Chad D. Vecitis

Electronic-Structure-Dependent Bacterial Cytotoxicity of Single-Walled Carbon Nanotubes

Single-walled carbon nanotubes (SWNTs) have been previously observed to be strong antimicrobial agents, and SWNT coatings can significantly reduce biofilm formation. However, the SWNT antimicrobial mechanism is not fully understood. Previous studies on SWNT cytotoxicity have concluded that membrane stress (i.e., direct SWNT-bacteria contact resulting in membrane perturbation and the release of intracellular contents) was the primary cause of cell death. Gene expression studies have indicated oxidative stress may be active, as well. Here, it is demonstrated for the first time how SWNT electronic structure (i.e., metallic versus semiconducting) is a key factor regulating SWNT antimicrobial activity. Experiments were performed with well-characterized SWNTs of similar length and diameter but varying fraction of metallic nanotubes. Loss of Escherichia coli viability was observed to increase with an increasing fraction of metallic SWNTs. Time-dependent cytotoxicity measurements indicated that in all cases the majority of the SWNT antimicrobial action occurs shortly after (<15 min) bacteria-SWNT contact. The SWNT toxicity mechanism was investigated by in vitro SWNT-mediated oxidation of glutathione, a common intracellular thiol that serves as an antioxidant and redox state mediator. The extent of glutathione oxidation was observed to increase with increasing fraction of metallic SWNTs, indicating an elevated role of oxidative stress. Scanning electron microscopy images of E. coli in contact with the SWNTs demonstrated electronic structure-dependent morphological changes consistent with cytotoxicity and glutathione oxidation results. A three-step SWNT antimicrobial mechanism is proposed involving (i) initial SWNT-bacteria contact, (ii) perturbation of the cell membrane, and (iii) electronic structure-dependent bacterial oxidation.

Covalent Binding of Single-Walled Carbon Nanotubes to Polyamide Membranes for Antimicrobial Surface Properties

We propose an innovative approach to impart nanomaterial-specific properties to the surface of thin-film composite membranes. Specifically, biocidal properties were obtained by covalently binding single-walled carbon nanotubes (SWNTs) to the membrane surface. The SWNTs were first modified by purification and ozonolysis to increase their sidewall functionalities, maximize cytotoxic properties, and achieve dispersion in aqueous solution. A tailored reaction protocol was developed to exploit the inherent moieties of hand-cast polyamide membrane surfaces and create covalent amide bonds with the functionalized SWNTs. The reaction is entirely aqueous-based and entails activation of the carboxylate groups of both the membrane and the nanomaterials to maximize reaction with ethylenediamine. The presence of SWNTs was verified after sonication of the membranes, confirming the strength of the bond between the SWNTs and the membrane surface. Characterization of the SWNT-functionalized surfaces demonstrated the attainment of membranes with novel properties that continued to exhibit high performance in water separation processes. The presence of surface-bound antimicrobial SWNTs was confirmed by experiments using E. coli cells that demonstrated an enhanced bacterial cytotoxicity for the SWNT-coated membranes. The SWNT membranes were observed to achieve up to 60% inactivation of bacteria attached to the membrane within 1 h of contact time. Our results suggest the potential of covalently bonded SWNTs to delay the onset of membrane biofouling during operation.

Electrochemical Multiwalled Carbon Nanotube Filter for Viral and Bacterial Removal and Inactivation

Nanotechnology has potential to offer solutions to problems facing the developing world. Here, we demonstrate the efficacy of an anodic multiwalled carbon nanotube (MWNT) microfilter toward the removal and inactivation of viruses (MS2) and bacteria (E. coli). In the absence of electrolysis, the MWNT filter is effective for complete removal of bacteria by sieving and multilog removal of viruses by depth-filtration. Concomitant electrolysis during filtration results in significantly increased inactivation of influent bacteria and viruses. At applied potentials of 2 and 3 V, the electrochemical MWNT filter reduced the number of bacteria and viruses in the effluent to below the limit of detection. Application of 2 and 3 V for 30 s postfiltration inactivated >75% of the sieved bacteria and >99.6% of the adsorbed viruses. Electrolyte concentration and composition had no correlation to electrochemical inactivation consistent with a direct oxidation mechanism at the MWNT filter surface. Potential dependent dye oxidation and E. coli morphological changes also support a direct oxidation mechanism. Advantages of the electrochemical MWNT filter for pathogen removal and inactivation and potential for point-of-use drinking water treatment are discussed.

