Reagentless Detection of Low-Molecular-Weight Triamterene Using Self-Doped TiO2 Nanotubes.

TiO2 nanotube electrodes were self-doped by electrochemical cathodic polarization, potentially converting Ti4+ into Ti3+, and thereby increasing both the normalized conductance and capacitance of the electrodes. One-hundred (from 19.2 ± 0.1 µF cm-2 to 1.9 ± 0.1 mF cm-2 for SD-TNT) and two-fold (from ∼6.2 to ∼14.4 mS cm-2) concomitant increases in capacitance and conductance, respectively, were achieved in self-doped TiO2 nanotubes; this was compared with the results for their undoped counterparts. The increases in the capacitance and conductance indicate that the Ti3+ states enhance the density of the electronic states; this is attributed to an existing relationship between the conductance and capacitance for nanoscale structures built on macroscopic electrodes. The ratio between the conductance and capacitance was used to detect and quantify, in a reagentless manner, the triamterene (TRT) diuretic by designing an appropriate doping level of TiO2 nanotubes. The sensitivity was improved when using immittance spectroscopy (Patil et al. Anal. Chem. 2015, 87, 944-950; Bedatty Fernandes et al. Anal. Chem. 2015, 87, 12137-12144) (2.4 × 106 % decade-1) compared to cyclic voltammetry (5.8 × 105 % decade-1). Furthermore, a higher linear range from 0.5 to 100 µmol L-1 (5.0 to 100 µmol L-1 for cyclic voltammetry measurements) and a lower limit-of-detection of approximately 0.2 µmol L-1 were achieved by using immittance function methodology (better than the 4.1 µmol L-1 obtained by using cyclic voltammetry).

Assessment of semi-permanent hair dyes in wash water from beauty salons by liquid chromatography-tandem mass spectrometry-selected reaction monitoring (LC-MS/MS-SRM).

Herein, we present an approach for the analytical determination and quantification of semi-permanent hair dyes in wash water samples released during washing of dyed hair employing a liquid chromatography-tandem mass spectrometry-selected reaction monitoring (LC-MS/MS-SRM) method with electrospray ionization detection. Specifically, Basic Blue 99 (BB 99), Basic Brown 16 (BB 16), Basic Red 76 (BR 76), Basic Yellow 57 (BY 57) and Acid Violet 43 (AV 43) are hair dyes with properties known to be harmful to human health and the environment. The hair dyes are present in commercial formulation and are discharged into the effluents without fully effective treatment. The detection and quantification by the LC-MS/MS technique show a linear relationship for each studied hair dye in the concentration range from 1 to 200 ng mL-1 in aqueous solution. The limits of detection and quantification were found from 0.66 to 20 ng mL-1 and from 2.0 to 63 ng mL-1, respectively, values that are compatible with the level required in wash water analysis. The method was applied in samples collected from 5 successive washings of hair dyed with a commercial formulation using the established procedure. BB 99 and BY 57 dyes have lower fixation on the scalp and hair, showing 866 ng mL-1 and 145 ng mL-1 release on the first day of washing, respectively. The accumulation of dye and slow release after washing can lead to future problems for both the environment and living organisms.

Identification of biotransformation products of disperse dyes with rat liver microsomes by LC-MS/MS and theoretical studies with DNA: Structure-mutagenicity relationship using Salmonella/microsome assay.

Azo dyes are known as a group of substances with DNA damage potential that depend on the nature and number of azo groups connected to aromatic rings (benzene and naphthalene), chemical properties, e.g. solubility and reactive functional groups, which significantly affect their toxicological and ecological risks. In this paper, we used in vitro models to evaluate the metabolism of selected textile dyes: Disperse Red 73 (DR 73), Disperse Red 78 (DR 78) and Disperse Red 167 (DR 167). To evaluate the mutagenic potential of the textile dyes, the Salmonella mutagenicity assay (Ames test) with strains TA 98 and TA 100 in the presence and absence of the exogenous metabolic system (S9) was used. DR73 was considered the most mutagenic compound, inducing both replacement base pairs (TA 100) and also changing frameshift (TA 98) mutations that are reduced in the presence of the S9 mixture. Furthermore, we used rat liver microsomes in the same experimental conditions of the S9 mixture to metabolize the dyes and the resultant solutions were analyzed using a liquid chromatography coupled to a quadrupole linear ion trap mass spectrometry (LC-MS/MS) to investigate the metabolites formed by the in vitro biotransformation. Based on this experiment, we detected and identified two biotransformation products for each textile dye substrate analyzed. Furthermore, to evaluate the interaction and reactivity of these compounds with DNA, theoretical calculations were also carried out. The results showed that the chemical reaction occurred preferentially at the azo group and the nitro group, indicating that there was a reduction in these groups by the CYP P450 enzymes presented in the rat microsomal medium. Our results clearly demonstrated that the reduction of these dyes by biological systems is a great environmental concern due to increased genotoxicity for the body of living beings, especially for humans.

