Fabrication of column chip made of PMMA for μFIA

We proposed a low cost fabrication procedure of a poly(methylmethacrylate) (PMMA) column chip. 3D microchannel structure consisting of four columns in a chip for a mother die was fabricated using dry film photoresist and photolithography technique. Electroforming was applied to the mother die in order to obtain a Ni mold, then, the pattern was transferred to PMMA by hot press. The column had a dam structure to keep enzyme-immobilized microbeads with volume of 640 nL. The column chip was applied for a micro flow injection analysis (μFIA) system. For a demonstration, we measured lactose using two columns in series. One column was set on upper stream and filled with chitosan microbeads immobilized with β-galactosidase, the other was on downstream and filled with the beads immobilized with glucose oxidase. The lactose detection was accomplished less than 90s after the sample injection. The biosensing system also showed a high performance for lactose detection in wide range of 1 μM to 1mM. These results show that the column chip and our microfluidic biosensing system have the potential to assist minuaturization with small sample volume and short determination time for a sequential analysis.     

Sesquarterpenes (C35 terpenes) biosynthesized via the cyclization of a linear C35 isoprenoid by a tetraprenyl-β-curcumene synthase and a tetraprenyl-β-curcumene cyclase: identification of a new terpene cyclase

In this study, mono- and pentacyclic C(35) terpenes from Bacillus subtilis were biosynthesized via the cyclization of C(35) isoprenoid using purified enzymes, including the first identified new terpene cyclase that shows no sequence homology to any of the known terpene cyclases. On the basis of these findings, we propose that these C(35) terpenes should be called the new family of "sesquarterpenes."     

Reactivity of copper(II)-alkylperoxo complexes

Copper(II) complexes 1a and 1b, supported by tridentate ligand bpa [bis(2-pyridylmethyl)amine] and tetradentate ligand tpa [tris(2-pyridylmethyl)amine], respectively, react with cumene hydroperoxide (CmOOH) in the presence of triethylamine in CH(3)CN to provide the corresponding copper(II) cumylperoxo complexes 2a and 2b, the formation of which has been confirmed by resonance Raman and ESI-MS analyses using (18)O-labeled CmOOH. UV-vis and ESR spectra as well as DFT calculations indicate that 2a has a 5-coordinate square-pyramidal structure involving CmOO(-) at an equatorial position and one solvent molecule at an axial position at low temperature (-90 °C), whereas a 4-coordinate square-planar structure that has lost the axial solvent ligand is predominant at higher temperatures (above 0 °C). Complex 2b, on the other hand, has a typical trigonal bipyramidal structure with the tripodal tetradentate tpa ligand, where the cumylperoxo ligand occupies an axial position. Both cumylperoxo copper(II) complexes 2a and 2b are fairly stable at ambient temperature, but decompose at a higher temperature (60 °C) in CH(3)CN. Detailed product analyses and DFT studies indicate that the self-decomposition involves O-O bond homolytic cleavage of the peroxo moiety; concomitant hydrogen-atom abstraction from the solvent is partially involved. In the presence of 1,4-cyclohexadiene (CHD), the cumylperoxo complexes react smoothly at 30 °C to give benzene as one product. Detailed product analyses and DFT studies indicate that reaction with CHD involves concerted O-O bond homolytic cleavage and hydrogen-atom abstraction from the substrate, with the oxygen atom directly bonded to the copper(II) ion (proximal oxygen) involved in the C-H bond activation step.     

Dynamic behaviour attributed to chiral carbohydrate substituents of N-heterocyclic carbene ligands in square planar nickel complexes

Nickel complexes having acetylated glucopyranosyl group incorporated N-heterocyclic carbene (NHC) ligands with methyl or benzyl groups as an N-substituent exhibit two kinds of dynamic behaviours in solution (1)H NMR spectroscopy. One of the dynamic behaviours is attributed to the anti- and syn-rotamers, which occur by the rotation of the unsymmetrical NHC ligands around the axes of the Ni-C bonds. The other is attributed to the diastereomers of the syn-rotamers, which occur by opposite rotation of the imidazolylidene rings and the chiral carbohydrate group incorporated into the NHC ligands. Crystallographic analysis of the nickel complex having the NHC ligand with acetylated glucopyranosyl and benzyl groups as N-substituents showed CH-π interaction between the glucopyranosyl unit of each NHC ligand and the phenyl ring of the other NHC ligand in the complex in the solid state.     

Iridium-catalyzed direct tetraborylation of perylene bisimides

Treatment of perylene bisimides (PBIs) with bis(pinacolato)diboron in the presence of an iridium catalyst provides tetraborylated PBIs at 2,5,8,11-positions in good yields with perfect regioselectivity. The planar structure of the perylene core has been confirmed by X-ray diffraction analysis. Oxidation of tetraborylated PBI with hydroxylamine hydrochloride affords tetrahydroxy PBI in excellent yield, which exhibits a substantially blue-shifted absorption spectrum due to an intramolecular hydrogenbonding interaction between carbonyl and hydroxy groups.     

Functionalization of a simple dithienylethene via palladium-catalyzed regioselective direct arylation

The direct arylation on the thienyl groups of a diarylethene with various aryl iodides efficiently provided arylated dithienylethenes under palladium catalysis. Unsymmetrically substituted dithienylethenes were also synthesized by this protocol. This procedure allows a rapid access to a variety of aryl-substituted dithienylethenes from a single substrate of a simple dithienylethene.     

