Crystal structures of heptakis(2,6-di-O-tert-butyldimethylsilyl)cyclomaltoheptaose, heptakis(2-O-methyl-3,6-di-O-tert-butyldimethylsilyl)cyclomaltoheptaose and heptakis(2-O-methyl)cyclomaltoheptaose.

Crystal structures of heptakis(2,6-di-O-tert-butyldimethylsilyl)cyclomaltoheptaose, heptakis(2-O-methyl-3,6-di-O-tert-butyldimethylsilyl)cyclomaltohep taose and heptakis(2-O-methyl)cyclomaltoheptaose were determined from X-ray diffraction patterns obtained for single crystals of the title compounds grown from ethyl acetate and ethanol, respectively, as solvent. The crystal structures prove conclusively that quantitative migration of the tert-butyldimethylsilyl group from the 2-O- to the 3-O-position [D. Icheln, B. Gehrcke, Y. Piprek, P. Mischnick, W.A. Konig, M.A. Dessoy, A.F. Morel, Carbohydr. Res., 280 (1996) 237-250] was achieved during methylation of heptakis(2,6-di-O-tert-butyldimethylsilyl)cyclomaltoheptaose by iodomethane-sodium hydride.

4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyes modified for extended conjugation and restricted bond rotations.

Five new, constrained, aryl-substituted 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene (BODIPY) dyes (3f,g and 4h-j) were prepared and investigated to see if they have more favorable fluorescence characteristics than the unconstrained systems 2 that were prepared in previous studies. Dye types 3 and 4 have relatively rigid conformations caused by the heteroatom (3f and 3g) or ethylene bridge (4h-j) linkers that preclude free rotation of the substituted-benzene molecular fragments. In the event, the new dye types 3 and 4 have longer lambda(max abs) (620-660 nm) and lambda(max)(fluor) (630-680 nm) values than compounds 2. They also exhibit higher extinction coefficients (>100 000 M(-1) cm(-1), except for 3g). Their fluorescent quantum yields are high (up to 0.72 for 4j), with the exception of compound 3g, which has a quantum yield of only 0.05. The redox properties of dyes 3 and 4 have also been examined.

Atomic-level molecular modeling of the nonionic surfactant Triton X-100: the OPE9 component in vacuum and water.

The commercially available nonionic surfactant Triton X-100 is a mixture of polyoxyethylene tert-octylphenyl ethers (OPEn) with an average of n = 9.5 oxyethylene (OE) units in the molecules, and the population maximum at n = 9. Thus, the OPEn = 9 component was chosen to be studied by atomic level molecular modeling, using second-generation force fields. The 1,000 conformers generated via random sampling of torsional angles around single bonds yielded 11 clusters based on geometrical similarity. Representatives of geometrically distinctly different clusters with significant populations were chosen from a narrow energy range around the most probable energy to be analyzed for interaction with water. The effect of water on the conformation of the OE chain was found to be modest, similar to the situation that had been reported earlier for the anionic surfactant Aerosol-OT (AOT). The number of bound water molecules is strongly dependent on the conformation of the OE chain and is affected by electrostatic as well as steric effects. Unlike the case of AOT, for which the length of the hydrophobic tail was found to govern the size of reverse micelles in CCl4, the size of reverse micelles of OPEn = 9 cannot be predicted from the dimensions of the hydrophilic tail.