Chemistry Commons^™

Synthetic And Mechanistic Studies Of Coupling Reactions Involving C-H Bond Activation, Ki Hyeok Kwon

Dissertations (1934 -)

Transition metal-catalyzed C-C bond forming reactions involving C-H bond activation have been shown to be effective methods for functionalization of unreactive compounds. Since Murai's pioneering work on ruthenium-catalyzed regioselective arene-to-alkene coupling reactions, a number of well-defined, late transition metal catalysts have been shown to mediate regioseletive C-C bond forming reaction involving C-H bond activation. Recently, late transition metal complexes have also been found to catalyze the regioselective coupling reaction of nitrogen containing compounds with alkenes as well as sp3 bond insertions and oxidative coupling reaction of aimdes. The catalytic C-C bond forming reaction involving C-H bond activation would provide simple …

Novel Ion Trap Made Using Lithographically Patterned Plates, Ying Peng

Theses and Dissertations

A new approach of making ion trap mass analyzers was developed in which trapping fields are created in the space between two ceramic plates. Based on microfabrication technology, a series of independently-adjustable electrode rings is lithographically patterned on the facing surfaces of each ceramic plate. The trapping field can be modified or fine-tuned simply by changing the RF amplitude applied to each electrode ring. By adjusting the potential function applied to the plates, arbitrary trapping fields can be created using the same set of ceramic plates. Unlike conventional ion traps, the electrodes of planar ion traps have a non-equipotential surface, …

Generation Of Diverse Molecular Complexity From Simple Hydrocarbons, Anobick Sar

Dissertations (1934 -)

In an effort to make diverse molecular complexity from simple hydrocarbons, tricarbonyl(cyclohexadienyl)iron(+1) cation was prepared in two steps from 1, 3-cycloxehadiene. Reactivity of the symmetric iron cation with heteroatom nucleophiles and stabilized carbon nucleophiles was studied. Nucleophilic attack of potassium phthalimide at the dienyl terminus of the cation followed by oxidative decomplexation with Ce4+ provided the ligand N-(2,4-cyclohexadiene-1-yl)phthalimide. A series of stereochemically diverse polyhydroxyl aminocyclohexane "aminocyclitols" derivatives and a number of racemic and optically active hydroxy-and polyhydroxy 1,3-diaminocyclohexane derivatives have been synthesized from N-(2,4-cyclohexadiene-1-yl)phthalimide. The relative stereochemistries of the compounds ware assigned on the basis of the 1H NMR data …

Assessing Secondary And College Students’ Implicit Assumptions About The Particulate Nature Of Matter: Development And Validation Of The Structure And Motion Of Matter Survey, Marilyne Stains, Marta Escriu-Sune, Myrna Lisseth Molina Alvarez De Santizo, Hannah Sevian

Department of Chemistry: Faculty Publications

Development of learning progressions has been at the forefront of science education for several years. While understanding students’ conceptual development toward “big ideas” in science is extremely valuable for researchers, science teachers can also benefit from assessment tools that diagnose their students’ trajectories along the learning progressions. In this paper, we describe the development and validation of a teacher-friendly survey, the Structure and Motion of Matter (SAMM) survey, designed to measure students’ trajectories along aspects of a research-based learning progression on the particulate nature of matter. Specifically, the survey assesses students’ implicit assumptions about four concepts: the structure of solute …

Nanoencapsulated Drug-Carrying System For Photodynamic Antimicrobial Chemotherapy (Pact), Gopala Krishna Murthy Kalapala

All Capstone Projects

The purpose of this study is to develop nanoparticulate drug-carrying systems that are capable of directly delivering photodynamic antimicrobial agents to treat patients with chronic wounds. Chronic wounds are considered as a pandemic health problem. Approximately 1% to 2% of the population in developing countries has experienced a chronic wound during their lifetime. In the United State States, according to the American Academy of Dermatology, the expense of treating chronic wounds constitutes over half of the total cost for all skin diseases, which exceeds $10 billion annually. For the last decade extensive basic science and clinical research in chronic wounds …

