An urgent need for developing new chemical separations that address the capture of dilute impurities from fluid streams are needed. These separations include the capture of carbon dioxide from the atmosphere, impurities from drinking water, and toxins from blood streams. A challenge is presented when capturing these impurities because the energy cost for processing the bulk fluid stream to capture trace contaminants is too great using traditional thermal separations. The development of sorbents that may capture these contaminants passively has been emphasized in academic research for some time, producing many designer materials including metal-organic frameworks (MOFs) and polymeric resins. Scaffolds must be developed to effectively anchor these materials in a passing fluid stream. In this work, two design techniques are presented for anchoring these sorbents in electrospun fiber scaffolds.

The first technique involves imbedding sorbent particles inside the fibers: forming particle-embedded fibers. It is demonstrated that particles will spontaneously coat themselves in the fibers at dilute loadings, but at higher loadings some get trapped on the fiber surface. A mathematical model is used to show that when these particles are embedded, the polymeric coating provided by the fibers may be designed to increase the kinetic selectivity and/or stability of the embedded sorbents. Two proof-of-concept studies are performed to validate this model including the increased selectivity of carbon dioxide over nitrogen when the MOF ZIF-8 is embedded in a poly(ethylene oxide) and Matrimid polymer blend; and that increased hydrothermal stability is realized when the water-sensitive MOF HKUST-1 is embedded in polystyrene fibers relative to pure HKUST-1 powder.

The second technique involves the creation of a pore network throughout the fiber to increase accessibility of embedded sorbent particles. It is demonstrated that the removal of a blended highly soluble polymer additive from the spun particle-containing fibers leaves a pore network behind without removing the embedded sorbent. The increased accessibility of embedded sorbents is validated by embedding a known direct air capture sorbent in porous electrospun fibers, and demonstrating that they have the fastest kinetic uptake of any direct air capture sorbent reported in literature to date, along with over 90% sorbent accessibility.

Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis method, contain wrinkles affecting their gas separation characteristics and the method itself is difficult to scale up. Moreover, the production of graphene oxide membranes with fine-tuned interlayer spacing for improved molecular separation is still a challenge. These unsolved issues will affect their potential impact on industrial gas separation applications.

In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.

An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).

The engineering of microbial cell factories capable of synthesizing industrially relevant chemical building blocks is an attractive alternative to conventional petrochemical-based production methods. This work focuses on the novel and enhanced biosynthesis of phenol, catechol, and muconic acid (MA). Although the complete biosynthesis from glucose has been previously demonstrated for all three compounds, established production routes suffer from notable inherent limitations. Here, multiple pathways to the same three products were engineered, each incorporating unique enzyme chemistries and/or stemming from different endogenous precursors. In the case of phenol, two novel pathways were constructed and comparatively evaluated, with titers reaching as high as 377 ± 14 mg/L at a glucose yield of 35.7 ± 0.8 mg/g. In the case of catechol, three novel pathways were engineered with titers reaching 100 ± 2 mg/L. Finally, in the case of MA, four novel pathways were engineered with maximal titers reaching 819 ± 44 mg/L at a glucose yield of 40.9 ± 2.2 mg/g. Furthermore, the unique flexibility with respect to engineering multiple pathways to the same product arises in part because these compounds are common intermediates in aromatic degradation pathways. Expanding on the novel pathway engineering efforts, a synthetic ‘metabolic funnel’ was subsequently constructed for phenol and MA, wherein multiple pathways were expressed in parallel to maximize carbon flux toward the final product. Using this novel ‘funneling’ strategy, maximal phenol and MA titers exceeding 0.5 and 3 g/L, respectively, were achieved, representing the highest achievable production metrics products reported to date.

A comprehensive and systematic investigation on the diffusion and phase behaviors of nanoparticles and macromolecules in two component liquid-liquid systems via Molecule Dynamic (MD) simulations is presented in this dissertation.

The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.

Gene delivery is a broadly applicable tool that has applications in gene therapy, production of therapeutic proteins, and as a study tool to understand biological pathways. However, for successful gene delivery, the gene and its carrier must bypass or traverse a number of formidable obstacles before successfully entering the cell’s nucleus where the host cell’s machinery can be utilized to express a protein encoded by the gene of interest. The vast majority of work in the gene delivery field focuses on overcoming these barriers by creative synthesis of nanoparticle delivery vehicles or conjugation of targeting moieties to the nucleic acid or delivery vehicle, but little work focuses on modifying the target cell’s behavior to make it more amenable to transfection.

