Carbonylative Polymerization of Oxetanes Initiated by Acetyl Cobalt Complexes

Four acetyl cobalt complexes, [AcCo(CO)₃P(p‐tolyl)₃] ( 1 ; p‐tolyl=4‐Me‐C₆H₄), [AcCo(CO)₃P(OPh)₃] ( 2 ), [AcCo(CO)₃P(NMe₂)₃] ( 3 ), and [AcCo(CO)₂(dppp)] ( 4 ; dppp=1,3‐bis(diphenylphosphanyl)propane), were synthesized, characterized, and examined as catalysts for the unprecedented carbonylative polymerization of oxetanes. Copolymers containing ester (4‐hydroxyalkanoate) and/or ether units were obtained with complexes 1 and 2 , but not with complexes 3 and 4 either in the presence or absence of additional phosphorus ligands. The ester unit/ether unit ratio varied in the range 21:79–63:37, and the highest ester/ether ratio of 63:37 was achieved by using complex 1 in the presence of a further 5 equivalents of P(OPh)₃. Although direct carbonylative polymerization is possible, preformation and ring opening of the γ‐lactone is also suggested as an alternative pathway.     

Effects of preparation conditions on the synthesis of nano-sized Ag metal particles by the wet-process using 3-mercapto-propionic acid

By the addition of sodium borohydride as a reducing agent into an aqueous solution of AgNO₃ mixed with 3-mercapto-propionic acid as a protective agent, nano-sized Ag metal particles could be synthesized. Using this advanced wet-process the synthesis of an aqueous Ag colloid system with a high density became possible, because the surfaces of the synthesized nano-sized Ag metal particles were covered and protected by the adsorbed 3-mercapto-propionic acid. By changing the mix ratio of AgNO₃ to 3-mercapto-propionic acid, the particle size of synthesized nano-sized Ag metal particles could be controlled; a higher 3-mercapto-propionic acid/AgNO₃ ratio was preferable in the synthesis of smaller Ag metal particles. From the relationship between the Ag metal particle size and the residual S content adsorbed on the metal particles, the mechanism of dispersion of Ag particles can be proposed as that the 3-mercapto-propionic acid having a thiol group adsorbs on Ag particles by forming Ag-S bonds as a protective agent.     

Organic-inorganic hybrid polymer-encapsulated magnetic nanobead catalysts

A new strategy for the encapsulation of magnetic nanobeads was developed by using the in situ self-assembly of an organic-inorganic hybrid polymer. The hybrid polymer of {[Cu(bpy)(BF(4))(2)(H(2)O)(2)](bpy)}(n) (bpy=4,4'-bipyridine) was constructed on the surface of amino-functionalized magnetic beads and the resulting hybrid-polymer-encapsulated beads were utilized as catalysts for the oxidation of silyl enolates to provide the corresponding alpha-hydroxy carbonyl compounds in high yield. After the completion of the reaction, the catalyst was readily recovered by magnetic separation and the recovered catalyst could be reused several times. Because the current method did not require complicated procedures for incorporating the catalyst onto the magnetic beads, the preparation and the application of various other types of organic-inorganic hybrid-polymer-coated magnetic beads could be possible.     

Preconcentration and decomposition of perfluorinated carboxylic acids on an activated charcoal cartridge with sodium biphenyl reagent and its determination at microg L(-1) level on the basis of flow injection-fluorimetric detection of fluoride ion

Perfluorinated surfactants of heptafluorobutylate and pentadecafluorooctanoate ions were adsorbed on an activated charcoal cartridge and decomposed with sodium biphenyl (SBP) reagent to form inorganic fluoride ion. The fluoride ion thus formed was determined by flow injection analysis (FIA) using quercetin-Zr complex as a fluorimetric reagent, where λ_ex and λ_em were 422 and 491 nm, respectively. The limit of detection for fluoride ion by the FIA system was developed to 1.1 × 10⁻⁶ M (signal to noise ratio of three), when 50% (v/v) tetrahydrofuran (THF) was used as a dissolving solvent for quercetin. The perfluorinated surfactants in the sample solution were quantitatively adsorbed on the cartridge containing 100 mg of activated charcoal and were decomposed with 0.5 mL of sodium biphenyl reagent after drying thoroughly by flowing through dry nitrogen gas. The fluoride ion formed was recovered with 3 mL of purified water as an eluent, and it was determined by the fluorimetric flow injection system. The blank fluorescence signal accompanied during the adsorption/decomposition on the cartridge was reduced by washing the activated charcoal with acetone. The blank signal was also observed from dimethoxyethane, which was used in sodium biphenyl reagent. When 600 mL sample solution was used and 200 times enrichment was applied, the heptafluorobutylate and pentadecafluorooctanoate ions at the concentrations of 2.1 μg L⁻¹ were quantitatively recovered as fluoride ion, and the limit of detections for the perfluorinated surfactants were 0.3 and 0.3 μg L⁻¹ for the two perfluorinated surfactants, respectively (3 sigma of the blank signal).     