Micro Bca Analysis Of Proteins, Anusha Chennupati

All Capstone Projects

The main objective of this project was to develop and validate methods for detection and analysis of proteins using a newly introduced microdrop plate reader equipped with a 16 well microdrop reader (2 uL sample volume). We used commercially available BSA, egg albumin, trypsinogen, Pepsin, β-lactoblobulin and lysozyme as out test moieties. Protein drop size, time, BCA reagent quantity, was assessed at various levels using a microdrop micro-BCA protocol (Pierce Chemical Company) with the appropriate controls (PBS blank) the method validated using the appropriate statistical and method parameters (i.e %RSD, and regression analysis of the standard curves). The micro method …

Novel Ruthenium Complexes As Photodynamic Therapeutic Agents, Sareen Kumar Kushangari

All Capstone Projects

This project reviews the literature of novel ruthenium c complexes in photodynamic drug therapy. (Abstract by OPUS staff)

Analysis Of Anions In Water Samples From The Holy Land (Israel And Jordan) By Using Ion Chromatography, Ahalya Yalamanchili

All Capstone Projects

Ion chromatography is a form of liquid chromatography, which measures concentration of ionic species by separating them based on their interaction with resins. Ion chromatography is mainly useful for the separation and analysis of ions (cations or anions) in water. Analysis of anions in water is of greater importance because water is very important in daily life, especially in the Holy Land, where water is the very essence of life. If variety of chemicals, such as organic and inorganic salts enter into the water system, they make water toxic and poisonous to drink. In this project water samples from different …

Synthesis Of A Folate Receptor Mass Spectrometry Probe, Audrea Rhymes

All Capstone Projects

Drug delivery is one of the most important concepts for cancer patients because it is oftentimes very difficult or nearly impossible to exclusively target cancerous cells. In this study, the aim was to target receptors on cancerous cells, specifically the Folate Receptor (FR). This specific receptor was targeted because it has been proven to enhance intracellular delivery being that folic acid is an integral species in normal cell function and also that cancerous cells tend to exhibit an abnormally high concentration of Folic Acid on cell surfaces.

The application of dyes is a very common practice used to link folic …

Bis[2-(1h-Imidazol-2-Yl-Κn³)-1h-Imidazol-3-Ium]Silver(I) Trinitrate, Shelonda R. Finch, J. P. Harper, Amitava Choudhury, Ekkehard Sinn, Harvest L. Collier

Chemistry Faculty Research & Creative Works

The synthesis of the title salt, [Ag(C ₆H ₇N ₄) ₂](NO ₃) ₃, was carried out employing a 1:2 molar ratio of 2,2'-biimidazole and silver nitrate respectively. The cation has crystallographically-imposed C2 symmetry with the metal atom in an almost linear coordination environment [N - Ag - N = 177.01 (17)°]. The crystal structure displays N - H⋯O and C - H⋯O hydrogen-bonding interactions.

Insights Into Chemical Structure Changes Of Kerogen From Bituminous Coal In Response To Dike Intrusions Investigated By Advanced Solid-State 13C Nmr, Yuan Li

Chemistry & Biochemistry Theses & Dissertations

Variations in the chemical structures of kerogens From highly volatile bituminous coal located near two igneous dike intrusions in the Illinois Basin were examined in detail by advanced solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Spectral-editing techniques were used to identify specific functional groups. Direct polarization was used to quantify different functional groups. ¹H-¹³C two- dimensional heteronuclear NMR was used to examine connectivities and proximities, and ¹H-¹³C long-range recoupled dipolar dephasing was used to estimate aromatic cluster sizes. With decreasing distance to dike contacts and increasing thermal maturity (vitrinite reflectance R₀ from …

Encapsulated Antibiotic Nanoparticles For Cranial Transplantation, Adusumilli Naga Anusha

All Capstone Projects

The purpose of this research is to develop a unique nanoparticulate system that is capable of delivering antibiotics in a locally applied and extended-release manner for patients receiving cranial replacement implants and bone grafting. This study involves three major components: first, encapsulate both hydrophobic antibiotics (chloramphenicol and rifampicine) and hydrophilic antibiotics (vancomycine and acyclovir) into nanoparticles. Second, incorporate antibiotic nanoparticles in a polymeric coating material (nitrocellulose plus 7.0% (w/v) polyvinylpyrrolidone) with a volatile carrier solvent (ethyl acetate or ethanol). Third, directly apply the resulting product from component 1 and 2 to polymethyl methacrylate (PMMA) cranial implants and hydroxylapatite (HA) bone …

Design, Synthesis And Studies Directed Towards The Photophysical Properties Of The Polycyclic Aromatic Hydrocarbons, Rekha Sharma

