Chemistry Commons^™

Two-Dimensional Transient Spectroscopy Measuring Heterogeneity In Electronic And Rotational Dynamics, Haorui Wu

Theses and Dissertations

Multiple population-period transient spectroscopy (MUPPETS) is a picosecond, time resolved experiment that uses a sequence of six laser pulses. It was previously known that MUPPETS could measure heterogeneity in electronic-state decay. This dissertation presents two projects that extend MUPPETS to new processes. One process is the extension from 2-level system into 3-level system, another new process extends the kinetics from electronic decay to rotational decay. In addition, a third, ongoing project on rotational dynamics in ionic liquids will also be discussed briefly. The first project consisted of two main parts. The first part focused on the biexciton decay in semiconductor …

Applications Of Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy For Forensic Analysis, Zhenyu Lu

Theses and Dissertations

Blood stains, which are among the traces encountered most frequently at crime scenes, are important for potential extraction and amplification of DNA for suspect identification, as well for spatter pattern analysis to reveal a sequence of events. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was used in detection of blood stains and age estimation because of signature absorbances in the mid-infrared region at 3300 cm-1 (Amide A), 2800-3000 cm-1 (Amide B), ~1650 cm-1 (Amide I), ~1540 cm-1 (Amide II) ,and 1200-1350 cm-1 (Amide III). Position and intensity shifts for amide peaks were observed due to aging changes occurring as …

Sustainable Polymeric Materials Derived From Novel Soybean Based Monomers And Polymers: From Synthesis To Applications, Nathan Trenor

Theses and Dissertations

In this thesis, monomers and polymers derived from high oleic soybean oil are investigated. The properties of these monomers and polymeric materials are characterized and discussed. Chapter 1 describes an overall background of bio-based resources, monomers, polymers, and their potential impact on society. Polymerization techniques are introduced, and the overall objective of my research is described. Chapter 2 outlines the large scale preparation of a soybean based monomer and the use of this monomer in thermoset elastomers. The synthetic procedures and characterizations of the monomers and polymers are discussed. A model study using oleic acid is described and proved to …

Novel Block Copolymer Architectures For Lithography-Relevant Self-Assembly, Jeffery Hakim Hayat

Theses and Dissertations

This dissertation is focused on the synthesis, characterization, self-assembly, and materials processing of various functionalized block copolymer systems. A variety of monomers were prepared and polymerized through various polymerization techniques including atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, and ring-opening metathesis polymerization. Self-assembly of the functionalized block copolymers led to well-defined nanostructures in bulk and thin films. These materials have the capability to be utilized in various applications including ordered catalysts and templates for nanolithography. In Chapter 1, the overall background of diblock and triblock copolymers and their preparation methods is in this dissertation. Major research objectives of …

Supramolecular Coordination Networks Of S- And F-Block Metals Featuring The 1,8-Naphthalimide Tecton, Andrew Paul Leitner

Theses and Dissertations

The reactions of (S)-2-(1,8-naphthalimido)propanoic acid (HLala), and (S)-2-(1,8- naphthalimido)-3-hydroxypropanoic acid (HLser), protonated forms of ligands that contain a carboxylate donor group, an enantiopure chiral center and a 1,8-naphthalimide π...π stacking supramolecular tecton and in the case of HLser an alcohol functional group, with the appropriate alkali metal hydroxide followed by a variety of crystallization methods leads to the formation of crystalline K(Lala)(MeOH) (1), K(Lala)(H2O) (2), Na(Lala)(H2O) (3), KLser (4), CsLser (5) and CsLala (6). Each of these new complexes has a solid state structure based on six-coordinate metals linked into homochiral helical rod SBU central cores. In addition to the …

Direct Phenotypic Screening In Mice: Identification Of Individual, Novel Antinociceptive Compounds From A Library Of 734 821 Pyrrolidine Bis-Piperazines, Richard A. Houghten, Michelle L. Ganno, Jay P. Mclaughlin, Colette T. Dooley, Shainnel O. Eans Torrey Pines Institute For Molecular Studies, Radleigh Santos, Travis Lavoi, Adel Nefzi, Greg Welmaker, Marc A. Giulianotti, Lawrence Toll