Synthesis of photochromic diarylethene polymers for a write-by-light/erase-by-heat recording system

A functionalized styrene monomer (1a) having a photochromic diarylethene chromophore with functional properties of photocoloration, photostability of the colored state, and thermal erasion by heating was synthesized, and the polymer and copolymers of 1a were prepared by radical polymerization and copolymerization. Their polymers exhibited excellent photocoloration and rapid thermal bleaching above 150 °C in solution and in the solid state as well as the performance of the monomeric diarylethene chromophore. In addition, the colored state has a high photostability under visible room light. The diarylethene homopolymer had a glass transition temperature (T_g) as high as polystyrene. The copolymer of 1a with N-1-adamantylmaleimide exhibited extremely high T_g above 200 °C with keeping the photofunctional performance. Such photochromic polymer and copolymers with high T_g can be potentially applied to rewritable display materials and image recordings by a write-by-light/erase-by-heat system.     

Isoquinoline-based TQEN family as TPEN-derived fluorescent zinc sensors

The hexadentate nitrogen ligands 1-isoTQEN ( N,N,N',N'-tetrakis(1-isoquinolylmethyl)ethylenediamine) and 3-isoTQEN ( N,N,N',N'-tetrakis(3-isoquinolylmethyl)ethylenediamine) have been prepared. The structures of these ligands are based on that of TPEN ( N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine). The introduction of a benzene ring into TPEN affords fluorescence ability upon zinc-ion binding. Compared to the quinoline isomer TQEN, isoquinoline derivatives 1-isoTQEN and 3-isoTQEN exhibit a lower-energy shift in the excitation and emission wavelengths and an enhanced fluorescence intensity, probably because of the energy-transfer mechanism between adjacent isoquinoline rings. Importantly, an increase in the Zn (2+)/Cd (2+) discriminating ability and a reduction in the background fluorescence induced by pH were also achieved for isoquinoline derivatives. The zinc-ion-induced fluorescence of these isoTQENs was not quenched by an addition of TPEN, which demonstrates the significantly high zinc-ion binding ability of these isoTQEN ligands.     

High performance n-type organic field-effect transistors based on pi-electronic systems with trifluoromethylphenyl groups

Novel pi-electron systems with trifluoromethylphenyl groups and/or a thiazolothiazole unit were developed as n-type semiconductors for OFETs. They showed excellent n-type performances with high electron mobilities. The trifluoromethylphenyl group was found to be very effective in inducing n-type behavior. The thiazolothiazole unit was favorable for forming stacking structures leading to efficient intermolecular pi-pi interactions.     

A new family of glucose-1-phosphate/glucosamine-1-phosphate nucleotidylyltransferase in the biosynthetic pathways for antibiotics

Aminoglycoside antibiotics are composed of aminosugars and a unique aminocyclitol aglycon including 2-deoxystreptamine (DOS), streptidine, actinamine, etc., and nucleotidylyltransferases, sugar modifying enzymes, and glycosyltransferases appear to be essential for their biosynthesis. However, the genes encoding those enzymes were unable to be identified by a standard homology search in the butirosin biosynthetic btr gene cluster, except that the btrM gene appeared to be a glycosyltransfease. Disruption studies of the btrD gene indicated that BtrD was involved in the supply of a glycosyl donor immediately prior to the glycosylation of DOS giving paromamine. As anticipated, BtrD expressed in Escherichia coli was able to catalyze UDP-D-glucosamine formation from D-glucosamine-1-phosphate and UTP. Both dTTP and UTP were good NTP substrates, and D-glucose-1-phosphate and D-glucosamine-1-phosphate were good sugar phosphates for the enzyme reaction. This finding is the first to identify an enzyme which activates a sugar donor in the DOS-containing antibiotics. Interestingly, BtrD homologues have been reported as functionally unknown open reading frames (ORFs) in the biosynthetic gene clusters for several antibiotics including teicoplanin, balhimycin, chloroeremomycin, and mitomycin C. It appears therefore that gene clusters for antibiotic biosynthesis provide their own nucleotidylyltransferases, and the BtrD homologues are among the secondary metabolism specific enzymes.     

Grand canonical monte carlo simulation study of methane adsorption at an open graphite surface and in slit-like carbon pores at 273 K

Grand canonical Monte Carlo (GCMC) simulation was used for the systematic investigation of the supercritical methane adsorption at 273 K on an open graphite surface and in slit-like micropores of different sizes. For both considered adsorption systems the calculated excess adsorption isotherms exhibit a maximum. The effect of the pore size on the maximum surface excess and isosteric enthalpy of adsorption for methane storage at 273 K is discussed. The microscopic detailed picture of methane densification near the homogeneous graphite wall and in slit-like pores at 273 K is presented with selected local density profiles and snapshots. Finally, the reliable pore size distributions, obtained in the range of the microporosity, for two pitch-based microporous activated carbon fibers are calculated from the local excess adsorption isotherms obtained via the GCMC simulation. The current systematic study of supercritical methane adsorption both on an open graphite surface and in slit-like micropores performed by the GCMC summarizes recent investigations performed at slightly different temperatures and usually a lower pressure range by advanced methods based on the statistical thermodynamics.     

Chiral amino alcohol-mediated asymmetric conjugate addition of arylalkynes to nitroolefins

[reaction: see text] The asymmetric reaction of nitroolefins with arylalkynes was mediated by dimethylzinc (or diethylzinc) and (1R,2R)-2-(dimethylamino)-1,2-diphenylethanol in toluene to provide the corresponding conjugate alkynylation products with high enantiomeric excess of up to 99% in good yields. The presence of 0.03 equiv of galvinoxyl improved the reaction yield.