Physical Sciences and Mathematics Commons^™

Bonding Theatre And Chemistry: An Educational Exploration, Matthew Gurniak

Senior Honors Projects, 2010-2019

This paper analyzes the educational aspects of theatre and music and the impact that they have on an audience. The goal was to begin a new conversation about science and theatre and how the two can learn and gain unique insight from each other. To examine how these two antithetical fields can interact, I composed a new, innovative musical that tells the love story between two professors through the use of concepts from general chemistry. The results and responses from the performance of the play were overwhelmingly positive from members of both disciplines. They have inspired continued interest in this …

Assessing The Impact Of A Constructed Wetland Biome On The Ecosystem Health Of Cedar Run, Thomas Vasilopoulos, Casey Lee

Senior Honors Projects, 2010-2019

A wetlands ecosystem is defined as “an area saturated by surface or groundwater at a frequency or duration sufficient to support...a prevalence of vegetation typically adapted for life in saturated soil conditions” (Batzer and Sharitz, 2007). Wetlands serve as biofilters and thus have been used to treat sewage and wastewater, as well as to restore the health of polluted water systems. Solly Walker and Lorinda Palin, owners of a certified natural and biodynamic farm called Avalon Acres located in Broadway, Virginia, constructed a wetland two years ago, using the stream, Cedar Run, that flows through their property. Pollution from agricultural …

The Synthesis And Characterization Of Photoluminescent Conjugated Frameworks Containing Silicon And Germanium, Douglas William Hammerstroem

Dissertations

Siloles and 9-heterofluorenes (Si, Ge) are conjugated π-electron systems containing Group 14 atoms which demonstrate unique properties such as high electron affinity, mobility, and bathochromically shifted optical spectra relative to their all-carbon analogs. This is due to their low-lying lowest-unoccupied molecular orbital (LUMO) which is resultant of the σ*-π* conjugation between the exocyclic groups at the Group 14 center and the butadiene unit of the ring. As a consequence, they have received considerable attention for their use as components for a wide variety of optical and electronic applications such as organic light emitting diodes (OLEDs), photovoltaic devices, field-effect transistors (FETs), …

Biogenetically Inspired Total Synthesis Of Lingzhiol. Design And Synthesis Of Axially Chiral N-Heterocyclic Carbene Catalysts., Krishna Sharmah Gautam

Arts & Sciences Electronic Theses and Dissertations

A stereo- and enantio-selective synthesis of lingzhiol has been achieved, mimicking a proposed biogenetic pathway via Brønsted acid-catalyzed semipinacol rearrangement of a 2,3-epoxy alcohol. A new and improved method was developed for alkylation of anilines using a domestic microwave oven. The resulting racemic chiral anilines were resolved via classical resolution and transformed into axially chiral thiazolylidene-based NHC organocatalysts, which were applied to asymmetric benzoin condensation.

Synthesis Of Metal-Containing Phosphines And Their Use In Coordination, Polymer, And Materials Chemistry, Amir Rabiee Kenaree

Electronic Thesis and Dissertation Repository

This thesis describes the investigation of a novel strategy for the synthesis of metal-containing small molecules, polymers, and nanomaterials. In this context, a new family of air-stable, homo- and heterometallic primary, secondary, and tertiary phosphines were prepared via the radical-initiated hydrophosphination reaction of PH₃ with vinylferrocene and/or vinylruthenocene. The full characterization of the phosphines confirmed their targeted structures and proved that the properties of the starting metallocenes are reflected in those of the resulting phosphines.

To study the coordination behavior of this family of phosphines, primary, secondary, and tertiary ethylferrocene phosphines were reacted with Group 6 metal carbonyl adducts …

Separation Of Nitrito- And Nitropentamminecobalt (Iii) Chloride By High Performance Liquid Chromatography, Tisha Hutchinson

Seton Hall University Dissertations and Theses (ETDs)

Reversed phase high performance liquid chromatography, chosen because of its ability to collect many data points over a long period of time with minimal involvement, was used to separate pentaamminenitritocobalt(III) chloride and pentaamminenitrocobalt(III) chloride. Pentaamminenitritocobalt(III) chloride was prepared, made into a concentrated solution, divided into aliquots and allowed to isomerize to pentaamminenitrocobalt(III) chloride over a period of twelve to eighteen hours. An injection was made approximately every forty-five minutes. The samples were analyzed at three wavelengths, 254 nm, 460 nm and 490 nm. The absorbance was collected and was used to determine the kinetics of the reaction.

