Chemical Engineering Commons^™

Functionalization Of Gold Nanoparticles (Gnpss) Using The Isolate, Functionalize, And Release (Isofure) Methodology, David Spencer, Hariharasudhan D. Chirra, J. Zach Hilt

Kaleidoscope

No abstract provided.

Biocomaptibility Analysis And Cancer Therapy Applications Of Core-Shell Composite Magnetic Nanoparticles, Anastasia Kruse, Robert J. Wydra, J. Zach Hilt, Kimberly W. Anderson

Kaleidoscope

No abstract provided.

Functionalized Silica Materials And Mixed-Matrix Membranes For Environmental Applications, Noah Daniel Meeks

Theses and Dissertations--Chemical and Materials Engineering

Functionalized silica materials are synthesized for various environmental applications. The overall objective is functionalization with sulfur-containing moieties for mercury sorption and as a platform for nanoparticle synthesis. The first objective is quantifying this functionalization for various silica platforms. The second objective is development of effective mercury sorbents, for both aqueous mercury and elemental mercury vapor. Third, those sorbents are incorporated into mixed matrix membranes (MMM) for aqueous mercury sorption. Fourth, functionalized silica materials are developed as platforms for the synthesis of reactive metal nanoparticles (NP) for the degradation of trichloroethylene.

Thiol-functionalized silica is used as a sorbent for aqueous mercury, …

Development Of Strategies To Minimize The Release Of Trace Elements From Coal Waste Sources, Mohammad Rezaee

Theses and Dissertations--Mining Engineering

To assess strategies aimed at minimizing the release of trace elements and the impact of disposal of coal waste materials on the environment, two long-term leaching experiments of up to five months duration were performed using waste materials from two plants cleaning high and low sulfur bituminous coal. The tests evaluated the mobility of major trace elements under different disposal scenarios: (i) a static leaching test designed to simulate the quiescent conditions encountered by coal waste material stored under water in a stable impoundment, and (ii) a dynamic test to simulate waste materials exposed to the atmosphere, either in variable …

Protein Based Biomimetic Approachs To Surface Hemocompatibility And Biocompatibility Enhancement, Matthew Thomas Dickerson

Theses and Dissertations--Chemical and Materials Engineering

T. pallidum can survive a primary immune response and continue growing in the host for an extended period of time. T. pallidum is thought to bind serum fibronectin (FN) through Tp0483 on the surface to obscure antigens. A Tp0483 fragment (rTp0483) was adsorbed onto functionalized self-assembled monolayers (SAMs) with FN. FN capture by adsorbed rTp0483 depended greatly on surface chemistry with COO- groups being best for FN binding. Hemocompatibility was determined by analysis of plasma protein adsorption, intrinsic pathway activation, and platelet activation. rTp0483+FN bound an equal or lesser amount of fibrinogen (Fg), human serum albumin (HSA), and factor XII …

Effect Of Ionic Surfactants On Electrostatic Charging Of Spray Droplets, Mark T. Warren

Theses and Dissertations--Chemical and Materials Engineering

Dust capture for small coal particles (<2.5µm) can be improved if one takes advantage of electrostatic charges that resides on the surface of coal dust particles and on the surface of water spray droplets used to capture coal dust. Traditional dust capture methods that use water sprays are ineffective in capturing small dust particles since the motion of small dust particles is governed by electrostatic forces. If additives such as ionic surfactants could be added to water that would enhance the surface charge on water spray droplets, dust capture with water sprays could be improved.

The results presented show that n-sodium octyl sulfate causes the greatest charge enhancement versus the longer chained n-sodium dodecyl sulfate and n-sodium octadecyl sulfate. This can be explained by considering the factors that lead to droplet charge enhancement. Those factors are the mass of surfactant ions at the droplet surface, and the diffusion rate of the surfactant ions from the bulk droplet to the surface of the droplet. Sodium octyl sulfate will have a faster diffusion rate to the droplet surface because of its relatively short length, and will also maximize the mass …

Nanoparticle Additives For Multiphase Systems: Synthesis, Formulation And Characterization, Vinod Kanniah

Theses and Dissertations--Chemical and Materials Engineering

Study on nanoparticle additives in multiphase systems (liquid, polymer) are of immense interest in developing new product applications. Critical challenges for nanoparticle additives include their synthesis, formulation and characterization. These challenges are addressed in three application areas: nanofluids for engine lubrication, ultrathin nanocomposites for optical devices, and nanoparticle size distribution characterization.

