Physical Sciences and Mathematics Commons^™

Development Of Quantitative Methods To Study Pfas Using Proton Induced Gamma-Ray Emission, Colin Langton

Honors Theses

Per- and polyfluoroalkyl substances (PFAS) are man-made chemicals that have become a major environmental concern. They can be found in a broad range of everyday products and pose a significant risk to the public due to their adverse health effects. They are persistent, bioaccumulate and do not break down in the environment. This project specifically aims to determine the concentration of Fluorine, a key identifier of PFAS, in environmental samples. To do this, we employ proton induced gamma-ray emission (PIGE) to screen for Fluorine within our samples. PIGE is performed at the Union College Ion Beam Analysis Laboratory using a …

Electron-Positron Annihilation Lifetime Spectroscopy Of Mgo And Aluminum-Doped Mgo, Elise Liebow

Honors Theses

Radiation is a form of energy that can damage materials at an atomic level. This has implications for the mobility of radioactive waste through containment materials. We are characterizing atomic defects in materials by using Electron-Positron Annihilation Lifetime Spectroscopy (EPALS). When an electron and positron come into contact with each other, they annihilate and release two antiparallel 511-keV gamma rays. In a pristine crystalline sample, positrons can easily annihilate with electrons, but in a sample with vacancies/defects in the crystal structure, positrons take longer to annihilate. Therefore, the more vacancies in a sample, the longer the average lifetime of a …

Synthesis Of Alkyl Aryl Ethers Using A Halogen Exchange Coupled To An Ullmann Etherification, Antonio Campedelli

Honors Theses

The Ullmann ether synthesis is a reaction that couples aryl halides to aliphatic alcohols. It works best with aryl iodides because the aryl bromides are much less reactive, and aryl chlorides are even more so. A Finkelstein type halogen exchange reaction has been shown to effectively substitute iodide for bromide on aryl bromides with high yields. The goal of this project is to develop a one pot halogen exchange, Ullmann coupling reaction to allow for aryl bromides to be coupled successfully to aliphatic alcohols. This is feasible because the reaction conditions of the two reactions are so similar. Several condition …

Development Of Catalytic Chromia-Based Aerogels, Fiona Fitzgerald

Honors Theses

Over one billion automobiles are in use around the world, the majority of which employ internal combustion engines. Catalytic converters are used to convert the toxic compounds found in car exhaust -- carbon monoxide, nitrogen oxides (NOx) and hydrocarbons -- to less harmful gases. The typical catalytic converter employs as catalysts expensive raw materials (platinum, palladium and/or rhodium) wash-coated onto an alumina-based ceramic substrate. Aerogel materials have high surface area and thermal stability, properties that make them attractive for catalysis applications. Aerogels made with transition metal oxides are candidates to replace platinum in the catalytic converter. Chromium oxide (chromia) materials …

Gama-Lactams And The Reformatsky Reaction: New Tricks For Old Chemistry, Dylan Dupont

Honors Theses

DUPONT, DYLAN. An Alternative Synthetic Pathway to γ-Lactam Compounds

Through the Application of Novel Reformatsky-Type Chemistry. Department

of Chemistry, June 2020

ADVISOR: James C. Adrian Jr. Ph.D.

It is the intent of the present report to relate the results of our attempt to elucidate and optimize a novel preparation of γ-lactam compounds. To achieve this end, it is proposed that the use of novel Reformatsky-type chemistry may provide a viable means. Generally, it has herein been validated that employment of α-amino ketones in traditional Reformatsky chemistry will form the traditional Reformatsky ester-adduct, and that this adduct is capable of spontaneously …

Investigation Of Ceria-Nickel Containing Aerogels For Catalytic Converter Applications, Xiao Peng Li

