Laboratory simulations have been carried out to model chemical reactions that possibly take place in the stratosphere of Saturn's moon, Titan. The aerosol products of these reactions (tholin samples) have been systematically analyzed by mass spectrometry using electrospray ionization (ESI) and laser desorption (LD). A wide variety of ions with a general formula C x H y N z detected by ultrahigh resolution and accurate mass measurements in a Fourier transform/ion cyclotron resonance (FT-ICR) cell reflect the complexity of these polymeric products, both in chemical compositions and isomeric distributions. As a common feature, however, tandem mass spectral (MS/MS) data and H/D exchange products in the solution phase support the presence of amino and nitrile functionalities in these (highly unsaturated) "tholin" compounds. The present work demonstrates that ESI-MS coupled with FT-ICR is a suitable and "intact" method to analyze tholin components formed under anaerobic conditions; only species with C x H y N z are detected for freshly prepared and harvested samples. However, when intentionally exposed to water, oxygen-containing compounds are unambiguously detected. (J Am Soc Mass Spectrom 2005, 16, 850 -859)

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 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.

The spectroscopic properties of enoxacin (ENO), oxolinic acid (OXO) and nalidixic acid (NAL) were studied in various H2O-CH3OH and H2O-CH3CN mixed solvents because these solvents were thought to behave as a biological mimetic system. ENO has piperazinyl group, but OXO and NAL do not have this substituent. The fluorescence emission spectra of ENO were very sensitive to the composition of the solvents. In the Lippert-Mataga analysis of the steady-state fluorescence data, clear reverse solvatochromism was exhibited for ENO in both mixed solvents. This observation can be explained using the excited state twisted intramolecular charge transfer (TICT) from the nitrogen of the piperazinyl group to the keto oxygen. Theoretical calculations further support this observation. The nonradiative and radiative rate constants of these molecules were analyzed as a function of dipolarity-polarizability (pi*) and hydrogen bond donor acidity (alpha) of the mixed solvents. These results for ENO were consistent with the suggested mechanism of the TICT very well. The influence of bulk dielectric effect was more significant relative to the specific hydrogen bonding interactions. The emission spectra of OXO and NAL do not exhibit any characteristic responses to the properties of the solvent.

The spectroscopic properties of enoxacin (ENO), oxolinic acid (OXO) and nalidixic acid (NAL) were studied in various H2O-CH3OH and H2O-CH3CN mixed solvents because these solvents were thought to behave as a biological mimetic system. ENO has piperazinyl group, but OXO and NAL do not have this substituent. The fluorescence emission spectra of ENO were very sensitive to the composition of the solvents. In the Lippert-Mataga analysis of the steady-state fluorescence data, clear reverse solvatochromism was exhibited for ENO in both mixed solvents. This observation can be explained using the excited state twisted intramolecular charge transfer (TICT) from the nitrogen of the piperazinyl group to the keto oxygen. Theoretical calculations further support this observation. The nonradiative and radiative rate constants of these molecules were analyzed as a function of dipolarity-polarizability (pi*) and hydrogen bond donor acidity (alpha) of the mixed solvents. These results for ENO were consistent with the suggested mechanism of the TICT very well. The influence of bulk dielectric effect was more significant relative to the specific hydrogen bonding interactions. The emission spectra of OXO and NAL do not exhibit any characteristic responses to the properties of the solvent.