The static and dynamic fluorescence behavior of a series of hexaalkyl benzenehexacarboxylates (R(6)BHC; R = methyl (Me), tert-butyl (tBu), (-)-menthyl (Men), (-)-bornyl (Bor), (-)-1-methylheptyl (MHp), neopentyl (neoPn), and 2-adamantyl (Ad)) was studied by steady-state and time-resolved fluorescence spectroscopy. Dual fluorescence from both the partially relaxed metastable Franck-Condon-like (FC') and the fully relaxed (RX) state was observed for tBu(6)BHC, Men(6)BHC, Bor(6)BHC, MHp(6)BHC, neoPn(6)BHC, and Ad(6)BHC, whereas only single fluorescence from the RX state was observed for Me(6)BHC. Picosecond time-resolved fluorescence spectroscopic measurements clearly demonstrated that the initially formed Franck-Condon (FC) state sequentially converts to the FC' and then to RX state, with the relaxation hindered to such an extent that it shows variation with the steric bulk of the R groups. Thus, the fluorescence lifetimes (tau's) of FC' and RX are critically dependent on the bulkiness of the R groups, varying from 17 to 130 ps and from 0.6 to 1.1 ns, respectively. The relative intensity of FC' and RX fluorescence (I(RX)/I(FC)(')) was found to be dependent on the excitation wavelength, suggesting that the conformational relaxation from the FC' to RX state can compete with the vibrational relaxation of the FC' state. The temperature and pressure dependences were studied by steady-state fluorescence spectroscopy to give the activation energies of 1-3 kcal/mol for the FC'-to-RX relaxation of congested R(6)BHCs, as well as the activation volumes of 2.0, -0.62, and 7.4 mL/mol for tBu(6)BHC, Men(6)BHC, and Bor(6)BHC at room temperature. The fluorescence anisotropy (rho), as a measure of molecular motion, was also determined to be in the ranges of 0.03-0.3 for FC' and 0.003-0.01 for RX. The much larger rho's for the FC' fluorescence by a factor of 2-100 are attributed to the shorter tau's. The I(RX)/I(F' ratio was found to be insensitive to solvent polarity, but critically dependent on solvent viscosity, exhibiting an excellent linear relationship with the reciprocal viscosity. The potential use of these sterically congested R(6)BHCs as microenvironmental viscosity probes is proposed.
The in vivo and in vitro pharmacokinetics of mercury (Hg) were compared between methylmercury chloride (MeHg·Cl) and methylmercury cysteine (MeHg-Cys) using rats and Caco2 cells because humans can be exposed to MeHg compounds through dietary fish. The in vivo pharmacokinetics of Hg immediately after the digestion of MeHg compounds are still obscure. In Caco2 cells, membrane uptake and subcellular distribution of MeHg compounds were examined. When rats received it intravenously, MeHg·Cl showed 20-fold greater plasma and 2-fold greater blood concentrations of Hg than MeHg-Cys, indicating that their pharmacokinetic properties are different. One hour later, however, Hg concentrations in plasma and blood became virtually identical between MeHg·Cl and MeHg-Cys, although blood Hg concentrations were >100-fold greater than those in plasma. When administered into the closed rat's jejunum loop, MeHg·Cl and MeHg-Cys were rapidly and efficiently taken up by intestinal membranes, and Hg was retained in intestinal membranes for a relatively long time. When administered orally, no difference was observed in plasma and blood Hg concentrations between MeHg·Cl and MeHg-Cys: plasma and blood Hg concentrations increased gradually and reached steady levels at 8 h after administration. In Caco2 cells, uptake of MeHg-Cys was significantly suppressed by L-leucine, although this was not seen with MeHg·Cl. In Caco2 cells, 81 % of Hg was recovered from cytosol fractions and 13 % of Hg from nuclear fractions (including debris) after a 2-h incubation with MeHg-Cys. In conclusion, the mechanism of membrane uptake and volume of distribution in the initial distribution phase were clearly different between MeHg·Cl and MeHg-Cys. However, such pharmacokinetic differences between them disappeared 1 h after intravenous and after oral routes of administration, possibly due to the metabolism in the body.
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