Physical Sciences and Mathematics Commons^™

Development Of Bismuth Oxyhalide Photocatalysts For Environmental And Industrial Applications, Robert Arthur

Electronic Theses and Dissertations

Heterogeneous semiconductor photocatalysis, of interest for water splitting and environmental remediation applications, uses light to drive reactions. Metal oxide and sulfide semiconductors have been previously studied but have limitations that include large band gap energies and high rates of recombination. Bismuth oxyhalides (BiOX) are an emerging class of photocatalysts with tunable band gaps and low rates of recombination due to their unique crystal structures. Studies of BiOX photocatalytic activity have largely focused on removal of azo dyes from aqueous solutions, with little attention paid to degradation byproducts. Furthermore, these catalysts have not been explored as a means to conduct organic …

Optical Memory Behavior, Metallophilic Luminescence, And Chemical Sensing Ability Of Inorganic And Organometallic Complexes: Development Of Optoelectronic Materials, Aaron D. Nicholas

Electronic Theses and Dissertations

This dissertation is divided into three sections: (1) optical memory, (2) metallophilic-based luminescence, and (3) chemical sensors. (1) Optical memory behavior of d¹⁰metal Cu(I) thiocyanate salts are investigated to explore their potential use in the development of digital data storage devices. From this study we have discovered a new class of CuSCN(3-BrPy)₂optical memory material which undergo a reduction in emission intensity upon laser irradiation. This loss of emission intensity can be reversed simply by heating the sample to room temperature. The mechanism by which this emission loss occurs has been studied, revealing a migrating Br atom …

Luminescence Antenna Behavior In Lanthanide Complexes And Luminescence Sensing In Group 11 Iodides, Francis Barnes

Electronic Theses and Dissertations

In this thesis luminescent materials are studied. The luminescent materials studied are lanthanide complexes and group 11 iodide sensing abilities. Emission intensity of the lanthanide complexes through direct excitation of the lanthanide ion are relatively weak. To overcome this, three unique organic ligands were utilized to synthesize lanthanide nitrate complexes in which higher emission intensity can be observed via the antenna effect. Increased emission intensity resulted for Eu^III and Tb^III complexes for each ligand except triphenylphosphane oxide (only the Tb^III complex demonstrated increased emission intensity). Latva’s empirical rule allows for the antenna effect to occur, in which …

Controls On Phosphorus Export From An Agricultural Watershed: Amsden Brook, Fort Fairfield, Maine Usa., Gregory J. Mcdonald

Electronic Theses and Dissertations

This study explores the sources and mechanisms of phosphorus (P) mobilization during base flow within the Amsden Brook watershed, Fort Fairfield, Maine, USA. Amsden Brook is an agriculturally dominated watershed drained by a spring-fed and perennial first- to second-order stream. We characterized the P concentrations within the watershed to investigate connections between soils, stream sediment, surface water, and groundwater. Waters were monitored monthly during the 2017 snow-free period for temperature, pH, dissolved oxygen, conductivity, soluble reactive P (SRP), total P, strong acid anions, strong base cations, dissolved organic carbon (DOC), Al, Fe, and Mn. Phosphorus speciation within soils and sediment …

Thermochemical Conversion Of Guaiacol Over Unsupported Tungsten Oxide And Nickel Supported Catalysts, Pamela Ruiz Martinez

Electronic Theses and Dissertations

Interest in conversion of biomass into renewable fuels has motivated development of thermochemical methods for production of bio-oil and development of hydrodeoxygenation catalysts for upgrading the oil. Two types of catalysts were investigated. The catalytic activity of unsupported tungsten oxide bronze catalysts for the conversion of guaiacol was explored as a representative compound from bio-oil. The reactions were carried out in a trickle bed reactor at various concentrations of the reactant and hydrogen pressure, as well as varying catalyst activation and reaction temperatures. The reaction pathway from guaiacol to phenol by demethoxylation, followed by hydrogenation to cyclohexanol, and finally dehydration …

Mechanistic Studies Of Reducible Metal Oxides As Hydrodeoxygenation Catalysts, Akbar Mahdavi Shakib

