Physical Sciences and Mathematics Commons^™

Dom Control Of Mercury Methylation In The Water Column Of A Meromictic Lake, Madalyn Bozinski

Honors Capstone Projects - All

The trophic transfer and bioaccumulation of methyl mercury (MeHg) in aquatic ecosystems is a substantial concern, resulting in fish consumption advisories worldwide. Aquatic ecosystems have been identified as the critical environments that breed production of MeHg and low levels of initial accumulation in biota. MeHg production is a microbially-mediated process, occurring primarily at the transition between oxic and anoxic environments. This research aimed to assess the extent to which dissolved organic matter (DOM) affects methylation of mercury in the oligotrophic meromictic lake, Green Lake, in Fayetteville, NY and the warm monomictic lake, Seneca Lake, in Geneva, NY. General physical parameters …

A Closer Look At The Synthesis And Characterization Of Alkaline Earth Metal Tetraarylborates And Heteroleptic Tetraarylborate Pyrazolates, Ashley Clements

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Compounds containing s-block metals are highly sought after as precursor materials for the Metal Organic Chemical Vapor Deposition (MOCVD) process with applications for novel and improved electronic materials. Previous work in the Ruhlandt Group has been focused on the synthesis and characterization of novel homoleptic alkaline earth (Ae) metal pyrazolate and tetraarylborate complexes, while understanding the importance of secondary interactions such as M- in the isolation of these compounds. More recently, it was further proposed that the pyrazolate and tetraarylborate ligand systems combined with an Ae silyl amide via transamination may very well result in an improved heteroleptic MOCVD potential …

Studies Towards The Synthesis Of (-)-Centrolobine Via The Carbonyl Ene Reaction Of Exocyclic Enol Ethers, Brianna Shores

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The goal of this study is the synthesis of centrolobine 7, a naturally-occuring compound that exhibits anti-parasitic and anti-inflammatory activity.

The strategy is to utilize the carbonyl ene reaction to form the 2,6-disubstituted framework of centrolobine 7 from exocyclic enol ether 110 and aldehyde 111. Exocyclic enol ether 110 would be synthesized via literature procedures starting from commercially available glutaric anhydride 11 and anisole 114.

The work completed to date optimizing the following reactions: Friedel-Crafts acylation of glutaric anhydride 11 and anisole 114, the reduction of alcohol 116, and cyclization of alcohol 116 to lactone …

Synthesis Of Substituted Tetrahydropyrans Using Metal-Catalyzed Coupling Reaction, Amanda Lieu

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The purpose of this research is to explore the use of cobalt- and iron-catalyzed cross coupling reactions of alkyl iodides containing beta-tetrahydropyran groups to develop a general method to synthesize substituted tetrahydropyrans. Substituted tetrahydropyrans can be used towards the total syntheses of biologically active natural products. The starting iodide compounds underwent sp3-sp3 and sp3-sp2 cobalt- and iron-catalyzed cross-coupling reactions with different Grignard reagents. It was expected that the formation of the coupled product would be faster than the formation of the side products (elimination and homocoupling) and thus yield the desired substituted tetrahydropyrans. The results of this study showed that …

Structural Variations Involving S-Block Metal Pyrazolates, Joshua Woods

Honors Capstone Projects - All

Alkali and alkaline earth metal organometallics have been sought after for a variety of applications such as in electronic devices produced by novel metal organic chemical vapor deposition precursors, catalysts and as synthetic reagents. Despite significant advances in synthetic techniques, the chemistry of the highly reactive s-block metals is still relatively unexplored. It is difficult to predict properties, structure and binding modes of these compounds due to a number of factors including enhanced reactivity and tendency to aggregation due to the large metal diameter. On the other hand, many of the s-block metals are earth abundant and environmentally friendly, …

Investigation Of The Tandem Alkylation-Cyclization Of Endocyclic Enol Ethers For The Preparation Of Unusual Oxygen Heterocycles, Sarah Mehdi

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The purpose of this research is to study the alkylation and subsequent cyclization reaction of endocyclic enol ethers such as 2H-dihydropyran. This sequence is expected to yield oxygen heterocycles whose structures represent unique scaffolds with promising functionality.

