Chemical Engineering Commons^™

Occurrence Of Chlorinated Volatile Organic Compounds (Vocs) In A Sanitary Sewer System: Implications For Assessing Vapor Intrusion Alternative Pathways, Mohammadyousef Roghani, Olivia P. Jacobs, Anthony Miller, Evan James Willett, James A. Jacobs, C. Ricardo Viteri, Elham Shirazi, Kelly G. Pennell

Civil Engineering Faculty Publications

Sewer systems have been recently recognized as potentially important exposure pathways to consider during vapor intrusion assessments; however, this pathway has not been well-characterized and there is need for additional information about the occurrence of volatile organic compounds (VOCs) in sewer systems. This paper reports the results of sewer gas sampling conducted in a sanitary sewer over the years of 2014–2017. Sewer gas samples were collected and analyzed using several different techniques, including TO-15 (grab), TO-17 (passive), Radiello® (passive) and a novel continuous monitoring technique, the Autonomous Rugged Optical Multigas Analyzer (AROMA). The applicability of each of the different approaches …

Pit Evolution Around The Fusion Line Of A Nicrmov Steel Welded Joint Caused By Galvanic And Stress-Assisted Coupling Corrosion, Shuo Weng, Yuhui Huang, Fuzhen Xuan, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

The corrosion of NiCrMoV steel welded joints is performed in an aqueous solution of 3.5 wt% NaCl at 180 °C in a container at a pressure of 0.8 MPa. The specimens in the shape of cylindrical tensile rods are immersed in the aqueous solution under the action of tensile stress in a range of 0 to 0.9 of the yield stress of the base metal. The experimental results suggest that there is macro-galvanic corrosion in the welded joint with the coarse-grained heat affected zone (CGHAZ) as anode due to the highest corrosion susceptibility of the CGHAZ. The CGHAZ has the …

Correlation Of Structure, Function And Protein Dynamics In Gh7 Cellobiohydrolases From Trichoderma Atroviride, T. Reesei And T. Harzianum, Anna S. Borisova, Elena V. Eneyskaya, Suvamay Jana, Silke F. Badino, Jeppe Kari, Antonella Amore, Magnus Karlsson, Henrik Hansson, Mats Sandgren, Michael E. Himmel, Peter Westh, Christina M. Payne, Anna A. Kulminskaya, Jerry Ståhlberg

Chemical and Materials Engineering Faculty Publications

Background: The ascomycete fungus Trichoderma reesei is the predominant source of enzymes for industrial conversion of lignocellulose. Its glycoside hydrolase family 7 cellobiohydrolase (GH7 CBH) TreCel7A constitutes nearly half of the enzyme cocktail by weight and is the major workhorse in the cellulose hydrolysis process. The orthologs from Trichoderma atroviride (TatCel7A) and Trichoderma harzianum (ThaCel7A) show high sequence identity with TreCel7A, ~ 80%, and represent naturally evolved combinations of cellulose-binding tunnel-enclosing loop motifs, which have been suggested to influence intrinsic cellobiohydrolase properties, such as endo-initiation, processivity, and off-rate.

Results: The TatCel7A, ThaCel7A, …

Comparison Of Eosin And Fluorescein Conjugates For The Photoinitiation Of Cell-Compatible Polymer Coatings, Jacob L. Lilly, Anuhya Gottipati, Calvin F. Cahall, Mohamed Agoub, Brad J. Berron

Chemical and Materials Engineering Faculty Publications

Targeted photopolymerization is the basis for multiple diagnostic and cell encapsulation technologies. While eosin is used in conjunction with tertiary amines as a water-soluble photoinitiation system, eosin is not widely sold as a conjugate with antibodies and other targeting biomolecules. Here we evaluate the utility of fluorescein-labeled bioconjugates to photopolymerize targeted coatings on live cells. We show that although fluorescein conjugates absorb approximately 50% less light energy than eosin in matched photopolymerization experiments using a 530 nm LED lamp, appreciable polymer thicknesses can still be formed in cell compatible environments with fluorescein photosensitization. At low photoinitiator density, eosin allows more …

Understanding Inhibition Of A Biodesulfurization Enzyme To Improve Sulfur Removal From Petroleum, Yue Yu

