Chemistry Commons^™

Synthesis And Resolution Of A Substituted Dioxolane From Glycerol, Susannah Dawn Cox

Undergraduate Honors Thesis Collection

Glycerol (Figure 1) is one of the major byproducts in the manufacturing of biofuels. As the interest in biodiesel grows, production of glycerol will also increase. Investigating glycerol's potential as a chemical feedstock could lead to the discovery of new uses for this byproduct created from biofuel production. By developing pathways to use glycerol as a starting material and as a solvent we will be able to synthesize other chemically relevant compounds.

Suzuki-Miyaura Reactions Are Used To Synthesize Z-Alkenes From Cyclic Boronic Half-Acids, Daniel Lee French

Undergraduate Honors Thesis Collection

Cis-Alkenes provide the basic structure and reactivity for a variety of compounds, from the common chemicals found in any organic laboratory to advanced drugs used to treat cancer or suppress the immune system (Littke & Fu, 2002). Synthetically, alkenes are also of use in that they serve as a site for further chemistry. Historically, Z-alkenes have been more difficult to synthesize than their E-counterparts (McNulty et al., 2010; Siau, Zhang, & Zhao, 2012). Furthermore, in many reactions, a mixture of E- and Z- conformations of the alkene is produced. Such differences may seem trivial upon first inspection, but because there …

Synthesis And Purification Of The Glycosphingolipid Csa-13, Tyler Olsen, Dr. Paul Savage

Journal of Undergraduate Research

The need for novel antibiotic mechanisms is prevalent. Common antimicrobial medicines such as penicillin, ampicillin and vancomycin have started becoming obsolete as resistant strains of bacteria become more widespread. The main problem with antibiotics is the rapid mutations that bacteria undergo. Eventually one cell will develop resistance, and then have that mutation selected for as patients undergo antibiotic therapy. Bacteria are rapidly changing to combat the many new antibiotic variants that have come out.

Searching For Nascent Peptides That Cause Ribosome Stalling, Shankar Parajuli, Dr. Allen Buskirk

Journal of Undergraduate Research

Ribosomes are molecular machines that synthesize all the proteins for all living cells. Ribosomes sometimes stall and cannot complete the synthesis of a given protein. Some peptides interact with the ribosome during their own translation and induce stalling.1 The SecM and TnaC peptides in E. coli, for example, have been found to play a key regulatory role in translation of genes found on the same mRNA.2

The Total Synthesis Of S-Equol Using Phase Transfer Catalysis, Eric Bready, Dr. Merritt Andrus

Journal of Undergraduate Research

The purpose of this project was completion of the total organic synthesis of the anti-cancer compound (S)-equol. My goal was to carry out our planned synthesis of this molecule using Phase Transfer Catalysts, (PTCs), which promote the formation of the S enantiomer as opposed to the R enantiomer of equol (S and R enantiomers are like right and left hands, which are mirror images of each other—in organic synthesis usually only one form is desired) (1). In using PTCs it was our hope that we would be able to form (S)-equol with high yield and in a timely manner. Successful …

Synthesis Of S-Equol Using Heck Coupling Reaction And Phase-Transfer Catalysis, Chelsey Hancock

Journal of Undergraduate Research

Please list all accomplishments, achievements, publications, presentations, or other scholarly productivity that resulted from your ORCA project. This may include submissions to peer-reviewed journals, conference presentations or papers, performances, exhibitions, internships, scholarships, graduate school opportunities, local presentations, or awards that followed your mentoring experience.

(Η5‐Cyclopentadienyl)Tricarbonylmanganese(I) Complexes, Patrick N. Kirk, Michael P. Castellani

Chemistry Faculty Research

Since the initial preparation of (η⁵‐C₅H₅)Mn(CO)₃ by Fischer and Jira in 1954, many methods have been developed for the synthesis of this compound (often referred to as “cymantrene”) and its C₅ substituted derivatives. Interestingly, each of these preparations has at least one significant drawback from a preparative perspective (thallium reagents, high pressures, poor yields, or reactants that require significant preparative investment). Surprisingly missing from this collection of preparative methods is the direct reaction between commercially available Mn(CO)₅Br and NaC₅H₅. In 1988, however, Smart and coworkers found …

Size-Dependent Interactions Of Metal Nanoparticles With Fluorophores And Semiconductors, Liyana A. Wajira Ariyadasa