Electronic Theses and Dissertations

Hydrodeoxygenation of phenol to benzene using ruthenium supported titania catalysts strongly varies depending on the support crystal structure and preparation conditions. Here, we performed spectroscopic characterization of titania supports to identify the surface impurities common to commercial and synthesized titania samples using a variety of spectroscopic methods. Sulfate impurities were detected for the commercial anatase samples and a procedure for their elimination was proposed so that inactive catalysts gained reactivity. Surface hydroxyls of different TiO2 samples (anatase, rutile, and pyrogenic) were identified using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments performed on vigorously cleaned surfaces and a facet-specific assignment …

Biomass Based Monomers For Synthesis Of Renewably Sourced Polymers, Anushka E. Vithanage

Electronic Theses and Dissertations

Limited fossil resources have raised research focus on synthesizing novel, sustainable polymers and renewably sourcing existing petroleum based polymers. This work presents the synthesis and ring opening polymerization (ROP) of a new functionalized lactone monomer, methoxy-δ-hexalactone (MDHL), to yield a functionalized polyester (polyMDHL). MDHL can be renewably sourced from hydroxymethylfurfural, a renewable platform chemical. MDHL was synthesized from methyl cyclopentanone-2-carboxylate by a five-step synthesis with a global yield of 23%. ROP of MDHL was conducted with benzyl alcohol initiator, catalyzed by diphenyl phosphate. 1H Nuclear Magnetic Resonance spectroscopy verified polyMDHL chemical structure. Targeting higher molecular weights for polyMDHL by increasing …

Chemically Cross-Linked Polysaccharide-Based Hydrogels Via Thiol-Norbornene Reaction As Sustainable Biomaterials, Nayereh Dadoo

Electronic Theses and Dissertations

Hydrogels are 3D polymeric networks with high water content and are widely being investigated for biomedical applications such as tissue engineering. Polysaccharides have been used to fabricate hydrogels due to their natural abundance, biocompatibility, and immunogeniety. Additionally, polysaccharide-based hydrogels can provide mechanical and biological cues similar to those of the natural environments. In this work, thiol-norbornene chemistry was used to fabricate polysaccharide-based hydrogels including hyaluronic acid (HA), carboxymethyl cellulose (CMC), and cellulose nanofibrils (CNFs). Hydrogels with tunable physical and mechanical properties were achieved. The properties of these hydrogels were spatiotemporally modified by photopatterning. Also, high stem cell viability was achieved …

Developing A Risk Assessment Protocol To Quantify Distribution And Uptake Of Persistent Organic Pollutants In Glacial Outflows, Kimberley Rain Miner

Electronic Theses and Dissertations

Pollutants released by industrialized nations between 1960 and 2004 have been transported northward through atmospheric processes and deposited into glaciated alpine ecosystems. Many of these chemicals retain their original structure and are absorbed into the biota thousands of miles away from where they were originally utilized. With a warming climate increasing the melt of alpine glaciers, these glaciers may be introducing growing amounts of toxins into the watershed. While studies have demonstrated the existence of resident pollutants within glaciated ecosystems, no one has developed a risk assessment to identify sources and quantity of risk posed by these compounds when released …

Extraction And Purification Of (E)-Resveratrol From The Bark Of Maine's Native Spruces, Panduka S. Piyaratne

Electronic Theses and Dissertations

Resveratrol is a plant secondary metabolite which protects plants from pathogenic invasions and acts as a remedial agent against injury, stress, and tissue damage by UV radiation. With its characteristic stilbene structure, resveratrol adopts (E) and (Z) isomeric forms. However, the (E) isomer is the most biologically active and abundant form of resveratrol in nature.

(E)- Resveratrol confers a variety of benefits to human health and well-being. Besides its antioxidant activity, the role of (E)-resveratrol as an anti-inflammatory, anti-aging, cardioprotection, and anticancer agent has been a widely explored research interest. …

Surface Reaction And Diffusion Kinetics In Semiconducting Metal Oxide Film Gas Sensors, Aravind Reghu

Electronic Theses and Dissertations

Chemiresistive metal oxide gas sensors based on materials such as SnO₂, ZnO, and TiO₂, have been investigated extensively by many researchers for a wide range of applications. The band bending model, based on the surface chemistry of highly reactive ionosorbed species (O₂^- or O^-) and the semiconducting material properties of SnO₂, TiO₂ and ZnO, adequately predicts the dependence of the change in sensor conductivity (Δσ) as a function of target gas pressure and temperature. However, the band bending model is not applicable to gas sensors based on reducible oxides …

