No abstract

The fluorescence properties of ofloxacin (OFL), norfloxacin (NOR) and flumequine (FLU) were studied in H2O-CH3OH and H2O-CH3CN mixed solvents because these solvents were thought to behave as a biological mimetic system. The emission spectra of OFL and NOR were very sensitive to the composition of the solvents. In the Lippert-Mataga analysis of the steady-state fluorescence data of OFL and NOR, clear reverse solvatochromism was exhibited in both mixed solvents. This observation can be explained by the twisted excited-state intramolecular charge transfer, which is accelerated by water. Theoretical treatments further support these results. The radiative and nonradiative rate constants were analyzed as a function of solvent dipolarity-polarizability (pi*) and hydrogen-bond donor acidity (alpha). These results were well consistent with the suggested mechanism of the excited-state chemical process of OFL and NOR, which depended upon the solvent-solute interactions such as bulk dielectric effects and specific hydrogen-bonding interactions. However, the influence of dielectric effects was more significant. The solvent structures of H2O-CH3CN and the preferential solvation by water were also examined. The emission spectra of FLU do not exhibit any characteristic responses to the properties of the environment.

The characteristic fluorescence properties of quercetin (QCT) and apigenin (API) were studied in various CH3OH-H2O and CH3CN-H2O mixed solvents. The structure of QCT is completely planar. API is not planar at the ground state but becomes nearly planar at the excited state. If the molecules are excited to the S1 state in organic solvents, QCT exhibits no fluorescence due to excited state intramolecular proton transfer (ESIPT) between the -OH and the carbonyl oxygen, but API shows significant fluorescence because ESIPT occurs slowly. If the molecules are excited to the S2 state, both QCT and API exhibit strong S2 → So emission without any dual fluorescence. As the H2O composition of both solvents increases, the fluorescence intensity decreases rapidly due to the intermolecular hydrogen bonding interaction. The theoretical calculation further supports these results. The change in fluorescence properties as a function of the solvatochromic parameters was also studied.

The specific fluorescence properties of morin (3,2',4',5,7-pentahydroxyflavone) were studied in various CH3OH-H2O and CH3CN-H2O mixed solvents. Although the dihedral angle is large in the S0 state, morin has an almost planar molecular structure in the S1 state owing to the very low rotational energy barrier around the interring bond between B and the A, C ring. The excited state intramolecular proton transfer (ESIPT) at the S1 state cannot occur immediately after excitation, S1 → S0 fluorescence can be observed. Two conformers, Morin A and B have been known. At the CH3OH-H2O, Morin B will be the principal species but at the CH3CN-H2O, Morin A is the principal species. At the CH3OH-H2O, owing to the large Franck-Condon (FC) factor for S2 → S1 internal convernal (IC) and flexible molecular structure, only S1 → S0 fluorescence was exhibited. At the CH3CN-H2O, as the FC factor for S2 → S1 IC is small and molecular structure is rigid, S2 → S0 and S1 → S0 dual fluorescence was observed. This abnormal fluorescence property was further supported by the small pK1 value, effective delocalization of the lone pair electrons of C(2')-OH to the A, C ring, and a theoretical calculation.

Among fluoroquinolone antibiotics, ofloxacin (OFL) and norfloxacin (NOR) have piperazinyl groups but flumequine (FLU) does not have this substitutent. The emission spectra of OFL and NOR are strong, broad structureless bands with large Stokes' shifts in water but the emission intensities are very weak in organic solvents. Thus we find that these compounds exist as different chemical species in various solvents. A continuous red shift in the emission bands for OFL and NOR is observed as the water concentration within the aerosol-OT (AOT; sodium 1,4-bis[2-ethylhexyl]sulfosuccinate) micelle increases or temperature of this solution rises. From the fluorescence anisotropy measurements of OFL and NOR, we assume the intramolecular charge transfer after excitation from the nitrogen of the piperazinyl group to the keto oxygen. Theoretical calculations further support this observation. Multifrequency phase and modulation experiments and time-resolved emission spectra clearly show the occurrence of intramolecular charge transfer and the subsequent nanosecond water reorganization around OFL or NOR in the AOT micelle. Upon increasing the water concentration within the AOT micelle, the relaxation rate increases because of the large amount of free water. The emission spectra of FLU do not exhibit any significant response to the physical properties of their environment.

The spectroscopic behavior of catechin (5,7,3',4'-tetrahydroxyflavan-3-ol), has been studied in the presence and the absence of air using UV-vis absorption spectrophotometry and fluorescence spectroscopy. The UV-vis absorption spectrum of catechin shows a very sharp and strong absorption maximum peak at 275 nm in deaerated water. New absorption maximum peaks appeared in aerated water, as well as in basic aqueous solution, caused by the oxidation of catechin. The absorbances in the UV-vis absorption spectrum of catechin decreased when the solution was left in the dark for a long time. The fluorescence emission spectrum of catechin after a long time period differs markedly from that in freshly prepared solution; the fluorescence maxia shifted as time passes after adding catechin to the solutions. When the deaerated basic catechin solutions were left in the dark for a long time, their fluorescence quantum yields were found to be nearly zero. This suggests that the oxidized catechin molecules were seen to have slowly undergone successive chemical reactions in basic buffer solution.

The fluorescence properties of ofloxacin (OFL), norfloxacin (NOR) and flumequine (FLU) were studied in H2O–CH3OH and H2O–CH3CN mixed solvents because these solvents were thought to behave as a biological mimetic system. The emission spectra of OFL and NOR were very sensitive to the composition of the solvents. In the Lippert–Mataga analysis of the steady‐state fluorescence data of OFL and NOR, clear reverse solvatochromism was exhibited in both mixed solvents. This observation can be explained by the twisted excited‐state intramolecular charge transfer, which is accelerated by water. Theoretical treatments further support these results. The radiative and nonradiative rate constants were analyzed as a function of solvent dipolarity–polarizability (π*) and hydrogen‐bond donor acidity (α). These results were well consistent with the suggested mechanism of the excited‐state chemical process of OFL and NOR, which depended upon the solvent–solute interactions such as bulk dielectric effects and specific hydrogen‐bonding interactions. However, the influence of dielectric effects was more significant. The solvent structures of H2O–CH3CN and the preferential solvation by water were also examined. The emission spectra of FLU do not exhibit any characteristic responses to the properties of the environment.

A series of copolymers, poly[2-(dodecyloxy)-5-methyl-m-phenyleneethynylene] and poly[2-(dodecyloxy)-5-methyl-m-bis(ethynyl)phenyleneoligothienylene]s, in which ethynylene units are inserted into both of the meta positions of every phenylene for the elimination of the steric hindrance around the meta linkages, was synthesized by a Heck type coupling reaction. The resulting polymers were characterized by infrared and nuclear magnetic resonance spectroscopy and by elemental analysis and gel permeation chromatography. Their optical spectra show that the absorption and emission maxima regularly shift to lower energy with increasing number of the thiophene units between the consecutive m-phenylene linkages. It is confirmed that the role of the m-phenylene as an interrupting block does not come from the steric hindrance around the linkage but from the intrinsic property, e.g., the MO of the m-phenylene moiety. The quantum yields of their emissions gradually decrease with a decrease in concentration of the ethynylated m-phenylene units on the polymer backbone and the Stockes shifts increase. Both of the trends indicate that a nonradiative decay of the excited states increases with an increase in the possible configurations of thiophene rings within the repeating active block.