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Indiana University-Purdue University Indianapolis (IUPUI) / This clinical study investigated the efficacy of the new LED LCU technology when compared to that of the QTH LCU by evaluating retention and wear of Clinpro (3M ESPE) sealant material over six months of function. This study was designed as a split mouth, randomized clinical study. Sealants were placed and polymerized on contralateral teeth of 35 patients, 33 of which successfully completed the study. The sealants were evaluated for clinical retention at baseline, three months, and six months by two evaluators. For the wear analysis, the area of the sealant wear at six months is reported. Nine pairs of molars and 22 pairs of premolar teeth were used. This sample size is smaller than the original sample used for clinical evaluation, because a number of the baseline impressions had to be discarded due to poor impression quality. Subsequent impressions were taken at three months, and six months. Epoxy replicas were made from the impressions and the occlusal surface of each replica was digitized using SigmaScan software. A cummulative legit model was applied to the clinical data, and a linear model was applied to the wear analysis. The results for clinical retention over the six months of function were as follows. At Baseline, for the QTH, 97.3 percent of the teeth received an Alpha score; 2.7 percent received a score of B. For the LED, 87.7 percent received a score of A; 12.3 percent received a score of B. At three months follow-up, for the QTH, 93.1 percent received a score of A; 6.9 percent received a score of B. For the LED, 86.1 percent received a score of A; 12.5 percent received a score of B, and 1.14 percent received a score of C. At six months follow-up, for QTH; 91.7 percent received a score of A; 8.3 percent received a score of B. For the LED, 83.3 percent received a score of A; 15.3 percent received a score of B, and 1.14 percent received a score of C. The hypothesis was that there would be no significant difference in clinical retention and wear of Clinpro's sealant polymerized with the QTH or the LED light sources over six months of function. Based on the results of this clinical study, the following conclusions can be made: 1) At baseline, Clinpro's sealant polymerized with QTH light source showed marginally significant better retention than LED light source (p-value 0.05001). 2) There was no significant difference between light sources for sealant clinical retention at three-month and six-month follow up visits. 3) Wear analysis resulted in marginally significant more wear for molar sealants polymerized with LED LCU (p-value 0.0755). 4) Wear analysis showed no significant difference for premolar sealants polymerized with either light source.

The electrochemical behavior of the iodine-iodide couple was investigated in both basic and neutral acetic acid solutions at a platinum rotating ring-disk electrode. Voltammetric curves were obtained and discussed. Various kinetic parameters were determined and by comparing to theoretical kinetic parameters a probable reaction mechanism was deduced. The mechanism that best fit experimental results is the following I- + S = I(S) + e- I(S) + I- = I2 + S + e (slow). The electrochemical behavior of bromine, bromide, and chloride was also investigated in the same media. Voltammetric curves were recorded and discussed with emphasis on the hysteresis that occurs between anodic and cathodic scans. Surface phenomenon that cause this hysteresis were, in some cases, determined. The involvement of surface oxides and adsorption phenomena in causing the hysteresis were evident. Some kinetic parameters were obtained.

We derive tropospheric column BrO during the ARCTAS and ARCPAC field campaigns in spring 2008 using retrievals of total column BrO from the satellite UV nadir sensors OMI and GOME-2 using a radiative transfer model and stratospheric column BrO from a photochemical simulation. We conduct a comprehensive comparison of satellite-derived tropospheric BrO column to aircraft in-situ observations of BrO and related species. The aircraft profiles reveal that tropospheric BrO, when present during April 2008, was distributed over a broad range of altitudes rather than being confined to the planetary boundary layer (PBL). Perturbations to the total column resulting from tropospheric BrO are the same magnitude as perturbations due to longitudinal variations in the stratospheric component, so proper accounting of the stratospheric signal is essential for accurate determination of satellite-derived tropospheric BrO. We find reasonably good agreement between satellite-derived tropospheric BrO and columns found using aircraft in-situ BrO profiles, particularly when satellite radiances were obtained over bright surfaces (albedo >0.7), for solar zenith angle <80 degree and clear sky conditions. The rapid activation of BrO due to surface processes (the bromine explosion) is apparent in both the OMI and GOME-2 based tropospheric columns. The wide orbital swath of OMI allows examination of the evolution of tropospheric BrO on about hourly time intervals near the pole. Low surface pressure, strong wind, and high PBL height are associated with an observed BrO activation event, supporting the notion of bromine activation by high winds over snow. We also provide monthly climatological maps of free tropospheric BrO volume mixing ratio (VMR) derived using the so-called cloud slicing technique. In this approach, the derived slope of the total column BrO versus cloud pressure is proportional to free tropospheric BrO VMR. Estimated BrO VMR shows a minimum in the tropics and greater values at higher latitudes in both hemispheres. High tropospheric BrO VMR at high latitudes in spring could be influenced by near-surface bromine activation.

