Chemistry Commons^™

Thin Films Of Semiconducting Polymers And Block Copolymers By Surface-Initiated Polymerization, Sang Gil Youm

LSU Doctoral Dissertations

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices, including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g. spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of pre-synthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. This dissertation mainly focuses …

A Flipped Classroom Redesign In General Chemistry, Scott A. Reid

Chemistry Faculty Research and Publications

The flipped classroom continues to attract significant attention in higher education. Building upon our recent parallel controlled study of the flipped classroom in a second-term general chemistry course (J. Chem. Educ., 2016, 93, 13–23), here we report on a redesign of the flipped course aimed at scaling up total enrollment while keeping discussion sizes small (i.e.,students), and maintaining equivalent contact hour load for faculty and workload for students. To that end, the course format featured lecture contact pushed outside of the classroom in the form of video lectures (mean duration 13 minutes) paired with online …

Hydrogen-Atom Attack On Phenol And Toluene Is Ortho-Directed, Olha Krechkivska, Callan M. Wilcox, Tyler P. Troy, Klaas Nauta, Bun Chan, Rebecca Jacob, Scott A. Reid, Leo Radom, Timothy W. Schmidt, Scott H. Kable

Chemistry Faculty Research and Publications

The reaction of H + phenol and H/D + toluene has been studied in a supersonic expansion after electric discharge. The (1 + 1′) resonance-enhanced multiphoton ionization (REMPI) spectra of the reaction products, at m/z = parent + 1, or parent + 2 amu, were measured by scanning the first (resonance) laser. The resulting spectra are highly structured. Ionization energies were measured by scanning the second (ionization) laser, while the first laser was tuned to a specific transition. Theoretical calculations, benchmarked to the well-studied H + benzene → cyclohexadienyl radical reaction, were performed. The spectrum arising from the …

Fabrication Of Multifunctional Nanostructured Porous Materials, Ahmed A. Farghaly

Theses and Dissertations

Nanostructured porous materials generally, and nanoporous noble metals specifically, have received considerable attention due to their superior chemical and physical properties over nanoparticles and bulk counterparts. This dissertation work aims to develop well-established strategies for the preparation of multifunctional nanostructured porous materials based on the combination of inorganic-chemistry, organic-chemistry and electrochemistry. The preparation strategies involved one or more of the following processes: sol-gel synthesis, co-electrodeposition, metal ions reduction, electropolymerization and dealloying or chemical etching. The study did not stop at the preparation limits but extended to investigate the reaction mechanism behind the formation of these multifunctional nanoporous structures in order …

Synthetic Flexibility Of A Bromopyrrole Ester Intermediate : Toward Novel Biologically Active Compounds, Scott Cameron Yeudall

Honors Theses

Compounds containing the pyrrole ring as a core structural motif continue to show significant biological activity, and both natural product derivatives and novel chemical scaffolds show potential for use as pharmaceuticals in treating a variety of cancers, infections, and inflammation. Given the widespread and important applications of compounds containing this motif, novel, rapid, and selective methods for the synthesis of multifunctional pyrroles is of some importance. Previous work in our group has utilized palladium-mediated Suzuki cross-coupling as a powerful tool for functionalizing activated bromopyrrole esters, generating structural analogues of bioactive natural products. We have also used a similar approach to …

Structure-Function Relationships Affecting The Sensing Mechanism Of Monolayer-Protected Cluster Doped Xerogel Amperometric Glucose Biosensors, Luke T. Dipasquale

Honors Theses

The research conducted in the Leopold Bioanalytical and Nanomaterials Analytical Chemistry Lab prior to the summer of 2013 focused on the synthesis of a functional biosensor equipped with a nanoparticle network embedded in a xerogel film for the detection of glucose. Xerogel-based films featuring embedded glucose oxidase enzyme and doped with alkanethiolate-protected gold NPs, known as monolayer protected clusters (MPCs), exhibit significantly enhanced performance compared to analogous systems without NPs including higher sensitivity, faster response time, and extended linear/dynamic ranges.