Master's Theses (2009 -)

The cross conjugated molecules are also known as cruciforms, which effectively allow the HOMO-LUMO separation. The term Cruciform is used for diaxial chromophores in which the properties of the two axes can be manipulated upon suitable substitution with auxochromic substituents. Originally designed for molecular electronic applications, the discovery that these cruciforms possess a platform where Frontier Molecular Orbitals can be tuned, led to their investigative research as sensory flourophores. In the majority of organic chromophores, the HOMO and the LUMO are congruent. Thus, upon binding to an analyte both HOMO and LUMO are almost equally affected and hence large shifts …

Binding Energy Predictions Of Positron- And Positronium-Atom System, Xiang Cheng

Master's Theses (2009 -)

There has been a large amount of work studying positron and positronium (Ps) binding to atoms. Twelve atoms (including Ps) are known to bind with a positron and 14 atoms won't. For Ps binding, 12 atoms are found to bind with Ps and 2 atoms do not. For both positron and Ps binding to atoms, we find that the known binding energy can be fitted to a simple expression involving several common physical properties. Positron binding energies can be fitted using the parameters of ionization potentials, polarizabilities, and the number of s electrons of the atoms; while Ps binding energies …

Wavepacket Motion Via A Conical Intersection In The Photochemistry Of Aqueous Transition-Metal Dianions, Igor L. Zheldakov, Mikhail N. Ryazantsev, Alexander N. Tarnovsky

Chemistry Faculty Publications

The photochemical reaction paths in aqueous PtBr(6)(2-) and OsBr(6)(2-) have been studied by femtosecond broad-band pump probe spectroscopy supported by CASPT2 and DFT/TDDFT calculations. These paths lead to the separation of negative charges and propagate through distortions of nascent, penta-coordinated metal fragments caused by Jahn-Teller C(4v) and D(3h) conical intersections (CIs), respectively. Within 150 fs following 420 nm excitation of PtBr(6)(2-), the molecule undergoes internal conversion and intersystem crossing into the dissociative lowest triplet excited (3)T(1g) state, loses a ligand, and relaxes via the C(4v) CI to the nearly trigonal bipyramid (3)PtBr(5)(-) product in the triplet state. Direct 530 nm …

Application Of Raman Spectroscopy To Lubricants, Lubricated Surfaces And Lubrication Phenomena, David W. Johnson

Chemistry Faculty Publications

Recent advances in lasers and detector technologies and the development of low-cost instruments and fiber-optic probes have brought about an explosion in the lubrication systems being studied by Raman spectroscopy. This article provides examples of the use of Raman spectroscopy in the study of lubrication phenomena, including the characterization of liquid lubricants, lubricant additives, and solid lubricants; the study of vapor-phase lubrication; and the use of coated nanoparticles as lubricants.

Using Nanotechnology To Detect Nerve Agents, Mark N. Goltz, Dong-Shik Kim, Leeann Racz

Faculty Publications

Nanotechnology has opened a wide range of opportunities having potential impacts in areas as diverse as medicine and consumer products. In collaboration with researchers at the University of Toledo UT, Air Force Institute of Technology AFIT scientists are exploring the possibility of using a nanoscale organic matrix to detect organophosphate OP nerve agents. Current techniques for detecting OP compounds are expensive and time consuming. Developing a nanoscale organic matrix sensor would allow for direct, real-time sensing under field conditions. This article describes the science behind such a sensor and its possible applications. High-performance sensors are needed to protect Soldiers and …

Development And Applications Of Ionic Liquids And Near-Infrared Multispectral Imaging Techniques, Irena Mejac

Dissertations (1934 -)

In this work, we explore novel analytical applications of Ionic Liquids and Near-infrared multispectral imaging microscopy.

Ionic liquids (ILs) belong to a group of organic salts that are liquid at room temperature and can be, due to their unique chemical and physical properties, successfully used for a variety of applications. The main goal of this study was to explore the synergistic use of ILs in chemical separations. Specifically, chiral ILs were used as novel chiral selectors for Capillary Electrophoresis and as solvents for stationary phase in Gas Chromatography. As chiral selectors IL provides baseline-separation as well as enantiomeric separation of …

Spectroelectrochemistry And Voltammetry Of Metalloporphinones, Florentina Tutunea

Dissertations (1934 -)

Metalloporphinones have been found in a number of enzymes involved in nitrogen metabolism. The emphasis of this research project has been to develop spectroscopic markers in order to identify metal versus porphinone reduction. The carbonyl group in the porphinone has a very strong signal which is quite sensitive to the extent of reduction of the porphinone macrocycle.

