Chemical Engineering Commons^™

Molecular Understanding And Design Of Deep Eutectic Solvents And Proteins Using Computer Simulations And Machine Learning, Usman Lame Abbas

Theses and Dissertations--Chemical and Materials Engineering

Hydrophobic deep eutectic solvents (DESs) have emerged as excellent extractants. A major challenge is the lack of an efficient tool to discover DES candidates. Currently, the search relies heavily on the researchers’ intuition or a trial-and-error process, which leads to a low success rate or bypassing of promising candidates. DES performance depends on the heterogeneous hydrogen bond environment formed by multiple hydrogen bond donors and acceptors. Understanding this heterogeneous hydrogen bond environment can help develop principles for designing high performance DESs for extraction and other separation applications. This work investigates the structure and dynamics of hydrogen bonds in hydrophobic DESs …

Microalgae Immobilization With Filamentous Fungi: Process Development For Sustainable Food Systems, Suvro Talukdar

Theses and Dissertations--Biosystems and Agricultural Engineering

Demand for sustainable food sources has increased because of the rapid growth of the world's population.  In this study, microalgae cells of Haematococcus pluvialis were immobilized using the edible fungal strain Aspergillus awamori for potential food applications. The study investigated the impact of fungal loading, pellet geometry, and initial microalgae cell concentration on the immobilization performance and product characteristics. It was found that higher fungal loading and larger fungal pellets contributed to increased immobilization performance while increased initial microalgae concentration inhibited the process. Larger fungal pellets had decreased biomass density, which led to decreased surface concentration of immobilized microalgae but …

Recovery Of Valuable Metals From Electronic Waste Using A Novel Ammonia-Based Hydrometallurgical Process, Peijia Lin

Theses and Dissertations--Mining Engineering

The growing quantity of waste electrical and electronic equipment (WEEE), also known as electronic waste (E-waste), has been an area of growing public concern. The abundance of valuable metals contained in waste printed circuit boards (WPCBs) has made it a promising secondary resource, especially for Cu and Au. Although the recovery of metals from WPCBs via hydrometallurgical routes has been studied extensively over the past 20 years, most of the research has been limited in the laboratory. In current hydrometallurgical processes, strong acids and expensive oxidizers are often used to ensure a high recovery of metals without considering the sustainability …

Impact Of Spallation And Internal Radiation On Fibrous Ablative Materials, Raghava Sai Chaitanya Davuluri

Theses and Dissertations--Mechanical Engineering

Space vehicles are equipped with Thermal Protection Systems (TPS) that encounter high heat rates and protect the payload while entering a planetary atmosphere. For most missions that interest NASA, ablative materials are used as TPS. These materials undergo several mass and energy transfer mechanisms to absorb intense heat. The size and construction of the TPS are based on the composition of the planetary atmosphere and the impact of various ablative mechanisms on the flow field and the material. Therefore, it is essential to quantify the rates of different ablative phenomena to model TPS accurately. In this work, the impact of …

Molecular Understanding Of Zwitterions And Quantum Computing For Sustainability, Manh Tien Nguyen

Theses and Dissertations--Chemical and Materials Engineering

The sustainable development of society needs sustainable energy solutions and the mitigation of greenhouse gas emissions. One key subject in this area is the development of safe and efficient ion-based batteries. Moreover, CO₂ capture is a crucial pathway in mitigating emissions from the combustion of fossil fuels. Ongoing efforts are to improve both technologies' safety and efficiency. This thesis presents our efforts to conduct computational research on understanding advanced zwitterionic electrolytes and CO₂ capture. Chapters 2-4 illustrate the computational research to understand ionic solvation in zwitterionic electrolytes. Solid-state electrolytes are essential for safer batteries. While solid polymer electrolytes …

Effects Of Confinement On Ionic Liquids And Deep Eutectic Solvents For The Design Of Catalytic Systems, Electrochemical Devices, And Separations, Andrew Drake

Theses and Dissertations--Chemical and Materials Engineering

Confinement of ionic liquids (ILs) and deep eutectic solvents (DESs) within mesoporous materials such as silica helps to control the local environment within the pores for applications such as catalysis, electrochemistry, and absorption. Silica thin films with 2.5 and 8 nm pores and micron-sized silica particles with pore diameters of 5.4 and 9 nm were synthesized to study the effect of nanoconfinement on ILs 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]), 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), and DESs reline and ethaline (choline chloride and urea or ethylene glycol). Silica thin films with vertically aligned, well ordered, and accessible pores were synthesized via the evaporation-induced …

A Process Intensification Approach To Improve Volatile Fatty Acids Production, Extraction, And Valorization, Can Liu

Theses and Dissertations--Biosystems and Agricultural Engineering

Anaerobic digestion (AD) is a widely used biowaste conversion method. Recent studies have explored arrested methanogenesis as an alternative approach to leverage existing AD facilities and produce volatile fatty acids (VFAs) instead of biogas. VFAs have been recognized as precursors for a range of value-added chemicals and bioproducts. Arrested methanogenesis involves inducing acidic fermentation by halting the AD process before methanogenesis. It has been found that higher organic loading and thermophilic conditions enhance VFA accumulation and stabilize the acidic fermentation (AF) system.

