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- All Subjects: Chemistry
- Creators: Lindsay, Stuart
- Status: Published
Description
Atmospheric particulate matter has a substantial impact on global climate due to its ability to absorb/scatter solar radiation and act as cloud condensation nuclei (CCN). Yet, little is known about marine aerosol, in particular, the carbonaceous fraction. In the present work, particulate matter was collected, using High Volume (HiVol) samplers, onto quartz fiber substrates during a series of research cruises on the Atlantic Ocean. Samples were collected on board the R/V Endeavor on West–East (March–April, 2006) and East–West (June–July, 2006) transects in the North Atlantic, as well as on the R/V Polarstern during a North–South (October–November, 2005) transect along the western coast of Europe and Africa. The aerosol total carbon (TC) concentrations for the West–East (Narragansett, RI, USA to Nice, France) and East–West (Heraklion, Crete, Greece to Narragansett, RI, USA) transects were generally low over the open ocean (0.36±0.14 μg C/m3) and increased as the ship approached coastal areas (2.18±1.37 μg C/m3), due to increased terrestrial/anthropogenic aerosol inputs. The TC for the North–South transect samples decreased in the southern hemisphere with the exception of samples collected near the 15th parallel where calculations indicate the air mass back trajectories originated from the continent. Seasonal variation in organic carbon (OC) was seen in the northern hemisphere open ocean samples with average values of 0.45 μg/m3 and 0.26 μg/m3 for spring and summer, respectively. These low summer time values are consistent with SeaWiFS satellite images that show decreasing chlorophyll a concentration (a proxy for phytoplankton biomass) in the summer. There is also a statistically significant (p<0.05) decline in surface water fluorescence in the summer. Moreover, examination of water–soluble organic carbon (WSOC) shows that the summer aerosol samples appear to have a higher fraction of the lower molecular weight material, indicating that the samples may be more oxidized (aged). The seasonal variation in aerosol content seen during the two 2006 cruises is evidence that a primary biological marine source is a significant contributor to the carbonaceous particulate in the marine atmosphere and is consistent with previous studies of clean marine air masses.
ContributorsHill, Hansina Rae (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2011
Description
Nucleosomes are the basic repetitive unit of eukaryotic chromatin and are responsible for packing DNA inside the nucleus of the cell. They consist of a complex of eight histone proteins (two copies of four proteins H2A, H2B, H3 and H4) around which 147 base pairs of DNA are wrapped in ~1.67 superhelical turns. Although the nucleosomes are stable protein-DNA complexes, they undergo spontaneous conformational changes that occur in an asynchronous fashion. This conformational dynamics, defined by the "site-exposure" model, involves the DNA unwrapping from the protein core and exposing itself transiently before wrapping back. Physiologically, this allows regulatory proteins to bind to their target DNA sites during cellular processes like replication, DNA repair and transcription. Traditional biochemical assays have stablished the equilibrium constants for the accessibility to various sites along the length of the nucleosomal DNA, from its end to the middle of the dyad axis. Using fluorescence correlation spectroscopy (FCS), we have established the position dependent rewrapping rates for nucleosomes. We have also used Monte Carlo simulation methods to analyze the applicability of FRET fluctuation spectroscopy towards conformational dynamics, specifically motivated by nucleosome dynamics. Another important conformational change that is involved in cellular processes is the disassembly of nucleosome into its constituent particles. The exact pathway adopted by nucleosomes is still not clear. We used dual color fluorescence correlation spectroscopy to study the intermediates during nucleosome disassembly induced by changing ionic strength. Studying the nature of nucleosome conformational change and the kinetics is very important in understanding gene expression. The results from this thesis give a quantitative description to the basic unit of the chromatin.
ContributorsGurunathan, Kaushik (Author) / Levitus, Marcia (Thesis advisor) / Lindsay, Stuart (Committee member) / Woodbury, Neal (Committee member) / Yan, Hao (Committee member) / Arizona State University (Publisher)
Created2011
Description
Human breath is a concoction of thousands of compounds having in it a breath-print of physiological processes in the body. Though breath provides a non-invasive and easy to handle biological fluid, its analysis for clinical diagnosis is not very common. Partly the reason for this absence is unavailability of cost effective and convenient tools for such analysis. Scientific literature is full of novel sensor ideas but it is challenging to develop a working device, which are few. These challenges include trace level detection, presence of hundreds of interfering compounds, excessive humidity, different sampling regulations and personal variability. To meet these challenges as well as deliver a low cost solution, optical sensors based on specific colorimetric chemical reactions on mesoporous membranes have been developed. Sensor hardware utilizing cost effective and ubiquitously available light source (LED) and detector (webcam/photo diodes) has been developed and optimized for sensitive detection. Sample conditioning mouthpiece suitable for portable sensors is developed and integrated. The sensors are capable of communication with mobile phones realizing the idea of m-health for easy personal health monitoring in free living conditions. Nitric oxide and Acetone are chosen as analytes of interest. Nitric oxide levels in the breath correlate with lung inflammation which makes it useful for asthma management. Acetone levels increase during ketosis resulting from fat metabolism in the body. Monitoring breath acetone thus provides useful information to people with type1 diabetes, epileptic children on ketogenic diets and people following fitness plans for weight loss.
