Chemical Engineering Commons^™

Understanding Glycoside Hydrolase Processivity For Improved Biomass Conversion, Suvamay Jana

Theses and Dissertations--Chemical and Materials Engineering

In nature, organisms secrete synergistic enzyme cocktails to deconstruct crystalline polysaccharides, such as cellulose and chitin, to soluble sugars. The cocktails consist of multiple classes of processive and non-processive glycoside hydrolases (GH) that aid in substrate accessibility and reduce product inhibition. Processive GHs attach to chain ends and hydrolyze many glycosidic linkages in sequence to produce disaccharide units before dissociation, and as such, are responsible for the majority of hydrolytic bond cleavages. Accordingly, processive GHs are targets for activity improvements towards efficient and economical biomass conversion. However, the mechanism and factors responsible for processivity are still not understood completely at …

Synthesis And Energy Applications Of Mesoporous Titania Thin Films, Syed Z. Islam

Theses and Dissertations--Chemical and Materials Engineering

The optical and electronic properties of TiO₂ thin films provide tremendous opportunities in several applications including photocatalysis, photovoltaics and photoconductors for energy production. Despite many attractive features of TiO₂, critical challenges include the innate inability of TiO₂ to absorb visible light and the fast recombination of photoexcited charge carriers. In this study, mesoporous TiO₂ thin films are modified by doping using hydrogen and nitrogen, and sensitization using graphene quantum dot sensitization.

For all of these modifiers, well-ordered mesoporous titania films were synthesized by surfactant templated sol-gel process. Two methods: hydrazine and plasma treatments have been …

Functionalization Of Silver Nanoparticles On Membranes And Its Influence On Biofouling, Conor G. Sprick

Theses and Dissertations--Chemical and Materials Engineering

Ultrafiltration (UF) processes are often used as pretreatment before more retentive/costly processes, such as nanofiltration and reverse osmosis. This study shows the results of low-biofouling nanocomposite membranes, loaded with casein-coated silver nanoparticles (casein-Ag-NPs). Membranes were cast and imbedded with Ag-NPs using two approaches, physical blending of Ag-NPs in the dope solution (^PAg-NP/CA membranes) and chemical attachment of Ag-NPs to cast membranes (^CAg-NP/CA membranes), to determine their biofouling control properties. The functionalization of Ag-NPs onto the CA membranes was achieved via attachment with functionalized thiol groups with the use of glycidyl methacrylate (GMA) and cysteamine chemistries. The …

Pore-Confined Carriers And Biomolecules In Mesoporous Silica For Biomimetic Separation And Targeting, Shanshan Zhou

Theses and Dissertations--Chemical and Materials Engineering

Selectively permeable biological membranes composed of lipophilic barriers inspire the design of biomimetic carrier-mediated membranes for aqueous solute separation. This work imparts selective permeability to lipid-filled pores of silica thin film composite membranes using carrier molecules that reside in the lipophilic self-assemblies. The lipids confined inside the pores of silica are proven to be a more effective barrier than bilayers formed on the porous surface through vesicle fusion, which is critical for quantifying the function of an immobilized carrier. The ability of a lipophilic carrier embedded in the lipid bilayer to reversibly bind the target solute and transport it through …

Grain Boundary Induced Bias Instability In Soluble Acene-Based Thin-Film Transistors, Ky V. Nguyen, Marcia M. Payne, John E. Anthony, Jung Hun Lee, Eunjoo Song, Boseok Kang, Kilwon Cho, Wi Hyoung Lee

Chemistry Faculty Publications

Since the grain boundaries (GBs) within the semiconductor layer of organic field-effect transistors (OFETs) have a strong influence on device performance, a substantial number of studies have been devoted to controlling the crystallization characteristics of organic semiconductors. We studied the intrinsic effects of GBs within 5,11-bis(triethylsilylethynyl) anthradithiophene (TES-ADT) thin films on the electrical properties of OFETs. The GB density was easily changed by controlling nulceation event in TES-ADT thin films. When the mixing time was increased, the number of aggregates in as-spun TES-ADT thin films were increased and subsequent exposure of the films to 1,2-dichloroethane vapor led to a significant …

