Chemistry Commons^™

High-Performance Flexible Solid-State Supercapacitors Based On Mno2-Decorated Nanocarbon Electrodes, Yang Gao, Yun Shen Zhou, Min Qian, Hao Ming Li, Jody G. Redepenning, Li Sha Fan, Xiang Nan He, Wei Xiong, Masoud Majhouri-Samani, Lan Jiang, Yongfeng Lu

Department of Chemistry: Faculty Publications

Flexible energy storage units are highly desired to meet the ever-increasing demands for flexible electronics. In this paper, highly flexible solid-state supercapacitors are fabricated using MnO₂-decorated nanocarbon electrodes and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide–poly(vinylidene fluoride)- hexafluoropropylene ([EMIM][NTf2]–PVdF(HFP)) gel electrolytes. The flexible electrodes are prepared by electrodepositing MnO₂ onto the carbon nanotube/carbon nanoonion (CNT/CNO) films. CNT/CNO films have a large surface area for MnO₂ deposition and work as mechanical supports with high flexibility and light weight. CNOs act as spacers to separate CNTs, introducing mesopores inside the CNT/CNO films for preventing pore blocking during MnO₂ deposition. The supercapacitor exhibits …

Probing The Bifunctional Catalytic Activity Of Ceria Nanorods Towards The Cyanosilylation Reaction, Gonghua Wang, Lu Wang, Xiang Fei, Yunyun Zhou, Renat F. Sabirianov, Wai Ning Mei, Chin Li Cheung

Department of Chemistry: Faculty Publications

Ceria nanorods were demonstrated to be an active, bifunctional catalyst for the cyanosilylation of aldehydes. The catalytic activity of ceria was shown to be positively correlated with a decrease in the coordination numbers of neighbouring oxygen atoms around cerium atoms in the catalyst. Chemisorption and density functional theory studies suggested that the coordinatively unsaturated cerium sites exposed by the surface oxygen vacancy defects functioned as Lewis acid sites and the neighbouring oxygen atoms behaved as Lewis base sites in the catalytic cycle.

Dynamic Passivation With Bsa Overcomes Ltcc Mediated Inhibition Of Pcr, Jason Besecker, Kenneth A. Cornell, Greg Hampikian

Chemistry and Biochemistry Faculty Publications and Presentations

The increasing use of low temperature co-fired ceramic (LTCC) for the fabrication of biological microfluidic devices necessitates further research on LTCC biocompatibility. In this study we explore the inhibitory effect of DuPont's 951 LTCC on Polymerase Chain Reaction (PCR), and demonstrate a novel mechanism to increase biocompatibility between LTCC and PCR with the addition of a common passivation substance, bovine serum albumin (BSA). We show that DuPont's 951 LTCC binds negatively charged proteins including BSA and ovalbumin (OVA). This is a significant discovery as proteins (enzymes) are an essential component of most biological reactions, and a frequent addition to microfluidic …

Intercalation And Delamination Of Layered Carbides And Carbonitrides, Olha Mashtalir, Michael Naguib, Vadym Mochalin, Yohan Dall'agnese, Min Heon, Michel W. Barsoum, Yury G. Gogotsi

Chemistry Faculty Research & Creative Works

Intercalation and delamination of two-dimensional solids in many cases is a requisite step for exploiting their unique properties. Herein we report on the intercalation of two-dimensional Ti₃C₂, Ti₃ CN and TiNbC - so called MXenes. Intercalation of hydrazine, and its co-intercalation with N,N-dimethylformamide, resulted in increases of the c-lattice parameters of surface functionalized f-Ti₃C₂, from 19.5 to 25.48 and 26.8 Å, respectively. Urea is also intercalated into f-Ti₃C₂. Molecular dynamics simulations suggest that a hydrazine monolayer intercalates between f-Ti₃C₂ layers. Hydrazine is also intercalated …

Synthesis, Characterization And Application Of Pt Complexes With Pincer Ccc-Bis(Nhc) Ligands, Xiaofei Zhang

Electronic Theses and Dissertations

The unique metallation/transmetallation route for the synthesis of CCC-bis(NHC) pincer ligand supported transition metal complexes was extended to Pt. Several platinum complexes were synthesized. The identity of these complexes was confirmed through multiple technologies, including nuclear magnetic resonance spectroscopy, mass spectroscopy, elemental analysis, thermal analysis, and X-ray crystallography. The intriguing photophysical and thermal properties of these complexes are reported. These complexes were believed to be congeners of materials for organic light emitting diodes (OLEDs).

