Chemistry Commons^™

Detection Of Psilocybin Mushroom Analogs In Chocolate: Incorporating Current Events Into The Undergraduate Teaching Laboratory, Brandon Huskins, Christopher Dockery

Faculty Articles

In this experiment, tryptamine is used as a psilocin analog and is dispersed onto a Fisher brand cellulose laboratory sponge to simulate dehydrated mushrooms. The resulting “mushroom” material is ground, molded into chocolate, and presented to student groups for real-world and applied analyses. Students isolate the tryptamine from the chocolate using their knowledge of drug chemistry, solubility, pH, extractions, etc. Qualitative analysis is conducted by comparison to standards (Thin Layer Chromatography or Gas Chromatography) and quantitative analysis is conducted by Gas Chromatography using the method of internal standards.

Highly Nitrated Cyclopropanes As New High Energy Materials: Dft Calculations On The Properties Of C3H6−N(No2)N (N=3–6), Aloysus K. Lawong, David W. Ball

Chemistry Faculty Publications

As part of a continuing study of new potential high energy materials, here we present results of calculations on cyclopropane molecules with three or more nitro groups. DFT calculations suggest that all molecules can exist as minimum-energy stationary states. Energy calculations indicate that some nitrocyclopropanes have a specific enthalpy of decomposition in excess of 8kJg⁻¹, suggesting that they be explored as new potential high energy materials.

Indirect Gravimetric Determination Of Waters Of Hydration, Marina C. Koether

Faculty Articles

An alternate gravimetric experiment is described that can be employed in the general chemistry or the quantitative analysis laboratory course. The procedure takes less time than conventional methods and introduces students to waters of hydration and indirect determinations.

Double Superhelix Model Of High Density Lipoprotein, Zhiping Wu, Valentin Gogonea, Xavier Lee, Mathew A. Wagner

Chemistry Faculty Publications

High density lipoprotein (HDL), the carrier of so-called “good” cholesterol, serves as the major athero-protective lipoprotein and has emerged as a key therapeutic target for cardiovascular disease. We applied small angle neutron scattering (SANS) with contrast variation and selective isotopic deuteration to the study of nascent HDL to obtain the low resolution structure in solution of the overall time-averaged conformation of apolipoprotein AI (apoA-I) versus the lipid (acyl chain) core of the particle. Remarkably, apoA-I is observed to possess an open helical shape that wraps around a central ellipsoidal lipid phase. Using the low resolution SANS shapes of the protein …

Selective Complexation And Reactivity Of Metallic Nitride And Oxometallic Fullerenes With Lewis Acids And Use As An Effective Purification Method, Steven Stevenson, Mary A. Mackey, Jane E. Pickens, Melissa A. Stuart, Bridget S. Confait, J. Paige Phillips

Faculty Publications

Metallic nitride fullerenes (MNFs) and oxometallic fullerenes (OMFs) react quickly with an array of Lewis acids. Empty-cage fullerenes are largely unreactive under conditions used in this study. The reactivity order is Sc₄O₂@I_h-C₈₀ > Sc₃N@C₇₈ > Sc₃N@C₆₈ > Sc₃N@D_5h-C₈₀ > Sc₃N@I_h-C₈₀. Manipulations of Lewis acids, molar ratios, and kinetic differences within the family of OMF and MNF metallofullerenes are demonstrated in a selective precipitation scheme, which can be used either alone for purifying Sc₃N@I_{h …}

Solid State And Solution Dynamics Of Pyridine Based Tetraaza- Macrocyclic Lanthanide Chelates Possessing Phosphonate Ligating Functionality (Ln-Pctmb): Effect On Relaxometry And Optical Properties, Garry Kiefer, Mark Woods

Chemistry Faculty Publications and Presentations

The macrocyclic ligand 3,6,9-tris(methylenebutyl phosphonic acid)-3,6,9−15-tetraazabicyclo [9.3.1]pentadeca-1(15),11,13-triene (PCTMB) was synthesized and complexes of Eu³⁺, Tb³⁺, and Gd³⁺ studied by X-ray crystallography, luminescence, and relaxometry. In the crystal these complexes are dimeric and possess 8-coordinate Ln³⁺ centers that are linked by bridging phosphonates. The rigidity introduced by the pyridyl nucleus forces the EuPCTMB and TbPCTMB to adopt a twisted snub disphenoid (TSD) coordination geometry. Examination of the ⁵D₀ → ⁷F₀ luminescent transition of EuPCTMB in the solid state confirmed the existence of a single distinct Eu³⁺ coordination environment, whereas two …

Determination Of The Activation Parameters Of Reaction Between [Fe(Cn6]-4 And K[Co(Hedta)No2]., Sammy Eni Eni

Electronic Theses and Dissertations

The kinetics of the oxidation of [Fe(CN)₆]^-4 by K[Co(HEDTA)NO₂] was studied in order to get the mechanism and the activation parameters of the reaction. Using a freshly-made Na₃PO₄ solution as the reaction medium with a pH of 6.00 the ionic strength was maintained at 0.10 M and the buffer molarity was 0.001 M.