Capture And Recycle Of Industrial Co2 Emissions Using Mircoalgae, Michael H. Wilson, Daniel T. Mohler, John G. Groppo, Thomas E. Grubbs, Stephanie Kesner, E. Molly Frazar, Aubrey Shea, Czarena L. Crofcheck, Mark Crocker

Center for Applied Energy Research Faculty and Staff Publications

A novel cyclic flow photobioreactor (PBR) for the capture and recycle of CO₂ using microalgae was designed and deployed at a coal-fired power plant (Duke Energy’s East Bend Station). The PBR was operated continuously during the period May–September 2015, during which algae productivity of typically 0.1–0.2 g/(L day) was obtained. Maximum CO₂ capture efficiency was achieved during peak sunlight hours, the largest recorded CO₂ emission reduction corresponding to a value of 81 % (using a sparge time of 5 s/min). On average, CO₂ capture efficiency during daylight hours was 44 %. The PBR at East Bend …

Preparation And Microstructure Of Machinable Al2O3/Mica Composite By Ball Milling And Hot-Press Sintering, Qingbo Tian, Deyu Kong, Tongguang Zhai

Chemical and Materials Engineering Faculty Publications

A machinable α-Al₂O₃/mica composite was prepared by hot-press sintering. In this experiment, a mica-contained glass ceramic in the MgO-Al₂O₃-SiO₂-F glassy system was employed and the base glass powders were obtained by traditional melting-quenched method. Then, α-Al₂O₃ milling swarf was introduced by medium α-alumina milling ball to the glass powders. The test results indicate that the composites consist of mica crystal and mullite crystal, which are precipitated in the base glass. The α-Al₂O₃ shows an irregular polygon, which is inlayed in the base material. With …

Fast Diffusion Of Silver In Tio2 Nanotube Arrays, Wanggang Zhang, Yiming Liu, Diaoyu Zhou, Hui Wang, Wei Liang, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Using magnetron sputtering and heat treatment, Ag@TiO₂ nanotubes are prepared. The effects of heat-treatment temperature and heating time on the evolution of Ag nanofilms on the surface of TiO₂ nanotubes and microstructure of Ag nanofilms are investigated by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Ag atoms migrate mainly on the outmost surface of the TiO₂ nanotubes, and fast diffusion of Ag atoms is observed. The diffusivity for the diffusion of Ag atoms on the outmost surface of the TiO₂ nanotubes at 400 °C is 6.87 × 10⁻¹⁸ m²/s, …

Self-Similar Random Process And Chaotic Behavior In Serrated Flow Of High Entropy Alloys, Shuying Chen, Liping Yu, Jingli Ren, Xie Xie, Xueping Li, Ying Xu, Guangfeng Zhao, Peizhen Li, Fuqian Yang, Yang Ren, Peter K. Liaw

Chemical and Materials Engineering Faculty Publications

The statistical and dynamic analyses of the serrated-flow behavior in the nanoindentation of a high-entropy alloy, Al_0.5CoCrCuFeNi, at various holding times and temperatures, are performed to reveal the hidden order associated with the seemingly-irregular intermittent flow. Two distinct types of dynamics are identified in the high-entropy alloy, which are based on the chaotic time-series, approximate entropy, fractal dimension, and Hurst exponent. The dynamic plastic behavior at both room temperature and 200 °C exhibits a positive Lyapunov exponent, suggesting that the underlying dynamics is chaotic. The fractal dimension of the indentation depth increases with the increase of temperature, and …

Green Synthesis Nanocomposite Membranes, Dibakar Bhattacharyya, Vasile Smuleac, Rajender S. Varma, Subhas K. Sikdar

Chemical and Materials Engineering Faculty Patents

A nanocomposite membrane includes a macroporous polymer membrane having a plurality of pores. A plurality of metal nanoparticles are synthesized and immobilized within those plurality of pores. The nanoparticles are reduced and capped with a green reducing and capping agent such as green tea extract.