ContributorsPrabhakar, Amlendu (Author) / Tao, Nongjian (Thesis advisor) / Forzani, Erica (Committee member) / Lindsay, Stuart (Committee member) / Arizona State University (Publisher)
Created2013
Description
Deoxyribonucleic acid (DNA), a biopolymer well known for its role in preserving genetic information in biology, is now drawing great deal of interest from material scientists. Ease of synthesis, predictable molecular recognition via Watson-Crick base pairing, vast numbers of available chemical modifications, and intrinsic nanoscale size makes DNA a suitable material for the construction of a plethora of nanostructures that can be used as scaffold to organize functional molecules with nanometer precision. This dissertation focuses on DNA-directed organization of metallic nanoparticles into well-defined, discrete structures and using them to study photonic interaction between fluorophore and metal particle. Presented here are a series of studies toward this goal. First, a novel and robust strategy of DNA functionalized silver nanoparticles (AgNPs) was developed and DNA functionalized AgNPs were employed for the organization of discrete well-defined dimeric and trimeric structures using a DNA triangular origami scaffold. Assembly of 1:1 silver nanoparticle and gold nanoparticle heterodimer has also been demonstrated using the same approach. Next, the triangular origami structures were used to co-assemble gold nanoparticles (AuNPs) and fluorophores to study the distance dependent and nanogap dependencies of the photonic interactions between them. These interactions were found to be consistent with the full electrodynamic simulations. Further, a gold nanorod (AuNR), an anisotropic nanoparticle was assembled into well-defined dimeric structures with predefined inter-rod angles. These dimeric structures exhibited unique optical properties compared to single AuNR that was consistent with the theoretical calculations. Fabrication of otherwise difficult to achieve 1:1 AuNP- AuNR hetero dimer, where the AuNP can be selectively placed at the end-on or side-on positions of anisotropic AuNR has also been shown. Finally, a click chemistry based approach was developed to organize sugar modified DNA on a particular arm of a DNA origami triangle and used them for site-selective immobilization of small AgNPs.
ContributorsPal, Suchetan (Author) / Liu, Yan (Thesis advisor) / Yan, Hao (Thesis advisor) / Lindsay, Stuart (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2012
Description
With a recent shift to a more environmentally conscious society, low-carbon and non-carbon producing energy production methods are being investigated and applied all over the world. Of these methods, fuel cells show great potential for clean energy production. A fuel cell is an electrochemical energy conversion device which directly converts chemical energy into electrical energy. Proton exchange membrane fuel cells (PEMFCs) are a highly researched energy source for automotive and stationary power applications. In order to produce the power required to meet Department of Energy requirements, platinum (Pt) must be used as a catalyst material in PEMFCs. Platinum, however, is very expensive and extensive research is being conducted to develop ways to reduce the amount of platinum used in PEMFCs. In the current study, three catalyst synthesis techniques were investigated and evaluated on their effectiveness to produce platinum-on copper (Pt@Cu) core-shell nanocatalyst on multi-walled carbon nanotube (MWCNT) support material. These three methods were direct deposition method, two-phase surfactant method, and single-phase surfactant method, in which direct deposition did not use a surfactant for particle size control and the surfactant methods did. The catalyst materials synthesized were evaluated by visual inspection and fuel cell performance. Samples which produced high fuel cell power output were evaluated using transmission electron microscopy (TEM) imaging. After evaluation, it was concluded that the direct deposition technique was effective in synthesizing Pt@Cu core-shell nanocatalyst on MWCNTs support when a rinsing process was used before adding platinum. The peak power density achieved by the rinsed core-shell catalyst was 618 mW.cm-2 , 13 percent greater than that of commercial platinum-carbon (Pt/C) catalyst. Transmission electron microscopy imaging revealed the core-shell catalyst contained Pt shells and platinum-copper alloy cores. Rinsing with deionized (DI) water was shown to be a crucial step in core-shell catalyst deposition as it reduced the number of platinum colloids on the carbon nanotube surface. After evaluation, it was concluded that the two-phase surfactant and single-phase surfactant synthesis methods were not effective at producing core-shell nanocatalyst with the parameters investigated.