The isomerization from …

Formulation Of Colloidal Suspensions Of 3-Mercaptopropionic Acid Capped Pbs Quantum Dots As Solution Processable Qd "Inks" For Optoelectronic Applications, Chase Collier Reinhart

Dissertations and Theses

The use of colloidal quantum dots (QDs) for photovoltaic energy conversion is a nascent field that has been dominated for well over a decade by the use of 3-mercaptopropionic acid (3-MPA) capped PbS QDs. These QDs are routinely deposited via an in situ solid state ligand exchange process that displaces the native oleate ligand on the PbS QD surface. This ligand exchange procedure is wasteful of material and has been demonstrated to leave numerous impurities that limit electronic performance of the as-deposited QD devices. Until the last few years there was very little understanding in chemical literature as to many …

X-Ray Absorption And Emission Studies Of Anodic Titania Nanostructures, Jun Li

Electronic Thesis and Dissertation Repository

One-dimensional (1D) TiO₂ nanomaterials with ordered structure have been extensively applied in various fields, such as photocatalysts, solar cells, supercapacitors and rechargeable batteries, due to the unique structural and functional properties compared to the disordered nanoparticulate forms. Nevertheless, intrinsic disadvantages of TiO₂, such as its large band gap (~3 eV), fast recombination rate of photoexcited electron–hole pairs and insufficient ionic conductivity, severely limit the development of 1D TiO₂ nanomaterials for practical applications. To address the above issues, the scope of this thesis focus on the fundamental understandings of the electronic structure of highly ordered TiO_{2 …}

Creating Functional Materials With Phosphorus, Tyler John Cuthbert

Electronic Thesis and Dissertation Repository

Understanding the relationship between small molecules or polymers and how they affect the properties of materials they compose is the basis of materials science. Using unique and versatile components can impart useful and interesting properties to materials. Here, we aimed to extend this understanding to phosphorus, and the known properties it possesses. This included the production of photopolymerizable coatings containing phosphonium molecules and polymers for antifouling and antibacterial applications. The synthesis and characterization of these phosphonium components was completed and materials were produced utilizing UV curing technology. Addition of these components produced coatings that could resist bacteria attachment and efficiently …

Development Of An Hplc-Based Oligosaccharide Synthesizer, Salvatore Pistorio

Dissertations

Carbohydrates are the most abundant molecules on Earth. They are involved in a wide range of fundamental biological processes: anti-inflammation, immune response, joint lubrication, cell growth, antigenic determination. Carbohydrates are also held responsible for many damaging cellular processes, such as bacterial and viral infections, development of tumors, etc.. Therefore, the development of effective methods for the synthesis of complex carbohydrates has become a critical area of glycosciences. One challenge that stands out is the stereocontrol in the synthesis of glycosidic bonds, the linkage that serves as the only means to connect simple monosaccharides into complex oligomeric networks. Beyond this, the …

Properties Of High Nitrogen Content Carbon Nitride Thin Films Prepared By A Radio Frequency Magnetron Sputtering Deposition Technique, David Pipher

Electronic Thesis and Dissertation Repository

The properties of carbon nitride (CNx) films deposited onto various substrates using a radiofrequency magnetron sputtering technique were studied as a function of deposition parameters, especially magnetron power, gas pressure and nitrogen content in the plasma. Indium tin oxide (ITO) coated glass and fluorine tin oxide (FTO) coated glass as well as metal substrates (silver and tungsten) were used. Scanning electron microscopy (SEM) was used to study the surface morphology of the prepared CNx films. Energy-dispersive X-ray spectroscopy (EDX) as well as survey X-ray photoelectron spectroscopy (XPS) spectra were used to perform the elemental analysis of the CNx films.