The following presented research is a systematic study of the structure-function relationships critical to understanding the sensing mechanism of the …

A Novel Copper (Ii) Complex Identified As A Potent Drug Against Colorectal And Breast Cancer Cells And As A Poison Inhibitor For Human Topoisomerase Iiᶐ, Shayna Sandhaus, Rosella Taylor, Tiffany Edwards, Alexis Huddleston, Stephen J. Beebe, Alvin A. Holder

Bioelectrics Publications

A novel complex, [Cu(acetylethTSC)Cl]Cl · 0.25C₂H₅OH 1 (where acetylethTSC = (E)-N-ethyl-2-[1-(thiazol-2-yl)ethylidene]hydrazinecarbothioamide), was shown to have anti-proliferative activity against various colon and aggressive breast cancer cell lines. In vitro studies showed that complex 1 acted as a poison inhibitor of human topoisomerase IIᶐ which may account for the observed anti-cancer effects.

Spontaneous Helix Formation In Non-Chiral Bent-Core Liquid Crystals With Fast Linear Electro-Optic Effect, Sithara P. Sreenilayam, Yuri Panarin, Jagdish K. Vij, Vitaly P. Panov, Anne Lehmann, Marco Poppe, Marko Prehm, Carsten Tschierske Carsten Tschierske

Articles

Liquid crystals (LCs) represent one of the foundations of modern communication and photonic technologies. Present display technologies are based mainly on nematic LCs, which suffer from limited response time for use in active colour sequential displays and limited image grey scale. Herein we report the first observation of a spontaneously formed helix in a polar tilted smectic LC phase (SmC phase) of achiral bent-core (BC) molecules with the axis of helix lying parallel to the layer normal and a pitch much shorter than the optical wavelength. This new phase shows fast (∼30 μs) grey-scale switching due to the deformation of …

Crystal Structure Of (E)-2-[(2- Bromo-3-Pyridyl)Methylidene]-6-Methoxy-3,4-Dihydronaphthalen-1-One And 3-[(E)-(6- Methoxy-3,4-Dihydronaphth-2-Oylidene)Methyl]-1h-Pyridin-2-One, Sarah K. Zingales, Morgan E. Moore, Andrew D. Goetz, Clifford W. Padgett

Chemistry: Faculty Publications (1990-2023)

The title compounds C17H14BrNO2, (I), and C17H15NO3, (II), were obtained from the reaction of 6-meth­oxy-3,4-di­hydro-2H-naphthalen-1-one and 2-bromo­nicotinaldehyde in ethanol. Compound (I) was the expected product and compound (II) was the oxidation product from air exposure. In the crystal structure of compound (I), there are no short contacts or hydrogen bonds. The structure does display [pi]-[pi] inter­actions between adjacent benzene rings and adjacent pyridyl rings. Compound (II) contains two independent mol­ecules, A and B, in the asymmetric unit; both are non-planar, the dihedral angles between the meth­oxy­benzene and 1H-pyridin-2-one mean planes being 35.07 (9)° in A and 35.28 (9)°in B. In …

Systematic Postsynthetic Modification Of Nanoporous Organic Frameworks And Their Performance Evaluation For Selective Co2 Capture, Timur Islamoglu

Theses and Dissertations

Porous organic polymers (POPs) with high physicochemical stability have attracted significant attention from the scientific community as promising platforms for small gas separation adsorbents. Although POPs have amorphous morphology in general, with the help of organic chemistry toolbox, ultrahigh surface area materials can be synthesized. In particular, nitrogen-rich POPs have been studied intensively due to their enhanced framework-CO₂ interactions. Postsynthetic modification (PSM) of POPs has been instrumental for incorporating different functional groups into the pores of POPs which would increase the CO₂ capture properties. We have shown that functionalizing the surface of POPs with nitro and amine groups …

Sol-Gel Assembly Of Metal Nanostructures Into Metallic Gel Frameworks And Their Applications, Xiaonan Gao

Theses and Dissertations

The advent of nanoscience and nanotechnology has sparked many research forefronts in the creation of materials with control over size, shape, composition, and surface properties.^1,2 However, for most of the applications, nanoscale materials need to be assembled into functional nanostructures that exhibit useful and controllable physical properties. Therefore, numerous efforts on the assembly of nanoparticles (NPs) using organic ligands, polymers and polyelectrolytes have been reported.^3,4 However, the interactions between NPs are mediated by intervening ligands, which are detrimental to charge transport and limit the thermal stability. Hence, developing a new method to produce solid …