The spectral change makes IR an important tool in the process of structure determination of metalloporphyrins because the carbonyl group shift can be correlated with the metal oxidation state. It was observed from previously published studies that a higher metal oxidation state moves …

The Preparation And Characterisation Of Silver Nanomaterials And Their Application In Sensing Techniques, Aoife Power

Doctoral

In this work the impact of nanomaterial, specifically silver nanostructures, on sensing techniques is investigated. The work can be divided in to three sections, preparation and characterisation of silver nanoparticles, their application as a nanocomposite based chemiresistor humidity sensing device and finally their application within the surface enhanced (resonance) Raman spectroscopy, SE(R)RS, technique. In the first study silver nanoparticles were prepared as aqueous colloidal dispersions. The colloids were of either a defined diameter (average diameter ~ 20 nm) with high silver loading or lower loaded colloids of tuneable morphology and hence optical properties. In a subsequent study the high load …

Phytosterol Stearate Esters Elicit Similar Responses On Plasma Lipids And Cholesterol Absorption But Different Responses On Fecal Neutral Sterol Excretion And Hepatic Free Cholesterol In Male Syrian Hamsters, Mark M. Ash, Jiliang Hang, Patrick Dussault, Timothy P. Carr

Patrick Dussault Publications

The dietary impact of specific phytosterols incorporated into phytosterol fatty acid esters has not been elucidated. Therefore, we tested the hypothesis that phytosterol esters containing different sterol moieties (sitosterol, sitostanol, or stigmasterol) but the same fatty acid moiety (stearic acid) produce different effects on cholesterol metabolism. Male Syrian hamsters were fed sitosterol, sitostanol, and stigmasterol stearate esters (25 g/kg diet) in an atherogenic diet containing cholesterol (1.2 g/kg) and coconut oil (80 g/kg). The phytosterol stearates produced no decrease in cholesterol absorption or plasma non–high-density lipoprotein cholesterol despite a reduction in liver free cholesterol in hamsters fed both sitosterol and …

Fliposomes: Ph-Sensitive Liposomes Containing A Trans-2-Morpholinocyclohexanol-Based Lipid That Performs A Conformational Flip And Triggers An Instant Cargo Release In Acidic Medium, Nataliya M. Samoshina, Xin Liu, Barbora Brazdova, Andreas H. Franz, Vyacheslav V. Samoshin, Xin Guo

College of the Pacific Faculty Articles

Incorporation of a pH-sensitive conformational switch into a lipid structure enables a drastic conformational flip upon protonation that disrupts the liposome membrane and causes rapid release of cargo specifically in areas of increased acidity. pH-sensitive liposomes containing the amphiphile (1) with trans-2-morpholinocyclohexanol conformational switch, a phospholipid, and a PEG-lipid conjugate were constructed and characterized. The optimized composition—1/POPC/PEG-ceramide (50/45/5)—could be stored at 4 °C and pH 7.4 for up to 1.5 years, and was stable in blood serum in vitro after 48 h at 37 °C. Liposomes loaded with ANTS/DPX or methotrexate demonstrated an unusually quick content release (in a few …

Investigations Into Whole Water, Prototropic And Amide Proton Exchange In Lanthanide(Iii) Dota-Tetraamide Chelates, Mark Woods, Azhar Pasha, Piyu Zhao, Gyula Tircso, Somdatta Chowdhury, Garry Kiefer, Donald E. Woessner, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Lanthanide(III) chelates of DOTA-tetraamide ligands have been an area of particular interest since the discovery that water exchange kinetics are dramatically affected by the switch from acetate to amide side-chain donors. More recently these chelates have attracted interest as potential PARACEST agents for use in MRI. In this paper we report the results of studies using chemical exchange saturation transfer (CEST) and some more recently reported chelates to re-examine the exchange processes in this class of chelate. We find that the conclusions of Parker and Aime are, for the most part, solid; water exchange is slow and a substantial amount …

An In Vitro Spectroscopic Analysis To Determine The Chemical Composition Of The Precipitate Formed By Mixing Sodium Hypochlorite And Chlorhexidine, James B. Nowicki, Daniel S. Sem

Chemistry Faculty Research and Publications

Introduction—The purpose of this in vitro study was to determine the chemical composition of the precipitate formed by mixing sodium hypochlorite (NaOCl) and Chlorhexidine (CHX), and relative molecular weight of the components.

