Chemical Engineering Commons^™

New Mechanism Insight For The Hydrogenation Of Co/Co2 Gas Mixtures To Hydrocarbons Over Iron-Based Catalyst, Sandeep Badoga, Michela Martinelli, Muthu Kumaran Gnanamani, Young Koh, Wilson D. Shafer

Center for Applied Energy Research Faculty and Staff Publications

Iron-based catalysts are the most suitable candidates for converting CO₂ or CO₂-rich syngas to hydrocarbons. However, several issues about the mechanism of CO₂ hydrogenation are still unclear. In this work, we investigated the performance of an iron-based catalyst with H₂/CO₂, H₂/CO/N₂ and H₂/CO/¹³CO₂/N₂ gas mixtures at the same process conditions (T = 270°C, P = 175 psi and SV = 3 NL/h/g_cat). The CO₂ hydrogenation rate was much lower than that observed for CO hydrogenation. ¹³CO_{2 …}

Review On Carbon Dioxide Utilization For Cycloaddition Of Epoxides By Ionic Liquid-Modified Hybrid Catalysts: Effect Of Influential Parameters And Mechanisms Insight, Jimmy Nelson Appaturi, Rajabathar. Jothi Ramalingam, Muthu Kumaran Gnanamani, Govindasami Periyasami, Prabhakarn Arunachalam, Rohana Adnan, Farook Adam, Mohammed D. Wasmiah, Hamad A. Al‐Lohedan

Center for Applied Energy Research Faculty and Staff Publications

The storage, utilization, and control of the greenhouse (CO₂) gas is a topic of interest for researchers in academia and society. The present review article is dedicating to cover the overall role of ionic liquid-modified hybrid materials in cycloaddition reactions. Special emphasis is on the synthesis of various cyclic carbonate using ionic liquid-based modified catalysts. Catalytic activity studies have discussed with respect to process conditions and their effects on conversion and product selectivity for the reaction of cycloaddition of CO₂ with styrene oxide. The reaction temperature and the partial pressure of CO₂ have found to play …

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 …

The Characterization Of Purified Citrate-Coated Cerium Oxide Nanoparticles Prepared Via Hydrothermal Synthesis, Matthew L. Hancock, Robert A. Yokel, Matthew J. Beck, Julie L. Calahan, Travis W. Jarrells, Eric J. Munson, George A. Olaniyan, Eric A. Grulke

Chemical and Materials Engineering Faculty Publications

Hypothesis

Cerium oxide nanoparticles were synthesized using a hydrothermal approach with citric acid as a stabilizing agent. Citric acid adsorption onto the nanoceria particle surface can cease particle formation and create a stable dispersion for an extended shelf life. The product was dialyzed immediately following the synthesis to remove unreacted cerium that could contribute to biological effects. Nanoparticle characterization results are expected to help identify the surface citrate bonding structure.

Experiments

Many characterization techniques were utilized to determine size, morphology, surface properties, and citrate complexation on the nanoceria particle surface. These included transmission electron microscopy, electron energy loss spectroscopy, dynamic …

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 …

Scaling Realistic Fire Scenarios, James G. Quintiere

Progress in Scale Modeling, an International Journal

A review is made of work on scale modeling in fire and presented from the experience of the author. Primarily, scale modeling in air is discussed but there is a brief discussion of a scale model with salt and fresh water for smoke movement. A complete set of dimensionless groups is presented for fire, then it is illustrated how selections were made for the partial scaling of specific fire scenarios. Studies have been motivated by basic research interests as well as for fire investigations. The dynamics of floorcovering fire spread in a corridor is studied to reveal many features of …

Nanoceria Distribution And Effects Are Mouse-Strain Dependent, Robert A. Yokel, Michael T. Tseng, D. Allan Butterfield, Matthew L. Hancock, Eric A. Grulke, Jason M. Unrine, Arnold J. Stromberg, Alan K. Dozier, Uschi M. Graham

Pharmaceutical Sciences Faculty Publications

Prior studies showed nanoparticle clearance was different in C57BL/6 versus BALB/c mice, strains prone to Th1 and Th2 immune responses, respectively. Objective: Assess nanoceria (cerium oxide, CeO₂ nanoparticle) uptake time course and organ distribution, cellular and oxidative stress, and bioprocessing as a function of mouse strain. Methods: C57BL/6 and BALB/c female mice were i.p. injected with 10 mg/kg nanoceria or vehicle and terminated 0.5 to 24 h later. Organs were collected for cerium analysis; light and electron microscopy with elemental mapping; and protein carbonyl, IL-1β, and caspase-1 determination. Results: Peripheral organ cerium significantly increased, generally more …