In this work, a number of kinase enzymes have been identified by inhibition to be targets for enhancing polymer-mediated transgene expression (chapter 2), including the lead target which appears to affect intracellular trafficking of delivered nucleic acid cargo. The subsequent sections (chapters 3 and 4) of this work focus on targeting epigenetic modifying enzymes to enhance polymer-mediated transgene expression, and a number of candidate enzymes have been identified. Some mechanistic evaluation of these targets have been carried out and discussion of ongoing experiments and future directions to better understand the mechanistic descriptions behind the phenomena are discussed. The overall goal is to enhance non-viral (polymer-mediated) transgene expression by modulating cellular behavior for general gene delivery applications.

Silicone compounds have a very low surface energy due to highly flexible Si-O-Si backbone and large number of –CH3 groups, but these compounds are extremely hydrophobic and thus have limited applications in aqueous formulations. Modification of such silicone compounds by grafting hydrophilic chains provides a wide range of silicone products called "Silicone Surfactants". Silicone surfactants are surface active agents which get adsorbed at the air-water interface thereby, reducing the interfacial tension. Some of the larger applications of silicone surfactant are in the manufacture of plastic foams, in personal care products and as spreading and wetting agents (Hill, R.M, 2002).

In this thesis, a series of silicone surfactant graft copolymers were synthesized via hydrosilylation reaction. Poly(ethylene glycol) (PEG) of different chain length was grafted to a hydrophobic Poly(methylhydrosiloxane) (PMHS) backbone to improve the final hydrophilicity. Also, a positively charged quaternary ammonium salt (allyltriethylammonium bromide) was grafted to the PMHS backbone. The objective of this thesis was to synthesize polymers in predefined ratios of the above mentioned side groups and utilize these polymers to-

1) Study the effect of PEG chain length and its composition on the hydrophilicity of the polymer.

2) Study the effect of PEG: ammonium salt ratio on the surface tension of aqueous systems.

Analysis of FT-IR and 1H NMR spectra of the polymers confirmed the predicted structure. The absence of characteristic Si-H absorbance peak at 2160 cm-1 in FT-IR spectra indicates consumption of silane groups along the polymer backbone. The actual moles of the side chain grafted on the backbone are calculated by 1H NMR peak integration. The results of contact angle studies indicated an increase in hydrophilicity with an increase in the composition of PEG in molecule. A 2*2 factorial DOE analysis reported that the fraction of Si-H bonds converted to PEG grafts was the critical factor towards increasing the hydrophilicity (p value of 0.015). Surface tension studies report that the air-water interfacial tension of the synthesized polymers is between 28mN/m – 45mN/m. The amount of Si-H was concluded to be the deciding factor in lowering the surface tension.

Water recovery from impaired sources, such as reclaimed wastewater, brackish groundwater, and ocean water, is imperative as freshwater resources are under great pressure. Complete reuse of urine wastewater is also necessary to sustain life on space exploration missions of greater than one year’s duration. Currently, the Water Recovery System (WRS) used on the National Aeronautics and Space Administration (NASA) shuttles recovers only 70% of generated wastewater.1 Current osmotic processes show high capability to increase water recovery from wastewater. However, commercial reverse osmosis (RO) membranes rapidly degrade when exposed to pretreated urine-containing wastewater. Also, non-ionic small molecules substances (i.e., urea) are very poorly rejected by commercial RO membranes.

In this study, an innovative composite membrane that integrates water-selective molecular sieve particles into a liquid-barrier chemically resistant polymer film is synthetized. This plan manipulates distinctive aspects of the two materials used to create the membranes: (1) the innate permeation and selectivity of the molecular sieves, and (2) the decay-resistant, versatile, and mechanical strength of the liquid-barrier polymer support matrix.

To synthesize the membrane, Linde Type A (LTA) zeolite particles are anchored to the porous substrate, producing a single layer of zeolite particles capable of transporting water through the membrane. Thereafter, coating the chemically resistant latex polymer filled the space between zeolites. Finally, excess polymer was etched from the surface to expose the zeolites to the feed solution. The completed membranes were tested in reverse osmosis mode with deionized water, sodium chloride, and rhodamine solutions to determine the suitability for water recovery.

