Chemistry Commons^™

P1: Salt Concentration And Ph Affect The Size Of Elastin-Like Polypeptide Nanoparticles, Bryce Noe, Ilona Tsuper, Daniel Terano, Richard Schmitt

Undergraduate Research Posters 2017

The transport of therapeutic drugs to specific tissues in the body can be accomplished using nanoparticles that encapsulate the drugs. Elastin-like polypeptides (ELP) is a class of materials that can reversibly form such nanoparticles in response to environmental cues. FLPs transition from soluble compounds to a phase separated system under particular solution conditions and have been used to produce temperature responsive surfactants. When these ELP surfactants are above their transition temperature, they spontaneously form energetically stable spherical micelles. When the temperature drops below the transition temperature, the micelles break apart and the ELP goes into solution. The size of these …

P2: Light Scattering Study Of The Size And Shape Of Mixed Elastin-Like Polypeptide Micelles, Ilona Tsuper, Daniel Terrano, Bryce Noe

Undergraduate Research Posters 2017

Elastin-Like Polypeptides (ELP) can be used to form thermoreversible vehicles for drug delivery systems. The ELP nanoparticles are composed of three-armed star polypeptides. Each of the three arms extending from the negatively charged foldon domain include 20 repeats of the (GVGVP) amino acid sequence. In addition, linear constructs composed of 40 repeats of the same (GVGVP) sequence are introduced into the system. The mixed ELP polymer system is soluble at room temperature and becomes insoluble at the transition temperature (~ 50°C) forming micelles with the foldons on the exterior and linear constructs at the core. Above the transition, the size …

Synthesis, Characterization, And Activity Of Co/Fe Alumina/Silica Supported Ft Catalysts And The Study Of Promoter Effect Of Ruthenium, Sunday Azubike Esumike

Doctoral Dissertations

The alumina and hybrid alumina-silica FT catalyst were prepared by one-step solgel/oil-drop methods using metal-nitrate-solutions (method-I), and nanoparticle-metaloxides (method-2). The nanoparticle-metal-oxides did not participate in solubility equilibria in contrast to metal nitrate in method-1 causing no metal ion seepage; therefore, method-2 yields higher XRF metal loading efficiency than method-1. The thermal analysis confirmed that the metal loading by method-1 and method-2 involved two different pathways. Method-1 involves solubility equilibria in the conversion of metal-nitrate to metal- hydroxide and finally to metal-oxide, while in method-2 nanoparticle-metal-oxide remained intact during sol-gel-oil-drop and calcination steps.

The alumina supported catalysts were dominated by γ-alumina …

A Quartz Crystal Microbalance Study Of Thiol:Ene Poly(Ionic Liquid) Polymerization And Gas Absorption, Yueming Wu

Murray State Theses and Dissertations

ABSTRACT

The polymerization process of, and gas absorption by, imidazolium-containing thiol:ene poly (ionic liquid)s (PILs), prepared from bisallylimidazolium bis(trifluoromethyl sulfonyl)imide [NTf₂^-] and pentaerythritoltetrakis(3 mercaptopropionate), was studied. The thiol:ene PILs examined were recently reported by groups at Murray State University. The advantage of thiol:ene PILs over other reported PILs is that thiol:ene polymers are made rapidly by UV exposure and exhibit high mechanical and thermal stability due to high cross-linking. The properties of interest for the thiol:ene PILs were studied using a quartz crystal microbalance (QCM). QCM techniques are based on the piezoelectric effect, where certain crystals (e.g., …

A Miniaturized Spectrophotometric In Situ Ph Sensor For Seawater, Reuben C. Darlington

Graduate Student Theses, Dissertations, & Professional Papers

Since the Industrial Revolution, the world's oceans have absorbed increasing amounts of CO2 and the resultant changes to the marine carbonate chemical system have reduced the pH by > 0.1 units (~ 30%) in surface waters. This acidification of the oceans has many far reaching impacts on marine life and there is great need of quality instrumentation to assess and follow the changing carbonate system. This MIS project aims to develop a low cost pH sensor with high precision and accuracy for open sea measurements with special emphasis on reduced size and cost. Design effort is based on the commercially available …

Biomimetic Devices To Drive A Thermodynamically Uphill Reaction Using Light And To Degrade Industrial Waste Stream Components, Madison Joanne Sloan