Dissertations

In recent years, nanoscale metallic particles have gained considerable interest due to their potential applications in advanced technology. Despite such interest, synthetic procedures that produce gram-scale, well-defined metallic nanoparticles with controlled size and shape, especially with diameters less than 5 nm remains a challenge. Our work has focused on developing synthetic procedures that produce well-defined platinum and palladium metal nanoparticles in the 1-5 nm size range. Thioether ligands were used as stabilizers and resulted in metal nanoparticles with controlled size. The nanoparticles were characterized using transmission electron microscopy (TEM), x-ray diffraction (XRD), selected area electron diffraction (SAED), x-ray photoelectron spectroscopy …

Facile Synthesis And Characterization Of A Thermally Stable Silica-Doped Alumina With Tunable Surface Area, Porosity, And Acidity, Maryam Khosravi Mardkhe

Theses and Dissertations

Mesoporous γ-Al2O3 is one of the most widely used catalyst supports for commercial catalytic applications. The performance of a catalyst strongly depends on the combination of textural, chemical and physical properties of the support. Pore size is essential since each catalytic system requires a unique pore size for optimal catalyst loading, diffusion and selectivity. In addition, high surface area and large pore volume usually result in higher catalyst loading, which increases the number of catalytic reaction sites and decreases reaction time. Therefore, determination of surface area and porosity of porous supports is critical for the successful design and optimization of …

Synthesis Of Bioconjugate Dimers Used To Probe The Structure Of Pglycoprotein, Emily Parker, Dr. Merritt B. Andrus

Journal of Undergraduate Research

Chemotherapy is one of the primary treatments for cancer today. A patient’s life may depend on its efficacy, so when he or she develops multi-drug resistance (MDR) the results can be devastating. MDR, a clinical condition manifested by the failure of chemotherapy, is primarily due to the expression of P-glycoprotein (Pgp), a membrane-bound small molecule transport protein which is found normally in some cells but is greatly over expressed in drug resistant cancer cells1. It is believed that after chemotherapy drugs diffuse into the cell, Pgp effluxes them out using energy from ATP hydrolysis, thus imparting drug resistance.

Synthesis, Crystal Structure Refinement, And Electrical Conductivity Of Pb(8−X)Na2smx(Vo4)6o(X/2), Tatiana M. Savankova, Lev G. Akselrud, Lyudmyla I. Ardanova, Alexey V. Ignatov, Eugeni I. Get’Man, Roman E. Gladyshevskii, Stanislav N. Loboda

Biochemistry, Chemistry and Geology Department Publications

Solid solutions of Pb(8−x)Na2Smx(VO4)6O(x/2) were studied using X-ray diffraction analysis including Rietveld refinement and scanning electron microscopy and by measuring their electrical conductivity. Crystal structure of the solid solutions was refined and the solubility region 0 ≤ x ≤ 0.2 was determined for samarium substitution for lead under the scheme 2Pb2+ + ◻ → 2Sm3+ + O2-. The influence of degree of substitution on the electrical conductivity of solid solutions was established.

The Chemistry Concerned With The Sonochemical-Assisted Synthesis Of Ceo_2/Poly(Amic Acid) Nanocomposites, Shiva Yazdani, Mehdi Hatami, Seyed Mohammad Vahdat

Turkish Journal of Chemistry

A series of new poly(amic acid) (PAA) surface-modified cerium oxide (CeO_2) nanocomposites were prepared by sonochemical-assisted method. In the first step, treatment of the surface of CeO_2 nanoparticles with hexadecyltrimethoxysilane as a surface modifier was achieved. In the second step, the partially surface-treated nanoparticles were incorporated into PAA by different weight from 4% to 12%. PAA was synthesized by polycondensation reaction of benzophenone tetracarboxylic dianhydride and 3,5-diamino-N-(4-hydroxyphenyl) benzamide in N-methyl-2-pyrrolidone. The chemical structure of PAA was confirmed by ^1H NMR and FTIR spectroscopy. The polymer had an inherent viscosity of 0.38 dL/g. Three PAA/CeO_2 nanocomposite formulations were prepared from the …

Electrochemistry Of Fe(Iv) And Mn(Iv) Corroles Containing Meso-Dichlorophenyl Substituents And The Use Of These Compounds As Catalysts For The Electroreduction Of Dioxygen In Acid Media, Lina Ye, Zhongping Ou, Deying Meng, Mingzhu Yuan, Yuanyuan Fang, Karl M. Kadish