Microstructural Properties And Four-Point Bend Fatigue Behavior Of Ti-6.5al-2zr-1mo-1v Welded Joints By Electron Beam Welding, Peng Liu, Tongguang Zhai, Yuanbin Zhang

Chemical and Materials Engineering Faculty Publications

With the help of a four-point-bend of fatigue rig, high-cycle fatigue tests were carried out on an Ti–6.5Al–2Zr-1Mo-1V titanium alloy at room temperature, 20 Hz and R = 0.1 in ambient air. The test results indicated that the fatigue strength of base metal, 888 MPa, is about 120% of yield strength. The fatigue strength of joints is 814 MPa. It is about 110% of yield strength of base metal. When the loading stress is higher, the fatigue failure region is located in middle weld zone of weld face, which the cracks are propagated along coarse β phase’s grain boundary. When …

Large-Area Graphene-Based Nanofiltration Membranes By Shear Alignment Of Discotic Nematic Liquid Crystals Of Graphene Oxide, Abozar Akbari, Phillip Sheath, Samuel T. Martin, Dhanraj B. Shinde, Mahdokht Shaibani, Parama Chakraborty Banerjee, Rachel Tkacz, Dibakar Bhattacharyya, Mainak Majumder

Chemical and Materials Engineering Faculty Publications

Graphene-based membranes demonstrating ultrafast water transport, precise molecular sieving of gas and solvated molecules shows great promise as novel separation platforms; however, scale-up of these membranes to large-areas remains an unresolved problem. Here we demonstrate that the discotic nematic phase of graphene oxide (GO) can be shear aligned to form highly ordered, continuous, thin films of multi-layered GO on a support membrane by an industrially adaptable method to produce large-area membranes (13 × 14 cm²) in < 5 s. Pressure driven transport data demonstrate high retention (> 90%) for charged and uncharged organic probe molecules with a hydrated radius above 5 Å as well as modest (30–40%) retention of …

Biopolymeric Mucin And Synthetic Polymer Analogs: Their Structure, Function And Role In Biomedical Applications, Sundar Prasanth Authimoolam, Thomas D. Dziubla

Chemical and Materials Engineering Faculty Publications

Mucin networks are viscoelastic fibrillar aggregates formed through the complex self-association of biopolymeric glycoprotein chains. The networks form a lubricious, hydrated protective shield along epithelial regions within the human body. The critical role played by mucin networks in impacting the transport properties of biofunctional molecules (e.g., biogenic molecules, probes, nanoparticles), and its effect on bioavailability are well described in the literature. An alternate perspective is provided in this paper, presenting mucin’s complex network structure, and its interdependent functional characteristics in human physiology. We highlight the recent advances that were achieved through the use of mucin in diverse areas of bioengineering …

Direct Band Gap Gallium Antimony Phosphide (GasbXP1-X) Alloys, H. B. Russell, A. N. Andriotis, Madhu Menon, J. B. Jasinski, A. Martinez-Garcia, M. K. Sunkara

Center for Computational Sciences Faculty Publications

Here, we report direct band gap transition for Gallium Phosphide (GaP) when alloyed with just 1–2 at% antimony (Sb) utilizing both density functional theory based computations and experiments. First principles density functional theory calculations of GaSb_xP_1−x alloys in a 216 atom supercell configuration indicate that an indirect to direct band gap transition occurs at x = 0.0092 or higher Sb incorporation into GaSb_xP_1−x. Furthermore, these calculations indicate band edge straddling of the hydrogen evolution and oxygen evolution reactions for compositions ranging from x = 0.0092 Sb up to at least x = 0.065 …

Graphene Oxide Quantum Dots Covalently Functionalized Pvdf Membrane With Significantly-Enhanced Bactericidal And Antibiofouling Performances, Zhiping Zeng, Dingshan Yu, Ziming He, Jing Liu, Fang-Xing Xiao, Yan Zhang, Rong Wang, Dibakar Bhattacharyya, Timothy Thatt Yang Tan

