A major limitation of Stille coupling reactions arises from steric screening, especially in the
vinylstannane component. For example, with 1-substituted vinylstannanes and aryl perfluoroalkanesulfonates
or halides negligible or low yields are generally observed, due to very slow reaction rates and competing cine
substitution. This problem has been overcome in the present work through the discovery and application of
cuprous chloride as an accelerant for coupling. Thus, using a protocol for coupling that involves the system
Pd(PPh3)4/CuCl/LiCl under anaerobic conditions in dimethyl sulfoxide solution at 60 °C, a wide variety of
Stille coupling reactions which otherwise fail can be effected in excellent yield (Table ). The process has
been applied to the enantioselective synthesis of the chiral 1-(arylethyl)alkylcarbinol 26, a model for the natural
product nicandrenone. The acceleration of Stille coupling by cuprous chloride can be explained by the
intervention of a vinylstannane → vinylcopper(I) transmetalation step and a subsequent accelerated coupling
of ArPdX with the vinylcopper(I) intermediate.
Lipid bilayers in nanopores are stable for days. The stability depends on the nature of the lipid as well on the pore diameter as investigated by impedance spectroscopy. Bilayers formed of palmitoyl‐oleoyl‐phosphatidylcholine are stable up to 4 days in 200 nm pores regularly arrayed in a 300 nm thin silicon nitride support. The transport of K+ across bilayers by valinomycin demonstrates that this support material has a high potential to monitor functions of membrane proteins.
The hydrodynamics of laminar flow in a microfluidic device has been used to control the continuous self-assembly of gold nanoparticles (NPs) tethered with amphiphilic block copolymers. Spherical micelles, giant vesicles (500 nm-2.0 μm), or disk-like micelles could be formed by varying the flow rates of fluids. Such vesicles can release encapsulated hydrophilic species by using near-IR light.
Arrays of giant unilamellar vesicles (GUVs) with controllable geometries and occupancies are prepared by acoustic trapping and used to implement chemical signaling in protocell colonies and protocell/living cell consortia.
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