Ultraviolet-visible …

Synthesis Of Metal-Containing Polymers And Stable Organic Radical-Containing Polymers And Their Use As Advanced Functional Materials, Joseph A. Paquette

Electronic Thesis and Dissertation Repository

The work presented in this thesis details the synthesis and characterization of two different families of multifunctional polymers. The first family involved the incorporation of stable 6-oxoverdazyl radicals into polymer scaffolds. This was originally achieved by the polymerization of the radical precursors, phenyl- and isopropyl-6-oxotetrazanes, followed by post-polymerization oxidation to afford the phenyl- and isopropyl-6-oxoverdazyl polymers. A second methodology involved the direct polymerization of isopropyl-6-oxoverdazyl radicals using ring-opening metathesis polymerization (ROMP) to afford polymers with controlled molecular weights and narrow molecular weight distributions. The polymers were characterized by the close comparison of the physical and spectroscopic properties …

Polyol Induced Partitioning Of Essential Oils In Aqueous Organic Solvent Mixtures, Thomas Delmastro

Seton Hall University Dissertations and Theses (ETDs)

Polyol Induced Extraction (PIE) was developed and patented at Seton Hall University by Drs. John R. Sowa Jr., Wyatt R. Murphy, and Mithilesh Deshpande. It was originally discovered and implemented as a method to recycle and reuse waste acetonitrile during the production shortage in 2008. Through the use of PIE, a solvent mixture containing acetonitrile and water can be separated by employing a polyol mass separating agent, which induces a phase separation. The system is separated into its corresponding aqueous and organic phases, with the organic phase being a highly purified organic liquid. Based on the successful experimental results that …

Investigations Into The Effects Of Water Exchange And The Structure Of Lanthanide Chelates, Katherine Marie Payne

Dissertations and Theses

Lanthanide chelates are effective agents for improving contrast in MR images. Optimizing the relaxation of inner sphere water molecules is a common focus of research in this field. However, the efforts to design an optimal contrast agent have commonly over-looked the relationship of water position and water exchange kinetics. This work explores structural conformation, the impact of very fast water exchange kinetics on hydration, and differing tumbling rates for regioisomers of a number of lanthanide chelates. We have grown crystals of LnDOTMA and obtained structural data by X-ray diffraction that provide a picture of the chelate during water exchange and …

Synthesis, Reactivity, And Nmr Trends Of Early Transition Metal Compounds, Tabitha Marie Cook

Doctoral Dissertations

This dissertation focuses of three different subjects. The first is the synthesis and characterization of heptacoordinate amidinate compounds. Heptacoordinate compounds are not common, but their structures have been studied. Group 4 amidinate compounds have been used as precursors in the CVD/ ALD processes. Ancillary ligands, such as amidinates, have been used to reduce air-sensitivity of complexes. Reactions of these complexes with water have been used to make metal oxide thin films.

In the first study, the complexes Zr[MeC(NⁱPr)₂]₃Cl [zirconium trisamidinate chloride], Hf[MeC(NⁱPr)₂]₃Cl [hafnium trisamidinate chloride], Zr[MeC(NⁱPr) …

The Effect Of Illumination On The Conformation And Thermodynamics Of Conjugated Polymers, Brian Frank Morgan

Doctoral Dissertations

This dissertation explores the effects which illumination has on the structure and conformation of conjugated polymers, both in solution and the bulk. Conjugated polymers are an important class of optoelectronic polymeric materials which make up the active layer of key organic electronic devices such as organic photovoltaics, transistors, and light emitting diodes. Considering the strong link between polymer chain structure and device efficiency in these materials, a comprehensive understanding of certain experimental conditions which may influence this conformation and thusly alter the functionality of the devices predicated upon them is of vital importance.

The first part of this dissertation provides …

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …

Computational Quantum Chemistry Studies Of The Stabilities Of Radical Intermediates Formed During The Oxidation Of Melatonin, Constance E. Warden

Electronic Theses and Dissertations

Melatonin, a nontoxic natural antioxidant, is of interest as a possible spin trap for use in spectroscopic methods to observe and identify short-lived free radicals, which have been linked to oxidative stress that may result in serious health problems. However, the reaction mechanisms for the oxidation of melatonin to form the product N¹-acetyl-N²-formyl-5-methoxykynuramine are still not well understood. Computational quantum chemistry studies have been done on four proposed reaction mechanisms, involving the following major intermediate structures: a dioxetane, an epoxide, a melatonin radical cation, and a spin radical adduct. Molecular geometries were optimized at the …

Electrogenerated Chemiluminescence Study Of Semiconductor Nanoparticles Towards Sensitive Detection Of Biomolecules, Yiliyasi Wusimanjiang

