Relationship between reactivity and 13C chemical shifts of benzocyclobutenes

¹³C NMR spectra of benzocyclobutene derivatives have been investigated; substituent effects and the relationship between the chemical shifts and the reactivity of their cyclobutene ring are discussed.     

Photochemical Reduction of Low Concentrations of CO2 in a Porous Coordination Polymer with a Ruthenium(II)–CO Complex

Direct use of low pressures of CO₂ as a C1 source without concentration from gas mixtures is of great interest from an energy‐saving viewpoint. Porous heterogeneous catalysts containing both adsorption and catalytically active sites are promising candidates for such applications. Here, we report a porous coordination polymer (PCP)‐based catalyst, PCP‐Ru^II composite, bearing a Ru^II‐CO complex active for CO₂ reduction. The PCP‐Ru^II composite showed improved CO₂ adsorption behavior at ambient temperature. In the photochemical reduction of CO₂ the PCP‐Ru^II composite produced CO, HCOOH, and H₂. Catalytic activity was comparable with the corresponding homogeneous Ru^II catalyst and ranks among the highest of known PCP‐based catalysts. Furthermore, catalytic activity was maintained even under a 5 % CO₂/Ar gas mixture, revealing a synergistic effect between the adsorption and catalytically active sites within the PCP‐Ru^II composite.     

Identification of tetrapyrrole compounds excreted by Rhodobacter sphaeroides and sources of the methyl hydrogens of bacteriochlorophyll a biosynthesized by R. sphaeroides, based on 13C-NMR spectral analysis of coproporphyrin III tetramethyl ester

Red-fluorescent tetrapyrrole compounds excreted by Rhodobacter sphaeroides into the culture broth were concluded to be coproporphyrinogen (Copro'gen) III and uroporphyrinogen (Uro'gen) I, based on the (13)C-NMR spectral identification of coproporphyrin (Copro) III tetramethyl ester and uroproporphyrin (Uro) I octamethyl ester. The sources of the methyl hydrogens of bacteriochlorophyll a were established by analysis of the (13)C-NMR spectra of (2)H,(13)C-Copro III tetramethyl ester chemically derived from (2)H,(13)C-Copro'gen III biosynthesized through the feeding of delta-amino[2-(13)C]levulinic acid (ALA) to R. sphaeroides in medium containing 50% (2)H(2)O. We confirmed the previous finding that one of the methyl hydrogens was derived from water in the medium during decarboxylation of four acetyl side chains of Uro'gen III to generate Copro'gen III. It was further shown that the other hydrogen atoms, previously reported to be derived from methylene hydrogens at C-2 of ALA, had been exchanged with hydrogen of water in the medium in the biosynthetic pathways leading from ALA to Copro'gen III.     

Preparation of high efficiency and highly retentive monolithic silica capillary columns for reversed-phase chromatography by chemical modification by polymerization of octadecyl methacrylate

High efficiency and highly retentive monolithic silica capillary columns were obtained by polymerization of octadecyl methacrylate using alpha,alpha'-azobis-isobutyronitrile (AIBN) as a free radical initiator. Hybrid type monolithic silica columns (25 cm total length x 200 microm I.D.) prepared from a mixture of tetramethoxysilane and methyltrimethoxysilane were used as a support. The effects of the monomer and the radical initiator concentrations in the reaction mixture were examined. The performance of the columns was tested in terms of column efficiency and retention behavior by using alkylbenzenes and a few other compounds as solutes and compared with that of hybrid monolithic silica columns modified with octadecylsilyl-(N,N-diethylamino)silane (ODS-DEA). Highly retentive monolithic silica columns were obtained by polymerization at high monomer concentrations. Although a decrease in column efficiency was observed with the increase in the monomer concentration in a feed mixture, an improvement in efficiency was achieved (a plate height value lower than 10 microm) by increasing an initiator concentration without significant variations in column retention properties. Results obtained by polymerization using other monomers are also presented to demonstrate the applicability of the preparation method.     