Theses and Dissertations--Chemical and Materials Engineering

The biodesulfurization 4S-pathway is a promising complementary enzymatic approach to remove sulfur from recalcitrant thiophenic derivatives in petroleum products that remain from conventional hydrodesulfurization method without diminishing the calorific value of oil. The final step of this pathway involves the carbon-sulfur bond cleavage from HBPS, and the production of the final products 2-hydroxybiphenyl (HBP) and sulfite, has been recognized as the rate-limiting step, partially as a result of product inhibition. However, the mechanisms and factors responsible for product inhibition in the last step have not been fully understood. In this work, we proposed a computational investigation using molecular dynamic simulations …

Understanding The Thermodynamics And Oral Absorption Potential Of Pharmaceutical Amorphous Solid Dispersions, Nico Setiawan

Theses and Dissertations--Pharmacy

Supersaturating drug delivery systems, such as amorphous solid dispersions (ASDs), have been used extensively to elevate the apparent solubility and oral bioavailability of poorly water-soluble drugs. However, despite the numerous examples of success in increasing solubility and oral bioavailability using ASDs, physical stability challenges remain as formulators seek to employ high drug loading for cost reduction and improved patient compliance. Therefore, stability in both the solid and solution state must be considered for ASDs to be successful. In the solid state, the drug must remain amorphous in the solid matrix throughout the shelf life of the product. Although excipients, such …

Evaluation And Prevention Of Spontaneous Combustion During Handling And Storage Of Coal, Amir E. Najarzadeh

Theses and Dissertations--Mining Engineering

Spontaneous combustion of coal has historically been a major problem for the coal industry, predominantly during storage and transportation. Various methods have been used in the laboratory for evaluating the propensity of different coal sources to self-heat. However, the heterogeneity of coal and the complexity of the system has resulted in inconsistencies and sometimes conflicting results as indicated by the findings reported in several publications.

The primary objective of the current study was to build a laboratory scale apparatus that simulates the condition of a coal stockpile to evaluate the events leading to spontaneous combustion and develop potential remedies. As …

Pressure-Driven Stabilization Of Capacitive Deionization, Landon S. Caudill

Theses and Dissertations--Mechanical and Aerospace Engineering

The effects of system pressure on the performance stability of flow-through capacitive deionization (CDI) cells was investigated. Initial data showed that the highly porous carbon electrodes possessed air/oxygen in the micropores, and the increased system pressure boosts the gases solubility in saline solution and carries them out of the cell in the effluent. Upon applying a potential difference to the electrodes, capacitive-based ion adsorption occurs in competition with faradaic reactions that consume oxygen. Through the addition of backpressure, the rate of degradation decreases, allowing the cell to maintain its salt adsorption capacity (SAC) longer. The removal of oxygen from the …

Characterization Of Rotary Bell Atomizers Through Image Analysis Techniques, Jacob E. Wilson

Theses and Dissertations--Mechanical and Aerospace Engineering

Three methods were developed to better understand and characterize the near-field dynamic processes of rotary bell atomization. The methods were developed with the goal of possible integration into industry to identify equipment changes through changes in the primary atomization of the bell. The first technique utilized high-speed imaging to capture qualitative ligament breakup and, in combination with a developed image processing technique and PIV software, was able to gain statistical size and velocity information about both ligaments and droplets in the image data. A second technique, using an Nd:YAG laser with an optical filter, was used to capture size statistics …

Intermittency Effects On The Universality Of Local Dissipation Scales In Turbulent Boundary Layer Flows With And Without Free-Stream Turbulence, Sabah Falih Habeeb Alhamdi

Theses and Dissertations--Mechanical and Aerospace Engineering

Measurements of the small-scale dissipation statistics of turbulent boundary layer flows with and without free-stream turbulence are reported for Re_τ ≈ 1000 (Re_θ ≈ 2000). The scaling of the dissipation scale distribution is examined in these two boundary conditions of external wall-bounded flow.