Brewer's spent grain (BSG), a significant by-product of the brewing industry, was employed as the feedstock for VFA …

Development Of Soluble Bioactive Poly(Beta Amino Esters) (Pβaes) For Post-Synthesis Processing, Kelley Wiegman

Theses and Dissertations--Chemical and Materials Engineering

Polymers have proven to be a viable platform to facilitate the controlled and targeted release for a variety of therapeutic agents. Polymeric prodrugs are a growing area of drug delivery in which active pharmaceutical ingredients are covalently linked to a polymeric form in an effort to enhance stability, delivery, and pharmacology. One naturally occurring class of active ingredients, known as polyphenols, can potentially offer a vast array of beneficial therapeutic properties. However, the therapeutic efficacy of these compounds is severely limited due to poor solubility and bioavailability as well as an oxidative and thermal instability. To improve the efficacy of …

Versatile Functionalization Strategy For The Capture Of Antibodies Using Silica Nanoparticles, Sayma Afrin

Theses and Dissertations--Chemical and Materials Engineering

In this work, the synthesis of protein-functionalized nonporous silica nanoparticles and their application to capture antibodies was demonstrated. Silica nanoparticles were chosen as they offered particle and pore size tunability, low toxicity, thermal stability, ease of synthesis and ease of surface functionalization. A biotin-streptavidin-biotin bridge was constructed on the surface of the particles and used to attach biotinylated Protein A/G (PAG), which has high affinity for antibodies. The biotin-streptavidin-biotin bridge is hypothesized to orient the PAG in a favorable manner for efficient antibody capture. Nonporous silica nanoparticles (approximately 270 nm in diameter) were synthesized via the Stöber method. Following amine …

Photocatalytic Degradation Of Lignin By Supported Silver Nanoparticles, Ning Wei

Theses and Dissertations--Chemical and Materials Engineering

Lignin is the second most abundant form of biomass on earth. The phenolic structure and high carbon to oxygen ratio make lignin an attractive renewable source of fuel and chemicals. However, its recalcitrance and heterogeneous nature prove difficult for decomposing lignin’s polymer structure and separation of the products. This work has focused on the use of low-energy catalytic approaches to overcome these barriers. A mimic of the lignin degrading enzyme laccase, consisting of a copper cluster Cu4Py4I4 modified with AgNO3, was developed to function similarly to the laccase active site. The prepared copper complex solution was found to be active …

Lignin Valorization Via Reductive Depolymerization Using Promoted Nickel Catalysts And Sub- And Supercritical Methanol, Julia Parker

Theses and Dissertations--Biosystems and Agricultural Engineering

While lignin has been regarded as the most promising renewable feedstock for the sustainable manufacture of aromatic compounds, lignin valorization is necessary to improve the economic viability of biorefineries. Reductive catalytic fractionation (RCF), which combines delignification and lignin depolymerization into a single stage while maintaining the structure and integrity of the cellulose component, has evolved as an effective method for processing biomass. The ability of Cu and Fe to promote the performance of a 20% Ni/alumina catalyst when converting native lignin to alkylphenols by RCF in sub- and supercritical methanol was tested. The effectiveness of lignin extraction as measured by …

Modeling Of Rare Earth Solvent Extraction Process For Flowsheet Design And Optimization, Vaibhav Kumar Srivastava

Theses and Dissertations--Mining Engineering

The separation and purification of rare earth elements (REEs) into individual products has been a topic of significant interest for researchers and engineers for many decades. The prime reason for such sustained interest is due to REEs’ demand and application in modern technology, as well as the challenges associated with their separation and purification. The chemical similarity of rare earth group elements is responsible for difficult separability which makes purification of individual elements challenging. Despite associated complications, processes such as solvent extraction (SX) and ion-exchange have been successfully utilized in the separation and production of REEs on pilot and commercial …

Development Of Novel Polymeric Materials For Their Application In Monitoring And Remediation Of Environmental Pollutants, Rishabh Shah

