Zirconium phosphonate/1,4,5,8-naphthalenediimides self-assembled films

The formation and characterization of self-assembled films of zirconium phosphonate / N,N'-di(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (DPN) is presented. The films were produced on glass substrates by deposition of alternating layers of Zr+4 and DPN. Films containing up to 16 layers on each side of the substrate were obtained and monitored by absorption spectroscopy and ellipsometry. When irradiated, the initially colorless films turned to a persistent pinky color reminiscent of that of DPN anion radical. These films are a promising material to the development of photovoltaic devices

Covalent attachment of 3,4,9,10-perylenediimides onto the walls of mesoporous molecular sieves MCM-41 and SBA-15

This work describes the covalent grafting of 3,4,9,10-perylenediimides (PDI), which are fluorescent dyes with very interesting optical properties, onto the walls of mesoporous molecular sieves MCM-41 and SBA-15. The mesoporous materials were first treated with 3-aminopropyltriethoxysilane (APTES) in anhydrous toluene, generating amine-containing surfaces. The amine-containing materials were then reacted with 3,4,9,10-perylenetetracarboxylic dianhydride (PTCA), generating surface-grafted PDI. Infrared spectra of the materials showed that the reaction with amino groups took place at both anhydride ends of the PTCA molecule, resulting in surface attached diimides. No sign of unreacted anhydride groups were found. The new materials, designated as MCMN2PDI and SBAN(2)PDI, presented absorption and emission spectra corresponding to weakly coupled PDI chromophores, in contrast to the strongly coupled rings usually found in solid PDI samples. The materials showed a red fluorescence, which could be observed by the naked eye under UV irradiation or with a fluorescence microscope. The PDI-modified mesoporous materials showed electrical conductivity when pressed into a pellet. The results presented here show that the new materials are potentially useful in the design of nanowires. (C) 2007 Elsevier Inc. All rights reserved

Harvesting of Surfactant-Solubilized Asphaltenes by Magnetic Nanoparticles

Asphaltenes are a severe problem for the oil industry. The high content of aromatic and aliphatic hydrocarbons in asphaltenes poses a challenge for efficient methods of the solubilization and degradation of their components. The main goal of this study was to investigate an efficient and innovative method for asphaltene solubilization with surfactants to produce supramolecular aggregates with affinity by magnetic nanoparticles (Fe3O4) for magnetic separation and degradation. Asphaltene mixed with the cationic surfactant cetyltrimethylammonium bromide (CTAB) was both solubilized in chloroform and the solvent dried with N2 to produce a film that was resuspended in water and formed a stable colloid with asphaltene incorporated in CTAB micelles. The suspensions of CTAB/asphaltene supramolecular aggregates obtained at different surfactant/asphaltene ratios were characterized by dynamic and static light scattering (DLS and SLS) and by electrophoretic mobility for ζ potential determination. CTAB concentrations of 30 and 60 mM produced spherical supramolecular aggregates (SMAs) of size between 100 and 200 nm with polydispersity. The ζ potential of CTAB micelles loaded with asphaltenes increased from +9.17 +/– 4.6 to +56.7 +/– 5.8 eV. Electron paramagnetic resonance revealed that asphaltene forms stable free radicals in CTAB micelles. Classical molecular dynamics simulations were also used to study interactions of the functional groups of asphaltenes. The association with CTAB micelles provided the binding affinity of asphaltenes for nanoparticulate magnetite (Fe3O4) and precipitation of the most CTAB content. In this condition, Fe3O4 promoted the degradation of asphaltenes to low molecular mass products. Therefore, incorporation in CTAB micelles is a simple and innovative method contributing to asphaltene removal, degradation, and possible conversion to products with aggregated value

Spectroscopic, Structural, and Functional Characterization of the Alternative Low-Spin State of Horse Heart Cytochrome c

The alternative low-spin states of Fe3+ and Fe2+ cytochrome c induced by SDS or AOT/hexane reverse micelles exhibited the heme group in a less rhombic symmetry and were characterized by electron paramagnetic resonance, UV-visible, CD, magnetic CD, fluorescence, and Raman resonance. Consistent with the replacement of Met80 by another strong field ligand at the sixth heme iron coordination position, Fe3+ ALSScytc exhibited 1-nm Soret band blue shift and ɛ enhancement accompanied by disappearance of the 695-nm charge transfer band. The Raman resonance, CD, and magnetic CD spectra of Fe3+ and Fe2+ ALSScytc exhibited significant changes suggestive of alterations in the heme iron microenvironment and conformation and should not be assigned to unfold because the Trp59 fluorescence remained quenched by the neighboring heme group. ALSScytc was obtained with His33 and His26 carboxyethoxylated horse cytochrome c and with tuna cytochrome c (His33 replaced by Asn) pointing out Lys79 as the probable heme iron ligand. Fe3+ ALSScytc retained the capacity to cleave tert-butylhydroperoxide and to be reduced by dithiothreitol and diphenylacetaldehyde but not by ascorbate. Compatible with a more open heme crevice, ALSScytc exhibited a redox potential ∼200 mV lower than the wild-type protein (+220 mV) and was more susceptible to the attack of free radicals