Chemistry Commons^™

On-Metal Synthesis Of Some Aryl Substituted Rhenium Η5 Cyclopenta[C] Pyridazyl Complexes, Phenahas Gandu Sriramulu

Masters Theses & Specialist Projects

Heterocyclic organic and organometallic compounds (e.g. polypyrrole) and their derivatives have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to non-aromatic analogs (e.g. polyacetylene). We are interested in synthesizing organometallic pyridazines and rhenium pyridazyl complexes for polymer research. SeveraI5,6-fused ring pyridazines (1,2-CsH3(CRNH)(CRN) have been synthesized and characterized. Additionally, pyridazyl complexes of rhenium were synthesized in three steps beginning from fulvenes 1,2-CsH3(COHR)(COR). On-Metal synthesis and characterization of (Re(CO)3 {1,2- CSH3(CRN)(CRN)}] (R=C6RtOMe, C6RtCI, C4H30) and some off-metal pyridazines are reported here. Our research is focused on synthesis of a variety of 5,6- fused …

Photoreactive Crystalline Quasiracemates, Rebecca C. Grove, Steven H. Malehorn, Meghan E. Breen, Kraig A. Wheeler

Faculty Research and Creative Activity

Rationally designed racemic and quasiracemic sulfonamidecinnamic acids assemble to give hydrogen-bonded dimers with coplanar alignment of neighboring olefins. The quasiracemate phase contains near inversion-related motifs with chemically distinct components forming supramolecular heterodimers that undergo asymmetric photodimerization.

Molecular Orbitals And Organic Chemical Reactions (Book Review), Jeffrey H. Glans

Chemistry & Physics Faculty Publications

Book review by Jeffrey Glans.

Fleming, Ian. Molecular Orbitals and Organic Chemical Reactions. Wiley-Blackwell, 2010, c2009.

ISBN: 9780470746608; 9780470746592 (pbk.)

Photomediated Synthesis Of Silver Triangular Bipyramids And Prisms: The Effect Of Ph And Bspp, Jian Zhang, Mark R. Langille, Chad A. Mirkin

Department of Chemistry: Faculty Publications

The photomediated synthesis of silver right triangular bipyramids and prisms has been studied, and we have determined that pH and [BSPP]/[Ag⁺] ratio (bis(p-sulfonatophenyl)phenylphosphine, BSPP) finely control the reaction rate and, consequently, the crystal growth pathway and morphology of final products. A fast reaction rate, realized at a high pH such as 10 or 11 and a [BSPP]/[Ag⁺] ratio close to 1.0, is necessary to synthesize (100)-faceted right triangular bipyramids in high yield by preferential deposition on (111) facets of planar-twinned seeds. A slower reaction rate, which occurs at lower pH or higher [BSPP]/[Ag^{+ …}

Synthesis, Kinetic And Photocatalytic Studies Of Porphyrin-Ruthenium-Oxo Complexes, Yan Huang

Masters Theses & Specialist Projects

Macrocyclic ligand-complexed transition metal-oxo intermediates are the active oxidizing species in a variety of important biological and catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in Nature, namely the cytochrome P450 enzymes. Ruthenium porphyrin complexes have been the center of the research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes. This study focuses on kinetic and photocatalytic studies of oxidation reactions with wellcharacterized high-valent ruthenium-oxo porphyrin complexes.
The trans-dioxoruthenium(VI) porphyrins have been among the best characterized metal-oxo intermediates and their involvement as …

High Pressure Liquid Chromatography Studies Of The Reaction Of Platinum Complexes With Peptides, Khaja Muneeruddin

Masters Theses & Specialist Projects

Platinum complexes (cisplatin, carboplatin and oxaliplatin) are effective anticancer agents. However the major drawbacks of platinum chemotherapy are toxic side effects and resistance. The affinity of platinum complexes to sulfur donor ligands of side chains of methionine and cysteine amino acids was assumed to be responsible for toxicity and resistance. Recently, it was found that the reaction of platinum complex with proteins containing sulfur donor ligands could actually favor its anticancer activity. Copper transporter 1 (Ctr 1), a protein involved in the transport of copper into the cell, also helps in the influx of cisplatin by binding to N-terminal domain …

