Neomacrophorin I,II, and III,novel drimenyl cyclohexanes with hydroxylated butanoates from Trichoderma sp. 1212-03

Neomacrophorins I (1), II (2), and III (3) were isolated from the culture broth of Trichoderma sp. 1212-03, which was collected at Shirakami Mountainous area in Japan. Structural analyses disclosed that these resemble known macrophorins but possess axial-hydroxy group at C3 as well as different side chains at C7′. These are diastereomeric forms of macrophorins for 5′,6′-epoxide functionality. The NMR analyses suggested their relative configurational relationship between the C1–C15 drimene and C1′–C7′ epoxyquinone moieties. ECD spectral discussions verified them particularly for C5′,C6′-epoxyquinone (1), C5′,C6′-epoxysemiquinone (2 and 3), and 2″,3″-dihydroxybutanoate moiety in 1 and 2. The configuration of C3″-stereocenter of 3 was determined by chiral GC–MS after converting into methyl (S)-3″-hydroxybutanoate by basic of 3 methanolysis. Biological assays disclosed that 1 induces hyphal branching of Cochliobolus miyabeanus as well as cytotoxicity against human colorectal cancer COLO 201.     

Solvent effect on the photochemical properties of symmetrically substituted trans-3,3',5,5'-tetramethoxystilbene

Photochemical properties of trans-3,3',5,5'-tetramethoxystilbene (TMST) have been studied in various polar solvents. The Stokes shift of trans-TMST was found to be increased with increasing solvent polarity. The fluorescence lifetime of trans-TMST experienced a large solvent effect changing from 2.3 ns in cyclohexane to 16.6 ns in acetonitrile. These results indicate that the excited singlet state of trans-TMST has a charge-transfer (CT) character. On the basis of the obtained results, the interior polar environment of a water-soluble TMST dendrimer is discussed.     

Synthetic Utilization of α-Phosphonovinyl Anions

The α-phosphonovinyl anions, generated in situ from treatment of β-hetero-substituted vinyl-phosphonates 1a-c with LDA (or LTMP), were trapped with various electrophiles such as chlorotriorganosilanes, chlorotrimethylgermane, chlorotriorganotins, dimethyl disulfide, and halogen to afford the corresponding β-hetero-substituted α-functionalized vinylphosphonates 2–14 in good to excellent yields. The Friedel-Crafts reaction of α-(silyl) or α-(germyl)phosphonoketene dithioacetals 2, 9 or 4 with acid chlorides gave α-acylated phosphonoketene dithioacetals 15–19 in 53–91 % yields. The palladium-catalyzed cross-coupling reaction of β-ethoxy-α-(tributylstannyl)vinylphosphonate 13 with a variety of organic halides (R = acyl, allyl, aryl etc.) provided β-ethoxy-α-substituted vinylphosphonates 20–25 in good to moderate yields. The palladium-mediated cross-coupling reaction of α-(iodo)-vinyl-phosphonates 7, 14 with terminal acetylenes afforded α-alkynylated vinylphosphonates 26–29 in 69–83 % yields.     

Effects of amino acids on the formation of hematite particles in a forced hydrolysis reaction

The influence of amino acids on the formation of hematite particles from a forced hydrolysis reaction of acidic FeCl3 solution was examined. The spherical particles were produced on the systems with L-phenylalanine (L-Phe), L-serine (L-Ser) and L-alanine (L-Ala), though L-glutamine (L-Gln) and L-glutamic acid (L-Glu) gave ellipsoidal hematite particles. This morphological change in hematite particles is consistent with the order of stability constant of amino acids against to Fe3+ ions (K). The hematite particles produced with L-Glu, L-Gln and L-Ser were highly porous because they are formed by aggregation of cluster particles. These particles exhibited microporous behavior by outgassing the particles below 200 degrees C while they changed to mesoporous after treating above 300 degrees C by elimination of amino acids molecules remained between the cluster particles within the hematite particles. The hematite particles strongly depended on the nature of amino acids such as alternation of solution pH and adsorption affinity to beta-FeOOH and/or polynuclear primary (PN) particles. The systems on L-Ala and L-Phe, showing very rapid phase transformation from beta-FeOOH to hematite, exhibited the Ostwald ripening. A rotational particle preparation procedure suggested that the morphology of hematite particle is governed by the mode and strength of amino acid adsorption onto beta-FeOOH and/or PN particles.     