Chemical and Materials Engineering Faculty Publications

Covalent bonding of graphene oxide quantum dots (GOQDs) onto amino modified polyvinylidene fluoride (PVDF) membrane has generated a new type of nano-carbon functionalized membrane with significantly enhanced antibacterial and antibiofouling properties. A continuous filtration test using E. coli containing feedwater shows that the relative flux drop over GOQDs modified PVDF is 23%, which is significantly lower than those over pristine PVDF (86%) and GO-sheet modified PVDF (62%) after 10 h of filtration. The presence of GOQD coating layer effectively inactivates E. coli and S. aureus cells, and prevents the biofilm formation on the membrane surface, producing excellent antimicrobial activity and …

Development Of Pvdf Membrane Nanocomposites Via Various Functionalization Approaches For Environmental Applications, Douglas M. Davenport, Minghui Gui, Lindell E. Ormsbee, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

Membranes are finding wide applications in various fields spanning biological, water, and energy areas. Synthesis of membranes to provide tunable flux, metal sorption, and catalysis has been done through pore functionalization of microfiltration (MF) type membranes with responsive behavior. This methodology provides an opportunity to improve synthetic membrane performance via polymer fabrication and surface modification. By optimizing the polymer coagulation conditions in phase inversion fabrication, spongy polyvinylidene fluoride (PVDF) membranes with high porosity and large internal pore volume were created in lab and full scale. This robust membrane shows a promising mechanical strength as well as high capacity for loading …

Effect Of Spalled Particles Thermal Degradation On A Hypersonic Flow Field Environment, Raghava S. C. Davuluri, Huaibao Zhang, Alexandre Martin

Mechanical Engineering Faculty Publications

Two-way coupling is performed between a spallation code and a hypersonic aerothermodynamics CFD solver to evaluate the effect of spalled particles on the flow field. Time accurate solutions are computed in argon and air flow fields. A single particle simulations and multiple particles simulations are performed and studied. The results show that the carbon vapor released by spalled particles tend to change the composition of the flow field, particularly the upstream region of the shock.

Synthesis And Characterization Of Curcumin Polymer For Application In Radiation Induced Lung Damage, Mark C. Bailey

Theses and Dissertations--Chemical and Materials Engineering

Radiotherapy is used as a primary treatment for many cancers, including lung cancer. Although radiotherapy has proven to be an effective cancer treatment, its use is heavily limited due to the peripheral toxicity to healthy tissue. In this work, the antioxidant, curcumin, was tested as a radioprotectant to reduce radiation damage to healthy cells. Curcumin has been limited in use due to its poor bioavailability. In order to avoid problems associated with free curcumin delivery, curcumin poly(beta-amino ester) (CPBAE) was synthesized.

The first study investigated the in vitro radioprotection effect of curcumin in HUVEC dosed with gamma radiation. Cells treated …

Surface-Initiated Polymerizations For The Rapid Sorting Of Rare Cancer Cells, Jacob L. Lilly

Theses and Dissertations--Chemical and Materials Engineering

Cancer metastasis directly accounts for an estimated 90% of all cancer related deaths and is correlated with the presence of malignant cells in systemic circulation. This observed relationship has prompted efforts to develop a fluid biopsy, with the goal of detecting these rare cells in patient peripheral blood as surrogate markers for metastatic disease as a partial replacement or supplement to tissue biopsies. Numerous platforms have been designed, yet these have generally failed to support a reliable fluid biopsy due to poor performance parameters such as low throughput, low purity of enriched antigen positive cells, and insufficiently low detection thresholds …

Diffusion-Mediated Deposition Of Proteins, Ruiqian Zhan

Theses and Dissertations--Mechanical and Aerospace Engineering

Gradients of proteins play a prominent role in many biological processes, from development of multicellular organisms to chemical signaling in the immune system. Deposition of surface gradients is a way to permanently modifying a surface’s properties, resulting in the creation of novel materials which have widespread applications in biologically relevant fields, such as directed cell growth, production of biocompatible implantable materials, and creation of functional biosensors. These types of surfaces can also be used as an ex vivo tool to help understand many biological processes by mimicking the environment in gradient-related phenomena in a controllable way. However, despite the large …

