Effect of equilibration time on the structural gradient in the vertical direction for bicontinuous microemulsions in Winsor-III and -IV systems.

Bicontinuous microemulsions (BMEs), self-assembly systems consisting of oil and water nanodomains separated by surfactant monolayers, have many applications. However, changes in structure and properties of BMEs in the vertical direction can affect BMEs' utility. This study's objective was to determine the effect of equilibration time (τeq) on structural changes in the vertical direction for bicontinuous phases of Winsor-III (WIII) systems in situ or after being isolated, for D2O + H2O/1-dodecane/sodium dodecyl sulfate (SDS)/1-pentanol/NaCl at 22 °C. Small-angle neutron scattering (SANS) measurements were performed using a vertical stage sample environment that precisely aligned samples in the neutron beam. SANS data were fitted by the Teubner-Strey (TS) model and changes in TS-derived parameter values were observed. For 10 min ≤ τeq ≤ 4 h, the effective activity of the bicontinuous phase's surfactant monolayers increased with time at all vertical positions. At short equilibration (τeq = 10 min), small but significant amounts of water and oil were transiently emulsified near the WIII upper liquid-liquid interface. WIII systems underwent a relaxation process after being transferred to narrow 1 mm pathlength cells, resulting in a decrease of surfactant activity for the top half of the bicontinuous phase. For isolated bicontinuous phases, results suggest that SDS was desorbed from the BMEs by quartz near the bottom, while near the top, the water concentration near was relatively high. The results suggest that WIII systems should equilibrate for at least 4 hours after being prepared and transferred to a container that differs in cross sectional area and surfactant behavior in BMEs can change near interfaces.

Microemulsions: Breakthrough Electrolytes for Redox Flow Batteries.

Aqueous and non-aqueous redox flow batteries (RFBs) have limited energy and current densities, respectively, due to the nature of the electrolytes. New approaches to electrolyte design are needed to improve the performance of RFBs. In this work, we combined a highly conductive aqueous phase and an organic redox-active phase in a microemulsion to formulate a novel RFB electrolyte. As a proof-of-concept, we demonstrate an RFB using this microemulsion electrolyte with maximum current density of 17.5 mA·cm-2 with a 0.19 M posolyte and 0.09 M negolyte at a flow rate of only ∼2.5 ml·min-1, comparable to early vanadium electrolyte RFBs at similar flow rates on a per molar basis. The novel active negolyte component is an inexpensive oil-soluble vitamin (K3). By combining aqueous and organic phases, the solvent potential window and energy density may be increased without sacrificing current density and new redox couples may be accessed. Microemulsion electrolytes show great promise for improved performance and increased energy densities in aqueous RFBs but the path forward is complex. We end with discussion of areas that need work to achieve the potential of these electrolytes.

Surface-enhanced spatially-offset Raman spectroscopy (SESORS) for detection of neurochemicals through the skull at physiologically relevant concentrations.

Detection techniques for neurotransmitters that are rapid, label-free, and non-invasive are needed to move towards earlier diagnosis of neurological disease. Surface-enhanced Raman spectroscopy (SERS) allows for sensitive and selective detection of target analytes. The combination of SERS with spatially offset Raman spectroscopy (SORS) in a technique termed surface enhanced spatially offset Raman spectroscopy (SESORS) permits a sensitive and selective detection of neurotransmitters through the skull. Here, we present the SESORS detection of individual neurotransmitters and mixtures of neurotransmitters at physiologically relevant concentrations, while also establishing limits of detection.

Enzyme-catalyzed oxidation facilitates the return of fluorescence for single-walled carbon nanotubes.

In this work, we studied enzyme-catalyzed oxidation of single-walled carbon nanotubes (SWCNTs) produced by the high-pressure carbon monoxide (HiPco) method. While oxidation via strong acids introduced defect sites on SWCNTs and suppressed their near-infrared (NIR) fluorescence, our results indicated that the fluorescence of SWCNTs was restored upon enzymatic oxidation, providing new evidence that the reaction catalyzed by horseradish peroxidase (HRP) in the presence of H2O2 is mainly a defect-consuming step. These results were further supported by both UV-vis-NIR and Raman spectroscopy. Therefore, when acid oxidation followed by HRP-catalyzed enzyme oxidation was employed, shortened (<300 nm in length) and NIR-fluorescent SWCNTs were produced. In contrast, upon treatment with myeloperoxidase, H2O2, and NaCl, the oxidized HiPco SWCNTs underwent complete oxidation (i.e., degradation). The shortened, NIR-fluorescent SWCNTs resulting from HRP-catalyzed oxidation of acid-cut HiPco SWCNTs may find applications in cellular NIR imaging and drug delivery systems.