Results demonstrated that the local large-scale Reynolds number based on the measured longitudinal integral length-scale fails to properly normalize the dissipation scale distribution near the wall in these two free-stream conditions, due to the imperfect characterization of the upper bound of the inertial cascade by the integral length-scale. When a length-scale based on Townsend's …

NoX Formation In Light-Hydrocarbon, Premixed Flames, Robert T. Hughes

Theses and Dissertations--Mechanical and Aerospace Engineering

This study explores the reactions and related species of NO_x pollutants in methane flames in order to understand their production and consumption during the combustion process. To do this, several analytical simulations were run to explore the behavior of nitrogen species in the pre-flame, post- flame, and reaction layer regions. The results were then analyzed in order to identify all "steady-state" species in the flame as well as the determine all the unnecessary reactions and species that are not required to meet a defined accuracy. The reductions were then applied and proven to be viable.

Surface And Structural Modification Of Carbon Electrodes For Electroanalysis And Electrochemical Conversion, Yan Zhang

Theses and Dissertations--Chemistry

Electrocatalysis is key to both sensitive electrochemical sensing and efficient electrochemical energy conversion. Despite high catalytic activity, traditional metal catalysts have poor stability, low selectivity, and high cost. Metal-free, carbon-based materials are emerging as alternatives to metal-based catalysts because of their attractive features including natural abundance, environmental friendliness, high electrical conductivity, and large surface area. Altering surface functionalities and heteroatom doping are effective ways to promote catalytic performance of carbon-based catalysts. The first chapter of this dissertation focuses on developing electrode modification methods for electrochemical sensing of biomolecules. After electrochemical pretreatment, glassy carbon demonstrates impressive figures-of-merit in detecting small, redox-active …

Surface Engineering And Monomer Design For Light-Mediated Ring Opening Metathesis Polymerization, Ishan A. Fursule

Theses and Dissertations--Chemical and Materials Engineering

Stimuli-responsive materials are changing the landscape of actuated materials, optoelectronics, molecular machines, solar cells, temporary memory storage, and biomedical materials. Specifically, photo-responsive polymers have gained acceleration in research and application since the last two decades in the form of a surface coating and micro-patterns. Light as a stimulus can be coherent, mono or polychromatic, tunable for power (intensity) and energy (wavelength), and has precise spatiotemporal control. Conventional surface coating techniques such as spin coating are unable to impart properties to the coatings in terms of sturdiness, homogeneity, uniformity over the complex surface, post deposition modification, and process efficiency. Also, in …

Understanding Carbohydrate Recognition Mechanisms In Non-Catalytic Proteins Through Molecular Simulations, Abhishek A. Kognole

Theses and Dissertations--Chemical and Materials Engineering

Non-catalytic protein-carbohydrate interactions are an essential element of various biological events. This dissertation presents the work on understanding carbohydrate recognition mechanisms and their physical significance in two groups of non-catalytic proteins, also called lectins, which play key roles in major applications such as cellulosic biofuel production and drug delivery pathways. A computational approach using molecular modeling, molecular dynamic simulations and free energy calculations was used to study molecular-level protein-carbohydrate and protein-protein interactions. Various microorganisms like bacteria and fungi secret multi-modular enzymes to deconstruct cellulosic biomass into fermentable sugars. The carbohydrate binding modules (CBM) are non-catalytic domains of such enzymes that …

Application Of Process Systems Engineering Tools And Methods To Fermentation-Based Biorefineries, Kwabena Darkwah

Theses and Dissertations--Chemical and Materials Engineering

Biofuels produced from lignocellulosic biomass via the fermentation platform are sustainable energy alternatives to fossil fuels. Process Systems Engineering (PSE) uses computer-based tools and methods to design, simulate and optimize processes. Application of PSE tools to the design of economic biorefinery processes requires the development of simulation approaches that can be integrated with existing, mature PSE tools used to optimize traditional refineries, such as Aspen Plus. Current unit operation models lack the ability to describe unsteady state fermentation processes, link unsteady state fermentation with in situ separations, and optimize these processes for competing factors (e.g., yield and productivity). This work …

Design And Analysis Of Curcumin Conjugated Poly(Beta-Amino Ester) Networks For Controlled Release In Oxidative Stress Environments, Carolyn T. Jordan