Use Of Sweet Potato To Develop A Medium For Cultivation Of Lactic Acid Bacteria, Saeed A. Hayek

Dissertations

This study investigated the use of sweet potatoes (Ipomoea batatas) as a basic component to develop a medium for cultivation of lactic acid bacteria (LAB). Extract from baked sweet potatoes was used to form a sweet potato medium (SPM). SPM was supplemented with 4 g/L of each nitrogen source (beef extract, yeast extract, and proteose peptone #3). Lactobacilli MRS was used as a control medium. Ten LAB strains were used to determine the suitability of SPM serving the growth of LAB. Our results showed no significant (p < 0.05) differences in the optical density, maximum specific growth rates, and bacterial populations between MRS and SPM. SPM also maintained higher pH values throughout the incubation period compared to that in MRS. The cost of SPM was 47% less than the cost of MRS. Further step was taken to determine the suitability of SPM serving LAB enzymatic activity. LAB strains growing in SPM showed relatively higher β-glucosidases, acid phosphatase, and phytase activities and lower a-glucosidase compared to that in MRS. Strains of L. reuteri showed the …

N-Functionalized Benzimidazol-2-Ylidene Silver Complexes: Synthesis, Characterization, And Antimicrobial Studies, Yetki̇n Gök, Senem Akkoç, Özlem Özeroğlu Çeli̇kal, İlknur Özdemi̇r, Selami̇ Günal, Eli̇f Sayin

Turkish Journal of Chemistry

2-Methoxyethyl, 2-diethylaminoethyl, and 2-phenylethyl-substituted N-heterocyclic carbene (NHC) precursors were treated with Ag_2CO_3 to yield silver(I)-NHC complexes (1a--g) in dichloromethane as a solvent at room temperature. The 7 new silver-NHC complexes were fully characterized by means of ^1H NMR, ^{13}C NMR, and elemental analysis techniques. Using the agar dilution procedure recommended by the Laboratory and Clinical Standards Institute, the antimicrobial activities of all the silver-NHC complexes were studied against 2 gram-negative bacterial strains (Pseudomonas aeruginosa and Escherichia coli), 2 gram-positive bacterial strains (Enterococcus faecalis and Staphylococcus aureus), and 2 fungi (Candida tropicalis and Candida albicans).

Synthesis And Characterization Of Biodegradable Poly(Vinyl Esters) With Hdac Inhibitory Activity, Kyle Lawrence Horton

Wayne State University Theses

HDAC inhibitors are known to have anti-inflammatory properties. HDAC inhibitors are used in combination with Oct4 to generate induced pluripotent stem cells. I hypothesized that polyesters based on simple aliphatic HDAC inhibitors like valproic acid (VPA) and phenylbutyric acid (PBA) can serve as alternatives to existing polyester biomaterials with improved anti-inflammatory properties and as scaffolds for generation of iPSCs when used in combination with layer-by-layer thin films delivering reprogramming transcription factors. Vinyl ester of phenylbutyric acid (VEPA) and vinyl ester of valproic acid (VEVA) were synthesized from their carboxylic acid precursors using an iridium complex catalyst at yields as high …

Spliceosomal Prp24 Unwinds A Minimal U2/U6 Complex From Yeast, Chandani Manoja Warnasooriya

Wayne State University Theses

Splicing plays a major role in eukaryotic gene expression by processing pre-mRNA to form mature mRNA. Pre-mRNAs undergo splicing to remove introns, non–protein coding regions, and religate exons, protein coding regions. This process is catalyzed by the spliceosome, which consists of five small nuclear ribonucleoprotein particles (snRNPs: U1, U2, U4, U5 and U6) and numerous protein factors. Proper assembly of spliceosomal components is critical for function, and thus, defects in assembly can be lethal. Several spliceosomal proteins facilitate structural rearrangements important for spliceosomal assembly and function. Prp24 is an essential factor in U6 snRNP assembly, and it has been proposed …

Development, Evaluation And Application Of Cyclofructans As Separation Agents, Nilusha L.T Padivitage

Chemistry & Biochemistry Dissertations - Archive

Hydrophilic interaction chromatography (HILIC) is now considered as a viable and established analytical tool for the separation of very polar and hydrophilic compounds, which are not sufficiently retained under Reversed phase liquid chromatography (RPLC). HILIC is becoming a routine technique in the areas of proteomic and metabolomic research and it is steadily increasing in importance in the fields of pharmaceutical, biolological, environmental and food chemistry. HILIC shows a complementary selectivity to RPLC. The use of water-miscible organic rich mobile phases (generally a mixture of acetonitrile and water (1-40 % of water in the mobile phase) is compatible with atmospheric pressure …