Theses and Dissertations--Chemical and Materials Engineering

Remediation of environmental pollutants from water is one of the major challenges in the 21st century. Utilizing novel polymeric materials to accomplish this challenge has garnered a lot of interest in recent times. Flexibility in synthesizing as well as functionalizing makes them attractive for their application in pollutant remediation. This work is based on development and characterization of novel crosslinked polymeric as well as linear polymeric materials from biphenyl-based monomers, biphenyl based crosslinker and a temperature responsive monomer (Nisopropylacrylamide (NIPAAm)) for their application in remediation of toxic pollutants such as polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and iron oxide nanoparticle …

Optimization Of Gelatin-Based Cellular Coating Of Msc For Myocardial Infarction Therapy, Kara Amelle Davis

Theses and Dissertations--Chemical and Materials Engineering

Cardiovascular disease remains the number one threat to American lives. During an acute myocardial infarction (AMI), blood flow is blocked and results in the formation of scar tissue. As the body’s immune system responds, inflammatory signaling causes an increase in both scar tissue size and the patient’s risk for further chronic heart failure. In order to reduce the risk of continued heart disease inflammatory signaling must be reduced. Stem cell therapies have the ability to alter the immune system’s pro-inflammatory signal. However, stem cell retention is limited due to blood flow shear. Gelatin methacrylate (GelMA) based coatings have been shown …

Tailoring Thermoresponsive Poly(N-Isopropylacrylamide) Toward Sensing Perfluoroalkyl Acids, Dustin Thomas Savage

Theses and Dissertations--Chemical and Materials Engineering

Widespread distribution of poly- and perfluoroalkyl substances (PFAS) in the environment combined with concerns for their potentially negative health effects has motivated regulators to establish strict standards for their surveillance. The United States Environmental Protection Agency issued a cumulative domestic threshold of 70 ppt for water supplies, and this bar is even lower in some local districts and other countries. Monitoring PFAS consequently requires sensitive analytical equipment to meet regulatory specifications, and liquid chromatography with tandem mass spectroscopy (LC/MS/MS) is the most common technique used to satisfy these requirements. Though extremely sensitive, the instrument is often burdened by pretreatment regimens, …

Assessment Of A Decentralized Solution For Waste Plastic Management In Developing Regions, Chandniben Ashishkumar Joshi

Theses and Dissertations--Chemical and Materials Engineering

Rapid population growth, urbanization and availability of pre-packaged consumer goods have led to increased generation and consumption of plastic – so much so that it has become ubiquitous in the environment. An affordable, durable, and lightweight material of construction, plastic is used in innumerable products in every country on earth. However, this explosion of consumption coupled with the material’s significantly low degradability have led to serious plastic accumulation challenges, which are now an imminent threat to terrestrial and marine species globally. These challenges are especially acute in developing countries, where capital and infrastructure constraints, poor governmental regulation and lack of …

Interactions Of Lignin Dimers With Engineered Surfaces And Model Cell Membranes For Design Of Lignin-Based Materials, Mahsa Moradipour

Theses and Dissertations--Chemical and Materials Engineering

Capitalizing on byproducts of industrial and agricultural economies is among the utmost goals of sustainability. Of particular interest for commercial upgrading is lignin, a phenolic biopolymer found in the cell walls of plants which is the second most abundant biopolymer on Earth after cellulose. Due to its heterogeneous structure, deconstructing lignin to selected small molecules for use as chemicals or advanced materials has been elusive. This work capitalizes on a “bottom up” approach to the synthesis of lignin oligomers of known bond chemistry to better understand their interfacial interactions.

The potential pharmacological mechanism of lignin deconstruction components and their toxicological …

Understanding Absorption, Supersaturation, And Drug Activity In Solution: Working Towards Developing A More Biorelevant Media, Freddy Arce

Theses and Dissertations--Pharmacy

With the looming dominance of poorly water-soluble chemical entities within the pharmaceutical pipeline, the pharmaceutical industry has leaned on the use of supersaturating drug delivery systems (SDDSs) to achieve efficacious concentrations within the gastrointestinal fluids. SDDSs aim to achieve concentrations in solutions greater than the solubility of the lowest energy crystalline form. However, the generation of supersaturated solutions of active pharmaceutical ingredients (APIs) creates a strong crystallization potential, which is undesirable.

