Chemistry Commons^™

Apparent Retention Volume Variation With Flow Rate Change In High Performance Liquid Chromatography, Susanne Buntz Erz

Seton Hall University Dissertations and Theses (ETDs)

Recent studies have demonstrated noticeable flow rate dependency of the chromatographic zone retention volume with respect to migration within the empty capillary. This appears to be the result of superposition of asymmetric lateral diffusion and of the laminar flow profile. Although these effects have been studied on empty capillaries, in the presence of the packed column, the retention shift may be insignificant relative to the adsorption-based retention of the analytes. In the case of fast and ultrafast HPLC with short capillary columns, the effect of extra-column caused variation in the analyte retention may constitute an increase of up to 120 …

Adsorption And Wetting In Model Mesoporous Silicas And In Complex Metal Oxide Catalysts, Karthik Jayaraman

Seton Hall University Dissertations and Theses (ETDs)

The surface of most metal oxides is covered by hydroxyl groups which influence many surface phenomena such as adsorption and wetting, catalysis and surface reactions. Surface chemistry of silica is a subject of exhaustive studies owing to a wide variety of practical applications of silica. In Chapter 1, a brief review of classification, synthesis and characterization of silica is provided. The hydroxylation of silica surface i.e the number of hydroxyl (-OH) groups on the surface is of utmost importance for its practical applications. In Chapter 2, a brief introduction to surface hydration of silica is provided followed by the gas …

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 …

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 …

Structural Analysis Of Transient Receptor Potential Vanilloid Type 1 (Trpv1) Channel Protein And Proline Mimics Using Computational Techniques, Kelly A. Raymond

Seton Hall University Dissertations and Theses (ETDs)

Chapter I

The Transient Receptor Potential (TRP) family of ion channels encompasses more than 30 members, which are expressed in many different tissues and cell types.¹ Transient Receptor Potential Vanilloid Type 1 (TRPV1) is part of the TRP family gated by vanilloids, heat and protons.² Molecular modeling will be used in order obtain structural and functional data on TRPV1 in its membrane bound environment. In particular, the transmembrane and C-terminal domain regions of TRPV1 are of particular interest. The S1-S4 region of the channel is the putative ligand-binding segment, while the C-terminal domain is suggested to respond to …

Synthesis And Evaluation Of Biological Activity Of A Potential Immunomodulatory Zwitterionic Polysaccharide, Vikram Basava

Seton Hall University Dissertations and Theses (ETDs)

The gram-negative anaerobic bacterium Bacteroides fragilis is an integral component of the normal gastrointestinal flora. The bacterium colonizes the intestinal tract of human beings as it has no reservoir other than mammals. An unprecedented proportion of the genomic DNA of B. fragilus is involved in the production of capsular polysaccharides. These capsular polysaccharides are important virulence factors in most extracellular bacterial pathogens. Eight of these polysaccharides have been identified thus far, out of which two were found to be zwitterionic polymers, PSA1 and PSA2. PSA1 was found to stimulate T-cell lineage of the immune system because of the dual charge …

Epoxy Siloxane Self-Cleaning Coating Using F64pczn/Tio2 Photocatalyst Composite, James F. Sullivan

Seton Hall University Dissertations and Theses (ETDs)

A new photocatalytic composite powder incorporated into a siloxane epoxy polymer has been shown to yield a highly efficient self-cleaning coating. The composite, which makes greater use of light in the visible/near-infrared (NIR) region, was prepared by coating a nano-particle photocatalytic TiO₂ with 3% w/w of F₆₄PcZn photosensitizer resulting in a dark green powder. The F₆₄PcZn/P25 TiO₂ composite exhibited a greater photo-induced degradation of methyl red, a model surface contaminant, compared to traditional nano-particle photocatalytic TiO₂. Singlet oxygen (¹Δ_g ¹O₂), generated form the F₆₄PcZn, …

Functionalization Of Metal Oxide Surfaces Through Chemical Reactions And Physical Adsorption, Gabriel C. Graffius

Seton Hall University Dissertations and Theses (ETDs)

The synthesis of high surface area metal oxides is an area of extensive research with potential applications in catalysis, adsorption, and materials chemistry. The functionalization of a material’s surface can dramatically change its physical and chemical properties. The research described herein is built on the foundation of traditional techniques used for synthesis, characterization, and functionalization of metal oxides and develops new mechanisms and materials for the functionalization of surfaces.