Dioxygen And Peroxide Activation By An Unnatural Amino Acid Incorporated Cytochrome P450cam And P450 Bm3, Leticia Loredo

Chemistry & Biochemistry Dissertations - Archive

This study focuses on the process development for a nanobioreactor for the oxidation of aliphatic C-H bond by the dependent activation of molecular oxygen and hydrogen peroxide dependent catalysis of cytochrome P450cam and P450 BM3 and their genetically encoded 3-NH₂tyrosine mutant enzymes.Oxidation of aliphatic carbons is an enormous challenge in classical synthesis due to their inert nature. However, it is significant in the production of fine chemicals and commodity products, which are precursors for the production of other valuable compounds.Among these reactions is the conversion of cyclohexane to cyclohexanol which is an intermediate in the production of nylon …

Anion Detection In The Positive Ion Mode Electrospray Ionization Mass Spectrometry By Use Of Cationic Ion Pairing Agents: Behavior And Applications, Edra Dodbiba

Chemistry & Biochemistry Dissertations - Archive

Anion detection and quantitation has long been of great interest to many scientific areas of research in academic and industrial settings. Their importance extends to areas such as water and environmental analysis, biological system analysis, and also the pharmaceutical and food industries. A variety of sensitive detection methods have been developed for anions. Many of these methods have significant advantages, but also drawbacks. In my dissertation I have described a new method for the detection of anions using electrospray ionization mass spectrometry (ESI-MS) positive ion mode, and cationic ion pairing reagents. Using this method, anions are paired with a plethora …

Design And Synthesis Of Flavin-Based Organocatalysts For Biomimetic Aerobic Oxidation Reactions, Shuai Chen

Chemistry & Biochemistry Dissertations - Archive

Oxidation reactions are among the most costly and least selective transformations in synthetic chemistry. Catalytic methods that utilize O₂ as a terminal oxidant strive to reduce the inefficiency in this large area of synthesis. Recent efforts have been aimed primarily at metal-/organometallic- or enzyme-catalyzed transformations. The goal of the research described in this dissertation was to develop organocatalytic systems based on natural biosynthetic catalysts in order to develop selective metal-free aerobic oxidations that function at room temperature. Prior to our work, riboflavin mimics were previously investigated to understand flavoenzyme function and to perform catalytic oxidations of primarily heteroatom systems. We …

Studies Towards Identifying The Active Site Structure Of Human Ghrelin O-Acyltransferase (Hgoat), Rosemary Loftus

Chemistry - Theses

Ghrelin is a peptide hormone involved in appetite stimulation, regulation of insulin signaling, and other physiological processes. Ghrelin requires acylation of the hydroxyl group of a specific serine residue with an octanoyl group to bind its receptor and activate signaling. This modification is catalyzed by ghrelin O-acyltransferase (GOAT). Ghrelin is the only known substrate of GOAT, making GOAT inhibition a promising avenue for treatment of obesity and type II diabetes. Understanding the interactions between ghrelin and GOAT responsible for binding and catalysis will aid in developing specific GOAT inhibitors. To identify the nature and location of the ghrelin binding site …

Effects Of Retarder On Cement, Reuben James

A with Honors Projects

Applying chemical analysis gained from taking a chemistry class, the author reflects on his summer employment at a chemical plant where he tested the effect of tartaric acid had on one of the company's products, Redline Speed Crete.

Determination Of The Effects Of Zno And Ceo2 Nanoparticles In Mesquite (Prosopis Juliflora) And Soybean (Glycine Max): Synchrotron And Spectroscopic Approaches, Jose Angel Hernandez Viezcas

Open Access Theses & Dissertations

The rapid growth of nanotechnology is exposing the environment to abnormal concentrations of engineered nanoparticles (NPs). There is concern about the unknown consequences of NPs on the environment and human health. This Dissertation has relied significantly on Synchrotron and other spectroscopic techniques to give insights on the effects, speciation and distribution of two metal oxide nanoparticles (ZnO, CeO2) on two plant species (Mesquite and Soybean). We evaluated the effects of ZnO (10 nm) and CeO2 (8 nm) NPs on a plant species native to the semi-arid regions of North America, Mesquite (Prosopis juliflora velutina). Mesquite plants grown in hydroponic culture …

Spectroscopic Analysis Of Polymerization And Exonuclease Proofreading By A High-Fidelity Dna Polymerase During Translesion Dna Synthesis, Babho Devadoss, Irene Lee, Anthony J. Berdis