In product development, supersaturating products often fail in Phase I and Phase II clinical trials due to poor oral bioavailability and a lack of in vivo efficacy. Pre-clinical testing …

Extraction Of Micro- And Nano-Plastic Particles From Water Using Hydrophobic Natural Deep Eutectic Solvents, Jameson R. Hunter

Theses and Dissertations--Biosystems and Agricultural Engineering

The production of plastic and the amount of waste plastic that enters the environment increases every year. Synthetic polymers will gradually break down into particles on the micro- and nano-scale. The micro- and nano-plastics pose a significant ecological harm by transporting toxic chemicals and causing inflammation and cellular damage when ingested. Two common plastics are polyethylene terephthalate (PET) and Polystyrene (PS), and a newer bioplastic polylactic acid (PLA) that has become a popular alternative. Deep eutectic solvents are a recently discovered solvent composed of a hydrogen bond donor and hydrogen bond acceptor and have been proposed as a cheaper alternative …

Microfiltration Membrane Pore Functionalization Approaches For Chloro-Organic Remediation To Heavy Metal Sorption, Mohammad Saiful Islam

Theses and Dissertations--Chemical and Materials Engineering

Microfiltration polyvinylidene fluoride (PVDF) membranes have distinct advantage for open structure in terms of high internal surface area and ease of access in the pore domain. Functionalization of PVDF membranes with different functional groups (-COOH, -OH, -SH) enables responsive (pH, temperature) properties to membrane, tuning of effective pore size, controlling permeate flux. PVDF microfiltration membrane functionalization with suitable responsive polymer such as poly acrylic acid (PAA) to incorporate carboxyl (-COOH) group enables further modification of functionalized PAA-PVDF membranes for different application ranging from catalysis, bio reactor to heavy metal sorption platform. As a catalytic reactor bed, this PAA-PVDF membranes are …

A Framework For Heterologous Biosynthesis Of Natural Products In Mammalian Cells Via Polymer-Mediated Transfections, Logan Warriner

Theses and Dissertations--Chemical and Materials Engineering

With the promise to treat a multi-faceted list of serious inherited and acquired diseases, such as cancer, neurodegenerative and infectious diseases, and inherited genetic indications, gene therapy has continued to push the boundaries of traditional medicine since its earliest implementation. While much progress has been made, clinical success has largely remained elusive. Immunogenicity, difficulty producing commercially relevant quantities, and having a limited genetic payload still limits the ability of viruses to act as directed delivery agents for genetic material. As such, researchers have turned to cationic synthetic materials as a means of delivering nucleic acids, which can circumvent the immune …

Polymeric Nanocomposite Membranes With Phosphorene Based Pore Fillers For Fouling Control, Joyner Eke

Theses and Dissertations--Chemical and Materials Engineering

Phosphorene is a two-dimensional material exfoliated from bulk phosphorus. Specifically, relevant to the field of membrane science, the band gap of phosphorene provides it with potential photocatalytic properties, which could be explored in making reactive membranes able to control the accumulation of compounds on the surface during filtration, or fouling. Another reason phosphorene is a promising candidate as a membrane material additive is due to its catalytic properties which can potentially destroy foulants on the membrane surface.

The first goal of this study was to develop an innovative and robust membrane able to control and reverse fouling with minimal changes …

Bimetallic Nanoparticles Integrated Membranes For Groundwater Remediation: Synthesis, Characterization And Applications, Hongyi Wan

Theses and Dissertations--Chemical and Materials Engineering

The detoxification of chlorinated organics from groundwater, such as trichloroethylene (TCE), tetrachloroethylene (PCE), polychlorinated biphenyl (PCB) and carbon tetrachloride (CTC), is a challenging area. Reductive dechlorination has been investigated using iron and iron-based nanoparticles, such as bare Fe, sulfidized Fe (S-Fe) and palladized Fe (Pd-Fe). However, issues including particle agglomeration, difficulties in recycling and particle leaching have been reported to hinder the application and wide usage of these techniques. The integration of nanoparticles and membranes can address these issues because of the large surface area, stability, and the potential for versatile functionalities. In this study, commercial polyvinylidene difluoride (PVDF) microfiltration …

Characterization And Electrochemical Performance Of Dopamine-Sensitized Titania Thin Films, Joshua Garay

Theses and Dissertations--Chemical and Materials Engineering

Sensitization of mesoporous titania films with dopamine and polydopamine for visible light photoelectrochemical activity is investigated. Sensitization effectiveness is compared with 8 mM dopamine solutions of varying pH (acidic, basic, and neutral), as well as with a basic polydopamine solution. Vibrational changes due to dopamine attachment are determined from detached powders by Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) is used to quantify organics attached. X-ray photoelectron spectroscopy (XPS) of intact films probes the chemically induced charge shift from dopamine attachment. Cyclic voltammetry identifies the irreversible dopamine oxidation and tin reduction voltages. Finally, chronoamperometric curves are used to compare …