Honors Theses

Aerogels have physical properties that make them appealing for automotive exhaust catalysis: they are highly porous with low density and high surface area. Current catalytic converter technology uses precious metals (Pt, Pd and Rh) to oxidize CO and unburned hydrocarbons and reduce NO. Catalytic-metal-containing aerogel can potentially be a less expensive alternative for use in catalytic converters. Prior work with nickel-alumina aerogels indicated promise for this application; the goal of including ceria is to increase oxygen storage and thereby enhance catalytic ability. Here, cerium- and nickel-containing aerogels, with an alumina backbone and silica backbone, are fabricated using an epoxide-assisted recipe …

Synthesis And Characterization Of Organically Modified Hectorites For Sequestration Of Pfaas From Contaminated Drinking Water, Alexandra Pagano

Honors Theses

Perfluoroalkyl Acids (PFAAs), a family of industrial chemicals, are found in household products such as pizza boxes, microwave popcorn bags, and non-stick pans. PFAAs of different carbon chain lengths and ionic head groups exist, such as PFOA (perfluorooctanoic acid) and PFOS (perfluorooctane sulfonic acid). Used without regulation in industry for decades, PFAAs only recently became recognized as contaminants of emerging concern, since they are bioaccumulative in organisms, persistent in the environment, and toxic. PFAAs are known to accumulate in the blood, liver and kidneys, and drinking water contaminated with PFAAs has been linked to certain types of cancer. Therefore, it …

Optimization Of Superhydrophobic Surface Production Using Ambient-Dried Silica-Based Aerogels, Elizabeth Donlon

Honors Theses

Superhydrophobic surfaces exhibit particular properties that make them functional in various anti-sticking, anti-contamination, self-cleaning and drag reduction applications. Though such surfaces are found in nature - most notably the lotus leaf - they are difficult to produce. There are numerous methods and techniques for fabricating superhydrophobic surfaces. One such method is the sol-gel method, in which aerogel, a highly porous and lightweight material that can be made hydrophobic or superhydrophobic, is coated onto a surface. The purpose of this project is to devise a simple and repeatable procedure for making hydrophobic silica aerogel coatings that can be used for drag …

Comparative Analysis Of Drosophila Athabasca Cuticular Hydrocarbons For Generation Of Synthetic Material To Study Evolutionary Implications, Brittany Gay

Honors Theses

Cuticular hydrocarbons (CHCs) have been studied extensively and their roles explored for various species of insects. However, only a single reported study has focused on the role of CHCs in Drosophila athabasca, a species of fruit fly native to North America. The work herein describes advances in identification, synthesis and quantification of biologically relevant CHCs present in this species. Identifying CHC profile differences among D. athabasca sub-races (Eastern A, Eastern B and WestNorthern) was performed using multiple analytical techniques. Synthesis of proposed structures confirmed their identity. External standard curves were used to quantify CHCs. GC-MS analysis of CHCs from several …

A Systematic Investigation Of The Effects Of Chain Length And Ionic Head Group On Perfluoroalkyl Acid Binding To Human Serum Albumin, Jake Ulrich

Honors Theses

Perfluoroalkyl acids (PFAAs) are industrial chemicals used in everyday products ranging from non-stick coatings to fire-fighting foam. PFAAs are contaminants of emerging concern (CECs) and are bioaccumulative, persistent and toxic. Unlike other CECs, PFAAs bioaccumulate in areas of high protein concentration, such as the kidneys, liver and blood; therefore, it is vital to study PFAA-protein interactions. Human Serum Albumin (HSA) is the model protein used for PFAA-protein studies because it is the most abundant protein in the human body and it binds and transports endogenous and exogenous ligands. Previously, researchers have investigated PFAA-HSA binding, but most of these studies have …

Incorporation And Characterization Of Optical Oxygen Sensors In Silica Aerogel Monoliths, Nathaniel Patrick Hawthorne

Honors Theses

This thesis presents the preparation and spectroscopic characterization of silica aerogel monoliths containing one or more types of entrapped luminescent species. We are characterizing the response of aerogel-platform sensors to environments with varying amounts of oxygen and investigating whether it is possible to detect changes in luminescence signal based on the movement of oxygen through the aerogel monoliths.