Measuring Real-World Emissions From The On-Road Passenger Fleet, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

On-Road Remote Sensing Of Automobile Emissions In The Tulsa Area: Fall 2015, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Donald H. Stedman 50 Years Of Air Quality Instrument Inventions And Measurements (Presentation), Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

High-Mileage Light-Duty Fleet Vehicle Emissions: Their Potentially Overlooked Importance, Gary A. Bishop, Donald H. Stedman, Daniel A. Burgard, Oscar Atkinson

Fuel Efficiency Automobile Test Publications

No abstract provided.

Design Of First-Row Transition Metal Bis(Alkoxide) Complexes And Their Reactivity Toward Nitrene And Carbene Transfer, James Bellow

Wayne State University Dissertations

The novel alkoxide ligand [OCtBu2Ph], or [OR], was synthesized in a single step as a lithium salt. It was then reacted with a series of first-row transition metal(II) halides, with widely varying results. Upon reaction with chromium, manganese, iron, or cobalt(II) chloride, dimeric complexes of the form M2(OR)4Li2Cl2 were formed, which displayed rare seesaw geometry at the metal. This unusual geometry was confirmed by various spectroscopic and computational studies. Computational studies also indicate that the steric bulk of the ligand, as well as the inclusion of lithium atoms in the molecules, are what lead to the seesaw geometry. Reaction of …

Synthesis, Characterization, And Properties Of Peroxo-Based Oxygen-Rich Compounds For Potential Use As Greener High Energy Density Materials, Nipuni-Dhanesha Horadugoda Gamage

Wayne State University Dissertations

One main aspect of high energy density material (HEDM) design is to obtain greener alternatives for HEDMs that produce toxic byproducts. Primary explosives lead azide, lead styphnate, and mercury fulminate contain heavy metals that cause heavy metal poisoning. Leaching of the widely used tertiary explosive NH4ClO4 into groundwater has resulted in human exposure to ClO4– ions, which cause disruptions of thyroid related metabolic pathways and even thyroid cancer. Many research efforts to find replacements have gained little success. Thus, there is a need for greener HEDMs. Peroxo-based oxygen-rich compounds are proposed as a potential new class of greener HEDMs due …

Development Of Single And Array Electro-Chemical Sensors For Real-Time Trace Metal Analysis In Aqueous Environmental Media, Yuanyuan Yang

Wayne State University Dissertations

Detection of trace metals has great importance in environmental and biological applications. While traditional electrochemical techniques have played critical roles in this field, their usefulness is limited by temporal resolution, Hg toxicity and stability concerns. Recently, we developed a method using fast-scan cyclic voltammetry (FSCV) at carbon-fiber microelectrodes (CFMs) to achieve rapid measurement of metal ions with high sensitivity, selectivity, and stability. Through optimizations this method showed strengths in real-time trace metal analysis. ‬‬‬‬‬‬

‪Analytical selectivity was improved via covalent functionalization on CFMs. We employed diazonium electrochemical reduction followed by click chemistry to create robust covalent attachments. We showcased its …

Calculating Heat Of Formation Values Of Energetic Compounds: A Comparative Study, Michael S. Elioff, Jordon Hoy, John A. Bumpus

Faculty Work

Heat of formation is one of several important parameters used to assess the performance of energetic compounds. We evaluated the ability of six different methods to accurately calculate gas-phase heat of formation (Δ _𝑓𝐻^𝑜 _298,g) values for a test set of 45 nitrogencontaining energetic compounds. Density functional theory coupled with the use of isodesmic or other balanced equations yielded calculated results in which 82% (37 of 45) of the Δ _𝑓𝐻^𝑜 _298,g values were within ±2.0 kcal/mol of the most recently recommended experimental/reference values available. This was compared to a procedure using density functional theory …

The Periodical Winter 2016, Southern Adventist University

the Periodical – Chemistry Department Newsletter

Volume 3, issue 2 of the Periodical includes articles about the Chemistry Club's community service, a pictorial listing of May 2016 graduates, student Jeron Estwick's presentation at a chemistry conference, a feature on students recognized for academic achievement, and an alumni spotlight.

