Electrocatalytic oxidation of pyrrole on a quasi-reversible silver nanodumbbell particle surface for supramolecular porphyrin production.

Photoactive supramolecular porphyrin assemblies are attractive molecules for light-harvesting applications. This is due to their relatively non-toxicity, biological activities and charge and energy exchange characteristics. However, the extreme cost associated with their synthesis and requirements for toxic organic solvents during purification pose a challenge to the sustainability characteristics of their applications. This work presents the first report on the sustainable synthesis, spectroscopic and photophysical characterizations of a near-infrared (NIR) absorbing Ca(II)-meso-tetrakis (4-hydroxyphenyl)porphyrin using an electrolyzed pyrrole solution. The latter was obtained by cycling the pyrrole solution across the silver nanodumbbell particle surface at room temperature. The electrolyzed solution condensed readily with acidified p-hydroxybenzaldehyde, producing the targeted purple porphyrin. The non-electrolyzed pyrrole solution formed a green substance with significantly different optical properties. Remarkable differences were observed in the voltammograms of the silver nanodumbbell particles and those of the conventional gold electrode during the pyrrole cycling, suggesting different routes of porphyrin formation. The rationale behind these formations and the associated mechanisms were extensively discussed. Metalation with aqueous Ca2+ ion caused a Stokes shift of 38.75 eV. The current study shows the advantage of the electrochemical method towards obtaining sustainable light-harvesting porphyrin at room temperature without the need for high-energy-dependent conventional processes.

Fluorescence sensing and adsorption kinetics of Gd-doped AgInS2 I-III-VI quantum dots - A case study of Ag+ ions interactions.

The poor fluorescence properties of magneto-fluorescent paramagnetic-ion (Gd, Mn, or Co) doped I-III-VI quantum dots (QDs) at higher paramagnetic-ion doping concentrations have limited their use in magnetic-driven water-based applications. This work presents, for the first time, the use of stable magneto-fluorescent Gd-doped AgInS2 QDs at high Gd mole ratios of 16, 20, and 30 for the fluorescence detection and adsorption of Ag+ ions in water environments. The effect of pH, initial concentration, contact time, and adsorbent dosage were systematically evaluated. The AgInS2 QDs with the least Gd mole ratio (16) exhibited the best fluorescence characteristics (LOD = 0.88, R2 = 0.9549) while all materials showed good adsorption properties under optimized conditions (pH of 2, initial concentration of 30 ppm, contact time of 10 min and adsorbent dosage of 0.02 g) and a pseudo 2nd order reaction was followed. The adsorption mechanism was proposed to be a combination of ion-exchange, electrostatic interaction, complexation, and diffusion processes. Application in environmental wastewater samples revealed complete removal of Ag + ions alongside Ti2+ Pb2+, Ni2+, Cr3+, and Zn2+ ions.

A review on I-III-VI ternary quantum dots for fluorescence detection of heavy metals ions in water: optical properties, synthesis and application.

Heavy metal contamination remains a major threat to the environment. Evaluating the concentrations of heavy metals in water environments is a crucial step towards a viable treatment strategy. Non-cadmium photo-luminescent I-III-VI ternary QDs have attracted increasing attention due to their low toxicity and extraordinary optical properties, which have made them popular in biological applications. Recently, ternary I-III-VI-QDs have gained growing interest as fluorescent detectors of heavy metal ions in water. Here, we review the research progress of ternary I-III-VI QDs for the fluorescence detection of heavy metal ions in water. First, we summarize the optical properties and synthesis methodologies of ternary I-III-VI QDs. Then, we present various detection mechanisms involved in the fluorescence detection of heavy metal ions, which are mostly attributed to direct interaction between these unique QDs and the metal ions, seen in the form of fluorescence quenching and fluorescence enhancement. We also display the potential applications in environmental remediation such as water treatment and associated challenges of I-III-VI QDs in the fluorescence detection of Cu2+ and other metal ions.

Facile, large scale synthesis of water soluble AgInSe2/ZnSe quantum dots and its cell viability assessment on different cell lines.

I-III-VI chalcopyrite ternary quantum dots have emerged as a good alternative over the conventional II-VI and IV-VI chalcogenide binary QDs that usually consist of heavy metals such as Cd and Pb which has limited their bioapplications. Among the chalcopyrite QDs, AgInSe2 QDs has been the least developed due to the imbalanced cation reactivity, unwanted impurities, broad size distribution and resultant large particle sizes. In addition, the cell viability of these QDs still needs to be investigated on different cell lines both normal and cancerous ones. Herein, large-scale synthesis of water-soluble thioglycolic acid (TGA) capped and gelatin-stabilized AgInSe2 (AISe) core and AgInSe2/ZnSe (AISe/ZnSe) core/shell QDs in the absence of an inert atmosphere and their cell viability against different cell lines are reported. The optical and structural characteristics of the as-synthesized QDs were investigated by UV-visible (vis) absorption, photoluminescence (PL) and Fourier-transmission infrared (FTIR) spectroscopies, dynamic light scattering (DLS), X-ray diffraction (XRD), and high-resolution transmission electron microscope (HRTEM) techniques. Growth of ZnSe shell on the core AISe resulted in the blue shifting of the emission maximum position with the increased PL intensity. The QDs are small and spherical in shape with an average particle diameter of 2.8 nm and 3.2 nm for AISe and AISe/ZnSe QDs respectively. The in vitro cell viability assay revealed that the as-synthesized AISe/ZnSe QDs are not toxic towards cancerous (HeLa -cervical cancer and A549-lung cancer) and normal (BHK21 -Kidney) cell lines.