Dissertations

The main focus of this dissertation is to unfold the fundamental aspects of electrogenerated chemiluminescence (ECL) generation from semiconductor nanoparticles (also known as quantum dots or QDs) within different ECL systems. The ECL and photo-physical interactions between the CdTe QDs (λ_emission= ~760 nm) and the CdSe QDs (λ_emission= ~550 nm), as well as the effects of carbon nanotubes on ECL of QDs were separately investigated. Optimum experimental conditions for peptide bond formation on an electrode surface through EDC (1-ethyl-3-(-3-dimethylaminopropyl) carbodiimide hydrochloride)/NHS (N-Hydroxysulfosuccinimide) coupling were also revealed using cyclic voltammetry technique. Based on the information …

Ambient Ionization - Mass Spectrometry: Advances Toward Intrasurgical Cancer Detection, Alan Keith Jarmusch

Open Access Dissertations

My dissertation research has focused on the development of ambient ionization – mass spectrometry (MS) for clinical measurements, specifically intrasurgical cancer detection. The molecular differences between normal and cancerous tissue were detected via direct tissue analysis in vitro by touch spray ionization (TS) or by analyzing sectioned or smeared tissue using desorption electrospray ionization (DESI). The physical form of the tissue, e.g. in vitro sampling, sectioned, or smeared, was inconsequential in differentiating normal from cancerous tissue; however, the spectra acquired by TS and DESI differed due to differences in ionization processes. We envision that TS-MS and DESI-MS could impact diagnostic …

Preparative Mass Spectrometry Applications In Nanomaterials And Organic Synthesis, Michael Wleklinski

Open Access Dissertations

Preparative mass spectrometry was traditionally a vacuum based experiment where mass selected ion beams were deposited onto surfaces; however, recently ions have been manipulated in the open air to perform accelerated synthesis. The work of this dissertation focuses on the generation of charged ions from microdroplets and their use in organic synthesis and the preparation of atomically precise metal nanoclusters. First the mechanism for charging in the zero volt paper spray will be presented. This works builds a computational model based on the statistical fluctuation of positive and negative charges based on the theory of Dodd. It is found through …

Synthesis And Performance Of Novel Supramolecular Tools For Single-Particle Cryogenic Electron Microscopy And Drug And Gene Delivery, Kyle J. Wright

Open Access Dissertations

High-resolution biomacromolecular structure elucidation is fundamentally important to structure-based drug design and basic research into complex biochemical processes. Cryo-EM is an emerging alternative to XRD and NMR that is complementary in many ways relative to XRD and NMR. Materials approaches to cryo-EM are anticipated to greatly facilitate the cryo-EM process, allowing progress toward a more high-throughput application of cryo-EM to address challenges in structural biology. ^ Various affinity-based approaches inspired by approaches previously introduced for 2D crystallization were developed for facilitation of cryo-EM. A library of affinity lipopolymer constructs were synthesized consisting of lipopolymers of various PEG molecular weights conjugated …

Investigating Materials That Promote New Organic Methodology And Remediation Of Volatile Organic Compounds, Mckenzie Louise Campbell

All Dissertations

The need for environmentally safe reagents for the promotion of organic transformations is critical in order to reduce hazardous waste and byproducts associated with industrial-scale chemical processes. We have developed two practical methods that obviate the need for harsh oxidative and toxic brominating reagents in electrophilic halogenation reactions.

In our hands, a catalytic loading of the inexpensive, commercially available V2O5 (~$0.25/g) promotes the bromolactonization of a series of substituted alkenoic acids in isolated yields up to 97% by means of the in situ generation of bromenium (Br+) from bromide (Br−) at room temperature. This process obviates the need for molecular …

In-Column Polymer Modifications: Advancing Polymer Bonded Phases, Alexis G. Huckabee

Open Access Dissertations

Glycosylation is the most common post-translational modification affecting protein activities, including delivery to cell surface, binding affinity, and mediating different physiological effects. Separations of glycoproteins and their glycoforms are essential for drug discovery and development, identification of potential disease biomarkers and quality control. The efficiency of glycoprotein separations is limited by the bonded phases, requiring advances in chromatographic materials. Such advances would improve resolution, allowing for more species to be isolated from a mixture and studied.