The main distinguishing characteristics of the new membrane design compared with current composite membrane include: (1) the use of an impermeable polymer broadens the range of chemical resistant polymers that can be used as the polymer matrix; (2) the use of zeolite particles with specific pore size insures the high rejection of the neutral molecules since water is transported through the zeolite rather than the polymer; (3) the use of latex dispersions, environmentally friendly water based-solutions, as the polymer matrix shares the qualities of low volatile organic compound, low cost, and non- toxicity.

This is a two-part thesis assessing the long-term reliability of photovoltaic modules.

Part 1: Manufacturing dependent reliability - Adapting FMECA for quality control in PV module manufacturing

This part is aimed at introducing a statistical tool in quality assessments in PV module manufacturing. Developed jointly by ASU-PRL and Clean Energy Associates, this work adapts the Failure Mode Effect and Criticality Analysis (FMECA, IEC 60812) to quantify the impact of failure modes observed at the time of manufacturing. The method was developed through analysis of nearly 9000 modules at the pre-shipment evaluation stage in module manufacturing facilities across south east Asia. Numerous projects were analyzed to generate RPN (Risk Priority Number) scores for projects. In this manner, it was possibly to quantitatively assess the risk being carried the project at the time of shipment of modules. The objective of this work was to develop a benchmarking system that would allow for accurate quantitative estimations of risk mitigation and project bankability.

Part 2: Climate dependent reliability - Activation energy determination for climate specific degradation modes

This work attempts to model the parameter (Isc or Rs) degradation rate of modules as a function of the climatic parameters (i.e. temperature, relative humidity and ultraviolet radiation) at the site. The objective of this work was to look beyond the power degradation rate and model based on the performance parameter directly affected by the degradation mode under investigation (encapsulant browning or IMS degradation of solder bonds). Different physical models were tested and validated through comparing the activation energy obtained for each degradation mode. It was concluded that, for the degradation of the solder bonds within the module, the Pecks equation (function of temperature and relative humidity) modelled with Rs increase was the best fit; the activation energy ranging from 0.4 – 0.7 eV based on the climate type. For encapsulant browning, the Modified Arrhenius equation (function of temperature and UV) seemed to be the best fit presently, yielding an activation energy of 0.3 eV. The work was concluded by suggesting possible modifications to the models based on degradation pathways unaccounted for in the present work.

Ethylene vinyl acetate (EVA) is the most commonly used encapsulant in photovoltaic modules. However, EVA degrades over time and causes performance losses in PV system. Therefore, EVA degradation is a matter of concern from a durability point of view.

This work compares EVA encapsulant degradation in glass/backsheet and glass/glass field-aged PV modules. EVA was extracted from three field-aged modules (two glass/backsheet and one glass/glass modules) from three different manufacturers from various regions (cell edges, cell centers, and non-cell region) from each module based on their visual and UV Fluorescence images. Characterization techniques such as I-V measurements, Colorimetry, Different Scanning Calorimetry, Thermogravimetric Analysis, Raman spectroscopy, and Fourier Transform Infrared Spectroscopy were performed on EVA samples.

The intensity of EVA discoloration was quantified using colorimetric measurements. Module performance parameters like Isc and Pmax degradation rates were calculated from I-V measurements. Properties such as degree of crystallinity, vinyl acetate content and degree of crosslinking were calculated from DSC, TGA, and Raman measurements, respectively. Polyenes responsible for EVA browning were identified in FTIR spectra.

The results from the characterization techniques confirmed that when EVA undergoes degradation, crosslinking in EVA increases beyond 90% causing a decrease in the degree of crystallinity and an increase in vinyl acetate content of EVA. Presence of polyenes in FTIR spectra of degraded EVA confirmed the occurrence of Norrish II reaction. However, photobleaching occurred in glass/backsheet modules due to the breathable backsheet whereas no photobleaching occurred in glass/glass modules because they were hermetically sealed. Hence, the yellowness index along with the Isc and Pmax degradation rates of EVA in glass/glass module is higher than that in glass/backsheet modules.

The results implied that more acetic acid was produced in the non-cell region due to its double layer of EVA compared to the front EVA from cell region. But, since glass/glass module is hermetically sealed, acetic acid gets entrapped inside the module further accelerating EVA degradation whereas it diffuses out through backsheet in glass/backsheet modules. Hence, it can be said that EVA might be a good encapsulant for glass/backsheet modules, but the same cannot be said for glass/glass modules.

The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored.

First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.