Keishi Ohara

Scavenging rate constants of hydrophilic antioxidants against multiple reactive oxygen species

Scavenging rate constants of eight hydrophilic antioxidants, including caffeic acid, chlorogenic acid, genistein, glutathione, N-acetylcysteine, rutin, trolox, and uric acid against multiple ROS, namely superoxide anion, hydroxyl radical, singlet oxygen, and alkoxyl radical were determined with the electron spin resonance method. Direct flash photolysis measurement of the second-order rate constant in the reaction of alkoxyl radical plus the spin trap 5,5-dimethyl-pyrroline N-oxide made it possible to evaluate scavenging rate constants in antioxidants. The magnitudes of scavenging rate constants were notably dependent on the character of each ROS and the overall rate constants were highest in hydroxyl radical scavenging and the lowest in superoxide anion. The highest scavenging rate constant against superoxide anion was obtained by chlorogenic acid (2.9 × 105 M−1 s−1) and the lowest was by N-acetylcysteine (5.0 × 102 M−1 s−1). For singlet oxygen, the highest was by glutathione (9.4 × 108 M−1 s−1) and the lowest was by uric acid (2.3 × 106 M−1 s−1). All other numbers are listed and illustrated. Redox potential measurements of the antioxidants indicated that the antioxidants are likely to react with superoxide anion and singlet oxygen through electron transfer processes.

Hybridization of clay minerals with the floating film of a cationic Ir(III) complex at an air–water interface

The Langmuir–Blodgett films were prepared by hybridizing the clay minerals (synthetic saponite, synthetic hectorite and sodium montmorillonite) with the floating film of a cationic Ir(III) complex, [Ir(ppy)2(dc18bpy)]+ (ppy = 2-phenylpyridine; dc18bpy = 4,4′-dioctadecyl-2,2′-bipyridine). When the single-layered hybrid LB film was irradiated at 430 nm, it emitted light in the visible region, whose intensity responded reversibly to the pressure change of oxygen.

Singlet oxygen quenching by trolox C in aqueous micelle solutions

Singlet oxygen ((1)O(2)) quenching by trolox C (TC, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid), which is a water-soluble vitamin E analogue, in ethanol-water solutions and in aqueous SDS and CTAC micelles was studied by measuring the time-profiles of (1)O(2) phosphorescence at 1274 nm. The second-order rate-constant for (1)O(2) quenching by TC was determined in the ethanol-water solution to be 1.03 x 10(8), 6.22 x 10(7) and 6.23 x 10(7) M(-1) s(-1) at pH 2.0, 7.0, and 8.4, respectively. These values mean that the non-dissociated form of TC under acidic conditions has superior activity to the mono-anion form. In aqueous micelle systems, the decay rate of (1)O(2) at first decreased and then increased with increase of the concentration of TC. This behavior is explained in terms of the (1)O(2) quenching by TC in the bulk phase and in terms of shifting the environment surrounding (1)O(2) to lipophilic by dissolving TC in the hydrophobic region inside the micelle. The present investigation on (1)O(2) emission dynamics in inhomogeneous solutions made it possible to detect a little change in the solutions, which affects the environment around (1)O(2), such as the micelle formation and dissolving solute in the micelle.

Dual emitting Langmuir–Blodgett films of cationic iridium complexes and montmorillonite clay for oxygen sensing

Langmuir–Blodgett (LB) films were prepared by hybridizing a floating monolayer of an amphiphilic cationic iridium(III) complex with clay particles in a subphase. Two kinds of iridium(III) complexes were used: [Ir(dfppy)2(dc9bpy)]+ (denoted by DFPPY: dfppyH = 2-(4′,6′-difluoro-phenyl)pyridine; dc9bpy = 4,4′-dinonyl-2,2′-bipyridine) with the maximum emission wavelength (λmax) at 500 nm and [Ir(ppy)2(dc9bpy)]+ (denoted by PPY: ppyH = 2-phenylpyridine) with λmax at 550 nm. Stationary emission spectra were recorded on the following films under vacuum: {DFPPY or PPY/clay}n (n = 1–3), {DFPPY/clay/PPY/clay} and {PPY/clay/DFPPY/clay}. The intensity of emission from {PPY/clay}n or {DFPPY/clay}n increased nearly in proportion to the layer number (n). Both DFPPY and PPY emitted simultaneously from {DFPPY/clay/PPY/clay}, indicating the low contribution of energy transfer. Contrarily PPY emitted exclusively from {PPY/clay/DFPPY/clay} as a result of the efficient quenching of excited DFPPY in the lower layer by PPY in the upper layer. The introduction of oxygen gas resulted in the decrease of emission for all films. Notably {DFPPY/clay/PPY/clay} exhibited a dual emitting character under an oxygen atmosphere, that is, the broad emission maximum was observed around 530 nm at lower oxygen pressure (0 4 kPa).