Modified Carbon Paste Electrode for Kinetic Investigation and Simultaneous Determination of Ascorbic and Uric Acids

The present work explores, for the first time, the electrocatalytic oxidation of ascorbic acid (AscH₂) and its determination in the presence of uric acid (UA) on the in situ activated 4‐nitrophthalonitrile modified carbon paste electrode. The kinetic constant κ for the catalytic reaction for the electrocatalytic oxidation of ascorbic acid, evaluated by cyclic voltammetry, chronoamperometry and RDE voltammetry provided values around 10⁶ L mol^?1 s^?1. The sensor provided a linear response range for AscH₂ and UA from 5.0 up to 120.0 μmol L^?1 with detection limits of 1.6 μmol L^?1and 1.3 μmol L^?1, respectively. The sensor was applied for the simultaneous determination of AscH₂ and UA in urine samples and the average recoveries for these samples were 99.8 (±3.1)% and 99.9 (±2.1)%, respectively .     

Synthesis and application of a peroxidase-like molecularly imprinted polymer based on hemin for selective determination of serotonin in blood serum

This work reports the preparation of a molecularly imprinted polymer (MIP) for selective catalytic detection of serotonin (5-hydroxytryptamine, 5-HT). The process is based on the synthesis of polymers with hemin introduced as the catalytic center to mimic the active site of peroxidase. The copolymer MIP, containing artificial recognition sites for 5-HT, has been prepared by bulk polymerization using methacrylic acid (MAA) and hemin as the functional monomers, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. For the determination of 5-HT, a flow injection analysis system coupled to an amperometric detector was optimized using multivariate analysis. The effects of different parameters, such as pH, buffer flow rate, buffer nature, peroxide concentration and sample volume were evaluated. After optimizing the experimental conditions, a linear response range from 1.0 up to 1000.0 μmol L⁻¹ was obtained with a sensitivity of 0.4 nA/μmol L⁻¹. The detection limit was found to be 0.30 μmol L⁻¹, while the precision values (n = 6) evaluated by relative standard deviation (R.S.D.) were, respectively, 1.3 and 1.7% for solutions of 50 and 750 μmol L⁻¹ of 5-HT. No interference was observed by structurally similar compounds (including epinephrine, dopamine and norepinephrine), thus validating the good performance of the imprinted polymer. The method was applied for the determination of 5-HT in spiked blood serum samples.     

Preparation of highly monodisperse fluorescent polymer particles by miniemulsion polymerization of styrene with a polymerizable surfactant

Miniemulsion polymerization of styrene (St) in the presence of a hydrophobe (hexadecane:HD) using a cationic polymerizable surfactant (N,N-dimethyl-N-n-dodecyl-N-2-methacryloyloxyethylammonium bromide:C(12)Br) and a cationic initiator (2,2'-azobis(2-amidinopropane) dihydrochloride:V50), called St/C(12)Br/V50 hereafter, proceeded efficiently compared with that using sodium dodecyl sulfate (SDS) and potassium persulfate (KPS), i.e., St/SDS/KPS, providing monodisperse polystyrene latex particles with a narrower particle size distribution. In St/C(12)Br/AIBN, where an oil-soluble initiator, i.e., 2,2'-azobisisobutyronitrile (AIBN), was used in place of V50, little changes in polymerization kinetics or in particle size distribution were observed, while a significant drop in polymerization rate and a broad particle size distribution were observed with St/SDS/AIBN. A polymerizable pyrene derivative (1-pyrenylmethyl methacrylate: PyMMA) was quantitatively incorporated into monodisperse latex particles in St/PyMMA/C(12)Br/V50 compared to pyrene (Py) in St/Py/C(12)Br/V50. Contrary to our expectation, however, increased excimer emission was observed with St/PyMMA/C(12)Br/V50 particles, indicating less evenly distributed pyrene chromophores in the particles. The fluorescence lifetime of pyrene chromophores in St/Py/C(12)Br/V50 particles was determined to be 286 ns, which was 17 times longer than that of pyrene in THF solution.     