Theses and Dissertations--Chemistry

Given the amount of industrial waste produced each year, as well as the accruing amount of greenhouse gases in our atmosphere produced by the burning of fossil fuels, it is imperative that humanity develop environmentally-sustainable sources of energy and methods of remediation. Nature achieves both of these by use of enzymes as catalysts, inspiring interest in designing biomimetic systems capable of harnessing clean energy and remediating industrial waste. This study examined the ability of enzymes in electrochemical and convective flow systems to achieve these tasks. The first portion studied the incorporation of enzymes into an electrochemical system to drive the …

Preparation And Application Of Catalysts For The Stereospecific Reduction And Photooxygenation Of Olefins In Continuous Operations: A Novel Method For The Production Of Artemisinin, Daniel C. Fisher

Theses and Dissertations

Over the last two centuries, the discovery and application of catalysts has had a substantial impact on how and what chemicals are produced.Given their broad significance, our group has focused on developing new catalyst systems that are recoverable and reusable, in an attempt to reduce concomitant costs.

Our efforts have centered on constructing a recyclable chiral heterogeneous catalyst capable of effecting asymmetric hydrogenations of olefins with high stereoselectivity. A class of phosphinoimidazoline ligands, developed by researchers at Boehringer-Ingelheim, known as BIPI ligands, have proven efficacious in the asymmetric reduction of alkenes. However, these chiral ligands are homogeneous and coordinated to …

A Study On The Oxidation Of Hydrogen Peroxide At Au(111) And Au(100) Electrodes, Yong-Li Zheng, Jie Wei, Yan-Xia Chen

Journal of Electrochemistry

The oxidation reactions of hydrogen peroxide (H₂O₂) at Au(111) and Au(100) electrodes in 0.1 mol·L^-1 HClO₄ were investigated by using rotating disk electrode system. It was found that H₂O₂ could be readily oxidized to O₂ at both Au(100) and Au(111) surfaces with the onset potential close to its equilibrium potential. In contrast, the onset overpotential for H₂O₂ reduction was above 0.4 V, while the onset overpotential for H₂O₂ oxidation at Au(100) was ca. 0.1 V more negative than that at Au(111), this is probably …

Stm Investigation Of Oxygen Reduction Reaction On Solid Interface In Fuel Cell, Zhen-Feng Cai, Bing Sun, Wen-Jie Jiang, Ting Chen, Dong Wang, Li-Jun Wan

Journal of Electrochemistry

An electrocatalyst for oxygen reduction reaction (ORR) is an important component for fuel cells. An investigation at interfacial electrochemical reactions toward ORR at a molecular scale benefits mechanistic understanding as well as rational design of catalysts. Scanning tunneling microscopy (STM) has been proven to be a powerful tool to monitor chemical reactions and to provide in-situ information about the interfacial electrochemical reactions at a molecular level. This review summarizes the recent STM studies in monitoring the interface processes such as morphological changes, molecular changes, reaction intermediates, and oxidation products. The prospects of future development in this field are outlined.

Syntheses Of Ag@Pd@Pt Nanoparticles With Tunable Shell Thickness For Electrochemical Oxidation Of Formic Acid, Xiao-Dong Lin, Du-Hong Chen, Zhong-Qun Tian

Journal of Electrochemistry

In an effort to lower cost of a catalyst, the silver (Ag) core with palladium (Pd) layer then platinum (Pt) island (Ag@Pd@Pt) nanoparticles were synthesized and the electrocatalytic activity of Ag@Pd@Pt nanoparticles on formic acid was compared with that of Au@Pd@Pt nanoparticles reported previously. The results showed that the existence of a small amount of Pt could significantly improve the activity of the catalyst. When the surface coverage of Pt approached 0.5 monolayers, the activity of Ag@Pd@Pt nanoparticles reached the maximum. Though the onset potential of the electro-oxidation was slightly more positive (about 50 mV), the overall electrocatalytic activity of …

Chitosan/Nonahydrate Gel Derived Fe-N-Doped Porous Carbon Sheet As High-Efficient Orr Electrocatalyst, Fan-Lu Meng, Xin-Bo Zhang, Jun-Min Yan

Journal of Electrochemistry

The chitosan/nonahydrate gel was used as a precursor to realize the uniform mixture of N-polymer and metal salt. After lyophilization treatment, the gel went through heat treatment and acid etch. Accordingly, the Fe-N-doped porous carbon sheet with homogenous composition and microstructure was prepared. Compared with the commercial Pt/C catalyst, the Fe-N-doped porous carbon sheet exhibited more positive onset potential and half-wave potential, higher current density, and especially, excellent durability. The power density of 318 mW·cm^-2 was obtained in alkaline fuel cell with the Fe-N-doped porous carbon sheet as a cathode catalyst, which is higher than 267 mW·cm^-2 with …