The rate constant (k_obs) of the reaction between [Fe(CN)₆]^-4 and K[Co(HEDTA)NO₂] was determined at temperatures of 25.0°C, 27.5°C, 30.0°C, 35.0°, and 40.0°C. We explored this reaction by monitoring the evolution of ferricyanide, …

Modulation Of Restriction Enzyme Pvuii Activity By Metal Ion Cofactors, Charulata Bhaskaran Prasannan

Dissertations

Metal ions like Ca2+, Mn2+, Tb3+, Eu3+ etc., can bind at the active site and have varying effects on the enzymatic activity. In a crystal structure with DNA, two Ca2+ ions were bound to the active site of each PvuII monomer, and the metals share the ligands. Ca2+ ions promote DNA binding and not cleavage in many nucleases. We explored the role of Mg2+ and Ca2+ binding at the metal binding sites of PvuII to elucidate the role of each metal site. We monitored the cleavage kinetics of PvuII in presence of mixed metals. The cleavage kinetics data for Ca2+ …

Replacing Hydrogen Bonds With Coordinate Covalent Bonds In Coordination Networks, Colin Stewart Rodger

Dissertations

The overall theme of the dissertation is that metal ions such as silver(I) can replace H+ in hydrogen bonded organic frameworks. Because organic solids have been extensively studied, we can insert metal ions into the supramolecular assemblies, thus creating predictable coordination solids of varying dimensions. One example of an organic solid tested involves the organic compounds terephthalic and isophthalic acids. These dicarboxylic acids have previously been shown to self-assemble into tape-like structures via hydrogen bonding, with neighboring dicarboxylic acids located at angles of 180° and 120° respectively. By substituting the hydrogen bonds with coordination metal-ligand bonds similar assemblies are formed. …

Progress Toward The Total Synthesis Of Lyconadin A, Yu Zhang

Theses and Dissertations

Lyconadin A is a pentacyclic Lycopodium alkaloid isolated from the club moss Lycopodium complanatum with antitumor properties. We have developed a novel 7-exo/6-exo acyl radical cascade cyclization as a method of making the bicyclo[5.4.0]undecane ring system of lyconadin A. The model products are trans-fused ring systems, while a cis-fused ring system is needed in lyconadin A. We have discovered a method to convert the trans-fused model cascade cyclization product into the desired cis isomer. Based on Donohoe's pyridone synthesis, we developed a method for the construction of 5-alkyl and 3,5-dialkyl-6-carbomethoxy-2-pyridones, the former of which …

Rfx2 Is A Candidate Downstream Amplifier Of A-Myb Regulation In Mouse Spermatogenesis, Gary C. Horvath, Malathi K. Kistler, Wilson Stephen Kistler

Faculty Publications

Background: Mammalian spermatogenesis involves formation of haploid cells from the male germline and then a complex morphological transformation to generate motile sperm. Focusing on meiotic prophase, some tissue-specific transcription factors are known (A-MYB) or suspected (RFX2) to play important roles in modulating gene expression in pachytene spermatocytes. The current work was initiated to identify both downstream and upstream regulatory connections for Rfx2.

Results: Searches of pachytene up-regulated genes identified high affinity RFX binding sites (X boxes) in promoter regions of several new genes: Adam5, Pdcl2, and Spag6. We confirmed a strong promoter-region X-box for Alf, a germ cell-specific variant of …

Multidimensional Methods: Applications In Drug-Enzyme Intrinsic Clearance Determination And Comprehensive Two-Dimensional Liquid Chromatography Peak Volume Determination, Dennis Thekkudan