Exploring Zirconia As A Column Packing Material, Tushar Ghugare

Masters Theses & Specialist Projects

Zirconia is one of the most promising column packing materials for High Performance Liquid Chromatography (HPLC). The perfect HPLC support material should be energetically homogenous, have a high surface area on which different chemical species can reversibly attach and be physically and chemically stable over a wide range of pH, temperature and solvent conditions. Most existing supports do not have all of these properties. This project is also focused on a proteomics study. Zirconia, hafnium oxide and titanium oxide which are some of the more promising materials currently available, can be used for the separation and analysis of phosphorylated proteins. …

Plant Sterol And Stanol Substrate Specificity Of Pancreatic Cholesterol Esterase, Andrew W. Brown, Jiliang Hang, Patrick H. Dussault, Timothy P. Carr

Patrick Dussault Publications

Consumption of plant sterols or stanols (collectively referred to as phytosterols) and their esters results in decreased lowdensity lipoprotein cholesterol, which is associated with decreased atherosclerotic risk. The mechanisms by which phytosterols impart their effects, however, are incompletely characterized. The objective of the present study is to determine if pancreatic cholesterol esterase (PCE; EC 3.1.1.13), the enzyme primarily responsible for cholesterol ester hydrolysis in the digestive tract, is capable of hydrolyzing various phytosterol esters and to compare the rates of sterol ester hydrolysis in vitro. We found that PCE hydrolyzes palmitate, oleate and stearate esters of cholesterol, stigmasterol, stigmastanol and …

4-Bromo-N 2,N 2,N 6,N 6-Tetra­Ethyl­Pyridine-2,6-Dicarboxamide, Daniel T. De Lill, Ana De Bettencourt-Dias

Chemistry and Physics Faculty Articles

The title compound, C₁₅H₂₂BrN₃O₂, consists of a pyridine ring with a bromine atom in the para position and two diethyl­amide groups in the ortho positions of the ring. Despite the positions of the three substituents on the pyridine ring, the mol­ecule does not exhibit either local or crystallographic twofold symmetry as the two diethyl­amido units exhibit significantly different N_py—C—C—N_am torsion angles of 46.3 (4) and 62.7 (4)° (py is pyridine and am is amine). Inter­molecular C—H⋯O inter­actions support the packing.

Isu Chem-Letter, Fall 2010, Illinois State University, Department Of Chemistry

Chem Letter

Newsletter of the Illinois State University Department of Chemistry

Design, Synthesis, And Polymerization Of Novel Heterocyclic Monomers As Precursors For Functional Polyester, Poly(Ester Amide)S And Polyamides, Eylem Tarkin-Tas

Dissertations

The research presented in this dissertation involves the synthesis and polymerization of heterocyclic monomers which pave the way to biodegradable polyester nanocomposites, functional polyesters or poly(ester amide)s, functional polyamides and supramolecular polymers. The key monomers are ε-caprolactone, γ-acetamido-ε- caprolactone, γ-ethylene ketal-ε-caprolactam and α-amino-ε-caprolactam.

Poly(ε-caprolactone) organo-modified montmorillonite nanocomposites were prepared by in-situ polymerization using dibutyltin dimethoxide as initiator/catalyst. The montmorillonite was first modified with 1-decyl-2-methyl-3-(11-hydroxyundecyl)- imidazolium cation. The hydroxyl functionality was used for not only initiating polymer chains from the surface of the clay platelets but also for grafting polymer chains to the surface by acting as a reversible chain transfer …

Study On Energy Absorption Behaviors Of Hydrophobic Mesoporous Materials, Zhongyuan Sun

Theses and Dissertations - UTB/UTPA

Nanoporous energy absorption system has been developed tremendously as an advanced energy storage system in recent years. This research is to optimize the mesoporous energy absorption matrixes via surface treatment to find out the optimum conditions for higher energy conversion efficiency. Five mesoporous silica matrixes with pore size in a range of 3 to 31.6 nm were investigated. Six alkylchlorosilanes were used as the modification reagents. The results showed that the energy absorption density via pressure-induced infiltration is as high as 8.0 J/g which is 100 times larger than that of conventional energy absorption materials. The controllability of the energy …

Aryl Boronic Acid Inhibition Of Synthetic Melanin Polymerization, Jason M. Belitsky

Faculty & Staff Scholarship

Inhibitors of melanin formation are sought after for a range of applications. Boronophenylalanine is known to inhibit melanogenesis via boronic acid-catechol interactions. A spectroscopic assay was developed to study the polymerization of L-dopa to synthetic melanin in the presence of para-substituted aryl boronic acids. The best inhibition was observed for aryl boronic acids with electron-withdrawing substituents. The IC50 values exhibit a correlation with the Hammett sigma(p) parameter (rho = 0.97, r(2) = 0.92).