We began with Methyl-terminated poly(dimethylsiloxanes) (PDMSs), which are typically considered to be inert and not suitable for surface functionalization reactions because of the absence of readily hydrolysable groups. Nevertheless, these siloxanes …

Application Of An Ionic Liquid Column To The Analysis Of Flavor And Fragrance Ingredients, Nicole L. Curto

Seton Hall University Dissertations and Theses (ETDs)

Traditional, polar (polyethylene glycol/wax) stationary phase gas chromatography columns pose challenges for flavor and fragrance analysis particularly in regards to thermal instability at high temperatures, degradation when exposed to water, unchanging selectivity, and relatively short shelf lives. Recently, capillary columns using ionic liquids as stationary phases have become available. Ionic liquid columns offer a potential combination of high polarity and high temperature stability with unique selectivity. An in depth discussion about the history and development of column phase characterization, with specific emphasis on selectivity and polarity, will allow for a critical look at the polarity scale currently employed to characterize …

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. …

Asymmetric Transfer Hydrogenation Of Secondary Allylic Alcohols, Christopher Olugbenga Olusegun Shoola

Seton Hall University Dissertations and Theses (ETDs)

This dissertation highlights the developments and optimization of a new reaction method that transforms racemic secondary allylic alcohols into optically active secondary alcohols. The key step in this methodology occurs through a ruthenium catalyzed tandem isomerization and asymmetric transfer hydrogenation reaction. This reaction is a one pot, two-step process, which utilizes the unique ability of a transition metal catalyst to effect a combined reduction of the C-C double bond and the carbonyl group in a selected class of secondary allylic alcohols.

With a-vinyl benzyl alcohol as substrate, the optimal catalyst for this reaction was generated in situ from a …

Fluorinated Metallo Phthalocyanines For Chemical And Biological Catalysis, Hemantbhai H. Patel

Seton Hall University Dissertations and Theses (ETDs)

The rational design of robust oxidation catalysts based on organic molecules is hindered by the presence of labile C-H bonds. We have shown recently that replacing all C-H bonds by a combination of fluoro- and perfluoro-groups in a bioinspired Cytochrome P450 model based on a phthalocyanine, Pc, scaffold results in a stable yet reactive oxidation catalyst. The Pc cobalt complex catalyzes, for example, the aerobic oxidation of thiols to disulfides, a reaction of both biological significance and industrial importance.

The presence of robust C-F bonds, however, renders the catalyst unsuitable for attachment to solid-state supports, except via van der Waals …

Applications Of Green Chemistry In Asymmetric Transfer Hydrogenation And Chiral Separations, Ruoqiu Wu

Seton Hall University Dissertations and Theses (ETDs)

Green chemistry has been applied to all aspects of the life cycle of chemically related products, including design, usage, manufacturing, analysis, and disposal. In this thesis, I focus on the green chemistry applications in organic synthesis and analytical chemistry. More specifically, allylic and chiral alcohols are abundant in natural sources such as in essential oils, and widely utilized as starting materials. They are also major components in food, fragrance, biocides and the pharmaceutical compounds. In this thesis, I report the first Ru-catalysed asymmetric transfer hydrogenation (ATH) of prochiral allylic alcohols. This reaction provides chiral secondary alcohols in excellent enantioselectivities and …

Quechers (Quick, Easy, Cheap, Effective, Rugged, And Safe) Extraction – Gas Chromatography For The Analysis Of Drugs, Michelle L. Schmidt