Plasma And Serum Proteins Bound To Nanoceria: Insights Into Pathways By Which Nanoceria May Exert Its Beneficial And Deleterious Effects In Vivo, D. Allan Butterfield, Binghui Wang, Peng Wu, Sarita S. Hardas, Jason M. Unrine, Eric A. Grulke, Jian Cai, Jon B. Klein, William M. Pierce, Robert A. Yokel, Rukhsana Sultana

Chemistry Faculty Publications

Nanoceria (CeO2, cerium oxide nanoparticles) is proposed as a therapeutic for multiple disorders. In blood, nanoceria becomes protein-coated, changing its surface properties to yield a different presentation to cells. There is little information on the interaction of nanoceria with blood proteins. The current study is the first to report the proteomics identification of plasma and serum proteins adsorbed to nanoceria. The results identify a number of plasma and serum proteins interacting with nanoceria, proteins whose normal activities regulate numerous cell functions: antioxidant/detoxification, energy regulation, lipoproteins, signaling, complement, immune function, coagulation, iron homeostasis, proteolysis, inflammation, protein folding, protease inhibition, adhesion, protein/RNA …

Nanohybrid Membrane Synthesis With Phosphorene Nanoparticles: A Study Of The Addition, Stability And Toxicity, Joyner Eke, Philip Alexander Mills, Jacob Ryan Page, Garrison P. Wright, Olga V. Tsyusko, Isabel C. Escobar

Center of Membrane Sciences Faculty Publications

Phosphorene is a promising candidate as a membrane material additive because of its inherent photocatalytic properties and electrical conductance which can help reduce fouling and improve membrane properties. The main objective of this study was to characterize structural and morphologic changes arising from the addition of phosphorene to polymeric membranes. Here, phosphorene was physically incorporated into a blend of polysulfone (PSf) and sulfonated poly ether ether ketone (SPEEK) doping solution. Protein and dye rejection studies were carried out to determine the permeability and selectivity of the membranes. Since loss of material additives during filtration processes is a challenge, the stability …

Water Purification Device And A Method Of Decontaminating A Water Supply, Dibakar Bhattacharyya, Li Xiao

Chemical and Materials Engineering Faculty Patents

A water purification device is provided in the form of a hydrogel matrix containing immobilized nanoparticles that are directly synthesized in-situ in the hydrogel matrix. The hydrogel matrix is temperature sensitive, such that swelling draws in pollutants that are captured by the nanoparticles, while deswelling releases purified water. A related method of decontaminating the water supply contaminated with a target pollutant is also disclosed.

Current Status Of Magnetic Resonance On Saliva For Oral And Dental Health Early Diagnosis, Anastasia Katsavochristou, Dimitrios Koumoulis

Oral Health Practice Faculty Publications

Magnetic resonance spectroscopy of biomolecules has recently gained attention for clinical diagnosis. Its combination with saliva collection and analysis can promote early disease detection and monitoring, by identifying biomarkers of specific underlying pathology or disease as detected in saliva. With this novel, non-invasive technique, certain salivary biomarkers have been linked to dental and periodontal tissues pathology, as well as to specific head and neck cancer malignancies. At present, diagnostic biomarkers are still in need for further identification (e.g., diagnosis and monitoring of Sjögren’s syndrome), and nuclear magnetic resonance spectroscopy has been found to be a promising technique to compliment the …

Co2 Mass Transfer Enhancement Of Aqueous Amine Solvents By Particle Additives, Leland R. Widger, Guojie Qi, Kun Liu, Jonathan Bryant, Cameron A. Lippert, Kunlei Liu

Center for Applied Energy Research Faculty Patents

The present invention relates to methods for improving carbon capture by providing particles within an amine solvent. The particles provide for increased turbulence at the interface between the counter-flowing gas and solvent, which allows for increased amine and carbamate salt diffusion between the liquid film and bulk.

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 …

A Thermodynamic And Feasibility Study Of Green Solvents For The Fabrication Of Water Treatment Membranes, Xiaobo Dong

Theses and Dissertations--Chemical and Materials Engineering

Nonsolvent induced phase separation (NIPS) has been widely used to fabricate polymeric membranes. In NIPS, a polymer is dissolved in a solvent to form a dope solution, which is then cast on a substrate and immersed in a nonsolvent bath, where phase inversion occurs. Petroleum-derived organic solvents, such as N-Methyl-2-Pyrrolidone (NMP) and Dimethylacetamide (DMAc), have been traditionally used to fabricate polymeric membranes via NIPS. However, these solvents may have negative impacts on environmental and human health; therefore, using greener and less toxic solvents, preferably derived from biomass, is of great interest to make membrane fabrication sustainable. In this dissertation, two …