Biodegradable Acid-Based Fe2MnO4 Nanoparticles for Water Remediation.

This study demonstrated the synthesis of Fe2MnO4 modified by citric acid, a biodegradable acid, using a simple co-precipitation method. Characterization was performed using qualitative analysis techniques such as Fourier-transformed infrared spectroscopy, scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy, X-ray diffraction, selected-area electron diffraction, N2 adsorption-desorption, and zero-point charge. The prepared nanoparticles had a rough and porous surface, and contained oxygenous (-OH, -COOH, etc.) functional groups. The specific surface area and average pore size distribution were 83 m2/g and 5.17 nm, respectively. Net zero charge on the surface of the prepared nanoparticles was observed at pH 7.5. The prepared nanoparticles were used as an adsorbent to remove methylene blue dye from water under various conditions. Using small amounts of the adsorbent (2.0 g/L), even a high concentration of MB dye (60 mg/L) could be reduced by about ~58%. Exothermic, spontaneous, feasible, and monolayer adsorption was identified based on thermodynamics and isotherm analysis. Reusability testing verified the stability of the adsorbent and found that the reused adsorbent performed well for up to three thermal cycles. Comparative analysis revealed that the modified adsorbent outperformed previously reported adsorbents and unmodified Fe2MnO4 in terms of its partition coefficient and equilibrium adsorption capacity under different experimental conditions.

TEMPO Driven Mild and Modular Route to Functionalized Microparticles.

The synthesis of crosslinked polymeric microspheres (3.8-15.0 µm) via (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) initiated thiol-ene dispersion polymerization under ambient conditions is reported for the first time. The initiating ability of TEMPO for the thiol-ene reaction is validated by electron paramagnetic resonance (EPR) and 1 H nuclear magnetic resonance (NMR) spectroscopy on model reactions between 1-octadecanethiol and two electron deficient enes, n-butylacrylate and divinyl sulfone. Critically, the TEMPO resonance observed in the EPR spectra decreases with time when TEMPO is mixed with thiol and an electron deficient ene. The 1 H NMR spectra demonstrate formation of up to 90% of thioether under ambient conditions. Based on these model reactions, a variety of crosslinked polymeric microspheres are synthesized with excellent morphological stability using poly(vinyl pyrrolidone) as surfactant. The ability of the microspheres for a second TEMPO initiated thiol-ene reaction is demonstrated by the ligation of fluorescein-5-maleimide (an ene) to the microspheres' surface containing excess of thiol functionality and by ligation of cysteine (containing a thiol group) to the microspheres' surface containing an excess of ene functionality. The synthesized polymeric microspheres are characterized using scanning electron microscopy, differential scanning calorimetry, Fourier-transform infrared spectroscopy, zeta potential, and X-ray photoelectron spectroscopy.

Novel Conductive and Redox-Active Molecularly Imprinted Polymer for Direct Quantification of Perfluorooctanoic Acid.

This study developed a novel molecularly imprinted polymer (MIP) that is both conductive and redox-active for directly quantifying perfluorooctanoic acid (PFOA) electrochemically. We synthesized the monomer 3,4-ethylenedioxythiophene-2,2,6,6-tetramethylpiperidinyloxy (EDOT-TEMPO) for electropolymerization on a glassy carbon electrode using PFOA as a template, which was abbreviated as PEDOT-TEMPO-MIP. The redox-active MIP eliminated the need for external redox probes. When exposed to PFOA, both anodic and cathodic peaks of MIP showed a decreased current density. This observation can be explained by the formation of a charge-assisted hydrogen bond between the anionic PFOA and MIP's redox-active moieties (TEMPO) that hinder the conversion between the oxidized and reduced forms of TEMPO. The extent of the current density decrease showed excellent linearity with PFOA concentrations, with a method detection limit of 0.28 ng·L-1. PEDOT-TEMPO-MIP also exhibited high selectivity toward PFOA against other per- and polyfluoroalkyl substances (PFAS) at environmentally relevant concentrations. Our results suggest electropolymerization of MIPs was highly reproducible, with a relative standard deviation of 5.1% among three separate MIP electrodes. PEDOT-TEMPO-MIP can also be repeatedly used with good stability and reproducibility for PFOA detection. This study provides an innovative platform for rapid PFAS quantification using redox-active MIPs, laying the groundwork for developing compact PFAS sensors.

MnO2 decoration onto the guava leaves: A sustainable and cost-effective material for methylene blue dye removal.

Excessive number of dyes in water is becoming the main cause of water pollution, which is very important to remove because it is harmful. Dye contaminated water is being treated by various methods. Adsorption method can be considered best for the study of dye removal due to several technological reasons. The adsorption method has also been emphasized in this study. In the present work, a nano-bio-composite was fabricated by growing manganese oxide nanoparticles on abundant cellulosic guava leaf powder. This allows nanocomposite to be prepared in large quantities at nominal cost. The characterization technique confirmed the irregular growth of manganese oxide nanoparticles onto the guava leaf powder. The electrostatic and non-electrostatic interactions was confirmed in between manganese oxide nanoparticles and the carbon structure of guava leaf powder. The massive functional groups were found to be in the prepared nano-bio-composite. The grain size of prepared material was in nano range. The developed nano-bio-composite was used to remove methylene blue from water. This showed a very good adsorptive capacity for methylene blue. The analyzed adsorption data was modelled through isotherms, kinetics and thermodynamics models. The nature of the adsorption process was determined to be spontaneous and exothermic. The reusability test was carried out for five adsorption-desorption cycles. The reusability results suggested the better removal efficiency (%) in the first two cycles with only 20 % reduction in removal efficiency (%). The leaching test result revealed the good stability of MnO2/GL at neutral pH. It was a unique and cheap adsorbent of its kind, which had not been noticed anywhere before.