Methods—Using commercially available chlorhexidine gluconate (CHXg), a 2% solution was formed and mixed in a 1:1 ratio with commercially available NaOCl producing a brown precipitate. The precipitate as well as a mixture of precipitate and pure chlorhexidine diacetate (CHXa) was then analyzed using 1D and 2D NMR spectroscopy.

Results—The 1D and 2D NMR spectra were fully assigned, in terms of chemical shifts of all proton …

The Nature, Origin And Preservation Of Amide Organic Nitrogen In Organic Matter, Georgina Anne Mckee

Chemistry & Biochemistry Theses & Dissertations

Past studies have found much of nonliving sedimentary/aqueous nitrogen-containing organic matter (NCOM) is composed of amides, assumed to be peptides/proteins. Their lability calls into question their survival, and several hypotheses have been suggested to explain this. Using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and nuclear magnetic resonance (NMR) spectroscopy I investigated the molecular amide composition in sedimentary/aqueous systems while reassessing their preservation and formation routes.

Development of a suitable methodology is essential for successful NCOM study due to electrospray ionisation source requirements: sediment samples need to be rendered into solution. Based on NMR and FT-ICR-MS analysis, I determined …

Effect Of Freshman Chemistry On Student Performance In Sophomore Engineering Courses, Michael A. Collura, Shannon Ciston, Nancy Ortins Savage

Chemistry and Chemical Engineering Faculty Publications

The role of first year chemistry courses in engineering programs varies somewhat across programs and disciplines. Clearly most engineering majors will encounter chemistry topics of a general nature in some of their upper-level course work. The purpose of requiring chemistry in the first year, however, goes well beyond learning chemical concepts. As a quantitative science, chemistry requires the use of math, principally algebra, on a regular basis in solving various problems. Students should gain an appreciation of the importance of units in solving problems should come to understand the difference between implicit and explicit properties and should develop other quantitative …

Vibrational Spectroscopy Of N-Methyliminodiacetic Acid (Mida)-Protected Boronate Ester: Examination Of The B-N Dative Bond, Dana N. Reinemann, Ashley M. Wright, Jonathan D. Wolfe, Gregory S. Tschumper, Nathan I. Hammer

Chemistry Faculty Research & Creative Works

N-Methyliminodiacetic acid (MIDA)-protected boronate esters are a new class of reagents that offer great promise in iterative Suzuki-Miyaura cross-coupling reactions. Compared to earlier reagents, MIDA esters are easily handled and are benchtop stable under air indefinitely. The success of this new species is tied to its unique molecular architecture. Compared to the simpler B-N containing molecules ammonia borane and trimethylamine borane, MIDA esters are much larger, and the sp3 hybridized boron atom is secured by two five membered rings, making this molecular class stable for spectroscopic study. Here, we present infrared, Raman, and surface enhanced Raman (SERS) spectra of methylboronic …

Investigation Of The Effect Of Xanthophyll Composition On Energy Transfer And Quenching In Light-Harvesting Complexes From The Diatom, Phaeodactylum Tricornutum, Jose L. Robinson Duggon

Master's Theses

No abstract provided.

Development Of Two-Dimensional Gel Electrophoresis Procedures For Analysis Of Cupriavidus Necator H16 Subcellular Proteomes, Smita Joshi

Morehead State Theses and Dissertations

A thesis presented to the faculty of the College of Science and Technology at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science by Smita Joshi on June 17, 2011.

Development Of New Strategies For Expeditious Oligosaccharide Synthesis, Sophon Kaeothip

Dissertations

The important role that carbohydrates play in biology and medicine has been the major incentive for devising new methods for chemical and enzymatic glycosylation. The chemical approach to oligosaccharides involves multiple synthetic steps and the development of new strategies that allow for streamlining the synthesis of these complex biomolecules is a significant area of research. The aim of this doctoral dissertation is to develop new reagents and efficient methodologies for oligosaccharide synthesis. It was found that siver(I) tetrafluoroborate can be used as a powerful activator of various glycosyl donors for oligosaccharide synthesis. This study evolved into the development of a …