Bioactive Poly(Beta-Amino Ester) Biomaterials For Treatment Of Infection And Oxidative Stress, Andrew L. Lakes

Theses and Dissertations--Chemical and Materials Engineering

Polymers have deep roots as drug delivery tools, and are widely used in clinical to private settings. Currently, however, numerous traditional therapies exist which may be improved through use of polymeric biomaterials. Through our work with infectious and oxidative stress disease prevention and treatment, we aimed to develop application driven, enhanced therapies utilizing new classes of polymers synthesized in-house. Applying biodegradable poly(β-amino ester) (PBAE) polymers, covalent-addition of bioactive substrates to these PBAEs avoided certain pitfalls of free-loaded and non-degradable drug delivery systems. Further, through variation of polymer ingredients and conditions, we were able to tune degradation rates, release profiles, cellular …

Synthesis And Characterization Of Antioxidant Conjugated Poly(Βeta-Amino Ester) Micro/Nanogels For The Suppression Of Oxidative Stress, Prachi Gupta

Theses and Dissertations--Chemical and Materials Engineering

Oxidative stress is a pathophysiological condition defined by an increased production of reactive oxygen species (ROS), which can result in the growth arrest of cells followed by cell disintegration or necrosis. A number of small molecule antioxidants (e.g. curcumin, quercetin and resveratrol) are capable of directly scavenging ROS, thereby short-circuiting the self-propagating oxidative stress state. However, poor solubility and rapid 1^st pass metabolism results in overall low bioavailability and acts as a barrier for its use as a drug to suppress oxidative stress efficiently.

To overcome this limitation, these small molecule antioxidants were covalently conjugated into poly(β-amino ester) (PβAE) …

Peptide-Functionalized Magnetic Nanoparticles For Cancer Therapy Applications, Anastasia K. Hauser

Theses and Dissertations--Chemical and Materials Engineering

Lung cancer is one of the leading causes of cancer deaths in the United States. Radiation and chemotherapy are conventional treatments, but they result in serious side effects and the probability of tumor recurrence remains high. Therefore, there is an increasing need to enhance the efficacy of conventional treatments. Magnetic nanoparticles have been previously studied for a variety of applications such as magnetic resonance imaging contrast agents, anemia treatment, magnetic cell sorting and magnetically mediated hyperthermia (MMH). In this work, dextran coated iron oxide nanoparticles were developed and functionalized with peptides to target the nanoparticles to either the extracellular matrix …

Design Of Highly Stable Low-Density Self-Assembled Monolayers Using Thiol-Yne Click Reaction For The Study Of Protein-Surface Interactions, Leila Safazadeh Haghighi

Theses and Dissertations--Chemical and Materials Engineering

Protein adsorption on solid surfaces is a common yet complicated phenomenon that is not fully understood. Self-assembled monolayers have been utilized in many studies, as well-defined model systems for studying protein-surface interactions in the atomic level. Various strategies, including the use of single component SAMs[1, 2], combinations of long and short alkanethiolates with methyl- and hydroxyl- terminal groups[3, 4], and using mixtures of alkanethiolates with similar chain length and varying terminal functional group [5] have been used to effectively control the surface wettability and determine the effect of surface composition and wettability on protein adsorption. In this dissertation we report …

Synthesis Of Titania Thin Films With Controlled Mesopore Orientation: Nanostructure For Energy Conversion And Storage, Suraj R. Nagpure

Theses and Dissertations--Chemical and Materials Engineering

This dissertation addresses the synthesis mechanism of mesoporous titania thin films with 2D Hexagonal Close Packed (HCP) cylindrical nanopores by an evaporation-induced self-assembly (EISA) method with Pluronic surfactants P123 and F127 as structure directing agents, and their applications in photovoltaics and lithium ion batteries. To provide orthogonal alignment of the pores, surface modification of substrates with crosslinked surfactant has been used to provide a chemically neutral surface. GISAXS studies show not only that aging at 4°C facilitates ordered mesostructure development, but also that aging at this temperature helps to provide orthogonal orientation of the cylindrical micelles which assemble into an …