Seton Hall University Dissertations and Theses (ETDs)

QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) is an extraction technique developed by Anastassiades and co-workers initially for the extraction of veterinary drugs from animal tissue. Since its inception, it was discovered that this method is particularly adept for the extraction of polar and basic compounds, thus the majority of research previously performed using QuEChERS involves the extraction of pesticides from various matrices, especially fruits, vegetables, and other food products. Combining a liquid-liquid extraction (LLE) and a dispersive solid phase extraction (d-SPE) clean up, QuEChERS provides a clean sample for analysis by gas chromatography (GC) or liquid chromatography (LC) …

Monitoring Dissolution Of Nonsteroidal Anti-Inflammatory Drugs Using Infrared Spectroscopy, Julianne Berger

Seton Hall University Dissertations and Theses (ETDs)

A comparison study was conducted to look at the formulation of three brands of naproxen sodium. These brands included Bayer Aleve ®, CVS All Day Pain Relief and Walgreens All Day Pain Relief. The active and inactive ingredients were the same yet the size and shape of the tablets differ among the three brands. S-naproxen was extracted from the tablets and evaluated by GC-MS to determine the purity of naproxen in the tablets. Dissolution was monitored by an IR probe for eight hours while using 0.1M phosphate buffer pH 7.4, 0.05M phosphate buffer pH 4.5 and simulated gastric fluid pH …

Polycyclic Aromatic Hydrocarbon Determination In Liver Of Menhaden Exposed To The Deep Water Horizon Oil Spill, Rebecca Hawke

Seton Hall University Dissertations and Theses (ETDs)

The April 2010 BP® oil spill has caused great concern for ecological impacts in the Gulf of Mexico. Crude oil contains polycyclic aromatic hydrocarbon (PAHs) and oil spills increase the exposure of aquatic organisms to this class of chemicals. The overall detrimental health effects associated with PAH exposure depend on the exposure period, the concentration of PAHs, and the toxicity of the PAHs in the mixture. Brevoortia tyrannus and Brevoortia patronus are filter feeding fish commonly known as menhaden and account for over 40% of the commercial industry fisheries catch. As primary consumers, they are a major link in the …

Extending The Limits Of Solid Phase Microextraction, Shilpi Chopra

Seton Hall University Dissertations and Theses (ETDs)

Solid phase microextraction (SPME) is a solventless extraction technique that combines sample preparation and sample introduction into a gas chromatograph into a single step. For the past 20 years, solid-phase micro-extraction (SPME) has been used in numerous fields such as: food analysis, including juices, alcohols fruits and vegetables for volatiles, aroma, caffeine, fatty esters, environmental applications including volatile organic contaminants, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, phenols, pesticides, steroids, herbicides, acid/neutral/base compounds, and organometallic compounds from water, air, soil, sludge, and sediment samples and in biomedical analysis.

This work demonstrates the extension of the limitations of SPME with respect to extraction …

Polyol Induced Extraction (Pie) Of Water From Organic Solvents, Mithilesh Deshpande

Seton Hall University Dissertations and Theses (ETDs)

Acetonitrile (ACN) is used in huge quantities for Reversed Phase High Performance Liquid Chromatography (RP-HPLC) experiments. For most of the part, these results in waste that is only contaminated with large amounts of water, buffer and trace organic impurities. It would seem worthwhile to purify the ACN from water using a mass separating agent (MSA). In a quest for an MSA, our investigation reveals polyols as a new class of MSAs. It is observed that when a polyol such as glycerol, sorbitol, erythritol, xylitol, Isomalt® or maltitol is added to a mixture of ACN-water, the ACN separates out of the …

Branching Into Rnai: Synthesis, Characterization And Biology Of Branch And Hyperbranch Sirnas, Anthony Muriithi Maina

Seton Hall University Dissertations and Theses (ETDs)