Mathematics Faculty Articles

The hypothesis in the current study is that the simultaneous direct in vivo testing of thousands to millions of systematically arranged mixture-based libraries will facilitate the identification of enhanced individual compounds. Individual compounds identified from such libraries may have increased specificity and decreased side effects early in the discovery phase. Testing began by screening ten diverse scaffolds as single mixtures (ranging from 17 340 to 4 879 681 compounds) for analgesia directly in the mouse tail withdrawal model. The “all X” mixture representing the library TPI-1954 was found to produce significant antinociception and lacked respiratory depression and hyperlocomotor effects using …

Group 6 Metal Pentacarbonyl Complexes Of Air-Stable Primary, Secondary, And Tertiary Ferrocenylethylphosphines, Amir Rabiee Kenaree, Ethan R. Sauvé, Paul J. Ragogna, Joe Gilroy

Chemistry Publications

The synthesis and characterization of a series of Group 6 metal pentacarbonyl complexes of air stable primary, secondary, and tertiary phosphines containing ferrocenylethyl substituents are reported [M(CO)₅L: M = Cr, Mo, W; L = PH₂(CH₂CH₂Fc), PH(CH₂CH₂Fc)₂, P(CH₂CH₂Fc)₃]. The structure and composition of the complexes were confirmed by multinuclear NMR spectroscopy, IR and UV-Vis absorption spectroscopy, mass spectrometry, X-ray crystallography, and elemental analysis. The solid-state structural data reported revealed trends in M-C and M-P bond lengths that mirrored those of the …

Substituent Effects On The Binding Of Halides By Neutral And Dicationic Bis-Triazolium Receptors, Binod Nepal, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The effects of substituent and overall charge upon the binding of a halide anion by a bis-triazolium receptor are studied by M06-2X DFT calculations, with the aug-cc-pVDZ basis set. Comparison is also made between a receptor that engages in H-bonds, with a halogen-bonding species. Fluoride is clearly most strongly bound, followed by Cl-, Br-, and I- in that order. The dicationic receptor engages in stronger complexes, but not by a very wide margin compared to its neutral counterpart. The binding is enhanced as the substituent on the two triazolium rings becomes progressively more electron-withdrawing. Halogen-substituted receptors, whether neutral or cationic, …

Method And Apparatus For Cancer Screening, Yinfa Ma, Stephen Gibbons

Chemistry Faculty Research & Creative Works

A method and apparatus for detection of pteridine levels in a biological sample using CE-LIF which is useful for early cancer screening involving fully oxidizing pteridine compounds in a sample such as a urine sample, subjecting to CE-LIF to assess compound concentration, and compare to expected levels in for healthy or cancer-bearing patients.

Assessing The Accuracy Of Some Popular Dft Methods For Computing Harmonic Vibrational Frequencies Of Water Clusters, J. Coleman Howard, Jordan D. Enyard, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

A wide range of density functional theory (DFT) methods (37 altogether), including pure, hybrid, range-separated hybrid, double-hybrid, and dispersion-corrected functionals, have been employed to compute the harmonic vibrational frequencies of eight small water clusters ranging in size from the dimer to four different isomers of the hexamer. These computed harmonic frequencies have been carefully compared to recently published benchmark values that are expected to be very close to the CCSD(T) complete basis set limit. Of the DFT methods examined here, ωB97 and ωB97X are the most consistently accurate, deviating from the reference values by less than 20 cm^-1 on …

Uses Of Diaryliodonium Salts And Methods For Their Synthesis, Jordan M. Veness

Department of Chemistry: Dissertations, Theses, and Student Research

Diaryliodonium salts have been studied continuously since the first report of their synthesis in 1894. Diaryliodonium salts are I(III) derivatives that are air- and moisturestable. The reactivity of these compounds resembles the organometallic chemistry of heavy transition metal ions such as Pb(IV), Hg(II), Th(III), and Pd(II). A significant advantage of diaryliodonium salts is that they can carry undergo many of the aryl functionalization reactions of heavy metal organometallic complexes, yet they have little to no toxicity and they are relatively inexpensive to prepare. The DiMagno laboratory uses diaryliodonium salts as precursors in the final synthetic step of radiopharmaceuticals; given that …

