Characterization of certified reference material for quantification of polychlorinated biphenyls and organochlorine pesticides in fish

Fish certified reference material (CRM), NMIJ CRM 7404-a, for the analysis of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) was developed by the National Metrology Institute of Japan, part of the National Institute of Advanced Industrial Science and Technology. Fish samples (Japanese seabass) used for the preparation of the CRM were collected from Tokyo Bay, and the edible part was freeze-dried, pulverized, sieved, homogenized, and sterilized by γ-irradiation. This sample is in the form of a powder comprising approximately 10 g stored in a brown glass bottle. The certification was carried out using multiple analytical methods such as pressurized liquid extraction, Soxhlet extraction, saponification, and homogenization to ensure the reliability of analytical results; the certified values of target PCBs (PCB 28, PCB 70, PCB 105, PCB 153, and PCB 170) and OCPs (trans-nonachlor, dieldrin, p,p′-DDE, p,p′-DDT, and p,p′-DDD) were 1.05–14.0 μg kg⁻¹ and 1.57–18.0 μg kg⁻¹ for PCBs and OCPs, respectively. This is the first fish powder CRM in which PCBs and OCPs were determined by isotope dilution mass spectrometry.     

Laser-induced fluorescence and infrared spectroscopic studies on the specific solvation of tris(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)europium(III) in an ionic liquid

The extraction constant and the two-phase stability constant (K_D,Mβ₃) of tris(2-thenoyltrifluoroacetonato)europium(III) between 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C₄mim][Tf₂N]) as an ionic liquid and an aqueous phase were determined by considering the extraction equilibria including anionic tetrakis(2-thenoyltrifluoroacetonato)europate(III). Specific solute-solvent interactions between the neutral Eu(III) chelate and [C₄mim][Tf₂N] molecules were revealed from the relationships between the distribution constant of the enol form of 2-thenoyltrifluoroacetone (Htta) as a proton chelate and the distribution constant (K_D,M) of the neutral Eu(III) chelate because the [C₄mim][Tf₂N] system gave the high K_D,Mβ₃ value compared with those in conventional molecular solvents such as benzene and 1,2-dichloroethane. The coordination environment of Eu³⁺ in the neutral Eu(III) chelate in [C₄mim][Tf₂N] was investigated by time-resolved laser-induced fluorescence spectroscopy and infrared absorption spectroscopy. Both methods consistently indicated that not only the Eu(III) chelate extracted but also Eu(tta)₃(H₂O)₃ synthesized as a solid crystal were almost completely dehydrated in [C₄mim][Tf₂N] saturated with water. Consequently, the higher K_D,M or extractability of the neutral Eu(III) chelate in the [C₄mim][Tf₂N] system can be ascribed to the dehydration of the Eu(III) chelate, which is caused by the specific solvation with [C₄mim][Tf₂N] molecules.     

Interaction of bathocuproine with metals (Ca, Mg, Al, Ag, and Au) studied by density functional theory

Electronic structure of the interface between a bathocuproine (BCP) molecule and metal surface was studied by density functional theory. The bond energy of BCP with metal surface increased with decreasing work function of metals, that is, Au, Ag, Al, Mg, and Ca in this order. The charge transfer also increased with decreasing metal work function. It was analyzed that the Fermi level and the lowest unoccupied molecular orbital of BCP are composed of both BCP and metal orbital component, and electron transport properties across the BCP and metal is discussed based on these analyses.     

Packing manner of graft copolymers with rigid‐rod main chains and amorphous‐crystalline diblock copolymers as side chains

We have investigated the morphology and packing manner of graft copolymers consisting of rigid‐rod‐like poly(γ‐benzyl L ‐glutamate) (PBLG) main chains and grafted diblock copolymers of amorphous poly(propylene glycol) (PPG) and crystalline poly(ethylene glycol) (PEG). The results of differential scanning calorimetry and wide‐angle X‐ray scattering measurements for graft copolymers with higher side‐chain volume fractions suggest that the rodlike main chains and crystallized PEG chains exist in segregated domains. Small‐angle X‐ray scattering profiles for these samples show diffraction intensity maxima accompanied by higher order peaks, the positions of which suggest the formation of an ordered layered structure. From these observations, the graft copolymers are estimated to form repeated layered structure consisting of segregated PBLG, PPG, and PEG layers. A proposed model for molecular packing of the graft copolymers is consistent with the experimental observation that the repeating distance for the layered structure decreases with an increase in the volume fraction of side chains. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1904–1912, 2002     

Melt rheology of hyperbranched‐polystyrene synthesized with multisite macromonomer

Melt rheological behaviors of hyperbranched‐polystyrene (PS) copolymerized by dendric macromonomer technique are presented. The time–temperature superposition principle was applicable to the hyperbranched‐PS. The branched‐PS showed slightly lower zero‐shear viscosity in comparison with linear PS regardless of a presence of a number of branches expected from the dendric macromonomer technique. Although the influence of use of multimethacryloyl macromonomer in the polymerization process was marginal for linear viscoelastic regime, nonlinear shear and uniaxial elongational flows showed distinct differences between linear and branched‐PS. The strain dependence of the damping function became weak as increase of macromonomer content. The branched‐PS exhibited the growing elongational viscosity function comparing with linear PS. This prominent effect on the elongational flow behavior can be explained by the molecular architecture of the branched‐PS. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2226–2237, 2009     

Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol

A persistent dialkylsilanone was synthesized by the dehydrobromination of a dialkylbromosilanol with tris(trimethylsilyl)silyl potassium in solution at ?80 °C: It was characterized by NMR and IR spectroscopy, and was tested in several reactions. In ²⁹Si NMR spectrum in [D₈]toluene, the signal due to the unsaturated silicon nuclei was observed at 128.7 ppm. Reactions of the dialkylsilanone with water and mesitonitrile oxide gave a silanediol and a [2+3] cycloadduct, respectively. The silanone remains intact in [D₈]toluene below ?80 °C for at least two days, while it undergoes unprecedented isomerization to give a siloxysilene by means of 1,3‐silyl migration at higher temperatures.     

Toward the racemic total synthesis of hederacines A and B: construction of an advanced tricyclic intermediate

Progress toward the total synthesis of hederacines A and B is described. Our approach involves an allylic cyanate-to-isocyanate rearrangement, eneyne ring-closing metathesis, and a transannular reaction between the C-5 amino group and the C-12 position of the perhydroazuleno[5,6-b]furanone intermediate.