Red disperse dyes (DR 60, DR 73 and DR 78) at environmentally realistic concentrations impact biochemical profile of early life stages of zebrafish (Danio rerio).

Dyes have been used for more than twenty thousand years in textile, pharmaceutical, food, cosmetic, and photographic industries, among others. Despite their importance in these applications, dyes can be toxic and resistant to many degradation processes used in wastewater treatment plants. Although a large number of dyes have been released in the environments in high amounts, studies into the environmental toxicity of these substances are still scarce. The aim of this study was to evaluate the potential toxic effects of textile dyes Disperse Red 60, Disperse Red 73 and Disperse Red 78 in zebrafish early life stages. To this end, biochemical biomarkers were selected to evaluate non-enzimatic antioxidant (Total Glutathione), antioxidant enzymes (Glutathione S-transferase and Catalase), oxidative stress (lipid peroxidation), neurotransmission (acetylcholinesterase) and energetic metabolism parameters (energy available and energy consumed) after 96 h exposure to these dyes. Our results demonstrated that these disperse dyes induce biochemical alterations in zebrafish embryos at environmental realistic concentrations and that the discharge of these disperse dyes into water bodies should be carefully evaluated. The selected biomarkers were sensitive as early-warning endpoints of disperse dyes toxicity on zebrafish embryos. Implications for risk assessment and indications for future research are discussed.

Study of electrochemical oxidation and determination of albendazole using a glassy carbon-rotating disk electrode.

In this work, electrochemical oxidation of albendazole (ABZ) was carried out using a glassy carbon-rotating disk electrode. Development of electroanalytical methodology for ABZ quantification in pharmaceutical formulations was also proposed by using linear sweep voltammetric technique. Electrochemical oxidation is observed for ABZ at E(1/2)=0.99 V vs. Ag/AgCl(sat), when an anodic wave is observed. Kinetic parameters obtained for ABZ oxidation exhibited a standard heterogeneous rate constant for the electrodic process equal to (1.51+/-0.07) x 10(-5) cm s(-1), with a alphan(a) value equal to 0.76. Limiting current dependence against ABZ concentration exhibited linearity on 5.0 x 10(-5) to 1.0 x 10(-2) mol l(-1) range, being obtained a detection limit of 2.4 x 10(-5) mol l(-1). Proposed methodology was applied to ABZ quantification in pharmaceutical formulations.

Photoelectrocatalytic/photoelectro-Fenton coupling system using a nanostructured photoanode for the oxidation of a textile dye: Kinetics study and oxidation pathway.

In this study, a coupled photoelectrocatalytic/photoelectro-Fenton reactor was designed to enhance the degradation efficiency of organic pollutants and tested using the azo dye Orange G as a model compound. Pt-decorated TiO2 nanotubes were used as a photoanode with an air-diffusion polytetrafluoroethylene cathode for H2O2 generation. The sum of individual effects of coupling the photoelectrocatalytic and photoelectro-Fenton processes was evaluated as a function of the decolorization and mineralization of Orange G solutions. The dye solutions were only completely decolorized in more acidic conditions (pH 3.0). The mineralization of the Orange G solutions increased in the sequence photoelectrocatalytic

Fabrication of coaxial TiO2/Sb2S3 nanowire hybrids for efficient nanostructured organic-inorganic thin film photovoltaics.

We report on low-cost, all solution fabrication of efficient air-stable nanostructured thin film photovoltaics comprised of n-type Sb(2)S(3) chemically deposited onto TiO(2) nanowire array films, forming coaxial Sb(2)S(3)/TiO(2) nanowire hybrids vertically oriented from the SnO(2):F coated glass substrate, which are then intercalated with poly(3-hexylthiophene) (P3HT) for hole transport and enhanced light absorption.