Chemistry Faculty Publications

High fidelity DNA polymerases maintain genomic fidelity through a series of kinetic steps that include nucleotide binding, conformational changes, phosphoryl transfer, polymerase translocation, and nucleotide excision. Developing a comprehensive understanding of how these steps are coordinated during correct and pro-mutagenic DNA synthesis has been hindered due to lack of spectroscopic nucleotides that function as efficient polymerase substrates. This report describes the application of a non-natural nucleotide designated 5-naphthyl-indole-2′-deoxyribose triphosphate which behaves as a fluorogenic substrate to monitor nucleotide incorporation and excision during the replication of normal DNA versus two distinct DNA lesions (cyclobutane thymine dimer and an abasic site). Transient …

An Expanded Genetic Code In Mammalian Cells With A Functional Quadruplet Codon, Wei Niu, Peter G. Schultz, Jiantao Guo

Department of Chemistry: Faculty Publications

We have utilized in vitro evolution to identify tRNA variants with significantly enhanced activity for the incorporation of unnatural amino acids into proteins in response to a quadruplet codon in both bacterial and mammalian cells. This approach will facilitate the creation of an optimized and standardized system for the genetic incorporation of unnatural amino acids using quadruplet codons, which will allow the biosynthesis of biopolymers that contain multiple unnatural building blocks.

The Mechanism Of Photo-Hydrosilylation On Silicon And Porous Silicon Surfaces, Kurt W. Kolasinski

Chemistry Faculty Publications

No abstract provided.

Magnesium And Acidified Ethanol Based Treatment Systems For The Extraction And Dechlorination Of Polychlorinated Biphenyls From Contaminated Oils, Paints, And Soils, Simone Novaes-Card

Electronic Theses and Dissertations

Polychlorinated biphenyls (PCBs) are a class of environmentally persistent halogenated organic compounds that were once used as stabilizers to improve the properties of a variety of materials such as lubricants, heat transfer fluids, paints, and caulking materials. PCBs are also capable of migration through processes such as spillage into soils, leaching into groundwater, and volatilization into the atmosphere. Although banned in 1979 over health concerns, PCBs persist in these materials to this day because they are resistant to biotic degradation and natural weathering processes. The wide variety of contaminated materials means that many existing treatment options cannot be used across …

Photophysical And Photochemical Factors Affecting Multi-Photon Direct Laser Writing Using The Cross-Linkable Epoxide Su-8, Henry Williams

Electronic Theses and Dissertations

For the past decade, the epoxy based photoresist SU-8 has been used commercially and in the lab for fabricating micro- and nano-structures. Investigators have studied how processing parameters such as pre- and post-exposure bake temperatures affect the resolution and quality of SU-8 structures patterned using ultraviolet or x-ray lithography. Despite the advances in understanding the phenomena, not all of them have been explored, especially those that are specific to multi-photon direct laser writing (mpDLW). Unlike conventional exposure techniques, mpDLW is an inherently three-dimensional (3D) process that is activated by nonlinear absorption of light. This dissertation reports how several key processing …

Chemometric Applications To A Complex Classification Problem: Forensic Fire Debris Analysis, Erin Waddell

Electronic Theses and Dissertations

Fire debris analysis currently relies on visual pattern recognition of the total ion chromatograms, extracted ion profiles, and target compound chromatograms to identify the presence of an ignitable liquid. This procedure is described in the ASTM International E1618-10 standard method. For large data sets, this methodology can be time consuming and is a subjective method, the accuracy of which is dependent upon the skill and experience of the analyst. This research aimed to develop an automated classification method for large data sets and investigated the use of the total ion spectrum (TIS). The TIS is calculated by taking an average …

On The Capillary Electrophoresis Of Monohydroxy Metabolites Of Polycyclic Aromatic Hydrocarbons And Its Application To The Analysis Of Biological Matrices, Gaston Knobel

Electronic Theses and Dissertations

Polycyclic aromatic hydrocarbons (PAH) are a class of environmental pollutants consisting of a minimum of two fused aromatics rings originating from the incomplete combustion of organic matter and/or anthropogenic sources. Numerous possible anthropogenic and natural sources make the presence of PAH ubiquitous in the environment. The carcinogenic nature of some PAH and their ubiquitous presence makes their chemical analysis a topic of environmental and toxicological importance. Although environmental monitoring of PAH is an important step to prevent exposure to contaminated sites, it provides little information on the actual uptake and subsequent risks. Parent PAH are relatively inert and need metabolic …

Electrical, Optical And Chemical Properties Of Organic Photo Sensitve Materials, Zheng Shi