ContributorsAdame, Anthony (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Peng, Xihong (Committee member) / Tamizhmani, Govindasamy (Committee member) / Arizona State University (Publisher)
Created2012
Description
Low temperature fuel cells are very attractive energy conversion technology for automotive applications due to their qualities of being clean, quiet, efficient and good peak power densities. However, due to high cost and limited durability and reliability, commercialization of this technology has not been possible as yet. The high fuel cell cost is mostly due to the expensive noble catalyst Pt. Alkaline fuel cell (AFC) systems, have potential to make use of non-noble catalysts and thus, provides with a solution of overall lower cost. Therefore, this issue has been addressed in this thesis work. Hydrogen-oxygen fuel cells using an alkaline anion exchange membrane were prepared and evaluated. Various non-platinum catalyst materials were investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201) and compared with commercial noble metal catalysts. Co and Fe phthalocyanine catalyst materials were synthesized using multi-walled carbon nanotubes (MWCNTs) as support materials. X-ray photoelectron spectroscopic study was conducted in order to examine the surface composition. The electroreduction of oxygen has been investigated on Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT and commercial Pt/C catalysts. The oxygen reduction reaction kinetics on these catalyst materials were evaluated using rotating disk electrodes in 0.1 M KOH solution and the current density values were consistently higher for Co phthalocyanine based electrodes compared to Fe phthalocyanine. The fuel cell performance of the MEAs with Co and Fe phthalocyanines and Tanaka Kikinzoku Kogyo Pt/C cathode catalysts were 100, 60 and 120 mW cm-2 using H22 and O2 gases. This thesis also includes work on synthesizing nitrogen doped MWCNTs using post-doping and In-Situ methods. Post-doped N-MWNCTs were prepared through heat treatment with NH4OH as nitrogen source. Characterization was done through fuel cell testing, which gave peak power density ~40mW.cm-2. For In-Situ N-MWCT, pyridine was used as nitrogen source. The sample characterization was done using Raman spectroscopy and RBS, which showed the presence ~3 at.% of nitrogen on the carbon surface.
ContributorsShah, QuratulAin Jawed (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Tamizhmani, Govindasamy (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2012
Description
N-nitrosodimethylamine (NDMA) is a probable human carcinogen that has been detected in various environments including the atmosphere, clouds, surface waters, and drinking water. NDMA can form through natural reactions in the aqueous phase of the atmosphere and it can form as a disinfection byproduct in water treatment. Due to its carcinogenic nature, it is important to understand the mechanism of formation of NDMA in both engineered processes such as water treatment and in natural processes in fogs and clouds. NDMA might form through the reaction of chloramines with amines in both cases. This work analyzes polydiallyldimethyl ammonium chloride (PolyDADMAC), which is the most commonly used polymer at drinking water treatment plants and has the potential to form NDMA if free polymer is present during the chloramination (disinfection) process. The composition of industrial polyDADMAC solutions is not well understood and is difficult to analyze. This work uses 1H and 13C nuclear magnetic resonance (NMR) to analyze the polymer solution composition. Both 1H and 13C NMR allow investigation of the presence of trace impurities in the solution, gather structural information such as chain length, and inform on reaction mechanisms. The primary impurities of concern for NDMA formation were identified as dimethylamine (DMA) and short-chain oligomers of the polyDADMAC. 13C NMR was further used to confirm that NDMA likely forms from polyDADMAC via a Hofmann elimination.
Chloramines might also form in fogs and clouds although to date the potential for chloramines to form NDMA in atmospheric fog and cloud droplets has not been investigated. This work uses computational modeling to determine that at reported atmospheric conditions, the chloramine pathway contributes to less than 0.01% NDMA formation. The numerical modeling identified a need for more atmospheric HOCl measurements. This work proposes a concept of using HOCl to react to form chloramine, which can react to form NDMA as a way to quantify atmospheric HOCl.
ContributorsDonovan, Samantha Jo (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hayes, Mark (Committee member) / Arizona State University (Publisher)
Created2022
Description
Exploration of long-range conductance in non-redox-active proteins at the single molecule scale is aided by the development of innovative, tailor-made quantitative data analysis techniques. This thesis details the rationale behind the proposed approaches, the steps taken to design and implement every method, and the validation of the methodologies using appropriate experiments, benchmarks, and rigorous statistical data analysis. The first chapter conducts a thorough literature review, sets the stage for the subsequent investigation, and underscores the importance of the research questions addressed in this thesis. The second chapter describes the solvent effects on the electronic conductance of a series of Consensus Tetratricopeptide Repeat proteins (CTPR) measured with Scanning Tunneling Microscopy (STM). The study reveals a reversible reduction in electronic conductance when water (H2O) is replaced with heavy water (D2O) due to a ~6-fold decrease in the carrier diffusion constant as proteins become solvated by D2O. Similar observations are made in a ~7 nm long tryptophan zipper protein, while a phenylalanine zipper protein of comparable length remains unchanged in D2O, highlighting the critical role of aromatic residues in proteins lacking redox cofactors. As an extension to this finding, the third chapter describes the development of a machine-learning model to detect the presence of a protein and identify essential features helping in the detection. For this purpose, a solid-state device was engineered to measure the conductance of CTPR-16 protein wires. This approach addresses the limitations in characterizing the STM gap, enables the collection of stable current vs. time data, and provides a statistical understanding of the electronic transport through a protein. The final chapter investigates real-time changes in conductance in response to protein conformation alterations. A deoxyribonucleic acid (DNA) polymerase Φ29 was chosen for its potential utility as a single-molecule DNA sequencing device. The modified enzyme was bound to electrodes functionalized with streptavidin. Φ29 connected by one biotinylated contact and a second nonspecific contact showed rapid small fluctuations in current when activated. Signals were greatly enhanced with two specific contacts. Features in the distributions of conductance increased by a factor of 2 or more over the open-to-closed conformational transition of the polymerase.