Eu(3+)-mediated polymerization of benzenetetracarboxylic acid studied by spectroscopy, temperature-dependent calorimetry, and density functional theory

Thermodynamic parameters for the complexation of Eu(3+) with pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid, BTC) as a model system for polymerizable metal-complexing humic acids were determined using temperature-dependent time-resolved laser-induced fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC). At low metal and ligand concentrations (<50 μM Eu(3+), <1 mM BTC), a 1:1 monomeric Eu-BTC complex was identified in the range of 25-60 °C. At elevated concentrations (>500 μM Eu(3+) and BTC) a temperature-dependent polymerization was observed, where BTC monomers are linked via coordinating shared Eu(3+) ions. The two methods lead to comparable thermodynamic data (ΔH = 18.5 ± 1.5/16.5 ± 0.1 kJ mol(-1); ΔS = 152 ± 5/130 ± 5 J mol(-1) K(-1); TRLFS/ITC) in the absence of polymerization. With the onset of polymerization, TRLFS reveals the water coordination number of the lanthanide, whereas calorimetry is superior in determining the thermodynamic data in this regime. Evaluating the heat uptake kinetics, the monomer and polymer formation steps could be separated by "time-resolved" ITC, revealing almost identical binding enthalpies for the sequential reactions. Structural features of the complexes were studied by Fourier-transform infrared (FTIR) spectroscopy in combination with density functional theory (DFT) calculations showing predominantly chelating coordination with two carboxylate groups in the monomeric complex and monodentate binding of a single carboxylate group in the polymeric complex of the polycarboxylate with Eu(3+). The data show that pyromellitic acid is a suitable model for the study of metal-mediated polymerization as a crucial factor in determining the effect of humic acids on the mobility of heavy metals in the environment.     

Alkynylation of benzotriazole with silylethynyliodonium triflates. Regioselective synthesis of 2-ethynyl-2H-benzotriazole derivatives

Phenyl(trimethylsilylethynyl)iodonium and tert-butyldimethylsilylethynyl(phenyl)iodonium triflates were applied to alkynylation of benzotriazole. Treatment of the silylethynyliodonium triflates with the potassium salt of benzotriazole ion in (t)BuOH and CH(2)Cl(2) gave 2-(trimethylsilylethynyl)-2H-1,2,3-benzotriazole and 2-(tert-butyldimethylsilylethynyl)-2H-1,2,3-benzotriazole in 74% and 76% yields, respectively. The regioisomers, 1-silylethynyl-1H-1,2,3-benzotriazole derivatives, were minor. In both cases of the silyl-substitued ethynyliodonium salts, novel regioselective alkynylation of benzotriazole at the 2 position was observed.     

Two-photon absorption properties of two-dimensional π-conjugated chromophores: combined experimental and theoretical study

The two-photon absorption (TPA) properties of four TPEB [tetrakis(phenylethynyl)benzene] derivatives (TD, para, ortho, and meta) with different donor/acceptor substitution patterns have been investigated experimentally by the femtosecond open-aperture Z-scan method and theoretically by the time-dependent density-functional theory (TDDFT) method. The four compounds show relatively large TPA cross sections, and the all-donor substituted species (TD) displays the largest TPA cross-section σ(2) = 520 ± 30 GM. On the basis of the calculated electronic structure, TD shows no TPA band in the lower energy region of the spectrum because the transition density is concentrated on particular transitions due to the high symmetry of the molecular structure. The centrosymmetric donor-acceptor TPEB para shows excitations resulting from transitions centered on D-π-D and A-π-A moieties, as well as transition between the D-π-D and A-π-A moieties; this accounts for the broad nature of the TPA bands for this compound. Calculations for two noncentrosymmetric TPEBs (ortho and meta) reveal that the diminished TPA intensities of higher-energy bands result from destructive interference between the dipolar and three-state terms. The molecular orbitals (MOs) of the TPEBs are derivable with linear combinations of the MOs of the two crossing BPEB [bis(phenylethynyl)benzene] derivatives. Overall, the characteristics of the experimental spectra are well-described based on the theoretical analysis.     

Ligand field modification around Cu2+ ions in sodium borate glass by codoping

Understanding the effect of codoping on the properties of photonic glasses is important for improving their properties. The effect of codoping on the ligand field around Cu(2+) ions in a sodium borate glass is examined using optical absorption spectroscopy, continuous-wave electron paramagnetic resonance, and three-pulse electron-spin-echo envelope-modulation. Glass with a composition of 0.1CuO·5Na(2)O·95B(2)O(3) was codoped with 2 mol % of Al(3+), Si(4+), P(5+), Zr(4+), or La(3+) oxide. Three codoping effects are found: strengthening the ligand field, as observed for Zr-codoping, which induces a large blue shift of the optical absorption peak of Cu(2+); weakening the ligand field, as observed for P-codoping, which causes a red shift of the Cu(2+) absorption peak; and almost no effect on the ligand field, which is observed for Al-, Si-, and La-codoping. Coordination structure models based on local charge neutrality are proposed for the codoped glasses. The mechanism of the codoping effect is revealed by elucidating the local structure around Cu(2+).