Veronica A. Okello

Reduction of Hexavalent Chromium Using Naturally-Derived Flavonoids

Quercetin is a naturally occurring flavonoid that is known to form complexes with metals; a process that reduces the environmental availability of toxic metals such as chromium. We hereby report the first evidence of the removal of Cr(VI) from environmental samples using quercetin (QCR) and two synthetic derivatives: namely quercetin pentaphosphate (QPP) and quercetin sulfonic acid (QSA). We successfully synthesized both QPP and QSA using simple procedures while characterizing them with UV-vis spectroscopy, H(1)-NMR, (13)C NMR, (31)P-NMR, and LC-MS techniques. The solubility of QPP was found to be 840 mg/mL and aqueous solutions of both QPP and QSA were stable for over a period of 1 year. Quercetin and these derivatives were subsequently utilized for the reduction of Cr(VI) and QCR was found to have a higher reduction efficiency of 99.8% (30 min), followed by QPP/palladium nanoparticles mixture (PdNPs) at 96.5% (60 min), and finally QSA/PdNPs mixtures at 91.7% (60 min). PdNPs catalyst increased the efficiency by ∼36.5% while a change in operating temperature from 25 to 45 °C improved the efficiency by ∼46.8%. Electron paramagnetic resonance spectroscopy was used to confirm the presence of Cr (III) in the reaction products. This reduction approach was validated in environmental (Binghamton University) BU and standard reference material (BRS) soil samples. Results showed that the analysis could be completed within one hour and the efficiency was higher in BU soil than in BRS soil by 16.1%. QPP registered the highest % atom economy of 94.6%. This indicates enhanced performance compared to bioremediation approach that requires several months to achieve about 90% reduction efficiency.

Size-exclusive nanosensor for quantitative analysis of fullerene C60.

This paper presents the first development of a mass-sensitive nanosensor for the isolation and quantitative analyses of engineered fullerene (C₆₀) nanoparticles, while excluding mixtures of structurally similar fullerenes. Amino-modified beta-cyclodextrin (β-CD-NH₂) was synthesized and confirmed by ¹HNMR as the host molecule to isolate the desired fullerene C₆₀. This was subsequently assembled onto the surfaces of gold-coated quartz crystal microbalance (QCM) electrodes using N-dicyclohexylcarbodiimide/N-hydroxysuccinimide (DCC/NHS) surface immobilization chemistry to create a selective molecular configuration described as (Au)-S-(CH₂)²-CONH-beta-CD sensor. The mass change on the sensor configuration on the QCM was monitored for selective quantitative analysis of fullerene C₆₀ from a C₆₀/C₇₀ mixture and soil samples. About ~10¹⁴-10¹⁶ C₆₀ particles/cm² were successfully quantified by QCM measurements. Continuous spike of 200 μL of 0.14 mg C₆₀ /mL produced changes in frequency (-Δf) that varied exponentially with concentration. FESEM and time-of-flight secondary-ion mass spectrometry confirmed the validity of sensor surface chemistry before and after exposure to fullerene C₆₀. The utility of this sensor for spiked real-world soil samples has been demonstrated. Comparable sensitivity was obtained using both the soil and purified toluene samples. This work demonstrates that the sensor has potential application in complex environmental matrices.

Capture, isolation and electrochemical detection of industrially-relevant engineered aerosol nanoparticles using poly (amic) acid, phase-inverted, nano-membranes

Workplace exposure to engineered nanoparticles (ENPs) is a potential health and environmental hazard. This paper reports a novel approach for tracking hazardous airborne ENPs by applying online poly (amic) acid membranes (PAA) with offline electrochemical detection. Test aerosol (Fe2O3, TiO2 and ZnO) nanoparticles were produced using the Harvard (Versatile Engineered Generation System) VENGES system. The particle morphology, size and elemental composition were determined using SEM, XRD and EDS. The PAA membrane electrodes used to capture the airborne ENPs were either stand-alone or with electron-beam gold-coated paper substrates. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to conceptually illustrate that exposure levels of industry-relevant classes of airborne nanoparticles could be captured and electrochemically detected at PAA membranes filter electrodes. CV parameters showed that PAA catalyzed the reduction of Fe2O3 to Fe(2+) with a size-dependent shift in reduction potential (E(0)). Using the proportionality of peak current to concentration, the amount of Fe2O3 was found to be 4.15×10(-17)mol/cm(3) PAA electrodes. Using EIS, the maximum phase angle (Φmax) and the interfacial charge transfer resistance (Rct) increased significantly using 100μg and 1000μg of TiO2 and ZnO respectively. The observed increase in Φmax and Rct at increasing concentration is consistent with the addition of an insulating layer of material on the electrode surface. The integrated VENGES/PAA filter sensor system has the potential to be used as a portable monitoring system.

Chapter 29 – Green Remediation of Hexavalent Chromium Using Naturally Derived Flavonoids and Engineered Nanoparticles

Conventional methods (e.g., bioremediation and zerovalent iron (ZVI)) for in situ remediation of chlorinated organic solvents may produce undesirable by-products and the use of nanoscale bimetallic particles has succeeded in eliminating some of these by-products. Palladium nanoparticles (PdNPs), bimetallic particles, ZVI particles with various oxidants, reductants, and nutrients have been shown to be useful in promoting contaminant transformation from toxic to benign forms. This chapter examines the most current information regarding metal contamination in water and the in situ remediation of inorganic contaminants, specifically chromium. We focus on the use of PdNPs for the catalytic conversion of Cr(VI) to Cr(III) using formic acid (FA) and sulfur. Based on the experimental results, this approach has shown that colloidal PdNPs enhanced the rate of reduction of Cr(VI). Along with the discussion of their enormous technological and economic potential, this chapter also discusses the use of naturally occurring flavonoids as reducing agents for Cr(VI).