The local microenvironment surrounding dansyl molecules attached to controlled pore glass in pure and alcohol-modified supercritical carbon dioxide.

We report on the local microenvironment surrounding a free dansyl probe, dansyl attached to controlled pore glass (D-CPG), and dansyl molecules attached to trimethylsilyl-capped CPG (capped D-CPG) in pure and alcohol-modified supercritical CO2. These systems were selected to provide insights into the local microenvironment surrounding a reactive agent immobilized at a silica surface in contact with pure and cosolvent-modified supercritical CO2. Local surface-bound dansyl molecule solvation on the CPG surface depends on the dansyl molecule surface loading, the surface chemistry (uncapped versus capped), the bulk fluid density, and the alcohol gas phase absolute acidity. At high dansyl loadings, the surface-bound dansyl molecules are largely "solvated" by other dansyl molecules and these molecules are not affected significantly by the fluid phase. When the dansyl surface loading decreases, dansyl molecules can be accessed/solvated/wetted by the fluid phase. However, at the lowest dansyl loadings studied, the dansyl molecules are in a fluid inaccessible/restrictive environment and do not sense the fluid phase to any significant degree. In uncapped D-CPG, one can poise the system such that the local concentration of an environmentally less responsible cosolvent (alcohol) in the immediate vicinity of surface-immobilized dansyl molecules can approach 100% even though the bulk solution contains orders of magnitude less of this less environmentally responsible cosolvent. In capped C-CPG, the surface excess is attenuated in comparison to that of uncapped D-CPG. The extent of this cosolvent surface excess is discussed in terms of the dansyl surface loading, the local density fluctuations, the cosolvent and surface silanol gas phase acidities, and the silica surface chemistry. These results also have implications for cleanings, extractions, heterogeneous reactions, separations, and nanomaterial fabrication using supercritical fluids.

Entrainer effect on photochirogenesis in near- and supercritical carbon dioxide: dramatic enhancement of enantioselectivity.

Diethyl ether added as an entrainer (cosolvent) to near- and supercritical CO2 significantly enhanced the enantioselectivity of photocyclization of 5,5-diphenyl-4-penten-1-ol sensitized by saccharide naphthalenedicarboxylate to give a cyclization product in enantiomeric excesses much larger than those obtained in conventional organic solvents, revealing the unique features of nc- and sc-CO2 as well as the critical role of entrainer clustering to the intervening diastereomeric exciplex pair.

Comparison of dansylated aminopropyl controlled pore glass solvated by molecular and ionic liquids.

We compare how (i) four ionic liquids (ILs) (1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4mpy][Tf2N]), and trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([P(C6)3C14][Tf2N])) and (ii) two conventional molecular liquids (methanol and 1-octanol) solvate/wet luminescent organic moieties that are covalently attached to the surface of silica controlled pore glass (CPG). A series of aminopropyl CPG particles that have been covalently tagged with the solvatochromic fluorescent probe group dansyl were used in this study. The results demonstrate that ILs solvate/wet the silica surface differently in comparison to molecular liquids (MLs). Specifically, when comparing ILs and MLs that appear to solvate the free probe, dansylpropylsulfonamide (DPSA), equally in solution, we find that ILs do not solvate/wet the silica surfaces as well as the corresponding MLs. The cation component in these ILs is the significant factor in how the ILs solvate/wet silica surfaces. Solvation/wetting of surface-bound species at a silica surface depends on the cation size. Chlorosilane end-capping of the surface silanol and amine residues attenuates the cation's affects.

A cationic chalcogenoxanthylium photosensitizer effective in vitro in chemosensitive and multidrug-resistant cells.

Pentacyclic thio- (1) and seleno- (2) analogues of tetramethylrosamine (TMR) were prepared with a julolidyl fragment replacing the 3-dimethylamino substituent in the xanthylium core. The pentacylic structure increases the lipophilicity of 1 and 2 relative to TMR-S and TMR-Se and locks the lone-pair of electrons on the julolidyl N atom into conjugation with the xanthylium core. This conformational rigidization leads to longer wavelengths of absorption, but has little impact on other photophysical properties such as quantum yields for fluorescence and singlet-oxygen generation and fluorescence lifetimes in 1 and 2 relative to TMR-S and TMR-Se. Both 1 and 2 are effective photosensitizers against chemosensitive AUXB1 cells in vitro at 1x10(-7)M and compound 2 is an effective photosensitizer against multidrug-resistant CR1R12 cells in vitro at 1x10(-7)M. While the uptake TMR-S into CR1R12 cells as measured by fluorescence is significantly lower than uptake into chemosensitive AUXB1 cells, there is no significant difference in the uptake of 1 into either AUXB1 or CR1R12 cells. The addition of 2x10(-4)M verapamil to the cells prior to treatment with 1 had no significant effect on the uptake of 1 into either AUXB1 or CR1R12 cells. Treating lipid-activated, purified Pgp with 2 and light gave complete inhibition of Pgp ATPase activity.