Signature Of Coexistence Of Superconductivity And Ferromagnetism In Two-Dimensional Nbse2 Triggered By Surface Molecular Adsorption, Xiaojiao Zhu, Yuqiao Guo, Hao Cheng, Jun Dai, Xingda An, Jiyin Zhao, Kangzhen Tian, Shiqiang Wei, Xiao Cheng Zeng, Changzheng Wu, Yi Xie

Department of Chemistry: Faculty Publications

Ferromagnetism is usually deemed incompatible with superconductivity. Consequently, the coexistence of superconductivity and ferromagnetism is usually observed only in elegantly designed multi-ingredient structures in which the two competing electronic states originate from separate structural components. Here we report the use of surface molecular adsorption to induce ferromagnetism in two-dimensional superconducting NbSe₂, representing the freestanding case of the coexistence of superconductivity and ferromagnetism in one two-dimensional nanomaterial. Surface-structural modulation of the ultrathin superconducting NbSe₂ by polar reductive hydrazine molecules triggers a slight elongation of the covalent Nb–Se bond, which weakens the covalent interaction and enhances the ionicity of …

Engineering Escherichia Coli For High‑Yield Geraniol Production With Biotransformation Of Geranyl Acetate To Geraniol Under Fed‑Batch Culture, Wei Liu, Xin Xu, Rubing Zhang, Tao Cheng, Yujin Cao, Xiaoxiao Li, Jiantao Guo, Huizhou Liu, Mo Xian

Department of Chemistry: Faculty Publications

Background: Geraniol is an acyclic monoterpene alcohol, which exhibits good prospect as a gasoline alternative. Geraniol is naturally encountered in plants at low concentrations and an attractive target for microbial engineering. Geraniol has been heterologously produced in Escherichia coli, but the low titer hinders its industrial applications. Moreover, bioconversion of geraniol by E. coli remains largely unknown.

Results: Recombinant overexpression of Ocimum basilicum geraniol synthase, Abies grandis geranyl diphosphate synthase, and a heterotic mevalonate pathway in E. coli BL21 (DE3) enabled the production of up to 68.6 ± 3 mg/L geraniol in shake flasks. Initial fed-batch fermentation only increased geraniol …

Highly Porous Zirconium Metal−Organic Frameworks With Β‑Uh3‑Like Topology Based On Elongated Tetrahedral Linkers, Xin Zhang, Xu Zhang, Jacob A. Johnson, Yu-Sheng Chen, Jian Zhang

Department of Chemistry: Faculty Publications

Two non-interpenetrated zirconium metal−organic frameworks (Zr-MOFs), NPF-200 and NPF-201, were synthesized via the assembly of elongated tetrahedral linkers with Zr₆ and Zr₈ clusters. They represent the first examples of MOFs to have the β-UH₃-like, 4,12,12T1 topology. Upon activation, NPF-200 exhibits the largest BET surface area (5463 m²g⁻¹) and void volume (81.6%) among all MOFs formed from tetrahedral ligands. Composed of negative-charged boron-centered tetrahedral linkers, NPF-201 is an anionic Zr-MOF which selectively uptakes photoactive [Ru(bpy)₃]²⁺for heterogeneous photo-oxidation of thioanisole.

Additional supporting information files are attached below.

Close Encounters With Creative Chemical Thinking: An Outreach Presentation Using Movie Clips About The Elemental Composition Of Aliens And Extraterrestrial Minerals, Mark A. Griep, Marjorie L. Mikasen

Department of Chemistry: Faculty Publications

To introduce more chemistry into a middle and high school bioengineering camp experience, we developed an educational and entertaining presentation that examines the chemistry in movies about aliens and minerals from outer space. Our goal was to help the campers to think creatively about the bioengineering projects they are doing and about its chemistry. After watching each movie clip, we explain whether the chemistry in the clip is real or fake, and then describe the real chemistry that inspired it. The chemical touchstone for the presentation is the periodic table. First, the campers learn that aliens in five movies are …

Flexble Robotic Actuators, Aaron D. Mazzeo, Stephen A. Morin, Robert F. Shepherd, George M. Whitesides, William B. Kalb