Synthesis Of Ultrathin Co3O4 Nanoflakes Film Material For Electrochemical Sensing, Hui-Juan Wang

Journal of Electrochemistry

Ultrathin cobalt oxide (Co₃O₄) nanoflakes film material was synthesized by using an electro-deposited cobalt layer as a raw material through a simple oxidation method and followed by a heat treatment at 350 ^oC. The physical characterizations of the Co₃O₄ nanoflakes film were performed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) technologies, and the electrochemical activity was measured by cyclic voltammetry (CV). As a promising material for electrochemical sensing, the as-synthesized ultrathin Co₃O₄ nanoflakes film material exhibited excellent electrochemical activity for H₂O …

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …

Conformationally Superarmed S-Ethyl Glycosyl Donors As Effective Building Blocks For Chemoselective Oligosaccharide Synthesis In One Pot, Mithila Bandara, Jagodige Yasomanee, Nigam Rath, Christian Pedersen, Mikael Bols, Alexei Demchenko

Chemistry & Biochemistry Faculty Works

A new series of superarmed glycosyl donors has been investigated. It was demonstrated that the S-ethyl leaving group allows for high reactivity, which is much higher than that of equally equipped S-phenyl glycosyl donors that were previously investigated by our groups. The superarmed S-ethyl glycosyl donors equipped with a 2-O-benzoyl group gave complete β-stereoselectivity. Utility of the new glycosyl donors has been demonstrated in a one-pot one-addition oligosaccharide synthesis with all of the reaction components present from the beginning.

Photocatalytic Reduction Of Co2 With Tunable Bandgap And Bandedge Materials, Thuhuong T. Ngo

USF Tampa Graduate Theses and Dissertations

Solar energy is a sustainable resource which has substantial potential to meet the increasing demand for renewable energy. Though there has been some success in harvesting solar energy for electricity production, converting solar energy to chemical energy as fuels is still a challenge due to low efficiency.

Since the discovery of TiO₂ photocatalysts for splitting water (4) and reducing CO₂ (5) to form useful chemical feedstock such as H₂, CO and CH₄, much research has been done to increase the efficiency of photocatalysts. However, the current conversion efficiency of photocatalysts remains low (~5%) (6, …

Peridynamic Modeling Of Ruptures In Biomembranes, Michael Taylor, Irep Gözen, Samir Patel, Aldo Jesorka, Katia Bertoldi

Mechanical Engineering

We simulate the formation of spontaneous ruptures in supported phospholipid double bilayer membranes, using peridynamic modeling. Experiments performed on spreading double bilayers typically show two distinct kinds of ruptures, floral and fractal, which form spontaneously in the distal (upper) bilayer at late stages of double bilayer formation on high energy substrates. It is, however, currently unresolved which factors govern the occurrence of either rupture type. Variations in the distance between the two bilayers, and the occurrence of interconnections (“pinning sites”) are suspected of contributing to the process. Our new simulations indicate that the pinned regions which form, presumably due to …

Template-Assisted Hydrothermal Synthesis Of Nio@Co3O4 Hollow Spheres With Hierarchical Porous Surfaces For Supercapacitor Applications, Wen Zhou, Xue-Feng Lu, Ming-Mei Wu, Gao-Ren Li

Journal of Electrochemistry

Hollow structures have shown great potentials in a variety of important applications, such as energy conversion and storage. In order to further enhance the performance, the rational design of hollow structures with higher complexity in terms of composition and structure is highly desirable and still remains a great challenge. In this work, an efficient strategy was established for the fabrication of novel NiO@Co₃O₄ hollow spheres (HSs) with hierarchical porous surfaces by silica spheres template-assisted hydrothermal synthesis. The as-fabricated NiO@Co₃O₄ HSs showed high specific surface area of 219.68 m²·g^-1, and significant …

Continuous Synthesis And Condition Exploration Of Precursor Ni1/3Co1/3Mn1/3(Oh)2 Ternary Cathode Material, Zhi-Jun Jiang, Ya-Li Zhang, Qian Wang, Hui Zhang