ContributorsMukherjee, Sohini (Author) / Lindsay, Stuart (Thesis advisor) / Moore, Thomas (Committee member) / Qing, Quan (Committee member) / Arizona State University (Publisher)
Created2023
Description
The volume of end-of-life photovoltaic (PV) modules is increasing as the global PV market increases, and the global PV waste streams are expected to reach 250,000 metric tons by the end of 2020. If the recycling processes are not in place, there would be 60 million tons of end-of-life PV modules lying in the landfills by 2050, that may not become a not-so-sustainable way of sourcing energy since all PV modules could contain certain amount of toxic substances. Currently in the United States, PV modules are categorized as general waste and can be disposed in landfills. However, potential leaching of toxic chemicals and materials, if any, from broken end-of-life modules may pose health or environmental risks. There is no standard procedure to remove samples from PV modules for chemical toxicity testing in the Toxicity Characteristic Leaching Procedure (TCLP) laboratories as per EPA 1311 standard. The main objective of this thesis is to develop an unbiased sampling approach for the TCLP testing of PV modules. The TCLP testing was concentrated only for the laminate part of the modules, as they are already existing recycling technologies for the frame and junction box components of PV modules. Four different sample removal methods have been applied to the laminates of five different module manufacturers: coring approach, cell-cut approach, strip-cut approach, and hybrid approach. These removed samples were sent to two different TCLP laboratories, and TCLP results were tested for repeatability within a lab and reproducibility between the labs. The pros and cons of each sample removal method have been explored and the influence of sample removal methods on the variability of TCLP results has been discussed. To reduce the variability of TCLP results to an acceptable level, additional improvements in the coring approach, the best of the four tested options, are still needed.
ContributorsLeslie, Joswin (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Kuitche, Joseph (Committee member) / Arizona State University (Publisher)
Created2018
Description
In the past, the photovoltaic (PV) modules were typically constructed with glass superstrate containing cerium oxide and EVA (ethylene vinyl acetate) encapsulant containing UV absorbing additives. However, in the current industry, the PV modules are generally constructed without cerium oxide in the glass and UV absorbing additives in EVA to increase quantum efficiency of crystalline silicon solar cells in the UV regions. This new approach is expected to boost the initial power output of the modules and reduce the long-term encapsulant browning issues. However, this new approach could lead to other durability and reliability issues such as delamination of encapsulant by damaging interfacial bonds, destruction of antireflection coating on solar cells and even breakage of polymeric backbone of EVA. This work compares the durability and reliability issues of PV modules having glass without cerium oxide and EVA with (aka, UVcut or UVC) and without (aka, UVpass or UVP) UV absorbing additives. In addition, modules with UVP front and UVC back EVA have also been investigated (aka, UVhybrid or UVH). The mini-modules with nine split cells used in this work were fabricated at ASU’s Photovoltaic Reliability Laboratory. The durability and reliability caused by three stress variables have been investigated and the three variables are temperature, humidity/oxygen and UV dosage. The influence of up to 800 kWh/m2 UV dosage has been investigated at various dosage levels. Many material and device characterizations have been performed to ascertain the degradation modes and effects. The UVC modules showed encapsulant discoloration at the cell centers as expected but the UVH modules showed a ring-shaped encapsulant discoloration close to the cell edges as evidenced in the UV fluorescence (UVF) imaging study. The PV modules containing UVP on both sides of cells with limited access to humidity or oxygen through backsheet (covered backsheet with adhesive aluminum tape) seem to experience encapsulant delamination as evidenced in the UVF images. Plausible explanations for these observations have been presented.
ContributorsArularasu, Pooja (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Mu, Bin (Thesis advisor) / Varman, Arul M (Committee member) / Arizona State University (Publisher)
Created2019