Logistic Regression Models To Predict Solvent Accessible Residues Using Sequence- And Homology-Based Qualitative And Quantitative Descriptors Applied To A Domain-Complete X-Ray Structure Learning Set, Reecha Nepal, Joanna Spencer, Guneet Bhogal, Amulya Nedunuri, Thomas Poelman, Thejas Kamath, Edwin Chung, Katherine Kantardjieff, Andrea Gottlieb, Brooke Lustig

Faculty Publications, Chemistry

A working example of relative solvent accessibility (RSA) prediction for proteins is presented. Novel logistic regression models with various qualitative descriptors that include amino acid type and quantitative descriptors that include 20- and six-term sequence entropy have been built and validated. A domain-complete learning set of over 1300 proteins is used to fit initial models with various sequence homology descriptors as well as query residue qualitative descriptors. Homology descriptors are derived from BLASTp sequence alignments, whereas the RSA values are determined directly from the crystal structure. The logistic regression models are fitted using dichotomous responses indicating buried or accessible solvent, …

Controlled Hydrosilylations Of Carbonyl Compounds And Computational Investigations Of A Hydride Shuttle Mechanism For Alkene Hydrosilylation, Gabriela Trog

Chemistry & Biochemistry Theses - Archive

Chapter 1 describes tandem dual hydrosilylations of α,β-unsaturated enals. Hydrosilylations of both carbonyl compounds and alkenes have been utilized to create chiral alcohols. Tandem dual hydrosilylations (TDH) of α,β-unsaturated carbonyl compounds create five-membered oxasilacycles that can be further converted to 1,3- diols, which are a common structural motif in the polyketide natural product family. We present preliminary data and a substrate scope for the formation of these oxasilacycles en route to the 1,3-diol compounds. Chapter 2 describes hydrosilylations of esters that result in silyl acetals. The silyl acetals are chemical synthons of the corresponding aldehyde. This reaction can be coupled …

Evaluation Of Activated Carbon As A Commercial Drug Disposal Product Using Liquid Chromatography–Tandem Mass Spectrometry, Veronica B. Waybright

Chemistry & Biochemistry Theses - Archive

At present, pharmaceuticals, synthetic organic compounds, and endocrine disrupting compounds are ubiquitous in our environment. These have been introduced by consumers and manufacturers directly and indirectly for decades. There is plenty of published literature addressing the presence of these compounds, the development of newer and more sensitive techniques to detect them at low concentrations, as well as studies showing their effects in the environment and in human health. However, these studies are based on the measurement and detection of these compounds after the fact; and even though some have addressed the need to decrease these pollutants in the environment, procedures …

New Conductometric Detection Methods For Sensitive Ion Chromatographic Measurement Of Weak Electrolytes, Hongzhu Liao

Chemistry & Biochemistry Theses - Archive

Since Suppressed conductometric anion chromatography (SCAC) was proposed in the mid-1970s, SCAC has become a widely used tool for the determination of anion species in aqueous samples. Its application ranges from trace analysis in semiconductor manufacture to pharmaceutical analysis. This dissertation primarily focuses on three different projects on the conductometric determination of weak acids. Other work carried out during the same period both involved SCAC for the determination of anion composition of açaí Extracts and on the unusual ion exchange behavior of myo‐inositol phosphates. SCAC responds poorly and nonlinearly to weak acids, because they only ionize partially and the degree …

Determination Of Total And D-Amino Acid Content In Mice Brain Tissue By Achiral-Chiral Heart-Cutting Two-Dimensional Liquid Chromatography: Diagnostic And Clinical Relevance And A Comparison Between Non-Perfused And Perfused Tissue, Curran Parpia