Turkish Journal of Chemistry

Two meso-dichlorophenyl substituted metallocorroles were synthesized and characterized as to their electrochemical and spectroelectrochemical properties in dichloromethane, benzonitrile, and pyridine containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) as supporting electrolyte. The examined compounds are represented as (Cl_2Ph)_3CorFe^{IV}Cl and (Cl_2Ph)_3CorMn^{IV}Cl where (Cl_2Ph)_3Cor is the trianion of 5,10,15-tri(2,4-dichlorophenyl)corrole. Each metallocorrole was examined as to its catalytic activity for the electoreduction of dioxygen when coated on an edge-plane pyrolytic graphite electrode in 1.0 M HClO_4. Cyclic voltammetry combined with linear sweep voltammetry at a rotating disk electrode (RDE) and a rotating ring disk electrode (RRDE) was utilized to evaluate the catalytic activity for the …

New Soluble Amidoamine Substituted Phthalocyanines: Synthesis, Characterization, And Investigation Of Their Solution Properties, Senem Çolak, Sali̇h Zeki̇ Yildiz

Turkish Journal of Chemistry

The synthesis of tetraaminopropylamid substituted phthalocyanines was targeted to prepare enhanced soluble phthalocyanines in common solvents from hydrophobic to hydrophilic that bore nonionic groups on their periphery. Metal-free (H_2Pc) and metallophthalocyanines (Zn(II) (ZnPc), Cu(II) (CuPc) and Co(II) (CoPc)) were prepared and characterized by UV-Vis, FT-IR, and mass spectroscopies. The ^1H NMR spectra were recorded for the diamagnetic phthalocyanine species H_2Pc and ZnPc. The phthalocyanines showed sufficient solubility in common organic solvents such as dimethyl sulfoxide, tetrahydrofuran, and ethanol. However, methanol was not a good solvent for CuPc and H_2Pc. Solubility and aggregation studies of H_2Pc and ZnPc were performed in …

Using Structure-Based Organic Chemistry Online Tutorials With 2 Automated Correction For Student Practice And Review, Timothy O'Sullivan, Gráinne Hargaden

Articles

This article describes the development and implementation of an open-access organic chemistry question bank for online tutorials and assessments at University College Cork and Technological University Dublin. SOCOT (structure-based organic chemistry online tutorials) may be used to supplement traditional small-group tutorials, thereby allowing students to develop essential problem-solving skills in organic chemistry. This online approach may be used for both formative and summative assessment. Students complete one problem set weekly or fortnightly, which consists of a number of questions of varying difficulty. A wide range of question types is possible; for example, prediction of reaction products, identification of reaction intermediates …

Synthesis And Characterization Of New (E)-N'-(Substituted Benzylidene)-2-(3-(2-Methyl)-4-Oxo-3,4-Dihydroquinazolin-2-Ylthio)Acetohydrazides, Aamer Saeed, Shams-Ul Mahmood, Ulrich Flörke

Turkish Journal of Chemistry

A small library of new azomethine derivatives of 3-aryl-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones was synthesized. The key intermediates 2-thioxo-quinazolinones (3a--e), obtained in 2 steps from the corresponding anilines, were treated with methyl chloroacetate to afford S-substituted esters (4a,d), which were then converted into corresponding acetohydrazides (5a,d). Further, acetohydrazide (5d) was converted to the azomethines derivatives (6a--k) by reacting with a number of suitably substituted benzaldehydes. FTIR, ^1H NMR, ^{13}C NMR, GC-MS, and elemental analyses were used to confirm the assigned structures of the synthesized compounds. Further, compounds 3a, 5, and 6j were also confirmed by X-ray diffraction data.

Modified Seed Growth Of Iron Oxide Nanoparticles In Benzyl Alcohol: Magnetic Nanoparticles For Radio Frequency Hyperthermia Treatment Of Cancer, Stanley E. Gilliland Iii

Theses and Dissertations

Iron oxide nanoparticles have received sustained interest for biomedical applications as synthetic approaches are continually developed for precise control of nanoparticle properties. This thesis presents an investigation of parameters in the benzyl alcohol synthesis of iron oxide nanoparticles. A modified seed growth method was designed for obtaining optimal nanoparticle properties for magnetic fluid hyperthermia. With a one or two addition process, iron oxide nanoparticles were produced with crystallite sizes ranging from 5-20 nm using only benzyl alcohol and iron precursor. The effects of reaction environment, temperature, concentration, and modified seed growth parameters were investigated to obtain precise control over properties …

