Prussian blue-doped nanosized polyaniline for electrochemical detection of benzenediol isomers.

Simultaneous speciation of benzenediol isomers (BDIs), 1,2-benzenediol (catechol, CC), 1,3-benzenediol (resorcinol, RS), and 1,4-benzenediol (hydroquinone, HQ), was investigated by differential pulse voltammetry (DPV) using a graphite paste electrode (GPE) modified with Prussian blue-polyaniline nanocomposite. The modified GPE showed good stability, sensitivity, and selectivity properties for all the three BDIs. Prussian blue-doped nanosized polyaniline (PBNS-PANI) was synthesized first by using mechanochemical reactions between aniline and ferric chloride hexahydrate as the oxidants and then followed by the addition of potassium hexacyanoferrate(II) in a solid-state and template-free technique. The material was characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The DPV measurements are performed in phosphate electrolyte solution with pH 4.0 at a potential range of - 0.1 to 1.0 V. The proposed modified electrode displayed a strong, stable, and continuous three well-separated oxidation peaks towards electrooxidation at potentials 0.20, 0.31, and 0.76 V for HQ, CC, and RS, respectively. The calibration curves were linear from 1 to 350.5 µM for both HQ and CC, while for RS, it was from 2 to 350.5 µM. The limit of detection was determined to be 0.18, 0.01, and 0.02 µM for HQ, CC, and RS, respectively. The analytical performance of the PBNS-PANI/GPE has been evaluated for simultaneous determination of HQ, CC, and RS in creek water, commercial hair dye, and skin whitening cream samples with satisfactory recoveries between 90 and 106%. Overall, we demonstrated that the presence of NS-PANI and PB resulted in a large redox-active surface area that enabled a promising analytical platform for simultaneous detection of BDIs. Graphical abstract.

Electrochemical Detection of Gallic Acid-Capped Gold Nanoparticles Using a Multiwalled Carbon Nanotube-Reduced Graphene Oxide Nanocomposite Electrode.

Recently, a plethora of ecofriendly methods have been developed for the synthesis of AuNPs using a multitude of biogenic agents. Polyphenols from plants are particularly attractive for producing AuNPs because in addition to helping with the synthesis of AuNPs, the polyphenol capping of the NPs can be used as a platform for versatile applications. Polyphenol-capped AuNPs could also make the detection of AuNPs possible, should they be released into the environment. Because polyphenols are redox-active, they can be used as a probe to detect AuNPs using electrochemical techniques. In this work, we have developed an MWCNT-rGO nanocomposite electrode for the sensitive detection of AuNPs capped with gallic acid (GA, a green-tea-derived polyphenol) using differential pulse voltammetry (DPV). The reduction of gallic acid-capped AuNPs was used as the quantification signal, and the calibration curve displayed a detection limit of 2.57 pM. Using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), we have shown that the modification of the electrode surface with an MWCNT-rGO hybrid nanocomposite resulted in a 10-fold increase in current response leading to the sensitive detection of GA-AuNPs compared to unmodified electrodes. We have also demonstrated the applicability of the electrochemical sensor in detecting GA-AuNPs in various analytical matrixes such as human serum and natural creek water (Highland Creek, ON) with good recovery.

TiO2-coated 2D photonic crystals for reflectometric determination of malachite green.

A "detect and destroy" strategy is reported for the spectroscopic determination and photocatalytic degradation of Malachite Green (MG) in aqueous solutions. The intensity of the reflection peak maxima from the TiO2-coated 2D-photonic crystal (PhC) at 633 nm wavelength undergoes a gradual decrease with increasing concentrations of MG. The determination of MG was readily achieved in the nanomolar range due to the quenching of the reflection intensity of the peak, measured using a fiber optic probe. The assay works in the 1.0 nM to 10 µM MG concentration range with a detection limit of 1.3 nM. The same TiO2-coated 2D-PhC surface can photocatalytically degrade MG in aqueous solutions under UV irradiation. The photocatalytic degradation in the presence of TiO2-coated 2D-PhC becomes evident as the blue color of MG changes to colorless with increasing irradiation time. The decrease in absorption is detected at 617 nm. It was found that the photocatalytic efficiency of TiO2 was synergistically enhanced in the presence of 2D-PhCs. It is concluded that each component of the TiO2-coated 2D-PhC system plays a key role in the detection and degradation of MG. Graphical abstractSchematic representation for reflectometric detection and photocatalytic degradation of hazardous Malachite Green dye using TiO2-coated two-dimensional photonic crystals.