Theses and Dissertations--Chemical and Materials Engineering

Oxidative stress, the imbalance of free radical generation with antioxidant defenses, leads to cellular inflammation, apoptosis and cell death. This compromised environment results in debilitating diseases, such as oral mucositis (OM), atherosclerosis, and ischemia/reperfusion injury. Antioxidant therapeutics has been a proposed strategy to ameliorate these imbalances and maintain homeostatic environments. However, the success of these approaches, specifically curcumin, has been limited due to characteristics such as hydrophobicity and high reactivity when released as bolus doses to contest to oxidative stress induced diseases. The development of a controlled release system to aid in protection of the antioxidant capacity of curcumin, as …

The Development Of Microfluidic Devices For The Production Of Safe And Effective Non-Viral Gene Delivery Vectors, Jason Matthew Absher

Theses and Dissertations--Chemical and Materials Engineering

Including inherited genetic diseases, like lipoprotein lipase deficiency, and acquired diseases, such as cancer and HIV, gene therapy has the potential to treat or cure afflicted people by driving an affected cell to produce a therapeutic protein. Using primarily viral vectors, gene therapies are involved in a number of ongoing clinical trials and have already been approved by multiple international regulatory drug administrations for several diseases. However, viral vectors suffer from serious disadvantages including poor transduction of many cell types, immunogenicity, direct tissue toxicity and lack of targetability. Non-viral polymeric gene delivery vectors (polyplexes) provide an alternative solution but are …

Mixed Matrix Flat Sheet And Hollow Fiber Membranes For Gas Separation Applications, Nicholas W. Linck

Theses and Dissertations--Chemical and Materials Engineering

Mixed matrix membranes (MMM) offer one potential path toward exceeding the Robeson upper bound of selectivity versus permeability for gas separation performance while maintaining the benefits of solution processing. Many inorganic materials, such as zeolites, metal-organic frameworks, or carbon nanotubes, can function as molecular sieves, but as stand-alone membranes are brittle and difficult to manufacture. Incorporating them into a more robust polymeric membrane matrix has the potential to mitigate this issue.

In this work, phase inversion polymer solution processing for the fabrication and testing of asymmetric flat sheet mixed matrix membranes was employed with CVD-derived multiwall carbon nanotubes (MWCNTs) dispersed …

Synthesis Of Biologically-Inspired Nanofiltration Membranes Using Protected, Mutated, And Simulated Aquaporins, Priyesh Ashokrao Wagh

Theses and Dissertations--Chemical and Materials Engineering

Gram-negative bacterial cells are surrounded by a cell membrane which protects the cell and controls the transport of nutrients and waste products in and out of the cells at a fast rate. This rapid transport of nutrients and wastes through the cell membrane is made possible by channel proteins called porins. Various types of porins present in the cell membrane have specific functions depending on their selectivity towards different nutrients, and channel proteins selective towards water are called aquaporins. These proteins restrict the passage of all entities except water molecules and they provide a fast transport rate of water molecules …

Surface Functionalization Via Photoinitiated Radical Polymerization For Rare Cell Isolation And Mechanical Protection, Calvin Frank Cahall

Theses and Dissertations--Chemical and Materials Engineering

Surface functionalization of living cells for cell therapeutics has gained substantial momentum in the last two decades. From encapsulating islets of Langerhans, to cell laden gels for tissue scaffolds, to individual cell encapsulation in thin hydrogels, to surface adhesives and inert surface camouflage, modification of living cell surfaces has a wide array of important applications. Here we use hydrogel encapsulation of individual cells as a mode of protection from mechanical forces for high throughput cell printing, and chemical stimuli for the isolation of rare cells in blood.

In the first study, we review methods of surface functionalization and establish a …

The Role Of Catalytic Residue PKA On The Hydrolysis/Transglycosylation Partition In Family 3 Β-Glucosidases, Inacrist Geronimo, Christina M. Payne, Mats Sandgren

Chemical and Materials Engineering Faculty Publications

β-Glucosidases (βgls) primarily catalyze the hydrolysis of the terminal glycosidic bond at the non-reducing end of β-glucosides, although glycosidic bond synthesis (called transglycosylation) can also occur in the presence of another acceptor. In the final reaction step, the glucose product or another substrate competes with water for transfer to the glycosyl-enzyme intermediate. The factors governing the balance between the two pathways are not fully known; however, the involvement of ionizable residues in binding and catalysis suggests that their pK_a may play a role. Through constant pH molecular dynamics simulations of a glycoside hydrolase Family 3 (GH3) βgl, we …