A series of trichloroacetimidates were selected for the direct alkylation of 2H-dihydropyran. Following the alkylation, the addition of acid was expected to induce an intramolecular cyclization reaction that would yield the desired oxygen heterocycles. This stepwise scheme would then be converted into a tandem process in which the reaction would be expected to proceed in a single pot.

Studies showed that the alkylation …

Ruthenium Hydride Catalyzed Silylvinylation Of Terminal And Internal Alkynes And Synthesis Of Poly(Trimethylenecarbonate) And Poly(Dimethylacrylamide) Block Copolymer, Alec Beaton Jr.

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Various propargyl alcohols were synthesized via Grignard reactions. These alkynic alcohols are tethered with dimethyl and biphenyl silicon tethers. These terminal alkyne substrates are reacted with RuHCl(CO)(H₂IMes)(PPh₃) as a catalyst under high pressure (80 psi) ethylene atmosphere to afford the 5-exo-dig trans-silylvinylation product in poor yield. Internal alkyne substrates are found to be much more efficiently transformed into the silylvinylation product, favoring one cycloisomer product over the other.

The Use Of Shape Memory Polymers As A Tool To Study Human Fibrosarcoma And Murine Mesenchymal Stem Cell Migration, Justin N. Elkhechen

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Shape memory polymers (SMPs) are a class of “smart” materials that can transform between two distinct conformations through external stimuli, such as heat or electricity. Their usage in bioengineering has led to a promising field of research that lies at the interface of cell and mechanobiology, potentially providing insight into cancer therapies and tissue development—two processes that exist in dynamic environments in vivo. The present work involves creating new, shape changing, scaffolds for studies to analyze cell migration upon changes to the environmental topography. Specifically, this Capstone has been primarily focused on the development of a “half and half” fibrous …

Electrostatic Assembly Of Gold Nanoparticles Mediated By Polyoxomolybdates, Shannon M. Walter

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The electrostatic assembly of cationic gold nanoparticles (AuNPs) with core diameters of approximately 1.5 nm and 4.5 nm and the anionic sphere and wheel polyoxomolybdates (Mo-132a), (Mo‑132b), and (Mo‑154) was investigated. The AuNPs were capped with a trimethylammonium terminated ligand. Zeta potential and UV-Vis studies supported the successful assembly of the oppositely charged species. The ratio at which the precipitation of aggregates from solution occurred was consistent with the point of electroneutrality observed in the zeta potential results. The UV-Vis studies showed the loss of the surface plasmon resonance (SPR) band as this point of electroneutrality was approached.

In a …

Radiopharmaceuticals: The Application Of Technetium-99m And Rhenium Complexes, Angela Kristin Binion

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Nuclear imaging used in diagnostic medicine requires the use of radiopharmaceuticals to make biological areas visible under a gamma camera. Although much success has been found in the use of technetium based imaging agents, their corresponding rhenium complexes can provide insight into the chemical properties of these radiopharmaceuticals without the potentially damaging effects of radiation. Technetium and rhenium complexes utilize a bifunctional chelator to act as a linker between biological vectors and the metal, improving the coordination between the two. Ligands containing thiazole rings have been successfully coordinated to technetium or rhenium tricarbonyl complexes, although it is uncertain whether coordination …

Pd-­Catalyzed N-­Arylation Of Amides: Catalyst Development And Scope, Tara Brenner

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Recent development toward more efficient palladium catalyzed amidation reactions has been driven by mechanistic studies and the development of more efficient ancillary phosphine ligands. This review discusses these developments with regard to substrate scope and the nature of the corresponding catalyst systems. Emphasis will be placed on applications of palladium catalyzed amidation reactions and the synthetic utility of these methods.

The Conjugation Of Protein And Peptide Therapeutics To Vitamin B12 For The Oral Treatment Of Diabetes, Jamie L. Bernstein

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Currently patients with diabetes receive most of their treatments, including insulin, subcutaneously. Developing a method to orally deliver proteins, peptides, and potentially other therapeutics has the ability to increase patient compliance by making treatments easier to administer. Utilizing the Vitamin B12 uptake pathway is one proposed method of oral delivery of protein therapeutics. We investigated a way to synthesize a carboxylic acid derivative of Vitamin B12 (B12) that could increase the ease of its conjugation to proteins and peptides. The 5’-position of the ribose tail of B12 was oxidized using excess 2-iodoxybenzoic acid (IBX) and 2-hydroxypyridine (HYP). The synthesis of …