Silica Nanoporous Confinement Effects On Ionic Liquid Properties For Better Design Of Small Molecule Separation, Electrochemical Devices And Drug Delivery, Yuxin He

Theses and Dissertations--Chemical and Materials Engineering

Silica nanoconfinement provides a high level of control of ionic liquids (ILs) in localizing catalysts, creating distinct environment for tuning reactivity and controlling the partition of solvents, reactants and products. Silica thin films with two different pore sizes (2.5 nm and 8 nm) were synthesized to study the effect of nanopore confinement on ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]), and 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]). Silica thin films with accessible 8 nm pore diameters were synthesized using evaporation-induced self-assembly (EISA) with Pluronic P123 as templating surfactant on a chemically neutral modified substrate. The silica films with similar orthogonal aligned mesostructured but …

The Development Of Temperature And Ph Responsive Hydrogels And Membranes For Selective Sorption Of Perfluoroorganics And Nanoparticle Integrated Catalytic Degradation Of Pcb, Anthony Saad

Theses and Dissertations--Chemical and Materials Engineering

The functionalization and use of responsive and catalytic polymeric membranes and materials were explored for contaminant capture and degradation. While membranes have a wide variety of uses across multiple industries, the inclusion of materials that are temperature and pH responsive in the membrane pore domain yields a wide range of applications and possibilities for water treatment. Temperature and pH responsive polymers, as well as controlled nanostructured materials, were synthesized in membrane pores for advanced adsorption-desorption and catalytic treatment of emerging organic contaminants in water. In this study, supported by the NIEHS, poly-N-isopropylacrylamide (PNIPAm) was used as a model thermo-responsive polymer, …

Effect Of Silica Nanoconfinement Of Lipid Bilayers On Its Phase Transition And On The Colloidal Stability Of Silica Nanoparticles, Aniruddha Atul Shirodkar

Theses and Dissertations--Chemical and Materials Engineering

In this work, we incorporated 4-(N-Boc-aminometyl) phenylboronic acid (BA), at different concentrations, into 1,2-dipalmitoyl-sn-glycero-3- phosphocholine (DPPC) bilayers confined within nanopores of two different mean pore diameters of 7.4 nm and 11.7 nm of micron sized silica particles. The confinement of DPPC into nanopores resulted in the depression in the main phase transition temperatures compared to the liposomal system. The addition of BA was found to induce disruptions in the acyl chains of the lipid molecules at all concentrations of the solute. The lipid bilayer cooperativity was found to be higher in the confined systems compared to the liposomal systems despite …

Coarse-Grained Dynamically Accurate Simulations Of Ionic Liquids At Vacuum-Interface, Tyler D. Stoffel

Theses and Dissertations--Mechanical Engineering

Ionic liquids, possessing improved properties in many areas of technical application, are excellent candidates as components in development of next-generation technology, including ultra-high energy batteries. If they are thus applied, however, extensive interfacial analysis of any selected ionic configuration will likely be required. Molecular dynamics (MD) provides an advantageous route by which this may be accomplished, but can fall short in observing some phenomena only present at larger time/length scales than it can simulate. Often times this is approached by coarse-graining (CG), with which scope of simulation can be significantly increased. However, coarse-grained MD systems are generally known to produce …

Fabrication, Characterization And Applications Of Highly Conductive Wet-Spun Pedot:Pss Fibers, Ruben Sarabia Riquelme

Theses and Dissertations--Chemical and Materials Engineering

Smart electronic textiles cross conventional uses to include functionalities such as light emission, health monitoring, climate control, sensing, storage and conversion of energy, etc. New fibers and yarns that are electrically conductive and mechanically robust are needed as fundamental building blocks for these next generation textiles.

Conjugated polymers are promising candidates in the field of electronic textiles because they are made of earth-abundant, inexpensive elements, have good mechanical properties and flexibility, and can be processed using low-cost large-scale solution processing methods. Currently, the main method to fabricate electrically conductive fibers or yarns from conjugated polymers is the deposition of the …

Nanostructured Metal Thin Films As Components Of Composite Membranes For Separations And Catalysis, Michael J. Detisch

Theses and Dissertations--Chemical and Materials Engineering

Novel metallic thin film composite membranes are synthesized and evaluated in this work for improved separations and catalysis capabilities. Advances in technology that allow for improved membrane performance in solvent separations are desirable for low molecular weight organic separation applications such as those in pharmaceutical industries. Additionally, the introduction of catalytic materials into membrane systems allow for optimization of complex processes in a single step. By adding a nanostructured metallic thin film to its surface, a polymer membrane may be modified to exhibit these improved properties. Using magnetron sputtering, thin metal films may be deposited on commercially available membranes to …