Influence of Polyfluorinated Side Chains and Soft-Template Method on the Surface Morphologies and Hydrophobic Properties of Electrodeposited Films from Fluorene Bridged Dicarbazole Monomers.

A clear case of relationship between the monomer molecular structure and the capability of tuning the morphology of electrodeposited gas bubbles template polymer thin films is shown. To this end, a series of fluorene-bridged dicarbazole derivatives containing either linear or terminally branched polyfluorinated side chains connected to the fluorene subunit were synthesized and their electrochemical properties were investigated. The new compounds underwent electrochemical polymerization over indium tin oxide electrodes to give hydrophobic films with nanostructural and morphological properties strongly dependent on the nature of the side chains. Gas bubbles templated electropolymerization was next achieved by the addition of tiny amounts of water to the monomer solutions, without using surfactants. Within the investigated set of molecules, the nanostructural properties of the soft-templated films obtained from monomers bearing linear side chains could be fine-tuned by adjusting electrochemical parameters, leading to superhydrophobic surfaces.

Photocatalytic evaluation and characterization of TiO2-riboflavin phosphate film: analysis of reactive oxygen species.

The effect of Riboflavin-5'-phosphate (RFPO4) sensitization on photocatalytic properties of TiO2 film was studied. RFPO4 was adsorbed on film surface to investigate the photophysical properties of TiO2 upon blue-light photoexcitation. The film was characterized through scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, and diffuse reflectance spectroscopy. The efficiency of the TiO2/RFPO4 film was tested for pollutant elimination in aqueous media in a visible-light-driven system. The phenol paradigmatic model was employed in an aqueous solution as a contaminant target. TiO2/RFPO4 sensitized photodegradation of phenol, which produces catechol, hydroquinone, and benzophenone, was monitored by absorption spectroscopy and HPLC. The results indicated that phenol degradation with TiO2/RFPO4 film was due to the photogeneration of two reactive oxygen species, singlet molecular oxygen (O2(1Δg)) and superoxide radical anion (O2·-) identified through specific detection techniques. The presence of O2(1Δg) is reported here for the first time as generated from a sensitized TiO2 film upon visible-light photoirradiation. Based on the photophysical determinations, a photocatalytic mechanism for TiO2/RFPO4 was established.

Electrochemical bubble generation via hydrazine oxidation for the in situ control of an electrodeposited conducting polymer micro/-nanostructure.

Herein, a simple, in situ, on step and highly repeatable electrochemical method that allows controlling the nanostructure of electrodeposited polymer films is reported. As an example, the tuning of the electrodeposited polypyrrole nanostructures using inert gas bubbles as the template at the electrode surface generated by the electrochemical oxidation of hydrazine is shown. The hydrazine discharge occurs at a lower potential regarding the beginning of pyrrole electropolymerization process, which allows the modulation of the density and size of the bubbles on the surface electrode controlling electrochemical parameters (applied potential, concentration, time, etc.). Subsequently, the applied potential is moved to where the pyrrole polymerization begins, which induces the material discharges around the bubble template producing polypyrrole hollow structures with definite patterns on the electrode surface. This methodology is proposed as a simple model for the electrodeposition with the morphological control of a wide range of conductive polymers.

Photo-Fenton and Riboflavin-photosensitized Processes of the Isoxaflutole Herbicide.

The proherbicide Isoxaflutole (IXF) hydrolyzes spontaneously to diketonitrile (DKN) a phytotoxic compound with herbicidal activity. In this work, the sensitized degradation of IXF using Riboflavin (Rf), a typical environmentally friendly sensitizer, Fenton and photo-Fenton processes has been studied. The results indicate that only the photo-Fenton process produces a significant degradation of the IXF. Photolysis experiments of IXF sensitized by Riboflavin is not a meaningful process, IXF quenches the Rf excited triplet (3 Rf*) state with a quenching rate constant of 1.5 · 107  m-1  s-1 and no reaction is observed with the species O2 (1 Δg ) or O 2 · - generated from 3 Rf*. The Fenton reaction produces no changes in the IXF concentration. While the photo-Fenton process of the IXF, under typical conditions, it produces a degradation of 99% and a mineralization to CO2 and H2 O of 88%. A rate constant value of 1.0 × 109  m-1  s-1 was determined for the reaction between IXF and HO˙. The photo-Fenton process degradation products were identified by UHPLC-MS/MS analysis.

On the photooxidation of the multifunctional drug niclosamide. A kinetic study in the presence of vitamin B2 and visible light.

OBJECTIVES: The multifunctional drug niclosamide (NSD), extensively employed therapeutically, is a frequent pollutant of surface waters. Considering the environmental importance of photodegradative processes for this type of contaminant, the kinetic and mechanistic aspects of the possible visible-light-mediated photooxidation of NSD were studied under naturalistic conditions. METHODS: The visible-light absorber riboflavin (vitamin B2) was employed as a photosensitizer. The vitamin can usually be found in natural waters and is the most common endogenous photosensitizer in mammals. The interaction of NSD with electronically excited states of Rf and with photogenerated reactive oxygen species (ROS) was evaluated through conventional UV spectroscopy, laser flash photolysis, time-resolved phosphorescence detection of singlet molecular oxygen (O2((1)Δg)), and polarographic dosage of dissolved oxygen. RESULTS: Ground state NSD quenched the long-lived triplet excited state of Rf ((3)Rf*) and the photogenerated ROS (O2((1)Δg)) and superoxide radical anion (O2•−). As a result, NSD was photooxidized. The rate constants for the interaction NSD-O2((1)Δg) are particularly low, in the order of 10(6)/M/s, although the whole interaction is attributable to a pure reactive process. The O2((1)Δg) quenching was faster in alkaline medium, favored by the ionization of the NSD phenolic group. Under Rf-photosensitization, NSD was degraded very much more rapidly than phenol, the latter being considered a paradigmatic water-contaminant model compound. NSD may behave as an antioxidant in bio-environments, as demonstrated employing the photooxidizable amino acid tryptophan as a relevant biological target. DISCUSSION: The results indicate that a O2•−-mediated process is the main route for the Rf-sensitized photooxidation of NSD. Photodegradation of the biocide in the presence and absence of phenol and tryptophan was quantitatively evaluated, discussed, and interpreted in terms of competitive quenching processes of (3)Rf*, O2((1)Δg), and O2•− by the substrates.