Nanoparticle additives in oligomer mixtures can be used to develop extended temperature range motor oils. A model system includes poly(α-olefin) based oligomers with a modest fraction of poly(dimethylsiloxane) oligomers along with graphite as nanoparticle additive. Partition coefficients of each oligomer are determined since the oligomer mixture phase separated at …

Fabrication Of An Epithelial Cell-Based Ion-Selective Electrode And Its Application For Use As Alternative Tumor Angiogenesis Assay, Christina Nicole Simmons

Theses and Dissertations--Chemical and Materials Engineering

Previous studies have provided evidence that endothelial cell-based potassium ion selective electrodes possess the ability to quantify substances that have permeability-altering effects on those endothelial cells. The capability of these so-called biosensors to detect elevated concentrations of certain chemical agents found following tumor formation make them useful in the application as an alternative tumor angiogenesis assay. In this study an epithelial cell line, human colon adenocarcinoma epithelial cells (Caco-2), was used to fabricate membranes that were used to test concentrations of these chemical agents, known as cytokines, mimicking the concentrations that have been observed in the serum of healthy individuals …

Biodegradable Hydrogels And Nanocomposite Polymers: Synthesis And Characterization For Biomedical Applications, Ashley Marie Hawkins

Theses and Dissertations--Chemical and Materials Engineering

Hydrogels are popular materials for biological applications since they exhibit properties like that of natural soft tissue and have tunable properties. Biodegradable hydrogels provide an added advantage in that they degrade in an aqueous environment thereby avoiding the need for removal after the useful lifetime. In this work, we investigated poly(β-amino ester) (PBAE) biodegradable hydrogel systems. To begin, the factors affecting the macromer synthesis procedure were studied to optimize the reproducibility of the resulting hydrogels made and create new methods of tuning the properties. Hydrogel behavior was then tuned by altering the hydrophilic/hydrophobic balance of the chemicals used in the …

Application Of Thin Film Analysis Techniques And Controlled Reaction Environments To Model And Enhance Biomass Utilization By Cellulolytic Bacteria, Hsin-Fen Li

Theses and Dissertations--Chemical and Materials Engineering

Cellulose from energy crops or agriculture residues can be utilized as a sustainable energy resource to produce biofuels such as ethanol. The process of converting cellulose into solvents and biofuels requires the saccharification of cellulose into soluble, fermentable sugars. However, challenges to cellulosic biofuel production include increasing the activity of cellulose-degrading enzymes (cellulases) and increasing solvent (ethanol) yield while minimizing the co-production of organic acids. This work applies novel surface analysis techniques and fermentation reactor perturbations to quantify, manipulate, and model enzymatic and metabolic processes critical to the efficient production of cellulosic biofuels.

Surface analysis techniques utilizing cellulose thin film …

Membrane Immobilized Reactive Fe/Pd Nanoparticles: Modeling And Tce Degradation Results, Ruo He

Theses and Dissertations--Chemical and Materials Engineering

Detoxification of chlorinated organic compound is an important and urgent issue in water remediation nowadays. Trichloroethylene (TCE), as a model compound in this study, has been proved to be degraded effectively by bimetallic nanoparticles (NPs) in solution phase. In this study, Fe/Pd bimetallic NPs were synthesized in poly (acrylic acid) (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes. TCE dechlorination with these bimetallic NPs was conducted under different pH values and different metal loadings to study the role of corrosion on reaction rates.

One-dimensional mathematical model with pseudo first-order reaction kinetic was introduced to discuss the TCE dechlorination profile in membrane …

Study Of Characterization Of Submicron Coal Particles Dispersed In Air And Capture Of Coal Particles By Water Drops In A Scrubbing Column, Utshab Chakravorty

Theses and Dissertations--Chemical and Materials Engineering

Present day water spray based dust removal technologies do not effectively remove respirable submicron coal and silica dust particles in the underground coal mines causing Coal worker’s pneumoconiosis (CWP). The objective of this research was to study the electrostatic charges present in the airborne coal dust in order to develop efficient water spraying based dust removal technology where water drops charged using ionic compounds and surfactants would be used to capture the oppositely charged coal particles. In an experimental scrubbing column, coal particles dispersed in an air stream by a Fluidized Bed Aerosol Generator were captured by water drops sprayed …

Understanding And Improving Lithium Ion Batteries Through Mathematical Modeling And Experiments, Rutooj D. Deshpande

Theses and Dissertations--Chemical and Materials Engineering

There is an intense, worldwide effort to develop durable lithium ion batteries with high energy and power densities for a wide range of applications, including electric and hybrid electric vehicles. For improvement of battery technology understanding the capacity fading mechanism in batteries is of utmost importance. Novel electrode material and improved electrode designs are needed for high energy- high power batteries with less capacity fading. Furthermore, for applications such as automotive applications, precise cycle-life prediction of batteries is necessary.

