The functionalization of amphiphilic polymer co-networks with lightresponsive spiropyran and spirooxazine derivatives leads to a new type of light-responsive materials. The material consisting of hydrophilic nanochannels shows desirable properties such as light-responsive permeability changes of aqueous caffeine solutions, an exceptional repeatability of the photochromism, and tunable basic permeability rates. The versatility of the system is demonstrated by using different functionalization routes such as copolymerization of light-responsive monomers or crosslinker as well as postmodifi cation of the preformed amphiphilic network. Moreover, lightresponsive spirobenzopyran and novel spirooxazine derivatives are synthesized, which changes the properties of the light-responsive membranes after inclusion into the amphiphilic co-networks. Finally, the permeability of the delivery membrane can be tailored to match the properties of porcine skin, an in vitro model of human neonatal skin. One possible application might be the use of the light-responsive membranes as key-unit of a transdermal caffeinedelivery system for preterm neonates.
The preparation and characterization of micrometer gold and silver single-crystals of well-defined shapes are reported here. The shapes of the crystals can be described as plates, polyhedra, and wires. The orientation of the crystal faces was studied using electron and X-ray powder diffraction techniques, and a (111) orientation of the large faces of gold plates was experimentally shown. The surface morphology of the crystal faces was studied by atomic force microscopy. Modifications of gold microplates with the thiolated carborane clusters 1,2-(HS)2-1,2-C2B10H10 (1), 9,12-(HS)2-1,2-C2B10H10 (2), and 1,12-(HS)2-1,12-C2B10H10 (3) are described. The carboranethiol molecules 1 and 2 show dipole moments of 4.1 and 5.9 D. In comparison, the thiolate derivative of compound 1 has a dipole moment of 4.7 D in the opposite direction to 1, and the thiolate form of compound 2 has a dipole moment of 16.7 D in the same direction. On the basis of X-ray photoelectron spectroscopy (XPS) analyses and values of work functions, we revealed that the molecules of 1 and 2 attached to the gold surface have similar electron distribution and dipole moments as within the free thiol derivatives. Following the modification of microplate gold crystals with 3, a monolayer of gold nanoparticles was attached on top of the carborane moieties. The composition of the surface species was studied using XPS. Dynamic contact angles of water on the modified gold surfaces are also discussed.
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