Our experiments indicate that for platinum(II) octaethylporphyrin (PtOEP) aerogels, the decrease in luminescence in the presence of oxygen is not linear with respect to the increase of concentration of oxygen. Various two-site models can be used to determine the accessibility of the …

Kinetic Modeling Of Catalytic Aerogels, Yi Cao

Honors Theses

As pollution becomes an increasing concern globally, strict regulations have been set on vehicle pollutant emissions. The three-way catalytic converter is capable of converting toxic emissions such as carbon monoxide, unburned hydrocarbons and nitrogen oxides to less hazardous waste such as carbon dioxide, water, and nitrogen. Current catalysts employ platinum group metals, which are expensive and environmentally damaging to mine. Catalytically-active aerogels such as Co-Al, Cu-Al and V-Al aerogels have shown promise as alternatives to these metals. The work presented here adapts and extends a global kinetic model which predicts the conversion of hydrocarbons and carbon monoxide on platinum catalyst …

Mechanical Routes To Biocontinuous Conductive Polymer Networks For Solar Cell Applications, Erin Waterman

Honors Theses

We have successfully created the first example of a bicontinuous conductive polymer network for use in hybrid QD-polymer solar cells via a mechanochemical route. Heterometallic dicyanoaurate coordination polymers were used as intercalative hosts to promote in situ growth of emeraldine polyaniline (PANI), which provides electron conduction pathways within the active layer. Cu2+-excanged Laponite RD nanodiscs were used to direct the self-assembly of the bicontinuous polymer networks and nanomorphology within the nanocomposites. These PANI/Laponite coordination polymers were extensively characterized by scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and ultraviolet-visible absorption spectroscopy in order to probe polymer-nanoparticle and polymer-polymer interactions. …

3d Flowerlike Micro/Nanocomposite Ceria To Remove Arsenic And Chromium In Drinking Water, Taera Kim

Honors Theses

Ceria has received great attention for the removal of water contaminants due to its high oxygen storage capacity, marked oxygen ion conductivity, and tunable catalytic activity. Zhong et al. suggested that ceria (cerium oxide) microspheres with nanoscale 3D flowerlike morphology represent a promising inorganic synthetic material to remove water contaminants such as As(V) and Cr(VI) from drinking water. The 3D flowerlike micro/nanocomposite ceria offer key advantages over other nanoparticle based remediation systems as they can be easily removed via conventional microfiltration. The goals of this thesis project were to test the reproducibility of the synthesis of the 3D flowerlike ceria, …

Prediction Of Metal Charge-Dependent Amide Hydrogen Exchange Rates For The Proteins Rubredoxin And Azurin, Stephen Scoglio

Honors Theses

Although it has been shown that the hydrogen exchange rates between the most slowly exchanging amide protons of a protein and the solvent can be used to predict the global thermodynamic stability of a protein, the great majority of amide hydrogens along the backbone of a protein exchange from either partially or fully folded conformations, and their rate of exchange strongly depends upon the environment in that folded state. We are examining the electrostatic and conformational dependence of the hydrogen exchange kinetics of Pseudomonas aeruginosa azurin, which can bind either the diamagnetic Cu(I) or Zn(II) in its active site and …

Alumina-Based Aerogels By Rapid Supercritical Extraction For Use In Green Automotive Catalysis, Nicholas J. Dunn

Honors Theses

Aerogels are highly porous solids with low bulk density, high specific surface area, high thermal stability and tunable chemical composition. These properties make aerogels interesting for use as catalysts in automotive exhaust remediation. Noble metals such as platinum are currently used for this function, but are costly and harmful to the environment. Aerogels offer a potential alternative to noble metals that could reduce both the cost and environmental impact associated with catalytic converter production. Alumina and nickel-alumina aerogels have shown activity in catalyzing exhaust processing reactions. The environmental impact of the production of aerogel catalysts could be further reduced by …

