Bernardo A. Iglesias

New platinum(II)-bipyridyl corrole complexes: Synthesis, characterization and binding studies with DNA and HSA.

A simple methodology giving access to the metal-free corroles of trans-A2B type, 5,15-bis(pentafluorophenyl)-10-{3-[2-(pyridin-4-yl)vinyl]phenyl}corrole and 5,15-bis(pentafluorophenyl)-10-{4-[2-(pyridin-4-yl)vinyl]phenyl}corrole, and to the corresponding bipyridyl platinum(II) complexes is described. These new positional isomers were fully characterized and spectroscopic studies demonstrated the ability of Pt(II)-corrole complexes to establish non-covalent interactions with calf-thymus DNA (ct-DNA) and human serum albumin (HSA). Additionally, gel electrophoresis experiments demonstrated that Pt(II)-corrole complexes are able to bind plasmid pMT123 DNA, inducing alterations on its secondary structure.

Synthesis, characterization and electrochemical properties of meso-thiocarboxylate-substituted porphyrin derivatives

Considering the versatility of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPPF20) to react with nucleophiles we highlight here the synthesis and characterization of several mono- and tetra-thiocarboxylate derivatives. The selective displacement of the para-fluorine groups in TPPF20 by thiocarboxylic acids demonstrates that TPPF20 is an ideal platform for the rapid formation of thiocarboxylate porphyrins. The optical and electrochemical features of the thiocarboxylate derivatives were also examined thinking on their potential use in photovoltaic devices. From their electrochemical characterization the following parameters were taken into account: (i) electronegative induced effect of the thiocarboxylate dyes owing the presence of the fluorine and sulfur atoms on the molecular structure of the porphyrin; and (ii) the free rotation and flexibility features that such S atom gives to the porphyrin relatively to the semiconductor.

β-(p-Carboxyaminophenyl)porphyrin derivatives: new dyes for TiO2 dye-sensitized solar cells

New β-(p-carboxyaminophenyl)porphyrin derivatives were efficiently synthesized via palladium-catalysed amination of methyl 4-iodobenzoate with (2-amino-5-10,15,20-tetraphenylporphyrinato)nickel(II), followed by a demetallation/metallation sequence and basic hydrolysis. Optical and electrochemical studies revealed their potentiality for being considered as dyes in DSSCs devices, in which a power conversion efficiency of about 30xa0% of the more conventional Ru(II)-sensitizer N719 was achieved.

A New Protocol for the Synthesis of New Thioaryl-Porphyrins Derived from 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin: Photophysical Evaluation and DNA-Binding Interactive Studies

A new protocol for the preparation of thioaryl-porphyrins is described. The compounds were prepared from different disulfides employing NaBH4 as a reducing agent. The methodology allowed the preparation of four different thioaryl-porphyrins in very-good to excellent yields under soft conditions, such as short reaction times and smooth heating. Additionally, the photophysical properties of new compounds were determined and experimental and theoretical DNA interactions were assessed.

Nitro- and Amino-­Porphyrins: Important Intermediates for Novel Porphyrin Derivatives Formation

The vital function played by porphyrin derivatives in nature has attracted the attention of many scientists for more than a century. Studies on the synthesis, functionalization, action of porphyrins and the search for potential applications of such macrocycles were carried out during the last century, and they have involved several research groups. In this context, the establishment of novel synthetic routes has been a major objective over the years. In this review, the importance of nitroand aminoporphyrins as templates for the formation of new specifically substituted porphyrins will be presented. Derivatives containing nitro and amino groups are presented as important starting materials for the formation of new highly functionalized porphyrin derivatives.

Adventures in corrole features by electrospray ionization mass spectrometry studies

In this short review the importance of electrospray mass spectrometry in corrole chemistry is highlighted. ESI-MS and ESI-MS/MS are depicted as important tools for the identification and characterization of novel corrole derivatives. Metallocorrole chemistry and differentiation of corrole isomers via ESI-MS/MS and/or TWIM-MS were chosen as two focal points.