In this work I describe various approaches to electrochemical energy storage at the grid-scale. Chapter 1 provides an introduction to energy storage and an overview of the history and development of flow batteries. Chapter 2 describes work on the hydrogen-chlorine regenerative fuel cell, detailing its development and the record-breaking performance of the device. Chapter 3 dives into catalyst materials for such a fuel cell, focusing on ruthenium oxide based alloys to be used as chlorine redox catalysts. Chapter 4 introduces and details the development of a performance model for a hydrogen-bromine cell. Chapter 5 delves into the more recent work I have done, switching to applications of quinone chemistries in flow batteries. It focuses on the pairing of one particular quinone (2,7-anthraquinone disulfonic acid) with bromine, and highlights the promising performance characteristics of a device based on this type of chemistry. / Engineering and Applied Sciences

Heavy metals have been known to possess antimicrobial properties against bacterial, fungal, and viral pathogens. Silver and copper in particular have been used for millennia to control bacterial and fungal contamination. Metal nanoparticles (aggregations of metal atoms 1-200 nm in size) have recently become the subject of intensive study for their increased antimicrobial properties due to their increased surface area and localized release of metal ions when attached to pathogens. In the current studies, metal and metalhalide nanoparticles including silver (Ag), silver bromide (AgBr), silver iodide (AgI), and copper iodide (CuI) nanoparticles were evaluated for their antibacterial efficacy against two common bacterial pathogens. All of the nanoparticles significantly reduced bacterial numbers within 24 hours of exposure and were more effective against the Gram-negative Pseudomonas aeruginosa than the Gram-positive Staphylococcus aureus. CuI nanoparticles were found to be highly effective, reducing both organisms by >4.43 log₁₀ within 15 minutes at 60 ppm Cu. CuI nanoparticles were selected for further evaluation against a range of microorganisms to determine their broad spectrum efficacy. CuI nanoparticles formulated with different stabilizers (sodium dodecyl sulfate, SDS; PVP) were tested against representative Gram-positive and Gram-negative bacteria, Mycobacteria, a fungus (Candida albicans), and a non-enveloped virus (poliovirus). Both nanoparticles caused significant reductions in most of the Gram-negative bacteria within five minutes of exposure (>5.09-log₁₀). The Gram-positive bacterial species were more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. Likewise, C. albicans was also more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. In contrast, the acid-fast Mycobacterium smegmatis was more resistant to the CuI-SDS than the CuI-PVP nanoparticle solutions (2.54-log₁₀ vs. 3.80-log₁₀ after 30 minutes). Poliovirus was more resistant than the other organisms tested except for Mycobacterium fortuitum. M. fortuitum was more resistant to both CuI nanoparticle solutions than any of the other organisms tested, requiring longer exposure times to achieve comparable reductions (~4.15 log₁₀ after 24 hours). As an example of a real world antimicrobial application, polymer surface coatings with embedded CuI nanoparticles were investigated to determine their potential use as self-disinfecting surfaces. Brushed polyurethane, spincoated acrylic, and powder coated polyester-epoxy coatings containing various concentrations of CuI nanoparticles were tested for antibacterial efficacy against P. aeruginosa and S. aureus. Polyester-epoxy powder coatings were superior to the other coatings in terms of uniformity and stability under moist conditions and displayed antimicrobial properties against both organisms (>4.92 log₁₀) after six hours at 0.25% Cu. Polyester-epoxy coatings were selected for more rigorous testing under adverse conditions. These surfaces were negatively impacted when tested under dry conditions with high organic content, with organic content appearing to have a greater impact on antimicrobial efficacy. At 0.25% Cu, the antibacterial activity of the powder coatings was not impacted by washing with several commercial cleaners; however, at concentrations of 0.05% Cu, antibacterial activity was reduced by multiple washings with water, Windex®, and Pine Sol®. Additionally, ultrasonic cleaning of the coatings appeared to decrease their antimicrobial efficacy. Despite this, CuI nanoparticles were found in all studies to have great potential as a new class of fast-acting, broad-spectrum antimicrobial.

Glancing angle laser induced fluorescence was used to monitor the kinetics of the photodegradation of chlorophyll at the surface of various salt solutions. The loss was measured using varying wavelengths of actinic radiation in the presence and absence of gas phase ozone. The loss rate of illuminated chlorophyll was faster on salt water surfaces than fresh water surfaces, both in the presence and absence of ozone. On salt water surfaces, the dependence of the loss rate on [O3(g)] was different under illuminated conditions than in the dark. This was further investigated by measuring the excitation spectra and the dependence of chlorophyll loss on the concentration of salts at the salt water surface. The possible production of reactive halogen atoms is the likely reason for the observed enhancement. The following results provide evidence of photosensitized oxidation of halogen anions, in the UV-visible range of the spectrum, resulting in halogen atom release.

Glancing angle laser induced fluorescence was used to monitor the kinetics of the photodegradation of chlorophyll at the surface of various salt solutions. The loss was measured using varying wavelengths of actinic radiation in the presence and absence of gas phase ozone. The loss rate of illuminated chlorophyll was faster on salt water surfaces than fresh water surfaces, both in the presence and absence of ozone. On salt water surfaces, the dependence of the loss rate on [O3(g)] was different under illuminated conditions than in the dark. This was further investigated by measuring the excitation spectra and the dependence of chlorophyll loss on the concentration of salts at the salt water surface. The possible production of reactive halogen atoms is the likely reason for the observed enhancement. The following results provide evidence of photosensitized oxidation of halogen anions, in the UV-visible range of the spectrum, resulting in halogen atom release.