Observation of B(0)-->D(*-)tau(+)nu(tau) decay at Belle

We report an observation of the decay B{0}-->D{*-}tau{+}nu{tau} in a data sample containing 535x10{6} BB pairs collected with the Belle detector at the KEKB asymmetric-energy e{+}e{-} collider. We find a signal with a significance of 5.2sigma and measure the branching fraction B(B{0}-->D{*-}tau{+}nu{tau})=(2.02{-0.37}{+0.40}(stat)+/-0.37(syst))%. This is the first observation of an exclusive B decay with a b-->ctaunu{tau} transition.     

Structural design of easy-axis magnetic anisotropy and determination of anisotropic parameters of Ln(III)-Cu(II) single-molecule magnets

Four dinuclear Ln^III? Cu^II complexes with Ln=Tb ( 1 ), Dy ( 2 ), Ho ( 3 ), and Er ( 4 ) were synthesized to investigate the relationship between their respective magnetic anisotropies and ligand‐field geometries. These complexes were crystallographically isostructural, and a uni‐axial ligand field was achieved by using three phenoxo oxygen groups. Complexes 1 and 2 displayed typical single‐molecule magnet (SMM) behaviors, of which the out‐of‐phase susceptibilities were observed in the temperature range of 1.8–5.0 K ( 1 ) and 1.8–20.0 K ( 2 ). The Cole–Cole plots exhibited a semicircular shape with α parameters in the range of 0.08–0.18 (2.6–4.0 K) and 0.07–0.24 (3.5–7.0 K). The energy barriers Δ/k_B were estimated from the Arrhenius plots to be 32.9(4) K for 1 and 26.0(5) K for 2 . Complex 3 displayed a slow magnetic relaxation below 3.0 K, whereas complex 4 did not show any frequency‐dependent behavior for both in‐phase and out‐of‐phase susceptibilities, which indicates that easy‐axis anisotropy was absent. The temperature dependence of the dc susceptibilities for the field‐aligned samples of 1 – 3 revealed that the χ_MT value continuously increased as the temperature was lowered, which indicates the presence of low‐lying Stark sublevels with the highest |J_z| values. In contrast, complex 4 displayed a smaller and temperature‐independent χ_MT value, which also indicates that easy‐axis anisotropy was absent. Simultaneous analyses were carried out for 1 – 3 to determine the magnetic anisotropy parameters on the basis of the Hamiltonian that considers B₂⁰, B₄⁰, and B₆⁰.     

Analysis of AlGaAs/GaAs superlattices by means of sputter-assisted AES,SEM and TEM

This paper reports the developments of evaluation methods on epitaxially grown superlattices by means of sputterassisted Auger electron spectroscopy (AES), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). AlGaAs/GaAs semiconductor superlattics were grown epitaxially by metal–organic chemical vapour deposition (MOCVD). The layer thickness of the superlattices ranged from a few to ten nanometers. Firstly, developments of Auger depth profiling were tried by using: (1) a differential pumping-type ion gun instead of a static pressure type to reduce the oxygen adsorbates on the AlGaAs layer; (2) low-energy Auger signals instead of high-energy ones to shorten the escape depth; and (3) the lowest ion etching energy of 0.2 keV instead of 1 keV to reduce the surface roughening effects. It is shown that the depth resolution of sputter-assisted AES is attainable to 1.5 nm. Secondly, high-resolution SEM can be used as an easy evaluation method by observing the cleaved surface of superlattices, since the layers can be distinguished by signal contrast. Also, TEM can be used as an evaluation method by observing the (110) cross-section thinned sample. The dark field image has a high contrast between AlGaAs and GaAs using the (002) diffraction. It is confirmed from these AES, SEM and TEM evaluations that the hetero-interface abruptness of AlGaAs/GaAs superlattices grown by MOCVD is of the order of one monoatomic layer.