Electrochemical carbon-nanotube filter performance toward virus removal and inactivation in the presence of natural organic matter.

The performance of an electrochemical multiwalled carbon nanotube (EC-MWNT) filter toward virus removal and inactivation in the presence of natural organic matter was systematically evaluated over a wide range of solution chemistries. Viral removal and inactivation were markedly enhanced by applying DC voltage in the presence of alginate and Suwannee River natural organic matter (SRNOM). Application of 2 or 3 V resulted in complete (5.8 to 7.4 log) removal and significant inactivation of MS2 viral particles in the presence of 5 mg L(-1) of SRNOM or 1 mg L(-1) of alginate. The EC-MWNT filter consistently maintained high performance over a wide range of solution pH and ionic strengths. The underlying mechanisms of enhanced viral removal and inactivation were further elucidated through EC-MWNT filtration experiments using carboxyl latex nanoparticles. We conclude that enhanced virus removal is attributed to the increased viral particle transport due to the applied external electric field and the attractive electrostatic interactions between the viral particles and the anodic MWNTs. The adsorbed viral particles on the MWNT surface are then inactivated through direct surface oxidation. Minimal fouling of the EC-MWNT filter was observed, even after 4-h filter runs with solutions containing 10 mg L(-1) of natural organic matter and 1 mM CaCl(2). Our results suggest that the EC-MWNT filter has a potential for use as a high performance point-of-use device for the removal of viruses from natural and contaminated waters with minimal power requirements.

Kinetics and Mechanism of the Sonolytic Conversion of the Aqueous Perfluorinated Surfactants, Perfluorooctanoate (PFOA), and Perfluorooctane Sulfonate (PFOS) into Inorganic Products

The perfluorinated surfactants perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are recognized as widespread in the environment as well as recalcitrant toward most conventional water treatment technologies. In this study, acoustic cavitation as driven by high-frequency ultrasound is shown to be effective in the degradation of aqueous solutions of PFOS and PFOA and effective over a wide range of concentrations from 10 nM to 10 muM for a given compound. Sulfur, fluorine, and carbon mass balances indicate that mineralization occurs immediately following the degradation of the initial perfluorinated surfactant. Near complete conversion of PFOS and PFOA to CO, CO2, F-, and SO42- occurs due to pyrolytic reactions at the surface and vapor phase of transiently collapsing cavitation bubbles. The initial PFOS or PFOA pyrolytic degradation occurs at the bubble-water interface and involves the loss of the ionic functional group leading to the formation of the corresponding 1H-fluoroalkane or perfluoroolefin. The fluorochemical intermediates undergo a series of pyrolytic reactions in the bubble vapor leading to C1 fluoro-radicals. Secondary vapor-phase bimolecular reactions coupled with concomitant hydrolysis converts the C1 fluoro-radicals to carbon monoxide, carbon dioxide, and HF, forming a proton and fluoride upon dissolution. Sonochemical half-lives, which are calculated from high-temperature gas-phase kinetics, are consistent with kinetic observations and suggest that mineralization occurs shortly after initial perfluorinated surfactant interfacial pyrolysis.

Reductive defluorination of aqueous perfluorinated alkyl surfactants : effects of ionic headgroup and chain length