The cancer epidemic continues to afflict millions of humans world-wide each year and despite a renewed hope with the development of new and improved forms of therapy, a cure for cancer remains an elusive goal. This is partly related to the rise of resilient forms of tumors that have evolved with resistance towards conventional chemotherapy and radiation treatments. Moreover, these non-specific therapeutic regimens are highly toxic, leading to severe immunosuppressive effects which poisons the body and compromises the road towards remission. In an effort to mitigate these limitations, cancer-targeting approaches are currently experiencing a renaissance in the translation of new …

Ionic Liquids In Micro Extractions And Gas Chromatographic Stationary Phases, Ramkumar Dhandapani

Seton Hall University Dissertations and Theses (ETDs)

Ionic liquids are salts that exist entirely as ionic species. They are composed of cation, anion and side chain or linkage group. Due to the different combination of the these groups, the ionic liquid exhibits unique selectivity. Their applications are enormous in the field of analytical chemistry.

The interest of using ionic liquids as gas chromatographic stationary phase has increased in recent years. The low volatility, tailorable physico-chemical property and high thermal stability of ionic liquids make them an ideal choice for gas chromatographic stationary phase. For the present research, commercially available ionic liquid capillary columns were investigate for thermodynamics …

Porphyrin Cross-Linkers For Generating Soluble Molecularly Imprinted Polymers From Polyethyleneimine, Mohammed R. Elshaer

Seton Hall University Dissertations and Theses (ETDs)

Molecular recognition is vital to many biochemical processes and is at the heart of promising bio-medically related technologies. Molecular imprinting has a long-standing history as a successful method for mimicking the molecular recognition phenomena exhibited by nature, whereby artificial receptors are prepared for a given target molecule based on synthetic polymers. The molecularly imprinted polymer (MIP) contains a three dimensional network with a memorized cavity specific to the shape and functionality of the templated target molecule. The utility of traditional MIPs has been limited due to an inherent lack of solubility. We have worked toward developing a system that allows …

Polymers For Dna Binding, Sue Yuan Li

Seton Hall University Dissertations and Theses (ETDs)

.

Chemical Analysis Of Ophthalmic Solutions, Pagagiotis Tavlarakis

Seton Hall University Dissertations and Theses (ETDs)

.

Real-Time Reaction Monitoring And Flash Separation As A Process Analytical Technology Tool And Hplc Method Development For Melamine In Infant Formula, Gopalakrishnan Venkatasami

Seton Hall University Dissertations and Theses (ETDs)

.

Novel Methods For The Synthesis Of Septanose Sugars/Extended Ring Systems From Hexose Sugars, Nada Khan

Seton Hall University Dissertations and Theses (ETDs)

.

Synthesis, Modification, And Characterization Of Spherical Sba-15 Ordered Mesoporous Silica And Evaluation In High Performance Liquid Chromatography, Alexander P. Giaquinto

Seton Hall University Dissertations and Theses (ETDs)

.

Analysis Of Street Drugs Using Comprehensive Two Dimensional Gas Chromatography Coupled With Time Of Flight Mass-Spectrometry, Brian B. Barnes

Seton Hall University Dissertations and Theses (ETDs)

.

Influence Of Ionic Mobile Phase Additives With Low Charge Delocation On The Retention Of Ionic Analytes In Reversed Phase Hplc, Cesar Florez

Seton Hall University Dissertations and Theses (ETDs)

.

Adsorbents With Chemically Bonded Saccharide Surfaces: Synthesis And Application For Stereoisomer Separation And The Synthesis Of Chiral Porous Silicas Using Templates Chiral Surfactant, Edwin Vega

Seton Hall University Dissertations and Theses (ETDs)

.

Scope And Mechanistic Studies Of The Palladium On Carbon Catalyzed Suzuki Cross Coupling Reaction, Carl Leblond

Seton Hall University Dissertations and Theses (ETDs)

No abstract provided.