Department of Chemistry: Faculty Publications

Some embodiments of the disclosed subject matter includes a laminated robotic actuator. The laminated robotic actuator includes a strain-limiting layer comprising a flexible, non extensible material in the form of a sheet or thin film, a flexible inflatable layer in the form of a thin film or sheet in facing relationship with the Strain-limiting layer, wherein the inflatable layer is selectively adhered to the strain-limiting layer, and wherein a portion of an un-adhered region between the strain-limiting layer and the inflatable layer defines a pressurizable channel, and at least one fluid inlet in fluid communication with the pressurizable channel. The …

Oxyhalogen-Sulfur Chemistry: Kinetics And Mechanism Of Oxidation Of N-Acetylthiourea By Aqueous Bromate And Acidified Bromate, Kudzanai Chipiso, Wilbes Mbiya, Thai Tran, Reuben H. Simoyi

Chemistry Faculty Publications and Presentations

The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess bromate conditions. The reaction displays an induction period before formation of bromine. The stoichiometry of the reaction was determined to be 4:3: 4BrO 3 – +3(CH 3 CO)NH(NH 2 )C=S+3H 2 O®4Br – +3(CH 3 CO)NH(NH 2 )C=O+3SO 4 2– +6H + (A) with a complete desulfurization of ACTU to its urea analogue. In excess bromate conditions the stoichiometry was 8:5: 8BrO 3 – + 5(CH 3 CO)NH(NH 2 )C=S + H 2 O ® 4Br 2 + 5(CH 3 CO)NH(NH 2 …

Electrochemistry-Coupled To Mass Spectrometry In Simulation Of Metabolic Oxidation Of Methimazole: Identification And Characterization Of Metabolites, Kudzanai Chipiso, Reuben H. Simoyi

Chemistry Faculty Publications and Presentations

Methimazole (MMI), an antithyroid drug, is associated with idiosyncratic toxicity. Reactive metabolites resulting from bioactivation of the drug have been implicated in these adverse drug reactions. Mimicry of enzymatic oxidation of MMI was carried out by electrochemically oxidizing MMI using a coulometric flow-through cell equipped with a porous graphite working electrode. The cell was coupled on-line to electrospray ionization mass spectrometry (EC/ESI-MS). ESI spectra were acquired in both negative and positive modes. In acidic medium, ESI spectral analysis showed that the dimer was the main product, while in neutral and basic media, methimazole sulfenic acid, methimazole sulfinic acid and methimazole …

Medium-Sized Au40(Sr)24 And Au52(Sr)32 Nanoclusters With Distinct Gold-Kernel Structures And Spectroscopic Features, Wen Wu Xu, Yadong Li, Yi Gao, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We have analyzed the structures of two medium-sized thiolateprotected gold nanoparticles (RS-AuNPs) Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ and identified the distinct structural features in their Au kernels [Sci. Adv., 2015, 1, e1500425]. We find that both Au kernels of the Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ nanoclusters can be classified as interpenetrating cuboctahedra. Simulated X-ray diffraction patterns of the RS-AuNPs with the cuboctahedral kernel are collected and then compared with the X-ray diffraction patterns of the RS-AuNPs of two other prevailing Au-kernels identified from previous experiments, namely the Ino-decahedral kernel and icosahedral kernel. …

Correction: Surprising Impact Of Remote Groups On The Folding–Unfolding And Dimer-Chain Equilibria Of Bifunctional H-Bonding Unimers, Rui Liu, Shuang Chen, Erin S. Baker, Richard D. Smith, Xiao Cheng Zeng, Bing Gong

Xiao Cheng Zeng Publications

The authors regret that in the original article the spelling of one author’s surname is incorrect. The correct name of the author is ‘Shuang Chen’.

The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

Surprising Impact Of Remote Groups On The Folding–Unfolding And Dimer-Chain Equilibria Of Bifunctional H-Bonding Unimers, Rui Liu, Shuang Cheng, Erin S. Baker, Richard D. Smith, Xiao Cheng Zeng, Bing Gong

Xiao Cheng Zeng Publications

Oligoamide 1, consisting of two H-bonding units linked by a trimethylene linker, was previously found to form a very stable, folded dimer. In this work, replacing the side chains and end groups of 1 led to derivatives that show the surprising impact of end groups on the folding and dimer-chain equilibria of the resultant molecules.