Perfluorinated chemicals (PFCs) are distributed throughout the environment. In the case of perfluorinated alkyl carboxylates and sulfonates, they can be classified as persistent organic pollutants since they are resistant to environmentally relevant reduction, oxidation, and hydrolytic processes. With this in mind, we report on the reductive defluorination of perfluorobutanoate, PFBA (C(3)F(7)CO(2)(-)), perfluorohexanoate, PFHA (C(5)F(11)CO(2)(-)), perfluorooctanoate, PFOA (C(7)F(15)CO(2)(-)), perfluorobutane sulfonate, PFBS (C(4)F(9)SO(3)(-)), perfluorohexane sulfonate, PFHS (C(6)F(13)SO(3)(-)), and perfluorooctane sulfonate, PFOS (C(8)F(17)SO(3)(-)) by aquated electrons, e(aq)(-), that are generated from the UV photolysis (lambda = 254 nm) of iodide. The ionic headgroup (-SO(3)(-) vs -CO(2)(-)) has a significant effect on the reduction kinetics and extent of defluorination (F index = -[F(-)](produced)/[PFC](degraded)). Perfluoroalkylsulfonate reduction kinetics and the F index increase linearly with increasing chain length. In contrast, perfluoroalkylcarboxylate chain length appears to have a negligible effect on the observed kinetics and the F index. H/F ratios in the gaseous fluoro-organic products are consistent with measured F indexes. Incomplete defluorination of the gaseous products suggests a reductive cleavage of the ionic headgroup occurs before complete defluorination. Detailed mechanisms involving initiation by aquated electrons are proposed.

Electrochemical Carbon Nanotube Filter Oxidative Performance as a Function of Surface Chemistry

An electrochemical carbon nanotube filter has been reported to be effective for the removal and electrooxidation of aqueous chemicals and microorganisms. Here, we investigate how carbon nanotube (CNT) chemical surface treatments including calcination to remove amorphous carbon, acid treatment to remove internal residual metal oxide, formation of surficial oxy-functional groups, and addition of Sb-doped SnO(2) particles affect the electrooxidative filter performance. The various CNT samples are characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) and electrochemically evaluated by cyclic voltammetry, open circuit potential versus time analysis, and electrochemical impedance spectroscopy. Voltammetry results indicate that the near CNT surface pH is at least two units lower than the bulk pH. The electrooxidative performance of the various CNT samples is evaluated with 1 mM of methyl orange (MO) in 100 mM sodium sulfate at a flow rate of 1.5 mL min(-1). At both 2 and 3 V, the efficacy of electrochemical filtration is observed to be function of CNT surface chemistry. The samples with the greatest electrooxidation were the calcinated then HCl-treated CNTs, i.e., the CNTs with the most surficial sp(2)-bonded carbon, and the Sb-SnO(2)-coated CNTs, i.e., the CNTs with the most electrocatalytic surface area. At 3 V applied voltage, these CNT samples are able to oxidize 95% of the influent MO within the liquid residence time of <1.2 s. The broader applicability of electrochemical filtration is evaluated by challenging the C-CNT-HCl and C-CNT-HNO(3) networks with various organics including methylene blue, phenol, methanol, and formaldehyde. At 3 V applied voltage, both CNTs are able to degrade a fraction of all the organics with the extent organic degradation dependent on both CNT and organic properties. The C-CNT-HCl network generally had the better oxidative performance than the C-CNT-HNO(3) network with an exception being the positively charged methylene blue. The extent of MO degradation, steady-state current, anode potential, effluent pH, and back pressure are also measured as a function of applied voltage (1-3 V) and CNT surface chemistry. Mass spectrometry of electrochemical CNT filter effluent at 2 and 3 V is utilized to evaluate plausible electrooxidation products. Energy consumption as compared to state-of-the-art electrodes and strategies to tailor the CNT surface for a specific target molecule are discussed.

Carbon nanotube membrane stack for flow-through sequential regenerative electro-Fenton.

Electro-Fenton is a promising advanced oxidation process for water treatment consisting a series redox reactions. Here, we design and examine an electrochemical filter for sequential electro-Fenton reactions to optimize the treatment process. The carbon nanotube (CNT) membrane stack (thickness ∼ 200 μm) used here consisted of 1) a CNT network cathode for O2 reduction to H2O2, 2) a CNT-COOFe(2+) cathode to chemical reduction H2O2 to (•)OH and HO(-) and to regenerate Fe(2+) in situ, 3) a porous PVDF or PTFE insulating separator, and 4) a CNT filter anode for remaining intermediate oxidation intermediates. The sequential electro-Fenton was compared to individual electrochemical and Fenton process using oxalate, a persistent organic, as a target molecule. Synergism is observed during the sequential electro-Fenton process. For example, when [DO]in = 38 ± 1 mg L(-1), J = 1.6 mL min(-1), neutral pH, and Ecell = 2.89 V, the sequential electro-Fenton oxidation rate was 206.8 ± 6.3 mgC m(-2) h(-1), which is 4-fold greater than the sum of the individual electrochemistry (16.4 ± 3.2 mgC m(-2) h(-1)) and Fenton (33.3 ± 1.3 mgC m(-2) h(-1)) reaction fluxes, and the energy consumption was 45.8 kWh kgTOC(-1). The sequential electro-Fenton was also challenged with the refractory trifluoroacetic acid (TFA) and trichloroacetic acid (TCA), and they can be transferred at a removal rate of 11.3 ± 1.2 and 21.8 ± 1.9 mmol m(-2) h(-1), respectively, with different transformation mechanisms.