Fabrication And Analysis Of Teos- And Mtes-Based Aerogels Prepared Via Rapid Supercritical Extraction, Suzanne K. Estok

Honors Theses

Silica aerogels were prepared using the precursor tetraethylorthosilicate (TEOS) and an organically modified TEOS derivative (methyltriethoxysilane, MTES) via a rapid supercritical extraction (RSCE) method. Multiple consistent batches of monolithic TEOS-based aerogels were fabricated via an eight-hour RSCE process. Fabricating TEOS-based aerogels with an RSCE method offers some distinct advantages. The main advantage is the relative simplicity of the RSCE approach: liquid precursors are mixed and poured into a mold in a hydraulic hot-press, where gelation, aging and extraction of liquid from the pores occur. The precursor recipe employs TEOS, ethanol, water, oxalic acid to catalyze hydrolysis, and ammonia to catalyze …

Progress Towards An Aza-Michael Addition To Ketones, Bowman Potter

Honors Theses

The aza-Michael addition to unsaturated ketones under neutral to mildly basic condition is a difficult transformation due to the inherent unreactivity of ketones toward the addition of weak nucleophiles. This thesis reports on efforts to develop an environmentally friendly, stereoselective and low-cost organo-catalyzed aza-Michael reaction between unsaturated ketones and nitrogen nucleophiles, such as phthalimide, under neutral to mildly basic conditions using the most inexpensive chiral secondary amine catalyst, proline.1 Both proline and the organic base triethylamine were found to be catalytic in the testing platform of cyclohexen-2-one and phthalimide, and another testing platform of 4-hexen-3-one and phthalimide. Likewise, when screened …

Synthesis And Structural Characterization Of Isotopically Labeled Asymmetric Metal Complexes : Through Metal Coupling Of Nmr Active Nuclei, Jenna Lynn Welby

Honors Theses

No abstract provided.

Preparation Of C2 Symmetric Transition Metal Complexes As Potential Chiral Catalysts, Lauren Jean Carlson

Honors Theses

Catalytic asymmetric synthesis is of great importance to the industrial production of biologically active substances such as pharmaceuticals, flavoring and sweetening agents, and insecticides. A special class of C2 symmetric transition chiral metal complexes has proven very useful in catalytic asymmetric synthesis.

Spectroscopic Analysis Of Oxygen Sensing Aerogels, John Robert Ferrarone

Honors Theses

No abstract provided.

The Synthesis And Evaluation Of A More Highly Conjugated Molecular Transporter, Aaron M. Almeida

Honors Theses

No abstract provided.

Α-Arylation Of Cyclopentanone : Palladium-Catalyzed Coupling Of Enamines And Aryliodides & N-Acyloxazines As Novel Bicyclic Weinreb Amides, Kristina M. Gehring

Honors Theses

The introduction of an aryl group a to a carbonyl is a useful step in the preparation of a variety of biologically interesting compounds. The palladium-catalyzed a-arylation of ketones and esters, through their enolates, has received a great deal of attention lately. Despite these efforts, cyclopentanones remain one of the most difficult classes ofketones to arylate. Many of these methods suffer from the limitation of the relatively basic reaction conditions needed in order to prepare the enolate nucleopbiles in­situ. The direct palladium-catalyzed α-arylation of enamines as an alternative route to α­aryl ketones bas received very little attention and might be …

Synthesis And Characterization Of Novel 1-Substituted Meta-Terphenyls For Platinum Complexes, Sarah Marie Sparks

Honors Theses

The unique luminescent properties of aryl, tridentate platinum complexes has led to an increased interest and investigation of various binding modes, with an emphasis on ligand design. These complexes are anticipaterl to be useful in chemical sensing, organic light emitting diodes, and solar energy converters.

