Maral P. S. Mousavi

Effects of Humic and Fulvic Acids on Silver Nanoparticle Stability, Dissolution, and Toxicity

The colloidal stability of silver nanoparticles (AgNPs) in natural aquatic environments influences their transport and environmental persistence, while their dissolution to Ag(+) influences their toxicity to organisms. Here, we characterize the colloidal stability, dissolution behavior, and toxicity of two industrially relevant classes of AgNPs (i.e., AgNPs stabilized by citrate or polyvinylpyrrolidone) after exposure to natural organic matter (NOM, i.e., Suwannee River Humic and Fulvic Acid Standards and Pony Lake Fulvic Acid Reference). We show that NOM interaction with the nanoparticle surface depends on (i) the NOMs chemical composition, where sulfur- and nitrogen-rich NOM more significantly increases colloidal stability, and (ii) the affinity of the capping agent for the AgNP surface, where nanoparticles with loosely bound capping agents are more effectively stabilized by NOM. Adsorption of NOM is shown to have little effect on AgNP dissolution under most experimental conditions, the exception being when the NOM is rich in sulfur and nitrogen. Similarly, the toxicity of AgNPs to a bacterial model (Shewanella oneidensis MR-1) decreases most significantly in the presence of sulfur- and nitrogen-rich NOM. Our data suggest that the rate of AgNP aggregation and dissolution in aquatic environments containing NOM will depend on the chemical composition of the NOM, and that the toxicity of AgNPs to aquatic microorganisms is controlled primarily by the extent of nanoparticle dissolution.

Hierarchically Porous Polymer Monoliths by Combining Controlled Macro- and Microphase Separation

The ability to tune polymer monolith porosity on multiple length scales is desirable for applications in liquid separations, catalysis, and bioengineering. To this end, we have developed a facile synthetic route to nanoporous polymer monoliths based on controlled polymerization of styrene and divinylbenzene from a poly(lactide) macro-chain transfer agent in the presence of nonreactive poly(ethylene oxide) (PEO). Simple variations in the volume fraction and/or molar mass of PEO lead to either polymerization-induced microphase separation or simultaneous macro- and microphase separation. These processes dictate the resultant morphology and allow for control of the macro- and microstructure of the monoliths. Subsequent selective etching produces monoliths with morphologies that can be tailored from mesoporous, with control over mesopore size, to hierarchically meso- and macroporous, with percolating macropores. This convenient synthetic route to porous polymer monoliths has the potential to be useful in applications where both rapid mass transport and a high surface area are required.

Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy

Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Reference electrodes with salt bridges contained in nanoporous glass: an underappreciated source of error.

In electroanalytical measurements, nanoporous glass plugs are widely used to contain the electrolyte solution that forms a salt bridge between the sample and the reference electrode. Even though reference electrodes with plugs made of nanoporous glass (such as Vycor or CoralPor glass) are commercially available and are frequently used, the limits of their use have not been explored thoroughly. It is shown here that at ionic strengths lower than 100 mM, the half-cell potentials of reference electrodes with nanoporous glass plugs are not sample independent, as it would be desirable, but they depend on the ionic sample composition. Sample dependent shifts of more than 50 mV in the half cell potential were encountered. Reference potentials were found to be affected in aqueous solutions by HCl, NaCl, KCl, and CaCl2 and in acetonitrile by CF3COOH and the supporting electrolyte tetrabutylammonium perchlorate. These observations cannot be explained by the liquid junction potential between two mutually miscible electrolyte solutions, as commonly described with the Henderson equation. Instead, they result from the surface charge density on the glass surface and the resulting electrostatic screening of ion transfer into the glass pores when the latter have dimensions comparable to or smaller than the Debye length. Users of reference electrodes with nanoporous glass plugs need to be aware of these limitations to avoid substantial measurement errors.

Dynamic silver speciation as studied with fluorous-phase ion-selective electrodes: Effect of natural organic matter on the toxicity and speciation of silver.