One of the critical challenges in advancing lithium ion battery technologies is fracture and decrepitation of the electrodes as a result …

Mathematical Modeling Of Clostridium Thermocellum’S Metabolic Responses To Environmental Perturbation, Bless Adotey

Theses and Dissertations--Biosystems and Agricultural Engineering

Clostridium thermocellum is a thermophilic anaerobe that is capable of producing ethanol directly from lignocellulosic compounds, however this organism suffers from low ethanol tolerance and low ethanol yields. In vivo mathematical modeling studies based on steady state traditional metabolic flux analysis, metabolic control analysis, transient and steady states’ flux spectrum analysis (FSA) were conducted on C. thermocellum’s central metabolism. The models were developed in Matrix Laboratory software ( MATLAB^® (The Language of Technical Computing), R2008b, Version 7.7.0.471)) based on known stoichiometry from C. thermocellum pathway and known physical constraints. Growth on cellobiose from Metabolic flux analysis (MFA) and Metabolic …

Solution Phase And Membrane Immobilized Iron-Based Free Radical Reactions: Fundamentals And Applications For Water Treatment, Scott Romak Lewis

University of Kentucky Doctoral Dissertations

Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, …

Studies Related To Coulombic Fissions Of Charged Droplets And Hygroscopic Behavior Of Mixed Particles, Harry Cook Hunter Iii

University of Kentucky Doctoral Dissertations

This dissertation describes two independent studies related to charged aerosols. The first study examines the role of electrical conductivity on the amounts of charge and mass emitted during the break-up of charged droplets via Coulombic fission. The second study examines the hygroscopic behavior of mixed particles. The results from both studies are presented here in detail along with an in-depth discussion of pertinent literature and applications in modern technologies.

Charged droplets break-up via a process termed Coulombic fission when their charge density reaches a certain level during which they emit a portion of their charge and mass in the form …

Studies On Silicon Nmr Characterization And Kinetic Modeling Of The Structural Evolution Of Siloxane-Based Materials And Their Applications In Drug Delivery And Adsorption, Jyotrhirmai Ambati

University of Kentucky Doctoral Dissertations

This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane- materials can be engineered for drug delivery and adsorption.

The phase behavior of polymerizing …

Synthesis And Energy Applications Of Oriented Metal Oxide Nanoporous Films, Qingliu Wu

University of Kentucky Doctoral Dissertations

This dissertation mainly addresses the synthesis of well-ordered mesoporous titania thin films by dip coating with PEO-PPO-PEO triblock copolymer surfactant template P123. Because P123 is composed of poly(ethylene oxide) [PEO] and poly(propylene oxide) [PPO] blocks, concentrations of ingredients are adjusted to tune the films’ wall thickness, pore size and mesophase. Structural changes are consistent with partitioning of species among PEO blocks, PPO blocks, and the PEO/PPO interface. Titanates localize near PEO and increase wall thickness (by 5 nm to 7 nm). Depending on aging temperature, PPG either swells the PPO cores (when it is hydrophobic) or introduces large (>200 …

Synthesis And Characterization Of Polymeric Antioxidant Delivery Systems, Paritosh P. Wattamwar

Theses and Dissertations--Chemical and Materials Engineering

Even though the role of oxidative stress in a variety of disease states is known, strategies to alleviate this oxidative stress by antioxidants have not been able to achieve clinical success. Particularly, treatment of oxidative stress by small molecule antioxidants has not received due attention because of the challenges associated with its delivery. Antioxidant polymers, where small molecule antioxidants are incorporated into the polymer backbone, are an emerging class of materials that can address some of these challenges.