Layer-By-Layer Assembled Membranes With Immobilized Porins, Sebastián Hernández, Cassandra Porter, Xinyi Zhang, Yinan Wei, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

New and advanced opportunities are arising for the synthesis and functionalization of membranes with selective separation, reactivity, and stimuli-responsive behavior. One such advancement is the integration of bio-based channels in membrane technologies. By a layer-by-layer (LbL) assembly of polyelectrolytes, outer membrane protein F trimers (OmpF) or “porins” from Escherichia coli with central pores ∼2 nm in diameter at their opening and ∼0.7 × 1.1 nm at their constricted region are immobilized within the pores of poly(vinylidene fluoride) microfiltration membranes, in contrast to traditional ruptured lipid bilayer or vesicle processes. These OmpF-membranes demonstrate selective rejection of non-charged organics over ionic solutes, …

Synergistic Interactions Of H2 And N2 With Molten Gallium In The Presence Of Plasma, Maria L. Carreon, Daniel F. Jaramillo-Cabanzo, Indira Chaudhuri, Madhu Menon, Mahendra K. Sunkara

Physics and Astronomy Faculty Publications

The present study examines the interaction of hydrogen and nitrogen plasmas with gallium in an effort to gain insights into the mechanisms behind the synergetic effect of plasma and a catalytic metal. Absorption/desorption experiments were performed, accompanied by theoretical-computational calculations. Experiments were carried out in a plasma-enhanced, Ga-packed, batch reactor and entailed monitoring the change in pressure at different temperatures. The results indicated a rapid adsorption/dissolution of the gas into the molten metal when gallium was exposed to plasma, even at a low temperature of 100 °C. The experimental observations, when hydrogen was used, indicate that gallium acts as a …

Synthesis And Characterization Of Thermoresponsive Hydrogels Based On N-Isopropylacrylamide Crosslinked With 4,4′-Dihydroxybiphenyl Diacrylate, Shuo Tang, Martha Floy, Rohit Bhandari, Manjula Sunkara, Andrew J. Morris, Thomas D. Dziubla, J. Zach Hilt

Chemical and Materials Engineering Faculty Publications

A novel crosslinker [4,4′-dihydroxybiphenyl diacrylate (44BDA)] was developed, and a series of temperature-responsive hydrogels were synthesized through free radical polymerization of N-isopropylacrylamide (NIPAAm) with 44BDA. The temperature-responsive behavior of the resulting gels was characterized by swelling studies, and the lower critical solution temperature (LCST) of the hydrogels was characterized through differential scanning calorimetry. Increased content of 44BDA led to a decreased swelling ratio and shifted the LCST to lower temperatures. These novel hydrogels also displayed resiliency through multiple swelling–deswelling cycles, and their temperature responsiveness was reversible. The successful synthesis of NIPAAm-based hydrogels crosslinked with 44BDA has led to a …

Reducing Biomass Recalcitrance By Heterologous Expression Of A Bacterial Peroxidase In Tobacco (Nicotiana Benthamiana), Ayalew Ligaba-Osena, Bertrand Hankoua, Kay Dimarco, Robert Pace, Mark Crocker, Jesse Mcatee, Nivedita Nagachar, Ming Tien, Tom L. Richard

Center for Applied Energy Research Faculty and Staff Publications

Commercial scale production of biofuels from lignocellulosic feed stocks has been hampered by the resistance of plant cell walls to enzymatic conversion, primarily owing to lignin. This study investigated whether DypB, the lignin-degrading peroxidase from Rodococcus jostii, depolymerizes lignin and reduces recalcitrance in transgenic tobacco (Nicotiana benthamiana). The protein was targeted to the cytosol or the ER using ER-targeting and retention signal peptides. For each construct, five independent transgenic lines were characterized phenotypically and genotypically. Our findings reveal that expression of DypB in the cytosol and ER does not affect plant development. ER-targeting increased protein accumulation, and …