Journal of Electrochemistry

Commercial LiNi_1/3Co_1/3Mn_1/3(OH)₂ ternary material is generally prepared by a combination of co-precipitation and solid state reaction method. The particle size distribution and morphology of Ni_1/3Co_1/3Mn_1/3(OH)₂ precursor have a great impact on the electrochemical performance of LiNi_1/3Co_1/3Mn_1/3O₂. In this work, the precursor Ni_1/3Co_1/3Mn_1/3(OH)₂ ternary cathode material was prepared by co-precipitation method with MnSO₄, NiSO₄, and CoSO₄ as raw materials, NaOH as a precipitating agent and NH_{3 …}

The Study Of Dynamical Electrochemical Impedance Spectroscopy For Oxygen Reduction Reaction On Pt/C Catalyst, Kun-Ming Shi, Jian-Wei Guo, Jia Wang

Journal of Electrochemistry

With joint techniques of rotating disc electrode(RDE) and electrochemical impedance spectroscopy(EIS), and further establishment on equivalent circuit model, this paper studied oxygen reduction reaction(ORR) on commercial Pt/C catalyst in acid medium. Our results found that the dynamical interface on Pt/C consists of two independent processes: 1) the PtO reduction from Pt surface, 2) the new PtO formation from ORR, thus providing key clues for catalyst stability and activity. This also implied that the dynamical interface facilitates reconstruction for porous electrode, and matches with mass transfer. One important issue is discovered that at high overpotential, the high reaction rate for ORR …

Recent Approaches In Designing Bioadhesive Materials Inspired By Mussel Adhesive Protein, Pegah Kord Forooshani, Bruce P. Lee

Department of Biomedical Engineering Publications

Marine mussels secret protein-based adhesives, which enable them to anchor to various surfaces in a saline, intertidal zone. Mussel foot proteins (Mfps) contain a large abundance of a unique, catecholic amino acid, Dopa, in their protein sequences. Catechol offers robust and durable adhe-sion to various substrate surfaces and contributes to the curing of the adhesive plaques. In this article, we review the unique features and the key functionalities of Mfps, catechol chemistry, and strategies for preparing catechol-functionalized poly- mers. Specifically, we reviewed recent findings on the contributions of various features of Mfps on interfacial binding, which include coacervate formation, surface …

Effect Of Surface Treatment On Liquid Adhesion Inside 3-D Structures, Madani A. Khan, Jeffrey Alston, Andrew Guenthner, Jacob Zavala

STAR Program Research Presentations

This study explores the relationship between chemical surface treatments on the interior of glass tubes and their resistance to fluid flow. By treating the interior of the tubes with functional silanes we can decrease or increase the interaction of the tube walls with the fluid column, which translates to changes in fluid column height for a given pressure differential. Resistance to fluid flow is quantified by using the tubes as integral parts of a barometric pressure column and measuring the changes in column height as the fluid is pulled into the tube by a set pressure differential. The barometric pressure …

An Unexpected Restructuring Of Combustion Soot Aggregates By Subnanometer Coatings Of Polycyclic Aromatic Hydrocarbons, Chao Chen, Xiaolong Fan, Tasneem Shaltout, Chong Qiu, Yan Ma, Andrew Goldman, Alexei F. Khalizov

Chemistry and Chemical Engineering Faculty Publications

We investigated the effect of thin polycyclic aromatic hydrocarbon (PAH) coatings on the structure of soot aggregates. Soot aerosol from an inverted diffusion burner was size classified, thermally denuded, coated with six different PAHs, and then characterized using scanning electron microscopy, light scattering, and mass-mobility measurements. Contrary to our expectation, significant restructuring was observed in the presence of subnanometer layers of pyrene, fluoranthene, and phenanthrene. These PAHs remained in subcooled liquid state in thin films, whereby the liquid layer acted as a lubricant, reducing the force required to initiate the restructuring. Thin layers of PAH of higher melting temperatures (perylene, …

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 …

Hydrothermal One-Step Synthesis Of Layered Nickel/Cobalt Double Hydroxide With Using Shape-Directing Agent And Homogeneous Precipitating Agent, Li-Wei Zhu, Yun-Hai Yan, Hui Jia, Run-Fen Liang