High Capacity Silicon Electrodes With Nafion As Binders For Lithium-Ion Batteries, Jiagang Xu, Qinglin Zhang, Yang-Tse Cheng

Chemical and Materials Engineering Faculty Publications

Silicon is capable of delivering a high theoretical specific capacity of 3579 mAh g⁻¹ which is about 10 times higher than that of the state-of-the-art graphite based negative electrodes for lithium-ion batteries. However, the poor cycle life of silicon electrodes, caused by the large volumetric strain during cycling, limits the commercialization of silicon electrodes. As one of the essential components, the polymeric binder is critical to the performance and durability of lithium-ion batteries as it keeps the integrity of electrodes, maintains conductive path and must be stable in the electrolyte. In this work, we demonstrate that electrodes consisting of …

Chemical Processing Cell With Nanostructured Membranes, Dibakar Bhattacharyya, Scott R. Lewis, Saurav Datta

Chemical and Materials Engineering Faculty Patents

A chemical processing cell includes an upstream membrane and a downstream membrane. The upstream membrane generates a first reaction product. The downstream membrane converts the first reaction product to a second reaction product.

Electrode Kinetics Of Vanadium Flow Batteries: Contrasting Responses Of VIi-VIii And VIv-VV To Electrochemical Pretreatment Of Carbon, A. Bourke, M. A. Miller, R. P. Lynch, Xin Gao, James Landon, J. S. Wainright, R. F. Savinell, D. N. Buckley

Center for Applied Energy Research Faculty and Staff Publications

Electrochemical impedance spectroscopy and cyclic voltammetry were used to investigate the electrode kinetics of V^II-V^III and V^IV-V^V in H₂SO₄ on glassy carbon, carbon paper, carbon xerogel, and carbon fibers. It was shown that, for all carbon materials investigated, the kinetics of V^II-V^III is enhanced by anodic, and inhibited by cathodic, treatment of the electrode; in contrast, the kinetics of V^IV-V^V is inhibited by anodic, and enhanced by cathodic, treatment. The potential region for each of these effects varied only slightly with carbon material. Rate constants …

Structural And Functional Characterization Of A Lytic Polysaccharide Monooxygenase With Broad Substrate Specificity, Anna S. Borisova, Trine Isaksen, Maria Dimarogona, Abhishek A. Kognole, Geir Mathiesen, Anikó Várnai, Åsmund K. Røhr, Christina M. Payne, Morten Sørlie, Mats Sandgren, Vincent G. H. Eijsink

Chemical and Materials Engineering Faculty Publications

The recently discovered lytic polysaccharide monooxygenases (LPMOs) carry out oxidative cleavage of polysaccharides and are of major importance for efficient processing of biomass. NcLPMO9C from Neurospora crassa acts both on cellulose and on non-cellulose β-glucans, including cellodextrins and xyloglucan. The crystal structure of the catalytic domain of NcLPMO9C revealed an extended, highly polar substrate-binding surface well suited to interact with a variety of sugar substrates. The ability of NcLPMO9C to act on soluble substrates was exploited to study enzyme-substrate interactions. EPR studies demonstrated that the Cu²⁺ center environment is altered upon substrate binding, whereas isothermal titration …

The Study Of Plga Drug Delivery Systems: Implications For Management Of Crohn’S Disease, Christin Pramudiati

Kaleidoscope

The purpose of this research is to develop biodegradable drug delivery systems. One of the delivery systems that we have developed is a suture-like structure for the treatment of Crohn’s disease that utilizes a biodegradable polymer, poly(DL-lactideco-glycolide) acid (PLGA). Crohn’s disease is an inflammatory bowel condition. Aside from the gut involvement, perianal complications develop in the form of enterocutaneous fistulas. Medical management of Crohn’s disease consists of various drugs with immunosuppressive properties. Complicated disease manifestation requires surgical interventions in the form of bowel resection or fistula drainage with Setons. Setons are suture-like devices that help to drain associated abscesses and …