Multi-emitting properties of hybrid Langmuir–Blodgett films of amphiphilic iridium complexes and the exfoliated nanosheets of saponite clay

Mono- and multi-layered films comprised of amphiphilic cationic iridium(III) complexes hybridized with the exfoliated nanosheets of synthetic saponite were prepared by the modified Langmuir–Blodgett method. Three iridium(III) complexes with different emission maxima (λmax) were used as incorporated complexes: [Ir(dfppy)2(dc9bpy)]+ (λmax = 500 nm) (dfppyH = 2-(4′,6′-difluorophenyl)pyridine; dc9bpy = 4,4′-dinonyl-2,2′-bipyridine) [Ir(ppy)2(dc9bpy)]+ (λmax = 550 nm) (ppyH = 2-phenylpyridine) and [Ir(piq)2(dc9bpy)]+ (λmax = 590 nm) (piqH = 1-phenylisoquinoline) for blue, yellow and red emissions, respectively. Six triple-layered films with different layer sequences were fabricated by layer-by-layer deposition onto quartz substrates. Stationary emission spectra were recorded on the prepared films under vacuum and at various oxygen pressures. Notably the change in the spectral shape at surrounding oxygen pressure depended remarkably on the layer sequence. Quenching by oxygen molecules was analyzed by applying a two-site model to the Stern–Volmer plots. The present nanometer-thick films were regarded as a benchmark for an optical device emitting different visible lights in response to oxygen pressure.

Correlation between Excited-State Intramolecular Proton-Transfer and Singlet-Oxygen Quenching Activities in 1-(Acylamino)anthraquinones

Excited-state intramolecular proton-transfer (ESIPT) and singlet-oxygen ((1)O2) quenching activities of intramolecularly hydrogen-bonded 1-(acylamino)anthraquinones have been studied by means of static and laser spectroscopies. The ESIPT shows a substituent effect, which can be explained in terms of the nodal-plane model. The ESIPT activity positively and linearly correlates with their (1)O2 quenching activity. The reason for this correlation can be understood by considering ESIPT-induced distortion of their ground-state potential surface and their encounter complex formation with (1)O2. Intramolecularly hydrogen-bonded hydroxyanthraquinones found in aloe also show a similar positive and linear correlation, which can be understood in the same way.

Simultaneous control of carriers and localized spins with light in organic materials.

An organic insulating crystal reversibly becomes a magnetic conductor under UV irradiation. The rapid and qualitative change in the physical properties is wavelength selective and explained by charge transfer between donor and photochemically active acceptor molecules. The photochemical redox reaction in the crystal produces a partially filled band and localized spins simultaneously.

Correlation among Singlet-Oxygen Quenching, Free-Radical Scavenging, and Excited-State Intramolecular-Proton-Transfer Activities in Hydroxyflavones, Anthocyanidins, and 1-Hydroxyanthraquinones

Singlet-oxygen (1O2) quenching, free-radical scavenging, and excited-state intramolecular proton-transfer (ESIPT) activities of hydroxyflavones, anthocyanidins, and 1-hydroxyanthraquinones were studied by means of laser, stopped-flow, and steady-state spectroscopies. In hydroxyflavones and anthocyanidins, the 1O2 quenching activity positively correlates to the free-radical scavenging activity. The reason for this correlation can be understood by considering that an early step of each reaction involves electron transfer from the unfused phenyl ring (B-ring), which is singly bonded to the bicyclic chromen or chromenylium moiety (A- and C-rings). Substitution of an electron-donating OH group at B-ring enhances the electron transfer leading to activation of the 1O2 quenching and free-radical scavenging. In 3-hydroxyflavones, the OH substitution at B-ring reduces the activity of ESIPT within C-ring, which can be explained in terms of the nodal-plane model. As a result, the 1O2 quenching and free-radical scavenging activities negatively correlate to the ESIPT activity. A catechol structure at B-ring is another factor that enhances the free-radical scavenging in hydroxyflavones. In contrast to these hydroxyflavones, 1-hydroxyanthraquinones having an electron-donating OH substituent adjacent to the O-H---O═C moiety susceptible to ESIPT do not show a simple correlation between their 1O2 quenching and ESIPT activities, because the OH substitution modulates these reactions.

Anomalous spin polarization in the photoreduction of chromone-2-carboxylic acid with alcohol induced by hydrochloric acid

Abstract The addition effect of hydrochloric acid (HCl) on the photoreduction of chromone-2-carboxylic acid (CRCA) is studied by time-resolved EPR. The EPR lines of CRCA ketyl radical show an enhanced absorption in the presence of HCl, while without HCl these show an emissive character. On the other hand, the lines of the CRCA alkyl type radical show an emissive character whether HCl is included or not. The simultaneous reactions of the closely-lying two excited triplet states (T 1 and T 2 ) of CRCA may induce the above anomalous CIDEP behavior.

Synthesis of NIR-emitting O-chelated BODIPYs fused with benzene and acenaphthylene

A series of O-chelated BODIPYs fused with aromatic rings such as benzene and acenaphthylene at β,β-positions was synthesized as a near-infrared dye. The photophysical properties were examined by UV-vis-NIR absorption and fluorescence measurement. Acenaphthylene-fused O-BODIPYs showed a intense absorption at 750–840 nm with the e of 105 M-1.cm-1. and a fluorescence emission at 770–850 nm with the high Φ value of 0.06–0.43.