Multiwalled carbon nanotube filter: improving viral removal at low pressure.

The effective removal of viruses by a multiwalled carbon nanotube (MWNT) filter is demonstrated over a range of solution chemistries. MS2 bacteriophage viral removal by the MWNT filter was between 1.5 and 3 log higher than that observed with a recently reported single-walled carbon nanotube (SWNT) filter when examined under similar loadings (0.3 mg/cm(2)) of carbon nanotubes (CNTs). The greater removal of viruses by the MWNT filter is attributed to a more uniform CNT-filter matrix that allows effective removal of viruses by physicochemical (depth) filtration. Viral removal by the MWNT filter was examined under a broad range of water compositions (ionic strength, monovalent and divalent salts, solution pH, natural organic matter, alginate, phosphate, and bicarbonate) and filter approach velocities (0.0016, 0.0044, and 0.0072 cm/s). Log viral removal increased as the fluid approach velocity decreased, exhibiting a dependence on approach velocity in agreement with colloid filtration theory for Brownian particles. Viral removal improved with increasing ionic strength (NaCl), from 5.06 log removal at 1 mM NaCl to greater than 6.56 log removal at 100 mM NaCl. Addition of calcium ions also enhanced viral removal, but the presence of magnesium ions resulted in a decrease in viral removal. Solution pH also played an important role in viral removal, with log removals of 8.13, 5.38, and 4.00 being documented at solution pH values of 3.0, 5.5, and 9.0, respectively. Dissolved natural organic matter (NOM) had a negligible effect on viral removal at low concentration (1 mg/L), but higher concentrations of NOM significantly reduced the viral removal by the MWNT filter, likely due to steric repulsion. Addition of alginate (model polysaccharide) also caused a marked decrease in viral removal by the MWNT filter. This highly scalable MWNT-filter technology at gravity-driven pressures presents new, cost-effective options for point-of-use filters for viral removal.

Degradation of the Common Aqueous Antibiotic Tetracycline using a Carbon Nanotube Electrochemical Filter.

In this work, a carbon nanotube (CNT) electrochemical filter was investigated for treatment of aqueous antibiotics using tetracycline (TC) as a model compound. Electrochemical filtration of 0.2 mM TC at a total cell potential of 2.5 V and a flow rate of 1.5 mL min(-1) (hydraulic residence time <2 s) resulted in an oxidative flux of 0.025 ± 0.001 mol h(-1) m(-2). Replacement of the perforated Ti cathode with a CNT cathode increased the TC oxidative flux by 2.3-fold to 0.020 ± 0.001 mol h(-1) m(-2) at a total cell potential of 1.0 V. Effluent analysis by liquid chromatography-mass spectrometry and disk agar biocidal diffusion tests indicate that the electrochemical filtration process can degrade the TC molecular structure and significantly decrease its antimicrobial activity, respectively. Addition of dissolved natural organic matter (NOM) negatively affected the TC electrooxidation because of competition for CNT sorption and electrooxidation sites. At 2.0 V total cell potential, TC spiked (0.2 mM) into drinking water reservoir and wastewater treatment plant effluent samples had an oxidative flux of 0.015 ± 0.001 and 0.022 ± 0.001 mol h(-1) m(-2), respectively, and an energy requirement of 0.7 kWh kgCOD(-1) or 0.084 kWh m(-3). These results indicate a CNT electrochemical filter may have potential to effectively and efficiently treat antibiotics in water and wastewater effluent.