Synthesis and chemosensing behavior of fluorene‐based alternating copolymers containing ether side chains and Si–vinylene units in the main chain

Alternating copolymerization of 9,9‐bis(3,6,9‐trioxadecyl)‐2,7‐dibromofluorene (ODFl) or 9,9‐bis(3,6‐dioxaheptyl)‐2,7‐dibromofluorene with Si containing divinyl compounds, divinyldiphenylsilane (VPS), or divinyldimethylsilane (VMS) is investigated using the Mizoroki–Heck reaction with palladium(II) acetate. The corresponding alternating copolymer is obtained in the copolymerization of ODFl with VPS. The copolymerization of ODFl with VMS yields low molecular weight oligomers. Optical properties of the ODFl–VPS copolymer have been investigated with UV–vis absorption and photoluminescence (PL) spectroscopy. The ODFl–VPS copolymer shows absorption peaks due to π–π* transition and intramolecular charge transfer through σ–π moiety at around 330 and 360–400 nm, respectively. An emission peak is observed at 450 nm in the PL spectrum of the ODFl–VPS copolymer, and the PL quantum yield is 0.19. The PL spectroscopy of ODFl–VPS copolymer is investigated in the presence of Li⁺, Na⁺, and K⁺, and the intensity of emission peak is decreased by those metal cations, especially by Na⁺. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Spectrophotometric determination of spermine and related compounds using o-hydroxyhydroquinonephthalein and manganese(II).

A simple and highly sensitive spectrophotometric method for the determination of spermine (Spm) was established based on the ternary complex formation reaction of Spm with o-hydroxyhydroquinonephthalein (QP) as a xanthene dye and manganese(II) as a metal ion in the presence of a dispersion agent. The apparent molar absorptivity at 555 nm and the relative standard deviation of the proposed method were 1.4 x 10(5) dm(3) mol(-1) cm(-1) and 0.50% (n = 10), respectively. In the method for flow-injection analysis (FIA), which employs a single-channel flow manifold system, a good linear relationship was observed over the 2 - 20 pg microl(-1) range of Spm by direct injection.     

The thermolysin-catalyzed condensation reactions of n-substituted aspartic and glutamic acids with phenylalanine alkyl esters

The title reactions occur with concurrent peptide synthesis and optical resolutions of racemic substrates. With this method, Z-L-Asp-L-Phe-OME, the precursor to the synthetic sweetner, could be obtained in high yield.     

Spectrophotometric determination of glucosamine and its analogous amino sugars with o-hydroxyhydroquinonephthalein and palladium(II).

A simple and highly sensitive spectrophotometric method for the determination of glucosamine and its analogous amino sugars was established based on fading of the palladium(II)-o-hydroxyhydroquinonephthalein-hexadecyltrimethylammonium complex. In the determination of glucosamine, Beer's law is obeyed in the range of 0.02 - 0.18 microg ml(-1), with an effective molar absorptivity at 630 nm and the relative standard deviation being 8.4 x 10(5) dm3 mol(-1) cm(-1) and 1.08% (n = 10). This method is about 70-times more sensitive than the Elson-Morgan method. The method was successfully applied to the assay of glucosamine in actual samples.     

Facile access to (Z)-alkene-containing diketopiperazine mimetics utilizing organocopper-mediated anti-SN2′ reactions

Regio- and stereoselective anti-S_N2′ alkylation of γ-phosphoryloxy-α,β-unsaturated-δ-lactams with organocopper reagents allowing the preparation of N-alkylated-α,δ-substituted-β,γ-unsaturated-δ-lactams as highly functionalized diketopiperazine mimetics is presented.     

Active polycondensation of diethyl 2,3,4,5-tetrahydroxyadipate with diamines

Polycondensation of diethyl 2,3,4,5-tetrahydroxyadipate with various diamines was carried out in solutions under mild conditions. The polycondensation reaction occurred rapidly even at room temperature in polar solvents such as alcohols, and in aqueous solution a cyclic product was obtained instead of linear polymers although the reaction with diamines was completed within several minutes. Polymers obtained from diethyl 2,3,4,5-tetrahydroxyadipate were a linear polyamide having pendant hydroxyl groups, which decomposed on heating at around 200°C. A solid-phase polycondensation of the precursor polyamide yielded a high molecular weight polyamide.     

A general and highly efficient asymmetric synthesis of optically active anthracyclinones

The title asymmetric synthesis has been developed by featuring bromolactonization of (−)-acetals, derived from 2-acetyl-3,4-dihydronaphthacene-6,11-diones and (2R,3R)-(+)-N,N,N′,N′-tetraalkyltartaric acid diamides, as a key diastereoselective reaction. The produced bromolactone mixtures could be readily converted to the highly optically active key synthetic intermediates of 4-demethoxy- and 11-deoxy-4-demethoxyanthracyclinones.