Controlling stereochemical outcomes of asymmetric processes by catalyst remote molecular functionalizations: chiral diamino-oligothiophenes (DATs) as ligands in asymmetric catalysis

The synthesis, characterization, and structure-guided application of a new class of highly versatile chiral C(2)-symmetric diamine-oligothiophene ligands in Pd-catalyzed asymmetric transformations are presented. Experimental investigations of the intimate role of pendant pi-conjugate oligothiophenes in determining the catalytic activity of the corresponding chiral Pd complexes are described. Their unusual behavior opens up new routes toward the logical design of finely tuned organometallic catalysts by remote structural functionalizations.     

One-dimensional thermotropic dilatation area of lipid headgroups within lamellar lipid/DNA complexes

Using simultaneous synchrotron small- and wide-angle X-ray diffraction (SWAXD), we investigated the thermotropic behavior of a cationic lipid mixture of DOTAP-DOPC (1,2-dioleoyl-3-trimethylammonium-propane-dioleoylphosphatidylcholine) liposomes complexed with calf thymus DNA. The DOTAP-DOPC/DNA complex reacts to temperature change by a bilayer compression normal to its surface and an expansion of the DNA in the plane of the rod lattice. By applying two independent recently developed models, we show here for the first time that the thermotropic dilatation area of lipid headgroups within the complexes is not isotropic but occurs parallel to the 1D DNA lattice (i.e., along the direction perpendicular to the DNA axis). Our results shed light on the role of spatial dimensionality in the DNA packing density within lamellar lipoplexes and provide experimental evidence that the interaction between DNA molecules confined between lipid bilayers can be regarded as a 1D problem.