Theses and Dissertations

The goal of the first project was to evaluate strategies for determining the in vitro intrinsic clearance (CLint) of dextrorphan (DR) as metabolized by the UGT2B7 enzyme to obtain dextrorphan glucuronide (DR-G). A direct injection liquid chromatography-mass spectrometry (LC-MS) method was used to monitor products using the pseudo-first-order (PFO) model. Standard enzymatic incubations were also quantified using LC-MS. These data were fit utilizing both PFO and Michaelis-Menten (MM) models to determine estimates of kinetic parameters. The CLint was determined to be 0.28 (± 0.08) µL/min/mg protein for a baculovirus insect cell-expressed UGT2B7 enzyme. This is the first confirmation that dextrorphan …

Carbamothioates In The Synthesis Of Diaroyl Sulfides; Selectivity In The Addition Of Diaroyl Sulfides To Acetylenic And Ethylenic Π−Deficient Compounds, Ashraf A. Aly, Alan B. Brown, Alaa A. Hasaan, Kamal M. El-Shaieb, Tarek M. Bedair

Chemistry and Chemical Engineering Faculty Publications

Diaroyl sulfides were prepared in one-pot reaction from ethylenediamine and carbon disulfide, via reaction of in situ generated ethylene-bis- carbamodithioates with aroyl chlorides. The reaction of diaroyl sulfides with acetylenic and ethylenic π-deficient compounds such as dimethyl acetylenedicarboxylate, ethyl propiolate, (E)-1,4-diphenylbut-2-ene-1,4-dione and 1,4-diphenylbut-2-yne-1,4-dione afforded the corresponding thionylated products. NMR spectroscopic data of the isolated products were discussed. © ARKAT USA, Inc.

Isolation And X-Ray Structural Characterization Of A Dicationic Homotrimer Of 2,3,6,7-Tetramethoxy-9,10-Dimethylanthracene Cation Radical, Matthew J. Modjewski, Ruchi Shukla, Sergey V. Lindeman, Rajendra Rathore

Chemistry Faculty Research and Publications

Electrochemical oxidation of 2,3,6,7-tetramethoxy-9,10-dimethylanthracene (1) showed that it undergoes a highly reversible electrochemical oxidation (E_ox = 0.81 V vs SCE) and forms a modestly stable cation-radical salt in solution. X-ray crystallography established that 1⁺SbCl₆^- crystallizes as a (centrosymmetric) dicationic homotrimer via a close cofacial association of a pair of cationic and one neutral molecule of 1 with an interplanar separation of ∼3.2 Å. The structure of the dicationic homotrimer was also reproduced by DFT calculations. Furthermore, the structure of a dicationic spiro adduct, formed by a slow decomposition of a solution of 1^{+ …}

2,5-Dichlorothiophene 1,1-Dioxide, Jonathan B. Briggs, Wenling Jia, Mikael D. Jazdzyk, Glen P. Miller

Chemistry

The complete molecule of the title compound, C(4)H(2)Cl(2)O(2)S, is generated by crystallographic twofold symmetry, with the S atom lying on the rotation axis. In the crystal, the molecules are linked by C-H center dot center dot center dot O hydrogen bonds..

Synthesis And Cytotoxic Analysis Of Some Disodium 3Β,6Β-Dihydroxysterol Disulfates, Jianguo Cui, Hui Wang, Yi Xin, Aimin Zhou

Chemistry Faculty Publications

Disodium 3β,6β-dihydroxy-5α-cholestane disulfate (1) was synthesized in 4 steps with a high overall yield from cholesterol. First, cholesterol (4a) was converted to cholest-4-en-3,6-dione (5a) via oxidation with pyridinium chlorochromate (PCC) and then 5a was reduced by NaBH4 in the presence of NiCl2 to produce cholest-3β,6β-diol (6a). The reaction of 6a with the triethylamine-sulfur trioxide complex generated diammonium 3β,6β-dihydroxy-5α-cholestane disulfate (7a) and the treatment of 7a by cation exchange resin 732 (sodium form)(Na+) yielded the target steroid 1. Disodium 24-ethyl-3β,6β-dihydroxycholest-22-ene disulfate (2) and disodium 24-ethyl-3β,6β-dihydroxycholestane disulfate (3) were synthesized using a similar method. The cytotoxicity of these compounds against Sk-Hep-1 (human …

Investigation Of Novel Thiol "Click" Reactions, Justin William Chan

Dissertations

The thio-Michael addition reaction is traditionally considered a base catalyzed reaction which involves high catalyst concentrations and long reaction times. This reaction utilizes potent, simple nucleophiles to catalyze the reaction, decreases the catalyst concentration and greatly increases the reaction times. The free radical mediated thiol-ene click reaction uses light or heat and an initiator to catalyze the rapid and quantitative addition of thiols to most electron rich enes without the formation of side products and in the absence of solvent. Recently, the thiol-ene click reaction has been exploited for these reasons in materials science and organic synthesis. The research herein …

Investigation Of The Relationship Between Polymer Structures And Thermal, Mechanical, Viscoelastic Properties, Ethem Kaya

Dissertations

The research presented in this dissertation involves four distinct areas: physical crosslinking systems, UV curable coatings for enhanced oxygen and carbon dioxide barrier properties, synthesis, and investigation of melting behavior/crystallinity relations of linear polyamides with long alkyl chains, and synthesis and characterization of cyclic diamides as precursors to linear polyamides 6 4.

