IS SINGLET OXYGEN FORMATION DOMINANT IN TRIPLET QUENCHING PROCESSES? MEASUREMENT OF THE QUANTUM YIELD OF SINGLET OXYGEN FORMATION BY THE TIME-RESOLVED THERMAL LENS METHOD

The quantum yields of singlet oxygen formation (Ø_Δ) by the quenching of triplet states of organic sensitizers are measured at various concentrations of the sensitizers by using the time-resolved thermal lens method. Above a certain concentration, Ø_Δ is independent of the sensitizer concentration. Below the threshold, Ø_Δ gradually decreases as the concentration of the sensitizer decreases. The extrapolation of Ø_Δ to zero concentration indicates that singlet oxygen formation is not necessarily dominant in the quenching process even for the ³ππ* state in benzene.     

Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand

Heteroleptic zinc(II) complexes synthesized using achiral dipyrrinato and chiral bis(oxazoline) ligands show bright fluorescence with quantum efficiencies of up to 0.70. The fluorescence originates from the ¹π–π^* photoexcited state localized exclusively on the dipyrrinato ligand. Furthermore, the luminescence is circularly polarized despite the achirality of the dipyrrinato ligand. Single‐crystal X‐ray structure analysis discloses that the chiral bis(oxazoline) ligand undergoes intramolecular π–π stacking with the dipyrrinato ligand, inducing axial chirality in the dipyrrinato moiety.     

Consecutive determination of rutin and quercetin by spectrophotometric measurements

The consecutive determination of rutin and quercetin without any pretreatment for separation was examined in methanol solutions by a conventional and a two-wavelength spectrophotometry. Based the tendency of quercetin to form more stable metal complexes compared to rutin, quercetin can be determined through the tin(II) complex formation without interference from rutin. The method was applied to the determination of quercetin in the concentration range of 3.0 × 10^?6 to 2.0 × 10^?5M.Quercetin is apt to be oxidized by oxygen rather than rutin, especially in the presence of copper(II), whereas rutin is not decomposed under such a condition. After removal of quercetin through copper(II)-catalyzed oxidation, rutin ranging in concentration from 2.0 × 10^?6 to 2.0 × 10^?M was determined by the absorbance measurement of rutin-copper(II) complex in slightly alkaline methanol media.Both rutin and quercetin were determined directly by two-wavelength spectrophotometry, without adding any complex forming metals; the lower limit of detection was about 1.0 × 10^?5M. The method was extended to the determination of a smaller amounts of rutin and quercetin using the absorption peaks of their zirconium(IV) complexes, and the determination of both components in the range of 5.0 × 10^?6 to 3.0 × 10^?5M was made with a relative error of within ±4%.     

Radiation Chemical Studies of Protein Reactions: Effect of Irradiation Atmosphere and Temperature on Optical Rotation

When protein in various atmospheres such as N₂, O₂, H₂, CO₂, and NH₃ is irradiated by γ rays form a ⁶⁰Co source, the changes in the internal relationships of the atoms in the protein molecule vary with the gases composing the irradiation atmosphere. An empirical equation for the optical rotation was obtained. Protein irradiated by γ rays showed the effect of temperature by changes in the internal relationships of the atoms in the protein molecule. An empirical equation for the optical rotation was obtained. The behavior of optical rotation shows a similar dependence on irradiation atmosphere and temperature as shown in earlier viscosity experiments.     

Photoluminescent color tuning in fluorene derivative/copolymer composite films based on H-bonds

Reversible addition-fragmentation chain transfer (RAFT) polymerization is used to synthesize diblock and random copolymers of poly[(2-trifluoroethyl methacrylate)-co-(methacrylic acid)]. Copolymer films doped with fluorene derivatives comprised of pyridine groups exhibit reversible photoluminescent (PL) color tuning by adjusting the location of fluorene derivatives in H-bonds or non-H-bonds environments. The composite films exhibit green and blue photoluminescence with and without effective H-bonding between the pyridine ring in the fluorene derivative and the carboxylic acid side group, respectively. At elevated temperatures, the H-bonded structure dissociates and the fluorene derivative migrates to the hydrophobic block in the diblock polymer, and they do not form H-bonds upon cooling. However, re-formation of H-bonds also occurs upon cooling random copolymers. Moreover, adjusting the annealing temperature and the solvent annealing reversibly tunes the PL color in the diblock copolymer composite films.     

Mechanochromic Luminescence Characteristics of Pyridine‐Terminated Chromophores in the Solid State and in a Poly(vinyl alcohol) Matrix

Mechanoresponsive luminophores containing different substituted pyridine rings at the molecular terminus are synthesized and their photoluminescence properties are investigated. The solid chromophore with a 4‐substituted pyridine ring exhibits a reversible photoluminescent color change, while the 2‐substituted chromophore shows only a small change in luminescence, and the 3‐substituted chromophore displays an irreversible photoluminescent color change with mechanical grinding. A change of the sample color in response to mechanical grinding is also achieved for a dye‐dispersed poly(vinyl alcohol) film. Furthermore, a simultaneous acid and mechanoresponsive photoemission color change is achieved in the dye‐dispersed film.     

Radiation Chemical Studies of Protein Reactions: Effect of Alkaline-Earth Metals on the Breaking of Secondary Bonding in Protein

The radiation protective effect of the breaking of secondary bonding in protein was examined with alkaline-earth metals such as magnesium chloride, calcium chloride, strontium nitrate, and barium chloride, and alkaline metals and heavy metals such as lithium chloride, sodium chloride, potasium nitrate, ferrous chloride, ferric sulfate, nickel sulfate, aluminum nitrate, and zinc sulfate. An empirical equation for the viscosity change was obtained.     

Synthesis of Polybenzoacenes: Annulative Dimerization of Phenylene Triflate by Twofold C−H Activation

Polycyclic aromatic hydrocarbons (PAHs) represent an emerging class of π‐conjugated molecules in the area of optoelectronic devices and materials. Unprecedented synthetic routes to various PAHs from simple phenol derivatives by a palladium‐catalyzed annulative dimerization of phenylene triflate through twofold inter‐ and intramolecular C?H activation have been established. The initially formed partially fused PAHs can be smoothly transformed into a variety of fully fused PAHs by the Scholl reaction. Furthermore, the reactions of phenanthrene‐substituted aryl triflates proceeded regioselectively. The findings inspired the development of a rapid and efficient synthesis of polybenzoacene derivatives. This study not only allows transformation of phenyl triflates, but also discloses a new retrosynthetic strategy towards PAHs, especially polybenzoacenes.