Detrital Protein Contributes To Oyster Nutrition And Growth In The Damariscotta Estuary, Maine, Usa, Cheyenne M. Adams

Electronic Theses and Dissertations

Oyster aquaculture is an expanding industry that relies on identifying and utilizing natural estuarine conditions for the economically viable production of a filter-feeding crop. The eastern oyster, Crassostrea virginica, is the principal species currently cultured in Maine. In addition to preferentially consumed phytoplankton, various detrital complexes (non-algal and/or non-living organic matter) may provide some nutrition to C. virginica between times of phytoplankton abundance. Here I investigated the importance of detrital proteins in supporting the growth of oysters cultured in the upper Damariscotta Estuary. Oyster aquaculture in this area is highly successful and previous reports indicate that labile detrital protein …

Cellulose Nanofiber-Reinforced Impact Modified Polypropylene: Assessing Material Properties From Fused Layer Modeling And Injection Molding Processing, Jordan Elliott Sanders

Electronic Theses and Dissertations

The purpose of this research was to investigate the use of cellulose nanofibers (CNF) compounded into an impact modified polypropylene (IMPP) matrix. A IMPP was used because it shrinks less than a PP homopolymer during FLM processing. An assessment of material properties from fused layer modeling (FLM), an additive manufacturing (AM) method, and injection molding (IM) was conducted. Results showed that material property measurements in neat PP were statistically similar between IM and FLM for density, strain at yield and flexural stiffness. Additionally, PP plus the coupling agent maleic anhydride (MA) showed statistically similar results in comparison of IM and …

Water Chemistry Dynamics In Four Vernal Pools In Maine, Usa, Lydia H. Kifner

Electronic Theses and Dissertations

Vernal pools are small seasonal wetlands that are a common landscape feature that contribute to biodiversity in northeastern North American forests. However, even basic information about their biogeochemical functions, such as carbon cycling, is limited. Dissolved gas concentrations (CH₄, CO₂) and other water chemistry parameters were monitored weekly at the bottom and surface of four vernal pools in central and eastern Maine, USA, from April to August 2016. The vernal pools were supersaturated with respect to CH₄ and CO₂ at all sampling dates and locations. Concentrations of dissolved CH₄ and CO₂ ranged …

Creating Renewable Tunable Polymers From Hydroxymethylfurfural, Meredith C. Allen

Electronic Theses and Dissertations

The research here deals with the conversion of 5-hydroxymethylfurfural (HMF) into a tunable polymer. HMF is a known derivative that can be acquired from biomass via hydrolysis of cellulose followed by isomerization and finally selective dehydration. The process considered here is being developed to create tunable polymers from HMF and involves several different steps, three of which are covered here. The first step, an etherification, is the reaction of HMF with an alcohol. This step is significant because in this step the R-group from the alcohol is added to HMF and the branching portion formed is carried over to the …

Renewable Hydrogels From Norbornene-Functionalized Carboxymethyl Cellulose And A Short Dithiol Crosslinked Via A Thiol-Ene Reaction, Thomas Mcoscar

Electronic Theses and Dissertations

Cellulose-based hydrogels - three dimensional "solid" structures composed primarily of liquid water and held together by an interconnected polymer network - were created by first functionalizing carboxymethyl cellulose (CMC), a cellulose derivative, with carbic anhydride in a basic aqueous reaction with the intent of developing novel hydrogels from renewable materials. The product of this reaction, carbic CMC (cCMC), had a new norbornene group as a subsection of the carbic group. Norbornene is a reactive alkene structure that allows for further chemistry with cCMC, such as crosslinking. cCMC was crosslinked with 2,2'-(ethylenedioxy)diethathiol to create hydrogels using a water-soluble, UV-sensitive radical initiator …

Late Holocene Climate And Environmental Reconstruction Derived From The Asian Ice Core Array (Aica), Bjorn Grigholm

Electronic Theses and Dissertations

Recent climate change has impacted natural and human systems across the Earth, emphasizing the need for greater understanding of both the existing and changing natural and anthropogenic forcing mechanisms and subsequent responses of the Earth’s climate system. High-resolution, multi-parameter ice core records retrieved and analyzed from two Asian Ice Core Array (AICA) sites, Geladaindong (central Tibetan Plateau) and Inilchek (central Tien Shan) were utilized to reconstruct atmospheric chemical concentrations and composition over the past ~100-500 years, improving the understanding of late Holocene climate and environmental variability in Asia. Both ice cores were analyzed for major and trace elements, major soluble …