A High Quality And Quantity Hybrid Perovskite Quantum Dots (Cspbx3, X= Cl, Br And I) Powders Synthesis Via Ionic Displacement, Yuhang Yin, Weiling Luan, Chengxi Zhang, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Recently, all-inorganic perovskites CsPbX₃ (X= Cl, Br and I) quantum dots (QDs) have drawn great attentions because of their PL spectra tunable over the whole visible spectral region (400-700 nm) and adjustable bandgap, which revealed a promising potential on the field of photoelectronic devices, such as solar cells, LEDs and sensors. In this paper, CsPbX₃ QDs and hybrid QDs, CsPbClxBr3-x and CsPbBrxI3-x were synthesized via one-step and two-step methods comparably. The optical bandgaps of CsPbCl₃, CsPbBr₃, and CsPbI₃, were calculated as 3.08, 2.36, and 1.73eV, respectively, based on the Tauc's equation and …

Ptfe-Based Microreactor System For The Continuous Synthesis Of Full-Visible-Spectrum Emitting Cesium Lead Halide Perovskite Nanocrystals, Chengxi Zhang, Weiling Luan, Yuhang Yin, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Colloidal perovskite nanocrystals comprised of all inorganic cesium lead halide (CsPbX₃, X = Cl, Br, I or a mixture thereof) have potential as optical gain materials due to their high luminescence efficiency. In this work, cesium lead halide nanocrystals are continuously synthesized via a microreactor system consisting of poly(tetrafluoroethylene) (PTFE) capillaries. The synthesized nanocrystals possess excellent optical properties, including a full width at half maximum of 19–35 nm, high fluorescence quantum yield of 47.8–90.55%, and photoluminescence emission in the range of 450–700 nm. For the same precursor concentrations, the photoluminescence emission peak generally increases with increasing reaction temperature, …

Effect Of Oxide On Surface Tension Of Molten Metal, Chunkai Li, Yu Shi, Yufen Gu, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Oxides as one of the commonly activating fluxes used in active tungsten inert gas welding (A-TIG welding) can dramatically increase the penetration depth to 2–4 times that of conventional welding. Using the oscillation principle of inviscid fluid, a robust method is developed to measure the average surface tension of molten metal during A-TIG welding for four different oxide activating fluxes of B₂O₃, TiO₂, SiO₂, and MgO. The experimental results suggest that the oxygen released from the decomposition of oxides is the dominant factor contributing to the change of the surface tension, which …

Ga And In Modified Ceria As A Support For Cobalt Fischer-Tropsch Synthesis, Muthu Kumaran Gnanamani, Gary Jacobs, Wilson D. Shafer, Michela Martinelli, Donald C. Cronauer, A. Jeremy Kropf, Christopher L. Marshall, Burtron H. Davis

Center for Applied Energy Research Faculty and Staff Publications

Ceria modified by the addition of gallium or indium (20 mol%) was used as a support for cobalt Fischer-Tropsch synthesis. The addition of gallium to ceria improved the CO conversion for cobalt, whereas indium tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts that were doped with Ga or In. For Ag promoted catalysts, doping with Ga or In decreased methane and increased the product selectivities of olefins and alcohols. The sum of olefins and alcohols in terms of product selectivity for the Ag-promoted catalysts decreased in the following order: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. The H2-TPR-XANES …

Development Of Novel N-Isopropylacrylamide (Nipaam) Based Hydrogels With Varying Content Of Chrysin Multiacrylate, Shuo Tang, Martha Floy, Rohit Bhandari, Thomas D. Dziubla, J. Zach Hilt

Chemical and Materials Engineering Faculty Publications

A series of novel temperature responsive hydrogels were synthesized by free radical polymerization with varying content of chrysin multiacrylate (ChryMA). The goal was to study the impact of this novel polyphenolic-based multiacrylate on the properties of N-isopropylacrylamide (NIPAAm) hydrogels. The temperature responsive behavior of the copolymerized gels was characterized by swelling studies, and their lower critical solution temperature (LCST) was characterized through differential scanning calorimetry (DSC). It was shown that the incorporation of ChryMA decreased the swelling ratios of the hydrogels and shifted their LCSTs to a lower temperature. Gels with different ChryMA content showed different levels of response to …