In this work, biodegradable polymers incorporating phenolic antioxidants in the polymer backbone were synthesized. Antioxidant polymers were then characterized for their in …

Stability Of Affinity Based Layer-By-Layer Polymeric Self-Assemblies For Oral Wound Applications, Sundar Prasanth Authimoolam

Theses and Dissertations--Chemical and Materials Engineering

Oral mucositis is a painful and debilitating chronic inflammatory condition that can result from chemo and/or radiotherapy. While current treatment strategies which provide temporary relief exist, there is still an unmet clinical need for a robust long active barrier strategy which can simultaneously provide protection and release drug to enhance the wound healing response. It is proposed that an affinity based layer-by-layer self-assembled barrier administered as a series of mouth rinses can allow for wound specific drug delivery, providing an effective regenerative therapy.

In this work, biotinylated poly(acrylic acid) is used to develop LBL assemblies based upon biotin-streptavidin affinity interactions. …

Dynamic Relaxation Properties Of Aromatic Polyimides And Polymer Nanocomposites, Anthony C. Comer

Theses and Dissertations--Chemical and Materials Engineering

The dynamic relaxation characteristics of Matrimid^® (BTDA-DAPI) polyimide and several functionalized aromatic polyimides have been investigated using dynamic mechanical and dielectric methods. The functionalized polyimides were thermally rearranged to generate polybenzoxazole membranes with controlled free volume characteristics. All polyimides have application in membrane separations and exhibit three motional processes with increasing temperature: two sub-glass relaxations (ƴ and β transitions), and the glass-rubber (α) transition. For Matrimid, the low-temperature ƴ transition is purely non-cooperative, while the β sub-glass transition shows a more cooperative character as assessed via the Starkweather method. For the thermally rearranged polyimides, the ƴ transition is a …

Evaluation Of The Physicochemical Properties And Stability Of Solid Lipid Nanoparticles Designed For The Delivery Of Dexamethasone To Tumors, Melissa Howard

University of Kentucky Doctoral Dissertations

Pre-clinical and clinical trials suggest that pre-treatment with dexamethasone (Dex) may facilitate enhanced uptake of subsequently administered chemotherapeutic agents. To reduce the side effects associated with systemic administration of Dex, solid lipid nanoparticles (SLNs) containing dexamethasone palmitate (Dex-P) were prepared as a means of achieving tumor-targeted drug delivery. These studies were aimed at evaluating the physicochemical properties and both the physiological and storage stability of the SLNs.

SLNs were prepared using nanotemplate engineering technology. Stearyl alcohol (SA) was used as the lipid phase with Brij^® 78 and Polysorbate 60 as surfactants and PEG6000 monostearate as a long-chain PEGylating agent. …

Targeted Polymeric Biomaterials For The Prevention Of Post Surgical Adhesions, John M. Medley

University of Kentucky Doctoral Dissertations

Despite recent advances in surgical technique and the development of numerous therapeutic agents, the formation post surgical adhesions (PSA) continues to cause complications for many patients. In this research, we have employed a rational system to develop a novel treatment to address this clinical need. Based on an understanding of the biochemical events that lead to PSA formation, a series of targeted polymeric biomaterials was designed to interrupt the fibrin gel matrix propagation and suppress PSA formation.

Using group transfer polymerization, a series of well controlled block copolymers of polyacrylic acid and poly(ethylene glycol-methacrylate) based materials was synthesized. Subsequent functionalization …

Characterization Of Poly(Methyl Methacrylate Based Nanocomposites Enhanced With Carbon Nanotubes, Andrew Jonathan Placido

University of Kentucky Master's Theses

The viscoelastic relaxation dynamics of a series of poly(methyl methacrylate) [PMMA] based nanocomposites filled with carbon nanotubes have been studied using dynamic mechanical analysis and broadband dielectric spectroscopy. The networks were prepared using four methods: (i) melt mixing, (ii) solution processing, (iii) in-situ polymerization, and (iv) polymer grafting. Nanotube modifications included surface oxidation via acid exposure and surface functionalization for polymer grafting. The effect of variations in processing method and nanotube modification on glass transition temperature (T_g) and relaxation dynamics was investigated. The relaxation behavior of the nanocomposites was sensitive to processing method and nanotube functionalization. Nanotube loading …

Effect Of Fluorination On Partitioning Behavior And Bilayer Self Assembly, Vivian Aramide Ojogun

University of Kentucky Doctoral Dissertations

Fluorinated systems are defined by unique properties that offer advantages in drug delivery, material synthesis and industrial applications. In comparison to their hydrocarbon counterparts, the design of fluorinated solutes for tailored applications is limited by the inability to predict the effect of fluorination on phase behavior. This work examines and interprets the influence of fluorination on the phase behavior of fluorinated solutes and surfactants, with emphasis on their impact on vesicle bilayers.

