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From light harvesting to intracellular oxygen sensing: Chromophores and their novel applications in photovoltaics and molecular cardiobiology

Posted on:2009-08-04Degree:Ph.DType:Thesis
University:The Johns Hopkins UniversityCandidate:Carlisle, Rachael AFull Text:PDF
GTID:2444390005458762Subject:Chemistry
Abstract/Summary:
Chromophores, organic and inorganic molecules containing light absorbing moieties, have been utilized throughout the scientific community. In the present work, derivatives of the aromatic pyrene moiety and of the Ruthenium centered poylpyridyl complexes have been used to sensitize nanocrystalline (anatase), mesoporous TiO2 and ZrO2 thin films. Electrical and energetic properties of these dyes were investigated in solutions as well as on the thin film substrates. In a biological application, Ru(bpy) 32+, tris (2,2'-bipyridine) ruthenium(II) dichloride, a well characterized divalent ruthenium polypyridyl dye, was used to measure the intracellular pO2 of individual guinea pig ventricular cardiomyocytes.; Chromophore-linker bipodal systems were used to anchor pyrene or ruthenium polypyridyl complexes to the surface of TiO2 (anatase) and ZrO 2 nanoparticle thin films in hopes of increasing the coupling and conjugation to the surface. This in turn would improve electron injection into TiO 2 and therefore produce more efficient dye-sensitized solar cells. The properties of each dye varied with varying the spacer length and were therefore extensively studied.; In addition to the bipodal rigid rod linkers, a pyrene "tripodal" system was adsorbed to the metal oxide surfaces in a perpendicular orientation, preventing the possible pivoting action of the rigid bipodal systems. Furthermore, this pyrene tripod derivative, with it's large "footprint," helped to minimize sensitizer-sensitizer interactions when bound to the surface.; Chromophores have proven to be invaluable for efficient light harvesting energy for the advancement of photovoltaics; however, many of these dyes, due to their tuneable photophysical properties and energetics, have been useful in biologic and medicinal research.; The balance of energy supply and demand is a crucial determinant of cardiovascular health, but the mechanisms that regulate oxidative phosphorylation are still poorly understood. While oxygen consumption (VO2) can be measured in cell suspensions or tissues, measurements of respiratory flux in single cells have proven challenging. Here, we report a novel method for monitoring intracellular oxygen tension using a ruthenium polypyridyl complex, Ru(bpy) 32+. Ru(bpy)32+ was introduced into adult guinea pig cardiac cells via the whole cell patch clamp method, and Ru(bpy)32+ photoluminescence, mitochondrial redox potential, and sarcolemmal K,ATP currents were monitored simultaneously as indices of the cellular metabolic status. Application of this method to models of cardiovascular disease will provide novel insights into the role of mitochondrial dysfunction under pathological conditions.; This work was performed under the advisement of Professor Gerald J. Meyer, PhD, Department of Chemistry and Professor Brian O'Rourke, PhD, Institute of Molecular Cardiobiology. This thesis was read by Prof. Brian O'Rourke, PhD, Prof. Gordon Tomaselli, MD, Prof. John Toscano, PhD, and Prof. Tamara Hendrickson, PhD. The tripodal/rigid-rod sensitizer work was performed in collaboration with Elena Galoppini and co-workers at Rutgers University.
Keywords/Search Tags:Light, Work, Phd, Oxygen, Intracellular, Novel, Prof
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