The Use Of P53-Derived Stapled Peptides As Affinity Isolation Reagents, Kathryn Margaret Headley

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The transcription factor p53 can induce apoptosis and cell cycle arrest in response to cellular distress. Cancer cells often display increased cell survival. In most cases, this is due to a p53-related defect, such as mutation, deletion, degradation, or sequestration. HDM2 and HDMX are homologous proteins that regulate the function of p53, and their over-expression can lead to an ineffective p53 response. Various inhibitors, including hydrocarbon stabilized alpha-helices of p53 (SAH-p53s), have been developed to target HDM2 and HDMX and restore functionality to the p53 pathway. It has been recently found that SAH-p53 factors also elicit cell death responses in …

Characterization Of Dap2 (Defense-­‐Associated Aspartic Protease-­‐2) In Arabidopsis Thaliana And Determining Its Role In Plant Defense Responses, Kemardo Kitaro Henry

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Plants defend themselves from invading pathogens by coordinating activity of several plant defense-­‐associated genes. Defense-­‐Associated Aspartic Protease-­‐1 (DAP1) gene of Arabidopsis encodes for an atypical aspartic protease with a putative proteolytic activity. The DAP1 is a negative regulator of plant immunity and the transgenic plants ectopically expressing this genes support pathogen growth and pathogenicity. The Arabidopsis genome has another putative protese that has ~75% homology to DAP1 present in close proximity and therefore was named DAP2. Here, I describe the role of the DAP2 gene in plant defense responses. Two independent knockout dap2 mutants are found to be more susceptible …

Vitamin B12-Based Bioconjugate Probes For In Vitro And In Vivo Imaging, Anna Kahkoska

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Cancer is the second leading cause of death in the United States. This year, an estimated 577,190 Americans will die as a result of this family of diseases. Finding cancer at its most treatable stage gives patients the greatest chance of recovery; novel imaging agents that target primary and metastasized tumors offer hope for improved prognoses in the future. Based on the hypothesis that vitamin B12 (B12) and its association with specific transport proteins could offer selective access to cancer cell lines, a series of B12-based imaging agents were synthesized, characterized, and assayed for both in vitro and in vivo …

Synthesis Of Novel Alkaline Earth Tosylate Complexes Through Donor Studies, Adam J. Brooks

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Salt metathesis has become a critical reaction pathway in organometallic chemistry; however, for alkaline earth metals this process is hindered by the need of highly pure and expensive metal iodides as starting materials. This contribution highlights recent attempts to identify inexpensive reagents for salt metathesis. Alkaline earth-tosylates can be prepared cost effectively using p-toluenesulfonic acid in one-pot reactions in water. The coordinated water molecules can be removed by gentle heating under vacuum. The anhydrous tosylates, however, have major solubility limitations as the result of extensive aggregation networks. The goal of this study was to increase the solubility of the tosylates …

Nonamphiphilic Modification Of The Self-Assembly Behavior Of Surfactants And The Potential For Bolaamphiphile-Based Vesicle Formation In The Presence Of 5’Disodium Cromoglycate, Nemal S. Gobalasingham

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Emulsion systems stabilized by surfactants have historically been driven by the separation of hydrophobic oils from water, essentially creating surfactant micelles. As surfactant molecules aggregate around the oil, they self-assemble in such a way that the hydrophobic chains of the surfactants face inward toward the oil while the hydrophilic, or water-loving, “head” of the surfactant face outward toward the water medium. The emergence of water-in-water emulsions consisting of droplets of a water-solvated biocompatible liquid crystals, disodium cromoglycate (5’DSCG), with polymers has unlocked the potential for modifying the self-assembly behavior of surfactants. We report here on the capacity of 5’DSCG to …

Synthetic Dosage Lethality Screen With Actin Cytoskeleton In Yeast, Jessica Cho

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The actin cytoskeleton is a vitally important organizing structure found in the cytoplasm of our cells. It contributes to essential cell functions from growth and cell division, development, signal transduction, adaptation, to gene expression. Interest in how regulation of the actin cytoskeleton---due to actin cytoskeleton's importance to cell function-may contribute to diverse human disease states such as the rampant cell division and metastasis that occurs in cancerous tissues. It has been further elucidated that many human genetic disorders are the result of complex haploinsufficiencies (CHI) and/or altered gene dosages at multiple loci. By reviewing a large number of potential Synthetic …