Synthesis, Characterization, And Application Of High Surface Area, Mesoporous, Stabilized Anatase Tio2 Catalyst Supports, Rebecca Elizabeth Olsen

Theses and Dissertations

Nanomaterials have attracted substantial attention in the area of catalysis due to the unique properties they exhibit such as high surface areas, intricate pore networks and unique morphologies. TiO2 has attracted attention as a catalyst since the discovery of its high photocatalytic activity by Fuishima and Honda in 1972. Given its high thermal stability, low cost, low environmental impact, and versatility, TiO2 is a widely used commercial catalyst and catalyst support. TiO2 is used in many applications such as photocatalysis is also an excellent support material for noble metals in a number of oxidative synthesis and pollution-control reactions. Though TiO2 …

Synthesis Of Hiv Integrase Inhibitors, Carl Jones, Dr. Matt A. Peterson

Journal of Undergraduate Research

We have made significant progress toward the synthesis of one branch of the library of compounds that we plan to synthesize. The scheme we have followed is shown below. Once synthesized, we plan to have the compounds tested by expert collaborators to see how well they bind HTLV integrase. In addition, they will be tested against many viruses and cancers, as well as HIV. Because they are nucleoside based, it is impossible to predict exactly what type of biological activity these compounds will have. They could possibly treat a variety of diseases.

Synthesis Of Novel Isoprenoid Diphosphate Analogs As Chemical Tools To Investigate Protein Geranylgeranylation, Kayla Jo Temple

Open Access Dissertations

Many proteins require prenylation in order to be biologically functional. Some such proteins include the small Ras and Rho GTPase superfamilies, nuclear lamins A and B, and the kinesin motor proteins CENP-E and F. Prenyltransferase (PTase) inhibition is currently being explored as a possible treatment not only for cancer but for a wide variety of other diseases.

Clinical studies revealed that the effectiveness of farnesyltransferase inhibitors (FTIs) to treat Ras-dependent tumors is determined by which isoform of Ras is overactive. Unfortunately the majority of Ras-dependent tumors have a mutation in either the N- or K-Ras isoforms; both of these isoforms …

Continued Progress Towards Efficient Syntheses Of Cephalostatin North 1 Analogs, Daniel Preston Jamieson

Open Access Dissertations

Jamieson, Daniel P. Ph.D., Purdue University, December 2013. Continued Progress Towards Efficient Syntheses of Cephalostatin North 1 Analogs. Major Professor: PhilipL. Fuchs.

The cephalostatins and ritterazines represent an intriguing class of marine natural products in both structure and biological activity, and the progress towards the synthesis of high valued analogs with a focus on process orientated methodology is described herein. Included in the pages to follow, is the further advancement of the `Red-Ox' strategy toward the highly efficient synthesis of 25-epi-4,15-dihydro-North 1, Chapter 2. A short review focusing on the earlier efforts toward the main synthetic challenges of North 1 …

Total Synthesis Of The Natural Product Hasubanonine, Spencer Jones, Dr. Steven Castle

Journal of Undergraduate Research

Hasubanonine is a tetracyclic alkaloid with potential analgesic activity. The total synthesis of this alkaloid has been undertaken in order to demonstrate the applicability of the methodology developed for the synthesis of acutumine and to assay the potential medicinal activity of the compound. The key steps in the synthesis include the ruthenium catalyzed ring closing metathesis, anionic oxy-Cope rearrangement, and intramolecular Michael addition. Future work includes the completion of the racemic synthesis of hasubanonine as well as the investigation into the asymmetric allylation required for the enantioselective synthesis of hasubanonine.

Siloles Bearing Coordination-Active 2,5-Substituents: Synthesis, Reactivity, Structural And Spectral Properties., James Bryan Carroll

Dissertations

Siloles, or silacyclopentadienes and other group 14 metalloles are structurally analogous to their all-carbon analogue, cyclopentadiene, except for the heavy group 14 element (i.e., Si, Ge, Sn, and Pb) in the 1-position. The placement of the heavy element in this position allows for unique properties, such as high electron affinity, mobility, and bathochromically shifted optical spectra, as compared to cyclopentadienes, and the relatively low-lying lowest-unoccupied molecular orbital (LUMO) helps to account for these properties. The substituents about the silole have a significant impact on the electronics and properties observed, with 2,5-substituents inducing the most substantive changes. Even as many 2,5-substituents …

Latent Cysteine Residues From Polymers Prepared Via Free And Controlled Radical Polymerizations, Douglas Vincent Amato