Chemistry & Biochemistry Theses - Archive

A heart-cutting two dimensional liquid chromatographic method for the quantification of free amino acid enantiomers from mouse brain tissue is demonstrated. Evidence to support the occurrence of D-amino acids in significant concentrations in physiological samples has spurred studies toward the elucidation of their importance and function. In this work, the level and regional distribution of select amino acids were determined by achiral-chiral LC/LC. Additionally, the effect of tissue perfusion on these levels was investigated. The free amino acid extracts were analyzed as their 9-fluorenylmethyloxycarbonyl derivatives and separated in the reverse phase mode on superficially porous C18. In the second dimension, …

Development Of A Miniaturized Ambient Glow Discharge Ionization Source And Its Application In Elemental And Molecular Analysis, Xinyan Zhang

All Dissertations

Since the liquid sampling-atmospheric pressure glow discharge (LS-APGD) was first developed as an excitation source for atomic emission spectroscopy, it has been improved upon and demonstrated as an ionization source for elemental mass spectrometry, molecular mass spectrometry, and ambient desorption mass spectrometry. Multiple functions coming from one package allowed the LS-APGD to hold a unique position among all atmospheric pressure glow discharges. It also has the capabilities to work with different sample forms including liquids, bulk solids, and solution residues. The high salt/matrix tolerance reduces sample prep work and thus provides convenience for its potential use as a field-Based ionization …

Structure-Activity Relationships Of Ruthenium(Ii) Polypyridyl Complexes With Redox-Active Intercalating Ligands: Correlation Between Redox Activity, Dna Cleavage Capability And Cytotoxicity, Eugenia Soyo Narh

Chemistry & Biochemistry Theses - Archive

The investigation and development of transition metal complexes as cancer chemotherapeutics has gained a lot of interest in the past few decades and has become a promising area of research. Metal complexes of platinum and ruthenium in particular that have demonstrated success as anticancer drugs or are under exploration currently for clinical use are highlighted in Chapter 1. Chapter 2 describes studies undertaken to understand the neurotoxicity of ruthenium(II) polypyridyl complexes (RPCs), including toxicity in mice and inhibition of the enzyme acetylcholinesterase (AChE), as previous work by Dwyer demonstrated that RPCs could be acutely toxic in mice, presumably due to …

Synthesis Of Modified Ribose Spin-Label, Ke-Wei Chang

Chemistry & Biochemistry Theses - Archive

Transfer ribonucleic acids (tRNAs) from all organisms contain modified nucleosides, which are derived from four different nucleosides. Research has indicated that tRNA modifications affect translation and various metabolic pathways. Among these modifications, some of them need more than one enzyme to produce specific nucleosides. Researchers are interested in investigating the fundamental mechanisms and function of post-transcriptional modifying enzymes. A number of these enzymes are metal-dependent, such as MiaB and MiaE. MiaE enzyme (2-methylthio-N6-isopentenyl-adenosine(37)-tRNA monooxygenase) stereospecifically hydroxylates an adeonosine derivative at the 37th position of tRNA, ms2i6A37, to complete the hypermodification of 2-methylthio-N6-(4-hydroxyisopentenyl)-adenosine (ms2io6A37). Several studies showed that the ms2io6A37 modification …

Capillary-Channeled Polymer Fibers As Stationary Phases For Protein Chromatography, Marissa Pierson

All Theses

Capillary-channeled polymer (C-CP) fibers have been studied in this laboratory as stationary phases for protein separations in high-performance liquid chromatography (HPLC). C-CP fibers are uniquely shaped so as to include eight continuous capillary-channels which interdigitate once packed into a column. The packed column resembles a monolithic structure of unobstructed flow through capillary channels which reduces backpressure and increases linear velocity, reducing separation time. Fibers are effectively nonporous with respect to macromolecules, resulting in fast mass transfer and high sample recovery. C-CP fibers made from polypropylene (PP) yield a fairly homogenous hydrophobic surface suitable for reversed phase (RP) chromatography. In a …

Production And Harvest Of Microalgae In Wastewater Raceways With Resource Recycling, Alexander Colin Roberts

Master's Theses

Microalgae can be grown on municipal wastewater media to both treat the wastewater and produce feedstock for algae biofuel production. However the reliability of treatment must be demonstrated, as well as high areal algae productivity on recycled wastewater media and efficient sedimentation harvesting. This processes was studied at pilot scale in the present research.