Germline Cyst Formation And Development In Zebrafish, Tess Cherlin

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In developing pre-natal mice, germline cysts are clusters or packages of cells consisting of individual oocytes. They are formed after the primordial germ cells move to the ovary during embryogenesis. The primordial germ cells divide, but do not completely separate. The cells within the cysts are linked by intercellular bridges, which end up breaking down leading to the formation of primordial follicles. The primordial follicles are oocytes surrounded by somatic cells called granulosa cells. Only one third of the original oocytes survive cyst breakdown and become the eggs that will be used by the mouse for her reproduction. This developmental …

Exploring The Potential For B12-Based Oral Vaccine Delivery; Cubilin Mediated Uptake Of B12-Conjugate Systems Greater Than 160 Kda, Teresa Soldner

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This project aimed to create a novel oral tetanus vaccine by exploiting the B₁₂ uptake pathway. While many linkers were attempted, the only successful complex was created using CDT coupling. After synthesis, purification (with some difficulty), and characterization, tests were done in vitro and in vivo. These supported the conclusion that while the complex was being successfully taken up by the cell, the complex was not created a strong enough immune response for a positive titer. On a second note, simply the uptake of B₁₂-TT is remarkable because it is the largest molecule that has been …

Quantum Dot Biofunctionalization, Nathaniel J. Miska

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We have shown the efficacy of Quantum Dots (qdots), nano-scale fluorescent particles made of semi-conductive material, as versatile biologically functional research tools. This functionality depends upon a series of chemical transformations that produce stable, aqueous, biomolecule-bound qdots with high quantum yield. We utilize the metal binding and chelating properties of the amino acid histidine to displace hydrophobic surface ligands and to phase-transfer qdots from organic to aqueous media. The intermediate binding strength of histidine to qdot surface facilitates its exchange with a variety of strongly binding thiolated biomolecules. Ligand profiles are subsequently characterized via FTIR, NMR, and gel electrophoresis. Negatively-charged …

Tuning Quantum Dots Optical Properties By Temperature And Concentration Modulation, Amber Sexton

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Quantum dots have recently been awarded attention due to their tunable optical and spectroscopic properties. The optical and spectroscopic behavior of quantum dots was investigated as a function of mean particle size. Manipulation of the reaction conditions and constituents impact the controllability of size and surface conditions. Therefore, synthesis of CdSe and CdS semiconductor nanoparticles with tunable particle size were created using temperature, time, and composition as variables. Analytical techniques used to characterize the nanoparticles included fluorescence and electronic absorption. The effect of temperature, aside from changing the size of the particle, also eliminated defects on the surface and caused …

Production And In Vitro Investigation Of Vitamin B12-Based Bioprobes, Amy Rabideau

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Vitamin B₁₂ (B₁₂)-based bioprobes were produced and investigated in vitro for studying the B₁₂ uptake pathway in certain cancer cell lines and their target-specific capabilities as imaging and/or contrast agents in vivo. An intrinsic factor (IF)-bound B₁₂ conjugate (B₁₂-ReBQBA) was produced containing rhenium(I) for in vitro analysis of the cubilin-expressing placental choriocarcinoma cell line. B₁₂-ReBQBA has millimolar toxicity in vitro and excitation and emission wavelengths in the visible region, 488 nm and 560 nm, respectively. The rhenium metal in this bioprobe can be readily exchanged for the metastable radioactive metal technetium-99m …

The Synthesis And Characterization Of Novel Microporous Hybrid Organic/Inorganic Materials, Kelly Whitenack

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Inorganic chemistry is essential to the formulation and improvement of modern materials such as catalysts, semiconductors, optical devices, super conductors, and advanced ceramic materials.¹ New areas of inorganic chemistry are constantly being explored and new and often unusual inorganic compounds are constantly being synthesized and identified.¹ Recently the field of inorganic chemistry has witnessed the synthesis and characterization of microporous metal organic framework compounds (MOFs). Microporous organic/inorganic materials have a wide range of physical properties as well as applications. The physical properties and applications drive the investigation into the synthesis and discovery of new and useful hybrid MOF …

Synthesis Of Diruthenium Complexes As Connectable Molecular Components, George Ling

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There have been great advances in electronics and technology within the last few years. The field of nanotechnology can further improve electronics in terms of efficiency, size and costs. There exist nanowires and nanotransistors that could accomplish this, however there exists no good method of connecting the two components together. Using the bottom-up approach and chemical synthesis, the goal is to synthesize molecular jumper cables and connectable molecular components (CMCs).