Synthesis And Characterization Of Monolayer Protected Gold Nanoparticles And A Gold-Titanium Dioxide Nanocomposite Intended For Photocatalytic Degradation Of Environmental Pollutants, Piyadarsha Amaratunga

Dissertations

Semiconductor and metal clusters in the nanometer size regime display interesting optical, electronic and chemical properties that are size dependant. Highly monodisperse gold nanoparticles of different sizes have been synthesized and isolated by newly developed methodologies, using tiopronin as the capping ligand. Titanium dioxide nanoparticles (Ti0₂) have been used as the photocatalytic center and gold nanoparticles have been attached on Ti0₂ to make a nanocomposite. According to the findings, gold nanoparticles play a vital role in enhancing the photocatalytic activity of Ti0₂, by facilitating the charge separation. Further, the photocatalytic activity also can be tuned …

Isotropic And Anisotropic Metallic And Bimetallic Nanoparticles And Their Potential Applications In Biology, Minghong Liu

Dissertations

The development of synthetic procedures that produce nanoscale materials with controlled morphology is a significant area of investigation in nanotechnology. We have developed new synthetic procedures for fabrication of isotropic and/or anisotropic nanomaterials composed of palladium, ruthenium, nickel and alloys of palladium-ruthenium. The nanomaterials were fully characterized and were found to display unique size dependent properties. The electrochemical properties of isotropic palladium, ruthenium and palladium-ruthenium nanoparticles were investigated and the results showed that the particles were capable of charge storage and charge transfer on demand. Anisotropic palladium, ruthenium and palladium ruthenium nanoparticles were also fabricated and fully characterized. The nanoparticles …

Gold Nanoparticle - Modified Zinc Oxide Nanoparticles As Novel Photocatalytic Materials, Nayane Udawatte

Dissertations

The current study entails the construction of a novel nano-composite catalyst based on ZnO and Au nanoparticles and demonstrates its distinctive photocatalytic characteristics. Monodisperse gold nanoparticles (GNPs) passivated with monolayers of tiopronin or glutathione were synthesized via facile methods, and they were assembled on ZnO nanoparticles to form the nanocatalyst.

Steady state and time resolved photoluminescent studies on the nanocomposite revealed interesting charge transfer characteristics within the nanocomposite. Enhanced photooxidation of rhodamine 6G was observed for the nano-composite over bare ZnO, and modulation of photoactivity with the extent of GNP loading was illustrated. Photoreduction of thionine over the nanocomposite was …

Noninvasive, In-Vivo, Tissue Modulated Near Infrared Spectroscopy Of Fingertips: Resonance Raman Spectrum Of Human Hemoglobin, Bin Deng, Jerry Goodisman, George Shaheen, Rebecca J. Bussjager, Joseph Chaiken

Chemistry - All Scholarship

Tissue modulation refers to using external stimuli such as mechanical pressure and temperature to produce various spatiotemporal distributions of blood and conceivably other fluids in tissues. Having the capacity to execute tissue modulation¹ allows forms of difference spectroscopy to be used to isolate spectroscopic signals from specific components of the tissues noninvasively and in vivo. In the case of human fingertips we can think of the tissues present in the probed volume as being static tissue, plasma and red blood cells (RBCs). Static tissues deform under mechanical pressure based tissue modulation and the only possible fluid motions2 involve plasma …

Hydrogen Storage And Carbon Dioxide Capture In An Iron-Based Sodalite-Type Metal-Organic Framework (Fe-Btt) Discovered Via High-Throughput Methods, Kenji Sumida, Satoshi Horike, Steven S. Kaye, Zoey R. Herm, Wendy L. Queen, Craig M. Brown, Fernande Grandjean, Gary J. Long, Anne M. Dailly, Jeffrey R. Long

Chemistry Faculty Research & Creative Works

Using high-throughput instrumentation to screen conditions, the reaction between FeCl₂ and H₃BTT·2HCl (BTT^3- = 1,3,5-benzenetristetrazolate) in a mixture of DMF and DMSO was found to afford Fe₃[(Fe₄Cl)₃(BTT)₈] ₂·22DMF·32DMSO·11H₂O. This compound adopts a porous three-dimensional framework structure consisting of square [Fe₄Cl]⁷⁺ units linked via triangular BTT^3- bridging ligands to give an anionic 3,8-net. Mössbauer spectroscopy carried out on a DMF-solvated version of the material indicated the framework to contain high-spin Fe²⁺ with a distribution of local environments and confirmed the presence …