Efficient Synthesis Of N9-Alkylguanines : & Evaluation Of A More Highly Conjugated Analog Of Guanidinium-Rich Molecular Transporters Using A Ph Dependent Fluorescence Assay, David E. Olson

Honors Theses

Synthesis of N9-(2-chloroethyl)guanine from 2-amino-6-chloropurine was accomplished in three steps with an overall yield of 83%. All products were purified via crystalli7.ation and no chromatography was required. Selective crystallization of the desired N9 isomer subsequent to the key alkylation step completely and efficiently removed the N7 isomer. This compound was shown to be a versatile reagent in the synthesis of various N9-substituted guanines.

The Synthesis And Characterization Of A Metal Complex Containing Chemically Non-Equivalent Axial Cyanide Ligands, Derek D. Wayman

Honors Theses

In order to analyze the magnitude and factors which effect 13C-13C NMR coupling through a metal center, we have synthesized an octahedral dicyano cobalt (III) complex in which two trans cyanides are chemically non-equivalent. Although similar complexes have been reported, their spectroscopic characterization with isotopically labeled cyanide (13CN) has yet to be studied in detail.

The Synthesis And Characterization Of A Metal Complex Containing Chemically Non-Equivalent Axial Cyanide Ligands, Derek D. Waymand

Honors Theses

In order to analyze the magnitude and factors which effect 13C-13C NMR coupling through a metal center, we have synthesized an octahedral dicyano cobalt (III) complex in which two trans cyanides are chemically non-equivalent. Although similar complexes have been reported, their spectroscopic characterization with isotopically labeled cyanide ( 13CN) has yet to be studied in detail.

Inclusion Of Customized Quantum Dots Into Laponite Based Nanocomposites, Jennifer Rae Eliseo

Honors Theses

Quantum dot (QD) semiconductor nanocrystals offer unique electronic, magnetic, and optical properties, that can be used in advanced materials applications including optoelectronics, catalysis, sensing, and quantum computing. Tailoring of quantum dot surface coatings allows for control of self-assembly and facile inclusion into various host matrices. Querner and colleges have provided a novel synthetic route to graft aniline tetramer units onto quantum dots via a disulfide bridge. A key goal of our work has been the optimization of this synthesis for inclusion of functionalized QDs within Laponite/polyaniline nanoscaffolds. Uv/visible and fluorescence spectroscopy were used to study frequency resonance energy transfer within …

The Effects Of Water On The Physical Properties Of Silica Aerogels, Shira G. Mandel

Honors Theses

The research found in this report focuses on varying the amount of water used in the fabrication of silica aerogels and characterizing the effect this has on their physical properties, such as density, thermal conductivity and transmittance. So far, the aerogels made with the "original" recipe have produced average density of 0.09 g/cm3 and thermal conductivity of 0.04 W/mK; these properties are not significantly altered as the amount of water used is increased or decreased. However, there is an observable trend in transmittance; as more water is added to the "standard" recipe, the resulting monoliths become more transparent and less …

The Design, Synthesis And Analysis Of High-Affinity Peptide-Peptoid Hybrid Ligands That Bind Evh1 Domains & The Synthesis Of 1-Substituted M-Terphenyls That Seve As N^C^C And O^C^C Ligands For Use In Cyclometallated Platinum Complexes, Eric J. Dimise

Honors Theses

Protein-ligand interactions are often at the center of cellular regulatory processes. The Enabled/ vasodilator Stimulated Phosphoprotein Homology 1 (EVH1) domain of the Enabled/ Vasodilator Stimulated Phosphoprotein (Ena/VASP) protein family has been linked to the regulation of the actin cytoskeleton through multiple protein-protein interactions via the recognition of polyproline amino acid sequences. Here, we examine the structural and physicochemical features of the EVH1 domain in an effort to design high affinity peptide-peptoid hybrid ligands that compete with EVH1's natural binding partners. & The unique photophysical properties of aryl, tridentate complexes of platinum have recently led to a surge in ligand design …