₂O)(ClO₄)] (S = 2) and TBA[Ni(bdt)₂] (S = 1/2). In the crystal, [Ni(bdt)₂]^? anions form square lattices which are separated from each other by the layers of antiferromagnetically coupled binuclear cations [Mn₂(Saloph)₂(μ-OH)]⁺. The magnetic susceptibility of the material coincides with the sum of the S = 2 van Vleck dimer model and S = 1/2 Heisenberg ferromagnetic square lattice model with 2J = ?92.4 and +4.5 K, respectively. The origin of the ferromagnetic interaction can be explained by the T-shaped intermolecular overlap mode of SOMOs which spreads to the ends of [Ni(bdt)₂]^? molecules.     

Effects of hypochlorite treatment on the surface morphology and mechanical properties of polyethersulfone ultrafiltration membranes

Polyethersulfone membranes are widely used for ultrafiltration and microfiltration especially in the dairy industry, but they are believed to degrade when exposed to the sodium hypochlorite solution that is used to sanitize the processing equipment. Such membranes were exposed to sodium hypochlorite for up to 25,000 ppm-day at 55 °C, and pH 9 and 12. Mechanical properties as measured by dynamic mechanical analysis and tensile strength did not change greatly, but surface properties measured by FTIR-ATR, field emission scanning electron microscopy and associated energy dispersive X-ray spectroscopy detected significant changes in the surface. Surface pitting was observed and was found to be most severe at pH 9. It was thought that pitting was the likely cause of degradation in performance of the membranes and that pits could act as stress raisers leading to cracking.     

Development of a thermal neutron-sensitive liposome for a novel drug delivery system aiming for radio-chemo-concurrent cancer therapy

A thermal neutron-sensitive liposome has been developed focusing on irradiation site-specific-controlled release of a medicine. We recommended a ¹⁰B-borocaptate dimer as a detonator of liposome in expectation of effects of low-energy heavy ions produced by ¹⁰B(n, α)⁷Li reaction. As a result, an X-ray-sensitive liposome incorporating the detonator was vulnerable enough to release an anticancer agent, carboplatin, at a dose/dose–rate near clinical use. These results reveal, moreover, that the liposomes are also applicable to a heavy-ion beam.     

fac‐Trichloro(quinolin‐8‐ylimido‐N,N′)(triphenylphosphine‐P)rhenium(V)

The Re atom in [Re(C₉H₆N₂)Cl₃(C₁₈H₁₅P)] is octahedrally coordinated by three Cl atoms in facial positions, two N atoms from 8‐imido­quinoline (imq) and one P atom from tri­phenyl­phosphine. The Re—N(imido) distance [1.760 (9) and 1.772 (8) Å] for imq is very short and implies double‐bond character. The trans influence of the P atom is indicated. Intra‐ and intermolecular π–π interactions between the π‐rings in the complex are also observed.     

Intermolecular propargyl/allenyl group transfer from Pd(II) to Pt(0) and Pt(II) to Pd(0). Key reaction in metal-catalyzed isomerization between propargyl and allenyl metal complexes

Isomerization of phenyl-substituted propargylplatinum(II) complex, trans-Pt(CH₂CCPh)(Cl)(PPh₃)₂ (1) to allenyl complex, trans-Pt(CPh=C=CH₂)(Cl)(PPh₃)₂ (2) was found to be catalyzed by zerovalent complex Pd(PPh₃)₄. The reaction was proposed to proceed through the transfer of the propargyl/allenyl ligand both from Pt(II) to Pd(0) and Pd(II) to Pt(0). The former transfer, which seemingly has a thermodynamic disadvantage, has unambiguously been confirmed to take place; treatment of 1 with Pd(PPh₃)₄ or a mixture of Pd₂(dba)₃ and PPh₃ resulted in the formation of Pd(I) complex, Pd₂(μ-PhCCCH₂)(μ-Cl)(PPh₃)₂ which lies in equilibrium with a mixture of propargyl/allenylpalladium(II) and Pd(0) complexes.