Structure-Property Correlation In Cyclopolymerization Of New Acrylate-Based Functional Monomers, Huseyin Tas

Dissertations

New ether dimer; (ED-Od) and (ED-Eh) and diester; (ODE) and (EHDE) derivatives of α-(hydroxymethyl)acrylate, each having two octadecyl and 2-ethylhexyl side chains respectively, and an amine-linked di(2-ethylhexyl)acrylate (AL-Eh), having three 2-ethylhexyl side chains, were synthesized and (co)polymerized to evaluate the effects of differences in the structures of the monomers on final (co)polymer properties, particularly glass transition temperature, Tg. The free radical polymerizations of these monomers yielded high molecular weight polymers. Cyclopolymer formation of ED-Od, ED-Eh and AL-Eh was confirmed by 13C NMR analysis and the cyclization efficiencies were found to be very high (~100%). Copolymers of ED-Od, ODE, ED-Eh, EHDE, …

High Temperature Rare Earth Compounds: Synthesis, Characterization And Applications In Device Fabrication, Joseph R. Brewer

Department of Chemistry: Dissertations, Theses, and Student Research

As the area of nanotechnology continues to grow, the development of new nanomaterials with interesting physical and electronic properties and improved characterization techniques are several areas of research that will be remain vital for continued improvement of devices and the understanding in nanoscale phenomenon. In this dissertation, the chemical vapor deposition synthesis of rare earth (RE) compounds is described in detail. In general, the procedure involves the vaporization of a REClx (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho) in the presence of hydride phase precursors such as decaborane and ammonia at high temperatures and low …

Controlling Reductive Elimination From Novel I(Iii) Salts Using A Secure Method, Joseph W. Graskemper

Department of Chemistry: Dissertations, Theses, and Student Research

Positron Emission Tomography (PET) is a valuable clinical, research, and diagnostic technique for human and animal organ imaging. The current market for PET in the United States is $500 million per year and is projected to be $5.4 billion per year globally by 2015. To synthesize labeled radiotracers, we are most interested in using ¹⁸F as the isotope of choice because it is a nearly ideal positron emitting radionuclide.

Electron-rich aromatic substrates can be particularly difficult to fluorinate. We show that reductive elimination of I(III) diaryliodonium salts provide increased fluorination of electron-rich aromatic substrates. Modest yields of fluorinated product …

Theoretical And Experimental Studies In Nuclear Magnetic Resonance, Adrienne M. Roehrich

Department of Chemistry: Dissertations, Theses, and Student Research

Nuclear magnetic resonance (NMR) is a tool used to probe the physical and chemical environments of specific atoms in molecules. This research explored small molecule analogues to biological materials to determine NMR parameters using ab initio computations, comparing the results with solid-state NMR measurements. Models, such as dimethyl phosphate (DMP) for oligonucleotides or CuCl for the active site of the protein azurin, represented computationally unwieldy macromolecules. ³¹P chemical shielding tensors were calculated for DMP as a function of torsion angles, as well as for the phosphate salts, ammonium dihydrogen phosphate (ADHP), diammonium hydrogen phosphate, and magnesium dihydrogen phosphate. The …

Spectroelectrochemical Studies Of Metalloporphyrins In Room Temperature Ionic Liquid, Yong Soo Hoo

Master's Theses (2009 -)

The oxidation/reduction reactions of porphyrins and metalloporphyrins play an important role in medicinal, industrial and biochemical reactions. Metalloporphyrins are particularly useful as potential catalysts for a variety of processes including catalytic oxidations. The unique properties of metalloporphyrins make them good candidates as electrocatalysts for fuel cells. Metalloporphyrins also play some important roles in biological functions.

By incorporating spectroscopic experiments such as UV-visible or infra-red spectroscopy along with electrochemical experiments such as cyclic voltammetry, one is able to determine the structural changes of the molecule when oxidation or reduction reaction is carried out.

Synthesis And Reactions Of A Tungsten Dioxo Complex, Deborah Bryant

Master's Theses (2009 -)

Metal dioxo complexes are largely known for their ability to epoxidize olefins. The importance of these reactions is reflected in the patents for the ARCO and Halcon processes from the late 1960's. It is very difficult to find literature that shows other indications for metal dioxo complexes.