Calorimetric and spectroscopic detection of the interaction between a diazo dye and human serum albumin.

Dye effluents are one of the main causes of water pollution. Azo dyes, the most widely applied colorants, are particularly difficult to degrade. Exposure of such dyes to the aquatic environment is hazardous to human health and biota due to their intrinsic harmful mutagenic and carcinogenic properties. Congo Red (CR) is an anionic and synthetic diazo dye, which is recalcitrant to the biodegradative process and metabolizes to produce a potential carcinogen. Research on the interaction of this toxic dye with serum albumin, as a transport protein, is of paramount significance because the physiological and toxicological behaviours of the dye in vivo are associated with its interactive characteristics with the proteins. In this regard, a detailed binding profile of CR with human serum albumin (HSA) was studied using isothermal titration calorimetry (ITC) along with various spectroscopic and microscopic methods. The thermodynamic results from ITC indicated that the CR-HSA non-covalent interaction occured primarily due to favorable entropy and unfavorable enthalpy with a Ka of 106 M-1 at lower concentrations and 105 M-1 at higher concentrations. Steady-state fluorescence data revealed that the intrinsic fluorescence of HSA was quenched in the presence of CR via the static quenching mechanism. Using Förster's non-radioactive energy transfer theory (FRET), the specific binding distance r (2.73 nm) between the donor (Trp-214 from HSA) and the acceptor (CR) was calculated. Our preliminary results indicated that CR had a high affinity to HSA, which can have significant implications in the distribution and elimination of this toxic dye upon exposure.

Durum wheat semolina-modified ceramic membranes as novel porous separators for enhanced power generation and wastewater remediation using microbial fuel cell.

This proof-of-concept study describes the enhanced performance efficiency of the dual-chambered microbial fuel cell equipped with the fabricated unmodified ceramic membranes and ceramic membranes modified with 5 % and 10 % (w/w) durum wheat semolina in comparison with the commercially available NafionTM 117 membranes. The chemical oxygen demand removal efficiencies were determined to be 85.6 ± 0.1, 72.1 ± 0.2 and 68.6 ± 0.1 % for microbial fuel cell equipped with 10 % (w/w) semolina-modified, 5 % (w/w) semolina-modified and unmodified ceramic membrane, respectively, which indicated the improved wastewater treatment efficiency with increasing content of semolina. Preliminary studies showed that the 10 % (w/w) semolina-modified ceramic was cost-effective (64 USD/m2) with improved water uptake, good proton mobility, low oxygen diffusion in addition to the enhanced power and current density output. The semolina-modified ceramic membranes have the potential to become a cost-effective alternative for the high-efficiency production of bioelectricity using microbial fuel cells.

Angle-Sensitive Photonic Crystals for Simultaneous Detection and Photocatalytic Degradation of Hazardous Diazo Compounds.

Congo Red (CR) and Amido Black 10B (AB-10B) are anionic diazo dyes, which are metabolized to produce a bioaccumulative and persistent carcinogen, benzidine. In this regard, an angle sensitive sensor composed of photonic crystal supported photocatalyst was fabricated for the simultaneous detection and photocatalytic degradation of diazo dyes from aqueous solutions. Reflectance spectroscopy was used in the detection of CR and AB-10B, which was based on the emergence of the incident angle dependent reflection peaks from the TiO2 coated two-dimensional photonic crystal (2D-PhC) surfaces and their subsequent quenching due to the presence of dye molecules whose absorbance peak intensity overlapped the reflection peak intensity of TiO2 at the respective angle. Interestingly, ultraviolet (UV) mediated photocatalytic degradation of CR and AB-10B was achieved using the same TiO2 coated 2D-PhC surfaces. 2D-PhC underneath the TiO2 layer was able to confine and localize the light on the TiO2 coated 2D-PhC surface, which enhanced the light absorption by dye molecules on the TiO2 surface and the photocatalytic efficiency in the degradation of CR and AB-10B. Finally, this proof-of-concept study demonstrated the fabrication of copolymer film based photonic crystal supported photocatalytic device, which can be used for developing miniaturized sensors competent in on-field detection and degradation of pollutants.