The template of the CMC will have two ruthenium (Ru) metal centers connected by a conjugated, organic bridge. Coordinated to the ruthenium metal centers will be different ligands that affect …

Towards Novel Alkaline Earth Metal Pyrazolates: Opportunities In Materials Chemistry, Michael G. Bagnall

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Until recent years, the coordination chemistry of the alkaline earth metals remained relatively unexplored. Owing to the development of new synthetic methods and improved techniques for the exclusion of air and moisture, great progress has been made into our understanding of the alkaline earth metals and their compounds. These compounds are useful in a wide variety of applications, including as polymerization initiators, precursors for chemical vapor deposition (CVD) and in metal-organic frameworks (MOFs) for gas separation and storage. Current work in alkaline earth metal chemistry focuses on designing and tailoring ligand systems to expand their potential applications in materials chemistry. …

Rational Design And Synthesis Of Multifunctional Nanostructures For Biological And Medicinal Applications, Amy N. Otuonye

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Mobile Composite Material (MCM-41) was modified by the addition of various functional groups, which increase the materials’ efficiency for an assortment of applications. Mesoporous materials have demonstrated to be capable of adsorbing and releasing of model drug molecules, rhodamine 6G and ibuprofen. Mesoporous silica materials functionalized with mercaptopropyltrimethoxysilane (MPTS), vinyltrimethoxysilane (VTS), aminopropyltrimethoxysilane (APTS), and N-(2-animoethyl)-3-aminopropyltriethoxysilane (AAPTS) were used to test the adsorption and release of rhodamine 6G (R6G) and ibuprofen. The vinyl and mercaptopropyl groups adsorbed and released more rhodamine 6G than the primary and secondary amine groups. The adsorption and release of ibuprofen was the opposite of the R6G …

The Ligand Effects In The Rhodium Catalyzed 1,4-Addition Reaction Of Terminal Alkynes To -Unsaturated Ketones, Jocellie Marquez

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Ligand effects play an important role in reactivity and selectivity in many transition metal catalyzed processes. The role of the phosphine ligand is critical to the product ratio in rhodium-catalyzed reaction of methyl vinyl ketone and terminal alkynes. For a ligand with a hemilabile oxygen on the phosphine, smaller ligands shift the product ratio in favor of the 1,4-addition product while with bulky oxygen ligands a dimerization/addition product manifold is dominant. Ligand screen results show that tri-o-tolylphosphine (TOTP) provided the best yields and highest selectivity for dimer-addition product.

Novel Synthetic Routes Toward The Alkaline-Earth Metal Amides, Eli S. Mekhlin

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Metal organic chemical vapor deposition is a process used in the production of thin, crystalline films. The method involves the transportation of volatile, organometallic precursors to a heated substrate, where it undergoes chemical reactions to produce a thin, metallic layer on the substrate surface. Strontium and barium films of this nature are used as components in semi-conductor device fabrication, including among other things, the cell capacitors in Dynamic Random Access Memory computer chips. Additionally, organoalkaline-earth metal compounds are also desired for their potential to serve as polymerization initiators and reagents to modify polymers. Organocalcium derivatives are currently being explored as …

Synthesis Of Novel Alkaline Earth Metal Acetylides, Eva Baker

Honors Capstone Projects - All

Acetylide complexes of the heavy alkaline-earth metals were first introduced by our group. With our group being interested in how the ligand and donor affect the structural chemistry of the resulting complexes, my project was focused on the detailed analysis of past work and the extension towards new ligand and donor sets. The work required the analysis and development of synthetic procedures towards these highly reactive species.

Past synthetic work in our group had established several synthetic routes towards the target compounds including transamination and toluene elimination. Using toluene elimination, I was able to reproduce the synthesis of M(C≡CSiPh_{3 …}