We investigated the thermoelectric properties of metalloporphyrins connected by thiol anchor groups to gold electrodes. By varying the transition metal-centre over the family Mn, Co, Ni, Cu, Fe, and Zn we are able to tune the molecular energy levels relative to the Fermi energy of the electrodes. The resulting single-molecule room-temperature thermopowers range from almost zero for Co and Cu ce...

The present work deals with an attempt to study the effect of human and bovine serum albumin on kinetic parameters of chemiluminescence of luminol-hydrogen peroxide system catalyzed by manganese tetrasulfonatophenyl porphyrin (MnTSPP). The investigated parameters involved pseudo-first-order rise and fall rate constant for the chemiluminescence burst, maximum level intensity, time to reach maxim...

Cationic manganese-porphyrin complexes, free or targetted with an intercalating agent, are able to cleave DNA using oxygen atom donors like potassium monopersulfate or magnesium monoperphthalate as coreactants. Detailed studies of the cleavage of calf thymus DNA, before and after a heating step, show that free bases and 5-methylene-2-furanone are the main reaction products, indicating that hydr...

The synthesis of a pair of electron-deficient porphyrin building blocks and their resulting coordinatively linked supramolecular assemblies are described. The perfluorophenyl substituted porphyrins feature pendant pyridines which, upon reaction with Re(CO)5Cl assemble into discrete dimers and tetramers, as dictated by the geometry of the porphyrin monomer. The resulting supramolecular complexes...

We describe a new, specific, quantitative method for fecal blood, based on conversion of nonfluorescing heme to fluorescing porphyrins, that obviates serious deficiencies inherent in currently used tests. A two-reagent system is used to determine the two hemoglobin-related fractions that are found in feces. The hot citric acid extract includes only the variable fraction of porphyrins that have ...

Porphyria cutanea tarda is thought to result from an inherited deficiency of uroporphyrinogen decarboxylase (EC 4.1.1.37) in some patients. Present methods for determining uroporphyrinogen decarboxylase activity are time consuming, so we examined the pattern of porphyrins formed from porphobilinogen by hemolysates as a possible marker for hereditary porphyria cutanea tarda. After the hemolysate...

Despite the growing importance of fluorinated organic compounds in drug development, there are no direct protocols for the fluorination of aliphatic C-H bonds using conveniently handled fluoride salts. We have discovered that a manganese porphyrin complex catalyzes alkyl fluorination by fluoride ion under mild conditions in conjunction with stoichiometric oxidation by iodosylbenzene. Simple alk...

The in vitro autoxidation of N-hydroxyurea (HU) is catalyzed by Mn(III)TTEG-2-PyP(5+), a synthetic water soluble Mn(III) porphyrin which is also a potent mimic of the enzyme superoxide dismutase. The detailed mechanism of the reaction is deduced from kinetic studies under basic conditions mostly based on data measured at pH = 11.7 but also including some pH-dependent observations in the pH rang...

Recent investigations concerning the significance of porphyrins in erythrocytes indicate a need for a rapid quantitative assay, easily adaptable to routine clinical use. To till this need, we have developed a simplified procedure for the measurement of porphyrins (essentially protoporphyrin) in whole blood. Blood is stirred with acetone-ethyl acetate and the porphyrins are extracted with formic...

Solar fuel generation requires the efficient capture and conversion of visible light. In both natural and artificial systems, molecular sensitizers can be tuned to capture, convert, and transfer visible light energy. We demonstrate that a series of metal-free porphyrins can drive photoelectrochemical water splitting under broadband and red light (λ > 590 nm) illumination in a dye-sensitized TiO...