The widespread application of silver in consumer products and the resulting contamination of natural environments with silver raise questions about the toxicity of Ag(+) in the ecosystem. Natural organic matter, NOM, which is abundant in water supplies, soil, and sediments, can form stable complexes with Ag(+), altering its bioavailability and toxicity. Herein, the extent and kinetics of Ag(+) binding to NOM, matrix effects on Ag(+) binding to NOM, and the effect of NOM on Ag(+) toxicity to Shewanella oneidensis MR-1 (assessed by the BacLight viability assay) were quantitatively studied with fluorous-phase Ag(+) ion-selective electrodes (ISEs). Our findings show fast kinetics of Ag(+) and NOM binding, weak Ag(+) binding for Suwannee River humic acid, fulvic acid, and aquatic NOM, and stronger Ag(+) binding for Pony Lake fulvic acid and Pahokee Peat humic acid. We quantified the effects of matrix components and pH on Ag(+) binding to NOM, showing that the extent of binding greatly depends on the environmental conditions. The effect of NOM on the toxicity of Ag(+) does not correlate with the extent of Ag(+) binding to NOM, and other forms of silver, such as Ag(+) reduced by NOM, are critical for understanding the effect of NOM on Ag(+) toxicity. This work also shows that fluorous-phase Ag(+) ISEs are effective tools for studying Ag(+) binding to NOM because they can be used in a time-resolved manner to monitor the activity of Ag(+) in situ with high selectivity and without the need for extensive sample preparation.

Avoiding Errors in Electrochemical Measurements: Effect of Frit Material on the Performance of Reference Electrodes with Porous Frit Junctions

In many commercially available and in-house-prepared reference electrodes, nanoporous glass frits (often of the brand named Vycor) contain the electrolyte solution that forms a salt bridge between the sample and the reference solution. Recently, we showed that in samples with low ionic strength, the half-cell potentials of reference electrodes comprising nanoporous Vycor frits are affected by the sample and can shift in response to the sample composition by more than 50 mV (which can cause up to 900% error in potentiometric measurements). It was confirmed that the large potential variations result from electrostatic screening of ion transfer through the frit due to the negatively charged surfaces of the glass nanopores. Since the commercial production of porous Vycor glass was recently discontinued, new materials have been used lately as porous frits in commercially available reference electrodes, namely frits made of Teflon, polyethylene, or one of two porous glasses sold under the brand names CoralPor and Electro-porous KT. In this work, we studied the effect of the frit characteristics on the performance of reference electrodes, and show that the unwanted changes in the reference potential are not unique to electrodes with Vycor frits. Increasing the pore size in the glass frits from the <10 nm into the 1 μm range or switching to polymeric frits with pores in the 1 to 10 μm range nearly eliminates the potential variations caused by electrostatic screening of ion transport through the frit pores. Unfortunately, bigger frit pores result in larger flow rates of the reference solution through the pores, which can result in the contamination of test solutions.

Open-Source Potentiostat for Wireless Electrochemical Detection with Smartphones

This paper describes the design and characterization of an open-source “universal wireless electrochemical detector” (UWED). This detector interfaces with a smartphone (or a tablet) using “Bluetooth Low Energy” protocol; the smartphone provides (i) a user interface for receiving the experimental parameters from the user and visualizing the result in real time, and (ii) a proxy for storing, processing, and transmitting the data and experimental protocols. This approach simplifies the design, and decreases both the size and the cost of the hardware; it also makes the UWED adaptable to different types of analyses by simple modification of the software. The UWED can perform the most common electroanalytical techniques of potentiometry, chronoamperometry, cyclic voltammetry, and square wave voltammetry, with results closely comparable to benchtop commercial potentiostats. Although the operating ranges of electrical current and voltage of the UWED (±1.5 V, ±180 μA) are more limited than most benchtop commercial potentiostats, its functional range is sufficient for most electrochemical analyses in aqueous solutions. Because the UWED is simple, small in size, assembled from inexpensive components, and completely wireless, it offers new opportunities for the development of affordable diagnostics, sensors, and wearable devices.