A pilot facility was operated with nine CO₂-supplemented raceway ponds, each with a 33-m² surface area and a 0.3-m depth, continuously from March 6, 2013 through September 24, 2014. The ponds were operated as three sets of triplicates with two sets continuously fed …

An Enantiodivergent Synthesis Of CΑ-Methyl Nipecotic Acid Analogues From δ-Lactam Derivatives Obtained Through A Highly Stereoselective Cyclization Strategy, Souvik Banerjee, Emily R. Vogel, Daniel Hinton, Michael Sterling, Douglas S. Masterson

Faculty Publications

A stereoselective and enantiodivergent strategy for the construction of δ-lactams is described. The strategy utilizes chiral malonic esters prepared from enantiomerically enriched mono esters of disubstituted malonic acid. A cyclization occurs with the selective displacement of a substituted benzyl alcohol as the leaving group. The resulting δ-lactams are then converted into nipecotic acid analogues using straightforward transformations. The resulting nipecotic acid analogues proved capable organocatalysts in Mannich reactions.

Hybrid Sol–Gel Glasses With Glass-Transition Temperatures Below Room Temperature, Andrei Jitianu, Guadalupe Gonzalez, Lisa C. Klein

Publications and Research

Melting gels are hybrid gels that have the ability to soften and flow at around 100 ° C for some combinations of mono- and di-substituted alkoxysiloxanes, where substitutions are either all aromatic or all aliphatic. In this study, melting gels were prepared using phenyltriethoxysilane (PhTES) and dimethyldiethoxysilane (DMDES), meaning both an aromatic and aliphatic substitution. Differential scanning calorimetry was performed to identify glass-transition temperatures, and thermal gravimetric analysis coupled with differential thermal analysis (TGA-DTA) was performed to measure weight loss. The glass-transition temperatures ( T g ) ranged from – 61 ° C to + 5.6 ° C, which are …

Modification Of Cellular Dna By Synthetic Aziridinomitosenes, Chris M. Mallory, Ryan P. Carfi, Sangphil Moon, Kenneth A. Cornell, Don L. Warner

Chemistry and Biochemistry Faculty Publications and Presentations

Two synthetic aziridinomitosenes (AZMs), Me-AZM and H-AZM, structurally related to mitomycin C (MC) were evaluated for their anticancer activity against six cancer cell lines (HeLa, Jurkat, T47D, HepG2, HL-60, and HuT-78) and tested for their DNA-modifying abilities in Jurkat cells. Cytotoxicity assays showed that Me-AZM is up to 72-fold and 520-fold more potent than MC and H-AZM, respectively. Me-AZM also demonstrated increased DNA modification over MC and H-AZM in alkaline COMET and Hoechst fluorescence assays that measured crosslinks in cellular DNA. Me-AZM and H-AZM treatment of Jurkat cells was found to sponsor significant DNA-protein crosslinks using …

Analysis Of An Electrospun Nanofiber Device Applicable To Limb Salvage: Mass Loss, Morphological Changes, And Quantification Of Antibiotic Release, Caitlin Quinn

Honors Theses

The creation of an electrospun nanofiber embedded with two antibiotics that will be used to prevent infection while also stimulating bone regeneration will be explored. The nanofiber will contain an aminoglycoside and a glycopeptide, and it is sought to deliver a sustained release of antibiotics for up to 12 weeks. To determine release rate, nanofiber samples are immersed in 10.0 mL of MiliQ water (MQ), incubated at 37°C, assayed at specific time intervals, and then analyzed using ultra performance liquid chromatography in tandem with mass spectrometry. A hydrophilic interaction liquid chromatography (HILIC) method utilizing ultra-performance liquid chromatography (UPLC) in tandem …