Method Development For Vitamin C Quantification In Two Complex Matrices, Hannah D. Hutt

Electronic Theses and Dissertations

The following liquid chromatographic (LC) method developments and applied research studies were done using two complex food matrices, potatoes and elderberries, which are common to the state of Maine. Potatoes are Maine’s largest agricultural crop, a staple food in most U.S. households, and are, from an analytical standpoint, considered a complex matrix due to the high starch content that can be difficult to remove without degrading or removing nutrients in the process. Elderberries are an emerging crop in the U.S. because of their antioxidant and anti-viral properties and are found growing wild, throughout Maine. Elderberries are also considered a complex …

Detection Of Iron (Iii) Using Magnetic Nanoparticles, Kaiya Hansen

Electronic Theses and Dissertations

The goal of this work was to develop an iron (III) sensor which can be mounted on buoys and gliders and automatically measure iron (III) in the ocean. The method investigated in this thesis was based on anchoring the iron (III) chelator desferrioxamine B (DFB) to magnetic particles. DFB selectively binds iron (III), resulting in a complex which produces a broad absorbance band at 430 nm. This band can be measured via UV-Vis spectroscopy (UV-Vis). However, measuring oceanic iron (III) directly in solution is difficult because the concentrations can be very low, sometimes less than 1 nM. This problem could …

Dynamics Of Polyelectrolyte Adsorption On Surfaces: Applications In The Detection Of Iron In Water, Madhira N. Gammana

Electronic Theses and Dissertations

Layer by layer (LbL) self assembly is a simple multilayer thin (nanometer scale) film fabricating technique. The mechanism of film growth remains a topic of much controversy. For example, several models have been proposed to explain the origin of linear and exponential film growth that are attributed to differences in the dynamic processes that occur at the molecular level during film formation. The problem is that there are no methods that directly measure the dynamics of polymer formation during LbL film formation. In this thesis, I describe the essential elements of an ATR-IR spectroscopic method that was developed to enable …

Synthesis And Characterization Of Mesoporous Silica Membranes Modified By Atomic And Molecular Layer Deposition, David Emmett Cassidy

Electronic Theses and Dissertations

Inorganic membranes offer a means for chemical separations in a variety of applications including chemical processing, drug delivery systems, battery separators and fuel cells. There is currently a “pore size gap” in silica membranes between 1-2 nanometers. Synthesizing membranes with a fine control of the pore size and distribution within that gap is a significant challenge. This thesis reports findings on using atomic and molecular layer deposition as new synthesis approaches to controlling pore size and chemical functionality of silica membranes. Mesoporous silica membranes, prepared using surfactant-templates with pore diameters ~4nm, were modified using atomic layer deposition and molecular layer …

Synthesis And Characterization Of Catalysts For The Selective Transformation Of Biomass-Derived Materials, Isaac Tyrone Ghampson

Electronic Theses and Dissertations

The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silicasupported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, …

Exfoliated Graphite Nanoplatelet-Filled Impact Modified Polypropylene Nanocomposites, Alex Duguay

Electronic Theses and Dissertations

Exfoliated graphite nanoplatelets (xGnP)-filled polymer composites have demonstrated superior electrical, mechanical, physical and thermal properties and are becoming a major focus for both academic and industrial research and development (R&D) activities. The main objective of this study was to characterize the influence of xGnP particle diameter, filler loading and the addition of coupling agents on the mechanical, rheological and thermal properties of xGnP-filled impact modified polypropylene (IMPP) composites. IMPP is currently being used at the AEWC Advanced Structures and Composites Center in polymer impregnated (pre-preg) fiber reinforced polymer (FRP) tapes consisting of an IMPP matrix polymer and E-glass continuous fibers. …

The Removal Of Wood Components From Hardwood By Hot Water, Rory Jara

Electronic Theses and Dissertations

Hot-water extraction of hemicelluloses from wood is a promising technology in the integrated biorefmery concept. A particular case is where the pulp industry makes co-products such as ethanol and acetic acid besides pulp thereby maximizing the value of biomass. Similarly, the oriented strand board (OSB) industry appears to be suitable for this technical approach as it is composed of large centralized facilities. Many studies have been carried out on the kinetics and mechanism of hot-water extraction of lignocellulosics. However, most of these studies were performed in batch reactors which are not best suited to determine intrinsic kinetics of hemicellulose dissolution …