Our group found that submicrometer nonporous silica stationary phases with tethered polymer chains (acrylamide) give excellent hydrophilic liquid chromatography (HILIC), a common method used …

Redox-Active Ligand Uranium Complexes For Approaches To Multi-Electron Chemistry, John J. Kiernicki

Open Access Dissertations

While transition metal complexes are known to participate in multi-electron redox chemistry to facilitate important organometallic transformations, actinides, due to their low redox potentials, have a propensity to perform single electron chemistry. Because of its highly reducing nature, the ability to control the electronics of low-valent uranium is highly sought after as this may lead to unprecedented reactivity. Our lab has specifically been interested in mediating multi-electron transformations at uranium by employing redox-active ligands. Redox-active ligands can be used to facilitate multi-electron processes such as oxidative addition and reductive elimination at single metal centers. Using primarily 2,6-((Mes)N=CMe)2C5H3N) ( MesPDIMe) as …

Part 1: Design, Synthesis, And Evaluation Of Novel Gram-Positive Antibiotics Part 2: Synthesis Of Dihydrobenzofurans Via A New Transition Metal Catalyzed Reaction Part 3: Design, Synthesis, And Evaluation Of Bz/Gabaa Α6 Positive Allosteric Modulators, Christopher Michael Witzigmann

Theses and Dissertations

Part 1. Lead compound SK-03-92 represents a new scaffold for antibiotic drug discovery. Development of a new process for the synthesis of analogs has led to the development of a number of new ligands with even more potent activity against gram-positive bacteria, including drug-resistant strains of S. aureus. Compounds 36 and 38 represent some of the most potent analogs developed thus far, and preliminary results indicate that they are also not cytotoxic. Research into a Heck-mediated transition metal catalyzed pathway towards electron-rich stilbenoid analogs has greatly expanded the scope of future SAR studies. This development has led to 14 new …

Design And Synthesis Of Lipid Probes Used For Membrane Derivatization And Fusion, Stuart Allen Whitehead

Doctoral Dissertations

Lipids control a variety of complex biological processes. Bulk lipids such as phosphatidylcholine (PC), phosphatidylserine (PS), and phosphatidylethanolamine (PE) represent the major components of cellular membranes. In addition, unilamellar vesicles composed of lipids (liposomes) are valuable for delivery applications since they can encapsulate and transport drugs and other agents. In order to maximize delivery efficiency and target specific membranes, the ability to trigger and control vesicle-vesicle fusion is desirable. Such approaches generally seek to mimic the membrane fusion machinery present in nature while imparting specificity in the membranes that undergo fusion. The goal of this work is selective drug delivery …

Development Of An F-Element Separation Chemistry Using Solid Electrolytes, Kristian Guy Myhre

Doctoral Dissertations

The f‒elements (lanthanides and actinides) have numerous applications and are critically important to many industries, including the energy, security, and medical industries. One of the barriers to increased use and availability of the f‒elements is the difficulty in separating them from each other due to their similar chemistries. This is especially true of the trivalent f‒elements (lanthanides and minor actinides). The development of separation techniques that maximize the differences in the physicochemical properties of the f‒elements is therefore an important area of research. For these reasons, an effort was undertaken to explore the use of solid …

Catalytic Aziridination With A Borate-Containing N-Heterocyclic Tetracarbene Iron Complex, Preeti Pradip Chandrachud

Doctoral Dissertations

Aziridines, the nitrogen analog of epoxides, are an important class of compounds. They are present in many biologically active compounds having antibacterial and antitumor properties. Along with biological significance, it can also be considered as a synthetic tool for various functional group transformations. Being an important functional group we focused on the development of synthetic methodology using alkenes as substrates and organic azides as the nitrene source [C₂ (carbon2)+ N₁ (nitrogen1) addition reaction].

For the potential use as an aziridination catalyst a macrocyclic N-heterocyclic tetracarbene (NHC) ligand system was developed. First, the neutral NHC ligand was used …

Synthesis And Behavior Of Stimuli-Responsive Shape-Changing Linear Molecular Bottlebrushes, Daniel Mark Henn

Doctoral Dissertations

Molecular bottlebrushes are composed of polymer side chains densely grafted to a macromolecular backbone. The main focus of this dissertation work is the synthesis and behavior of linear molecular brushes that can undergo unimolecular size and shape changes in response to environmental stimuli in dilute aqueous solution. Chapter 1 provides an introduction to molecular bottlebrushes and stimuli-responsive polymers.

Chapter 2 presents the development of a robust method for the synthesis of well-defined molecular brushes by a “grafting to” approach using copper-catalyzed azide-alkyne cycloaddition “click” reactions. Well-defined, new azide-containing backbone polymers with different lengths and high degrees of azide functionality were …