Novel Methods For Identification Of Posttranslational Lipid Modified Proteins By Mass Spectrometry, Ruchika P. Bhawal

Chemistry & Biochemistry Dissertations - Archive

Study of posttranslational modifications (PTMs) is very important for developing potential new drugs for the treatment of several diseases. Posttranslational lipid modifications are major PTMs which help proteins to anchor to cell membranes and facilitate protein-protein interactions. There are several kinds of lipid modifications of proteins. The major lipid modifications are palmitoylation, myristoylation and prenylation. Prenylation are of two types - farnesylation and geranylgeranylation. These modifications are involved with several human cancers and genetic diseases. Hutchinson-Gilford progeria syndrome (HGPS), a disease which causes premature aging for children is the product of prenylation. Understanding the mechanism of prenylation and their substrates …

From Dye Sensitized Solar Cells To Organic Field Effect Transistors: A Computational Investigation Into The Structural And Electronic Properties Of Novel Phthalocyanines, Patrick J. Dwyer

Seton Hall University Dissertations and Theses (ETDs)

Phthalocyanines (Pc) have gained intense research attention in many diverse application areas due to their highly tunable electronic and structural properties through modification of the molecular periphery and metal center. Throughout this work a series of novel perfluoro-isopropyl substituted MPc have been investigated through theoretical methods. First, the synthetic mechanisms of these Pcs will be explored to gain insight into the experimentally observed Pc product distribution. By examining the electronic structure and formation energies of the various Pc precursors, we explain the product distribution as well as propose the formation of additional Pcs, which were not currently believed to form. …

Fabrication, Characterization, And Application Of Carbon Nanoparticles For The Detection Of Heavy Metal Ions In Aqueous Media, Aaron Michael Simpson

Graduate Theses/Dissertations

This research set out to develop a method for producing Carbon nanoparticles (CNPs) from glycerol and use them to detect Cu2+, Hg2+, and Pb2+ ions in aqueous solution. Three synthesis methods were developed using the following mixtures: (1) glycerol and silica, (2) glycerol, silica, and H3PO4, and (3) glycerol with H3PO4. The structure of the particles was characterized using a variety of spectroscopic techniques. Size distributions were obtained from scanning electron microscopy images. The particles were spherical with average diameters of 66, 58, and 89 nm respectively and believed to consist of a carbon core with carboxylic acid and alcohol …

Synthesis Of Medicinally Relevant Thiazolyl Aryl Ketones Under Mild Conditions, Danielle M. Gardner

Health, Human Performance and Recreation Undergraduate Honors Theses

Purpose: The growing amount of clinical resistance observed in current antifungal drugs and in anti-HIV pharmaceuticals is a concern in the medical community. The purpose of this study is to develop a mild synthetic process for biomedically relevant thiazolyl aryl ketones that can be used to develop antifungal and anti-HIV drugs. We hypothesized that the proposed synthetic technique would be more efficient, produce fewer unwanted byproducts, and be more tolerant of functional groups than existing methods.

Methods: Prior to each of the ketone reactions, the necessary salt was synthesized by mixing thiazole and 9-bromofluorene neat in a reaction tube heated …

Supporting Data For The Characterization Of Pna-Dna Four-Way Junctions, Douglas Van Iverson Ii, Crystal C. Serrano, Ann Marie Brahan, Arik Shams, Filbert Totsingan, Anthony J. Bell Jr.

Faculty Publications

Holliday or DNA four-way junctions (4WJs) are cruciform/bent structures composed of four DNA duplexes. 4WJs are key intermediates in homologous genetic recombination and double-strand break repair. To investigate 4WJs in vitro, junctions are assembled using four asymmetric DNA strands. The presence of four asymmetric strands about the junction branch point eliminates branch migration, and effectively immobilizes the resulting 4WJ. The purpose of these experiments is to show that immobile 4WJs composed of DNA and peptide nucleic acids (PNAs) can be distinguished from contaminating labile nucleic acid structures. These data compare the electrophoretic mobility of hybrid PNA–DNA junctions vs. …