The physical crosslinking section involves synthesis of monomers and polymers bearing cyclodextrin and adamantane pendent groups, and investigation of non-covalent interactions between these polymers (Chapter II). Two methacrylate monomers bearing cyclodextrin and adamantane were synthesized, and copolymerized with poly(ethylene glycol) methyl ether methacrylate. The specific interaction between copolymers …

Random And Block Copolymers Of Poly(Dodecamethyleneterephthalamide), Theodore Frank Novitsky Jr.

Dissertations

The following dissertation focuses on the synthesis and characterization of poly(dodecamethylene terephthalamide) (PA-12,T) and novel copolymers. Chapter I details the synthesis of PA-12,T homopolymer by melt condensation polymerization. A series of homopolymers with different molecular weights were obtained by adjusting the stoichiometry of the polymerization using 1,12-diaminododecane, terephthalic acid and benzoic acid. End group 13C NMR spectroscopy resonances were obtained by correlating peak intensities with intrinsic viscosity values. From the NMR data, total end group concentrations and molecular weights were determined for each sample. The data exhibited a linear trend when plotting log (IV) versus log (Mn), and previously unknown …

Preparation And Characterization Of Thiol Based Polymeric Materials, Junghwan Shin

Dissertations

The thiol click-type reaction is one of the most efficient chemical processes that can undergo at room temperature in the benign organic solvent providing excellent opportunity in the fabrication of new materials as well as development of new manufacturing processes. Moreover, the versatility of thiol click-type reactions with many different functional groups such as ene, yne, epoxy, isocyanate, and alkyl halide is the important aspect that should be differentiated from the classic azide-alkyne click chemistry. Although, there are tremendous studies on many areas using thiol click-type reactions, the efficiency and utilities for the material applications have been barely explored. Especially, …

Kinetic Studies Of The Sulfoxidation Of Aryl Methyl Sulfides By Trans-Dioxoruthenium(Vi) Porphyrin Complexes, Chris Abebrese

Masters Theses & Specialist Projects

The development of an efficient, catalytically active, biomimetic model for cytochrome P-450 enzymes has been an area of intense research activity. Ruthenium porphyrin complexes have been the center of this research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes, the epoxidation of alkenes and aromatic rings, and the N-oxidation of amines, among others. In this project, the kinetics of two-electron sulfoxidation of para-substituted phenyl methyl sulfides to the corresponding sulfoxides with well-characterized trans-dioxoruthenium(VI) porphyrin complexes were studied by rapid stopped-flow spectroscopy. The substituent effect in sulfides and in dioxoruthenium(VI) complexes were …

Off-Metal Synthesis Of Some Aryl Substituted Rhenium N5-Cyclopenta [C] Pyridazyl Complexes, James Leif Neathery

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). Our current interests focus upon the potential role of pyridazines in next generation electronic devices that utilize organics as the semiconducting material. Pyridazines, 6-membered aromatic rings with two adjacent nitrogens, are promising candidates for a variety of materials and commercial applications. These molecular electronic materials posses several advantages over traditional inorganic semiconducting materials including lower cost of production, higher processibility, and the ability to function on flexible …

Chemistry Of Zirconia And Its Bioanalytical Applications, Oge Anazia

Masters Theses & Specialist Projects

This research studies the chemical nature of zirconia and the complex surface chemistry of zirconia in order to better comprehend its behavior under chromatographic conditions. This research shows how the physical and chemical properties of zirconia depend strongly on the thermal treatment during synthesis. The morphology of the samples was also studied. The absorption capability of Adenosine Triphosphate (ATP) on zirconia was also monitored and spectrally characterized.