Electronic Theses and Dissertations

Light as a “green” source of energy has become increasingly attractive throughout the past century and has shown versatility for the application of activating chemical reactions. Compared with traditional energy sources, it provides a more direct, selective and controllable method. My PhD study was focused on the study of photochemistry of organic materials in two different systems. The first system is regarding reversible photoacids which generate protons on irradiation. With the aim of systematically studying these novel types of long lived photoacids, a series of photoacids was designed, synthesized and whose chemical mechanism was thoroughly investigated. This type of photoacid …

Development Of Novel Redox Sensors And Processes Towards Biological Applications, Jigna Patel

Electronic Theses and Dissertations

Research on the cure and early detection of diseases such as diabetes, Alzheimer's, and Parkinson's is becoming of great interest due to the increasing number of people affected by them every year. An accurate and quick detection of various damaging species is highly critical in treatments of such diseases not only for exploring possible cures but also for early detection. If these diseases are detected during the initial stages than the possibility of curing them is much higher. Motivated by this, many researchers today have developed numerous types of sensing devices that can detect various physiological and biological compounds. However, …

Novel Optical Properties Of Metal Nanostructures Based On Surface Plasmons, Haining Wang

Electronic Theses and Dissertations

Surface plasmons have been attracted extensive interests in recent decades due to the novel properties in nanometer sized dimensions. My work focused on the novel optical properties of metal nanostructures based on surface plasmons using theoretical simulation methods. In the first part, we investigated metal nanofilms and nanorods and demonstrated that extremely low scattering efficiency, high absorption efficiency and propagation with long distance could be obtained by different metal nanostructures. With a perforated silver film, we demonstrated that an extremely low scattering cross section with an efficiency of less than 1% can be achieved at tunable wavelengths with tunable widths. …

Biochemical Characterization Of The Nifb Enzyme And Nifb-Cofactor, Jirair Gevorkyan

Electronic Theses and Dissertations

The Mo-nitrogenase complex is composed of two components, Fe-protein and MoFe-protein. This complex is able to catalyze the reduction of N2 through the MgATP dependent transfer of electrons from the Fe-protein Fe4S4 cluster to the MoFe-protein P-cluster and, subsequently, to the iron-molybdenum cofactor (FeMoco). FeMo-co is a Fe7S9MoC-(R)-homocitrate cluster and has two biosynthetic precursors, NifB-co and L-cluster, of unknown structure and composition. The biosynthesis of FeMo-co is an enigmatic process that minimally requires NifB, NifEN, Fe-protein, MoO4 2- , (R)-homocitrate and S-adenolsylmethionine. A means to isolate the NifB enzyme for characterization has been developed through use of a GST-fusion tag. …

Chemical Reactivity Worksheet, Noaa, Jeffrey H. Glans

Chemistry & Physics Faculty Publications

Website overview by Jeffrey H. Glans.

NOAA. Office of Response and Restoration. "Chemical Reactivity Worksheet, NOAA." http://response.restoration.noaa.gov/crw

{2,2'-[N,N'-Bis(Pyridin-2-Ylmeth­Yl)Propane-1,3-Diyldi(Nitrilo)]Di­Acetato}­Cobalt(Iii) Hexa­Fluoridophosphate Aceto­Nitrile 0.064-Solvate, Craig C. Mclauchlan, Daniel S. Kissel, William R. Arnold, Albert W. Herlinger

Faculty Publications – Chemistry

In the title compound, [Co(C19H22N4O4)]PF6·0.064CH3CN, commonly known as [Co(bppd)]PF6·0.064CH3CN, where bppd represents the historical ligand name N,N'-bis(2-pyridylmethyl)-1,3-diaminopropane-N,N'-diacetate, the CoIII atom is coordinated in a distorted octa­hedral geometry with an N4O2 donor atom set. The acetate O atoms, which exhibit monodentate coordination, are oriented in a trans configuration with respect to each other, whereas the pyridyl N atoms are coordinated in a cis configuration. The compound crystallizes with two crystallographically unique cations and two anions per asymmetric unit along with a disordered, partially occupied (occupancy = 0.128) aceto­nitrile solvent mol­ecule. Crystals of the title …

Plastic Deformation, Wrinkling, And Recovery In Microgel Multilayers, Jeffrey C. Gaulding, Mark W. Spears Jr., L. Andrew Lyon

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Microgel multi-layer films assembled from anionic particles and linear polycation were prepared on elastomeric substrates and their self-healing properties studied. Dried films were imaged in situ during mechanical deformation and were determined to undergo plastic deformation in response to linear strain, leading to film buckling upon strain relaxation. Hydration leads to rapid reorganization of the film building blocks, permitting recovery of the film to the undamaged state. Additionally, films were determined to heal in the presence of high relative humidity environments, suggesting that film swelling and hydration is a major factor in the restoration of film integrity, and that full …