Biological Conversion Of Hemicellulose Extract Into Value-Added Fuels And Chemicals, Sara Lynn Walton

Electronic Theses and Dissertations

The research presented in this thesis describes the fermentation of hemicellulose extracts to produce ethanol and lactic acid. Hardwood hemicellulose extracts made at a variety of conditions using the green liquor and hot water extraction processes were characterized and then fermented by Escherichia coli K011 and Bacillus coagulans MXL-9. Hemicellulose extracts were found to contain a dilute amount of xylo-oligosaccharides and acetic acid as the major components, and many minor components including other organic acids, lignin-derived phenolics, and sugar degradation products. In order to generate ethanol economically, the fermentation must produce at least a 4% ethanol solution, which requires a …

Room Temperature Tunable Energy Transfer Systems In Different Solvents, Zhonghua Guo

Electronic Theses and Dissertations

The focus of this thesis is on d⁸ and d¹⁰ metal-metal interactions, e.g. weak bonding in homometallic and heterometallic systems in liquid solutions, the tunability of luminescent energy due to the variation of metal-metal interaction strength in different solvents and different concentrations, as well as energy transfer from the luminescent energy tunable d⁸ and d¹⁰ metal ions clusters as donor ions to the lanthanide ions as acceptor ions at room temperature. First, energy transfer has been studied between dicyanoaurate(I) luminescent nanocluster donor ions and Eu³⁺ and Tb³⁺ acceptor ions in aqueous solutions. The emission …

Synthesis And Oxidation Of Lignin-Carbohydrate Model Compounds, Mai Thanh Thi Nguyen

Electronic Theses and Dissertations

To decrease our dependence on foreign oil supply and in an effort to decrease the amount of green house gases into the atmosphere, researchers are focusing on ways of producing fuels and chemicals from renewable resources. A renewable source such as wood has great potential for the production of biofuels and biochemicals. An integrated biorefinery process that maximizes the usage of wood and complements existing pulp and paper technology was proposed to extract underutilize hemicelluloses and covert them into bioethanol. In this process, not only hemicelluloses are extracted; lignin, since it is covalently bonded to hemicelluloses is extracted as well. …

Technical Evaluation Of Hardwood Biorefinery Using The "Near-Neutral" Hemicellulose Extraction Process, Haibo Mao

Electronic Theses and Dissertations

A technical analysis was performed for a new process that produces ethanol and acetic acid from hardwood in addition to bleached hardwood Kraft pulp. The new process, termed the "near neutral" hemicellulose extraction process, involves the extraction of wood hemicellulose using green liquor prior to conventional Kraft pulping. This thesis assumes that the new process is located at an existing kraft pulp mill. Ancillary unit operations in the process include hydrolysis of the extracted carbohydrates using sulfuric acid, filtration of the extract to remove lignin that was extracted with the carbohydrates, liquid-liquid extraction of acetic acid and by-product furfural, liming …

Kinetics And Mechanism Of Oxygen Delignification, Yun Ji

Electronic Theses and Dissertations

Considerable research has been conducted into the kinetics and selectivity of the oxygen delignification process to overcome limitation in its use. However most studies were performed in a batch reactor whereby the hydroxide and dissolved oxygen concentrations are changing during the reaction time in an effort to simulate tower performance in pulp mills. This makes it difficult to determine the reaction order of the different reactants in the rate expressions. Also the lignin content and cellulose degradation of the pulp are only established at the end of the experiment when the sample is removed from the batch reactor. To overcome …

Modification Of Semi-Metal Oxide And Metal Oxide Powders By Atomic Layer Deposition Of Thin Films, Mark Q. Snyder

Electronic Theses and Dissertations

This work describes two methods of modifying, and the subsequent characterizing of, oxide nanopowders. The first method, atomic layer deposition, or ALD, is a series of surface-limited reactions that are repeated to deposit a thin, inorganic film on the surface of the nanopowder. Deposition of a thin film is a useful method to alter the surface properties of a material while retaining its bulk properties. Part of this thesis concerns the understanding of the growth mechanism of thin film titanium nitride (a material known for thermal and chemical stability as well as electronic conductivity) on silica through the ALD process. …