The results of this research showed how the properties of zirconia vary with thermal treatment. It was observed that the zirconia prepared at a higher temperature had lower surface area, lower pore size …

Department Of Chemistry News For Alumni And Friends, December 2009, Illinois State University, Department Of Chemistry

Chem Letter

Newsletter of the Illinois State University Department of Chemistry

Stimuli-Responsive Hydrogel Microdomes Integrated With Genetically Engineered Proteins For High-Throughput Screening Of Pharmaceuticals, Sylvia Daunert, Sapna K. Deo, Jason Douglas Ehrick, Tyler William Browning, Leonidas G. Bachas

Chemistry Faculty Patents

A hydrogel microdome that can swell in response to a stimuli or target molecule is formed by polymerizing a mixture comprising a monomer capable of forming a hydrogel with a biopolymer. An array of hydrogel microdomes can be formed on a substrate by microspotting the mixture and polymerizing. The array can be used for high-throughput screening of analytes as well as for use as an actuator and biosensor using the swelling property of the hydrogel.

A Characterization Of Caffeine Imprinted Polypyrrole Electrode, Deepika Mandadi

Masters Theses & Specialist Projects

Nanotechnology holds great potential for improving our lives by creating many new materials and devices in medical sciences, electronics and also in energy production. Molecularly imprinted polymers (MIPs) are highly stable synthetic polymers that possess molecular recognition properties due to cavities created in the polymer matrix that are complementary to an analyte both in shape and in positioning of functional groups. These MIPs have been widely employed for diverse applications (e.g., in chromatographic separation, drug screening, chemosensors, catalysis, immunoassays etc) due to their specificity towards the target molecules and high stability against physicochemical perturbations. Conductive polymers, (CPs) such as polypyrrole, …

Synthesis And Development Of Novel Fullerene-Based Structures For Photovoltaics, Electronic Applications And Mri Contrast Agents, Manuel Chaur

All Dissertations

Metallic nitride endohedral metallofullerenes (EMFs) are one of the most interesting types of metallofullerenes due to their high yields and interesting electronic properties. The synthesis of these compounds allows the encapsulation of different metals inside fullerenes making it possible to combine the properties of the metal with those of the fullerene. Their interesting electrochemical and optical features make them potential candidates for several applications such as molecular electronics, biomedical imaging, non-linear optical devices, and magnetic resonance imaging (MRI) agents. This thesis reports the synthesis of novel metallic nitride EMFs based on Gd, Nd, Pr, Ce and La. These families of …

The Ecology Of The Peaks Of Otter Salamander (Plethodon Hubrichti) In Sympatry With The Eastern Red-Backed Salamander (Plethodon Cinereus), Norman Reichenbach, Andrew Kniowski

Faculty Publications and Presentations

The Peaks of Otter Salamander, Plethodon hubrichti, is found along a 19 km length of the Blue Ridge Mountains, Virginia, USA, often in sympatry with the Eastern Red-backed Salamander, P. cinereus. In a sympatric area of Bedford County, Virginia, we conducted a mark-recapture study on a 10 × 10 m site. Surface densities of salamanders increased as the number of days without precipitation prior to a collection event increased. This suggests vertical movements in response to surface moisture. When salamanders returned to the surface after rain, individuals appeared to “shuffle” between rocks and likely, leaf litter. That is, we were …

Lead Optimization Of Cox-2 Inhibitor Nimesulide Analogs To Overcome Aromatase Inhibitor Resistance In Breast Cancer Cells, Bin Su, Shiuan Chen

Chemistry Faculty Publications

A series of COX-2 selective inhibitor nimesulide derivatives were synthesized. Their anti-cell proliferation activities were evaluated with a long-term estrogen deprived MCF-7aro (LTEDaro) breast cancer cell line, which is the biological model of aromatase inhibitor resistance for hormone-dependent breast cancer. Compared to nimesulide which inhibited LTEDaro cell proliferation with an IC50 at 170.30 μM, several new compounds showed IC50 close to 1.0 μM.

Thermochromic Absorption And Photoluminescence In [Pt(Ppy)(Μ-Ph2pz)]2, Aaron A. Rachford, Felix N. Castellano

Chemistry Faculty Publications

The temperature effects on the spectral properties and photophysics of a new d(8)-d(8) dinuclear Pt-II chromophore, [Pt(ppy)(mu-Ph(2)pz)](2) (ppy is 2-phenylpyridine and Ph(2)pz is 3,5-diphenylpyrazolate), have been investigated. The thermochromic shifts are tentatively ascribed to intramolecular sigma interactions between the two pseudocofacial d(Z2) orbitals. Substantial emission profile changes occur in the solid state, solution, and doped polymer films.