Journal of Electrochemistry

Nickel/cobalt double hydroxide (Ni/Co-DH) has been prepared by facile hydrothermal one-step synthesis method using hexamethylene tetramine (HMT) as a homogeneous precipitating agent and cetyltrimethylammonium bromide (CTAB) as a shape-directing agent. With the hydrolysis of HMT and the use of CTAB, the Ni/Co-DH could be synthesized without additional alkali source, and in the meantime, the Ni/Co-DH exhibited a controlled mesopore size of 13.4 nm and a large BET surface area of 93.6 m² •g^-1 . The X-ray diffraction (XRD) pattern displays that the Ni/Co-DH existed as a mixture of α-Ni(OH)₂-β-Co(OH)₂. The scanning electron microscope (SEM) …

Adsorption Kinetics Of Bovine Serum Albumin To Strong Anion Exchange Adsorbents: Application Of The Pore Diffusion Model To Resins And Membranes, Sarah Catherine Jensen

Graduate Theses - Chemical Engineering

The replacement of traditional bead-based chromatography by membranes has gained recent interest in the bioseparations industry. However, membranes have drawbacks such as lower binding capacity that make them unrealistic for some applications. The goal of this work is to compare the adsorption kinetics of anion exchange bead-based resin and membranes both on a theoretical modeling level and experimental level. Bovine serum albumin (BSA) was adsorbed to Q Sepharose FastFlow resin and Sartobind Q membrane to obtain adsorption equilibrium characteristics and kinetic data. A numerical solution was used to fit the pore diffusion model to the data and estimate a pore …

Synthesis, Structural Diversity, And Redox Control Of Cyclometalated Monoruthenium Complexes, Zhong-Liang Gong, Jiang-Yang Shao, Yu-Wu Zhong

Journal of Electrochemistry

Cyclometalated ruthenium complexes have received increasing attractions recently due to their excellent redox and photophysical properties. One structural feature of these complexes is that there is a ruthenium-carbon (Ru-C) σ bond presented in the molecule. Three common methods, namely, the “late metalation”, “early metalation”, and “transmetalation” methods, for the synthesis of cyclometalated ruthenium complexes are discussed and summarized. General strategies for the design of cyclometalating ligand and cyclometalated ruthenium complexes are introduced. By using different ancillary ligands, such as pyridine, imidazole, triazole, and pyrimidine, a great number of ruthenium complexes can be prepared. The presence of the Ru-C bond significantly …

Reduced Graphene Oxide (Rgo) Hollow Network Cages For High-Performance Electrochemical Energy Storage, Chi Zhang, Xu-Jun He, Gao-Ren Li

Journal of Electrochemistry

The reduced graphese oxide (RGO) hollow network cages were synthesized via zinc oxide (ZnO) template-assisted electrodeposition. The as-prepared RGO hollow network cages exhibited the multi-level architectures, from nano sheets, porous structures, networks, to 3D microscaled hollow cages, which can simultaneously optimize transport of electroactive species, utilization rate of electrode material, and super capacitive performance. Electrochemical measurements confirmed the superior performance of RGO hollow network cages for supercapacitors (SCs), such as high Csp (393 F⋅g^-1 at 1.0 A⋅g^-1), excellent rate capability (21.2% Csp loss from 1.0 to 20 A⋅g^-1), and superior cycling stability (< 1% Csp loss after 10000 cycles).

Developments Of Photo-Assisted Fuel Cells, Ling-Ling Zhang, Shao-Jun Dong

Journal of Electrochemistry

The exploitation and utilization of fossil fuels have led to serious energy crisis and environmental pollution. In this case, the development of renewable energy is an alternative to traditional energy consumption. Fuel cells (FCs) can convert chemical energy into electricity via the electrochemical reaction, which is green and environment-friendly. Photo-assisted FCs integrate photo-responsive components into FCs, leading to the dual routes of energy conversion including light energy to electricity and chemical energy to electricity, and thus, improving the energy utilization efficiency. The development of photo-assisted FCs is significant for practical application and promising to solve the coming energy crisis. In …

Development And Implementation Of Problem-Based Chemistry Experiments For Engineering Students In A Multi-Disciplinary Course, Tiffany Hesser, Stephanie R. Bunyea

Chemistry and Chemical Engineering Faculty Publications

This paper will describe the implementation and continuing development of five problem based laboratory experiments in a general chemistry course designed specifically for multiple disciplines of engineering students at the University of New Haven. The Problem Based Laboratory Experiments (PBLE) were developed to provide students with the opportunity to perform and develop experimental procedures working in interdisciplinary teams, while achieving a greater understanding of the role of chemistry in engineering fields. In each PBLE, students first complete a traditional chemistry experiment to gain an understanding of the chemical concepts and to become familiar with executing a written procedure with a …