Master's Theses

One less commonly used “click” reaction is thiazolidine chemistry. Thiazolidine chemistry is a commonly used reaction used in biological systems because the reaction requires the presence of both cysteine (a common amino acid) and an aldehyde or ketone. If cysteine residues could be incorporated into a polymer then a variety of applications could be developed. Polymers containing free thiols (aka thiomers) have developed in the last decade to become great mucoadhesives. If there was a facile route to control the amount of free thiols along the polymer then more fine-tuned and potentially stronger adhesives could be made. For these reasons …

Synthesis And Immunological Evaluation Of Type I, Type Ii, And Gamma Delta Nkt Cell Antigens, Brian L. Anderson

Theses and Dissertations

The purpose of the immune system is to protect our bodies from infection. One way it accomplishes this task is through the presentation of foreign pathogens to NKT cells. After an antigen is presented to the T cell receptor, activated NKT cells quickly release soluble chemical signals, termed chemokines and cytokines, that modulate the response of the immune system. Due to the immunological relevance of NKT cell activation, we developed and synthesised non-natural analogs of immunostimulatory type I, II, and gamma delta NKT cell antigens. The immunological evaluations of these analogs resulted in identification of sulfatide as a gamma delta …

Microwave Synthesis And Reactions Of Cpru(Dppe)Cl With Sulfur Containing Ligands, Srikanth Muthyala

Student Theses and Dissertations

The microwave synthesis of CpRu(dppe)Cl and CpRu(PPh3)(P(OMe)3)Cl were investigated. A new preparative method using microwave irradiation was found for CpRu(dppe)Cl and CpRu(PPh3)(P(OMe)3)Cl. Attempts to prepare CpRu(P(OMe)3)2Cl failed. Reactions of CpRu(dppe)Cl and CpRu(PPh3)(P(OMe)3)Cl with cyclothioether ligands were attempted. Pentamethylene sulfide (pms), tetrahydrothiophene (tht), and thietane (thie) were the ligands considered. The dppe-dithiooxamide complex {(µ-dtoxa)[CpRudppe]2}(BF4)2 was isolated and the structure was determined using X-ray diffraction techniques: space group P 21 21 21, a = 14.120 (7) Å, b = 16.099 Å, c = 30.917 Å. α = β = ϒ = 90O, V Å3 = 7028 (6), R(F), Rw (F) = 0.0531 …

Facile Synthesis And Improved Pore Structure Characterization Of Mesoporous Γ-Alumina Catalyst Supports With Tunable Pore Size, Baiyu Huang

Theses and Dissertations

Mesoporous γ-alumina is the most extensively used catalysts support in a wide range of catalytic processes. The usefulness of γ-alumina relies on its favorable combination of physical, textural, thermal, and chemical properties. Pore structure properties are among the most important properties, since high surface area and large pore volume enable higher loading of active catalytic phases, while design of pore size and pore size distribution is critical to optimize pore diffusional transport and product selectivity. In addition, accurate determination of surface area (SA), pore volume (PV) and pore size distribution (PSD) of porous supports, catalysts, and nanomaterials is vital to …

Optimization Of Synthesizing Glucose 1-Phosphate By Sodium Tripolyphosphate As A Phosphorus Acylating Agent Using Response Surface Methodology, Li 'E Jin, Fenfen Chang, Xiao Juan Wang, Qing Cao

Turkish Journal of Chemistry

With glucose as the starting material, sodium tripolyphosphate as the phosphorus acylating agent, and urea as the catalyst, glucose 1-phosphate was synthesized and its properties were analyzed. The synthesis conditions were selected according to the phosphorus content and optimized through the response surface methodology (RSM), based on a 3-level, 3-variable Box--Behnken experimental design. The results showed that the phosphorus content of glucose 1-phosphate was 8.12% using a reaction temperature of 70 °C, a molar ratio of glucose to sodium tripolyphosphate of 1.54:1, and catalyst amount of 3.7 g. It coincided well with the experimental value (8.34%). The structure of the …

The Bench Synthesis Of Silver Nanostructures Of Variable Size And An Introductory Analysis Of Their Optical Properties, Aoife Power, Tony Betts, John Cassidy

Articles

A laboratory practical was designed for use by both undergraduate and second level students to demonstrate the synthesis and characterisation of tuneable silver colloids. It clearly illustrates the novel optical properties of silver nanoparticles compared to the bulk metal. The synthesis is both rapid and repeatable, and can be conducted on the laboratory bench at room temperature.

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).