Catalytic olefin dimerization has become significant in the realm of green chemistry for "atom economical" reactions. Many transition metals have been examined as catalysts for olefin dimerization, but the largest volume of work has been performed using group 8 transition metals, particularly nickel, palladium and platinum. This is especially true for the specific …

Extraction Of Pesticides From Contaminated Soil Via Cyclodextrin Complexation, Bertil Nshime, Andrew Lantz

Student Summer Scholars Manuscripts

Cyclodextrins (CDs) were successfully used to extract numerous commonly used pesticides from contaminated soil via cyclodextrin complexation, a more environmentally friendly method compared to surfactants and organic solvents. A combination of five CDs (α-CD, β-CD, γ-CD, hydroxypropyl-β-CD (HP-β-CD), and methylated-β-CD (M-β-CD)) and eight pesticides (2,4-Dichlorophenoxyacetic acid (2,4-D) alachlor, acetochlor, diazinon, dicamba, dimethanamid, metalochlor and propanil) were examined in this study. It was found that a linear relationship exists between the concentrations of the M-β-CD and alachlor, which generally indicates that the amount of pesticide extracted depends on the concentration of the cyclodextrin present. With some pesticide-cyclodextrin combination, it was found …

Vibrational Spectroscopic Study Of The 1,3,5,7-Cyclooctatetraene At High Static Pressures, Edward Romano

UNLV Theses, Dissertations, Professional Papers, and Capstones

1,3,5,7-cyclooctatetraene (COT) is a single-ringed hydrocarbon that has not been studied extensively under high static pressures. It was the intent of this study to reveal its high-pressure behavior through its vibrational spectra. To this end, its infrared spectra as a function of pressure were collected at the National Synchrotron Light Source (NSLS) U2A beamline, as well as its Raman spectra over pressure using a micro-Raman spectrometer.

The spectra show the typical stiffening of force constants with increasing pressure for most peaks, particularly those which would theoretically exhibit a mode-softening behavior under hypotheses of molecular planarization and aromatization. Additionally, the data …

Synthesis And Characterization Of Photoactive Amorphous Molecular And Polymeric Pyridinium Materials, Alexi Kamenov Nedeltchev

UNLV Theses, Dissertations, Professional Papers, and Capstones

Pyridinium materials both molecular and polymeric are interesting class of multifunctional electrolytes and polyelectrolytes, which exhibit liquid-crystalline and light-emitting properties. Moreover, their properties could be easily tuned simply by modifying the chemical structures of counterions.

In this dissertation, we described the preparation and analysis of new ionic molecular materials based on bis(pyridinium salt)s and a new class of poly(pyridinium salt)s with various heterocyclic moieties in their backbones with various organic counterions. They were prepared by either ring-transmutation reaction or by metathesis reaction. Their chemical structures were confirmed by FTIR, 1H and 13C NMR spectroscopy and elemental analysis. They had excellent …

52nd Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 52nd annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-endorsed by the Colorado Section of the American Chemical Society and the Society for Applied Spectroscopy. Held in Snowmass, Colorado, August 1-5, 2010.

Biosynthesis Of Salinosporamides From Α,Β-Unsaturated Fatty Acids: Implications For Extending Polyketide Synthase Diversity, Yuan Liu, Christopher Hazzard, Alessandra S. Eustáquio, Kevin A. Reynolds, Bradley S. Moore

Chemistry Faculty Publications and Presentations

A new series of coenzyme A-tethered polyketide synthase extender units were discovered in relation to the biosynthesis of the salinosporamide family of anticancer agents from the marine bacterium Salinispora tropica. In vivo and in vitro experiments revealed that the crotonyl-CoA reductase/carboxylase SalG has broad substrate tolerance toward 2-alkenyl-CoAs that give rise to the salinosporamide C-2 substitution pattern.

Chemical Modification And Biological Activity Exploration Of The Natural Product-Gossypol, Juanjuan Yin

All Dissertations

Gossypol is a naturally occurring, highly colored yellow pigment indigenous to the small intercellular pigment glands of the cotton plant genus Gossypium, which is proposed to be part of plant's defense system. Gossypol is characterized by wide contraceptive, antiviral, anticancer and antifungal properties. However, the relatively high toxicity of gossypol precludes its application in medical therapy. For this reason the syntheses and tests of gossypol derivatives, have been tried to enable their application as drugs. In our study, gossypol based methylation, glycosylation and nanoconjugate reactions were explored. The gossypol derivatives were all fully characterized by NMR, MS, FT-IR, UV spectrometry, …