Cyclopalladation of the indole ring in palladium(II) complexes of 2N1O-donor ligands and its dependence on the O-donor properties

Synthetic, structural, spectroscopic, and kinetic studies have been carried out on the Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-(N-2-pyridylmethyl-N-2-hydroxy-5-methoxybenzylamino)ethylindole (HMeO-iepp), 3-(N-2-pyridylmethyl-N-2-hydroxy-5-nitrobenzylamino)ethylindole (HNO2-iepp), and (N-2-pyridylmethyl-3-indolylethylamino)acetic acid (Hiepc) (H denotes a dissociable proton). [Pd(MeO-iepp)Cl] (2), [Pd(NO2-iepp)Cl] (3), and [Pd(iepc)Cl] (4) were prepared and revealed by X-ray analysis to have a pyridine nitrogen, an amine nitrogen, a phenolate or carboxylate oxygen, and a chloride ion in the coordination plane. UV absorption and 1H NMR spectral changes indicated that all the complexes could be converted to the indole-binding complexes where the O donor was replaced by the indole C2 atom by cyclopalladation in DMSO or DMF in the temperature range of 40-60 degrees C. Formation of the indole-binding complex species obeyed the first-order kinetics, from which the activation parameters were estimated. The formation rate was dependent on the properties of the O-donor group, a lower pKa value of its conjugate acid causing faster conversion to the indole-binding species in the order 2 (methoxyphenolate) < 3 (nitrophenolate) < 4 (carboxylate). On the other hand, the ratio of the indole-binding complex to the O-donor complex as a result of the conversion was greater for the complexes with a higher pKa value of the ligand OH group, the order being 2 > 3 > 4.     

Mechanism of the mild functionalization of arenes by diboron reagents catalyzed by iridium complexes. Intermediacy and chemistry of bipyridine-ligated iridium trisboryl complexes

This paper describes mechanistic studies on the functionalization of arenes with the diboron reagent B(2)pin(2) (bis-pinacolato diborane(4)) catalyzed by the combination of 4,4'-di-tert-butylbipyridine (dtbpy) and olefin-ligated iridium halide or olefin-ligated iridium alkoxide complexes. This work identifies the catalyst resting state as [Ir(dtbpy)(COE)(Bpin)(3)] (COE = cyclooctene, Bpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl). [Ir(dtbpy)(COE)(Bpin)(3)] was prepared by independent synthesis in high yield from [Ir(COD)(OMe)](2), dtbpy, COE, and HBpin. This complex is formed in low yield from [Ir(COD)(OMe)](2), dtbpy, COE, and B(2)pin(2). Kinetic studies show that this complex reacts with arenes after reversible dissociation of COE. An alternative mechanism in which the arene reacts with the Ir(I) complex [Ir(dtbpy)Bpin] after dissociation of COE and reductive elimination of B(2)pin(2) does not occur to a measurable extent. The reaction of [Ir(dtbpy)(COE)(Bpin)(3)] with arenes and the catalytic reaction of B(2)pin(2) with arenes catalyzed by [Ir(COD)(OMe)](2) and dtbpy occur faster with electron-poor arenes than with electron-rich arenes. However, both the stoichiometric and catalytic reactions also occur faster with the electron-rich heteroarenes thiophene and furan than with arenes, perhaps because eta(2)-heteroarene complexes are more stable than the eta(2)-arene complexes and the eta(2)-heteroarene or arene complexes are intermediates that precede oxidative addition. Kinetic studies on the catalytic reaction show that [Ir(dtbpy)(COE)(Bpin)(3)] enters the catalytic cycle by dissociation of COE, and a comparison of the kinetic isotope effects of the catalytic and stoichiometric reactions shows that the reactive intermediate [Ir(dtbpy)(Bpin)(3)] cleaves the arene C-H bond. The barriers for ligand exchange and C-H activation allow an experimental assessment of several conclusions drawn from computational work. Most generally, our results corroborate the conclusion that C-H bond cleavage is turnover-limiting, but the experimental barrier for this bond cleavage is much lower than the calculated barrier.