Thermodynamic partitioning of functionalized series of fluorinated and hydrocarbon nicotinate prodrugs fashioned to promote solubility in a fluorocarbon solvent (perfluorooctyl bromide; PFOB) is measured. Predictive approaches are also …

Arsenite Oxidation By Pure Cultures Of Thiomonas Arsenivorans Strain B6 In Bioreactor Systems, Aniruddha Dastidar

University of Kentucky Doctoral Dissertations

The removal of arsenic toxicity from water is accomplished by a preliminary preoxidative step transforming the most toxic form, arsenite (As (III)), to the least toxic form, arsenate (As (V)). The potential of As (III) oxidation to As (V) was initially investigated in batch reactors using the chemoautotrophic Thiomonas arsenivorans strain b6 under varying initial As (III) and cell concentrations and at optimal pH and temperature conditions (pH 6.0 and temperature 30°C). The strain b6 completely oxidized As (III) to As (V) during exponential growth phase for lower levels of As (III) concentrations (≤ 100 mg/L) but continued into stationary …

Remote Controlled Hydrogel Nanocomposites: Synthesis, Characterization, And Applications, Nitin S. Satarkar

University of Kentucky Doctoral Dissertations

There is significant interest in the development of hydrogels and hydrogel nanocomposites for a variety of biomedical applications including drug delivery, sensors and actuators, and hyperthermia cancer treatment. The incorporation of nanoparticulates into a hydrogel matrix can result in unique material characteristics such as enhanced mechanical properties, swelling response, and capability of remote controlled (RC) actuation. In this dissertation, the development of hydrogel nanocomposites containing magnetic nanoparticles/carbon nanotubes, actuation with remote stimulus, and some of their applications are highlighted.

The primary hydrogel nanocomposite systems were synthesized by incorporation of magnetic nanoparticles into temperature responsive N-isopropylacrylamide (NIPAAm) matrices. Various nanocomposite properties …

Nanoscale Functionalization And Characterization Of Surfaces With Hydrogel Patterns And Biomolecules, Hariharasudhan Chirra Dinakar

University of Kentucky Doctoral Dissertations

The advent of numerous tools, ease of techniques, and concepts related to nanotechnology, in combination with functionalization via simple chemistry has made gold important for various biomedical applications. In this dissertation, the development and characterization of planar gold surfaces with responsive hydrogel patterns for rapid point of care sensing and the functionalization of gold nanoparticles for drug delivery are highlighted.

Biomedical micro- and nanoscale devices that are spatially functionalized with intelligent hydrogels are typically fabricated using conventional UV-lithography. Herein, precise 3-D hydrogel patterns made up of temperature responsive crosslinked poly(N-isopropylacrylamide) over gold were synthesized. The XY control of the hydrogel …

Synthesis And Characterization Of Magnetic Hydrogel Nanocomposites For Cancer Therapy Applications, Samantha Ann Meenach

University of Kentucky Doctoral Dissertations

Currently, cancer is the second leading cause of death in the United States. Conventional cancer treatment includes chemotherapy, radiation, and surgical resection, but unfortunately, all of these methods have significant drawbacks. Hyperthermia, the heating of cancerous tissues to between 41 and 45°C, has been shown to improve the efficacy of cancer therapy when used in conjunction with irradiation and/or chemotherapy. In this work, a novel method for remotely administering heat is presented. This method involves heating of tumor tissue using hydrogel nanocomposites containing magnetic nanoparticles which can be remotely heated upon exposure to an external alternating magnetic field (AMF). The …

Preparation And Hydrogen Absorption/Desorption Of Nanoporous Palladium Thin Films, Wen-Chung Li, Thomas John Balk

Chemical and Materials Engineering Faculty Publications

Nanoporous Pd (np-Pd) was prepared by co-sputtering Pd-Ni alloy films onto Si substrates, followed by chemical dealloying with sulfuric acid. X-ray diffractometry and chemical analysis were used to track the extent of dealloying. The np-Pd structure was changed from particle-like to sponge-like by diluting the sulfuric acid etchant. Using suitable precursor alloy composition and dealloying conditions, np-Pd films were prepared with uniform and open sponge-like structures, with interconnected ligaments and no cracks, yielding a large amount of surface area for reactions with hydrogen. Np-Pd films exhibited shorter response time for hydrogen absorption/desorption than dense Pd films, showing promise for hydrogen …