Analytical Chemistry Commons^™

Reverse-Phase Liquid Chromatography Of Small Molecules Using Silica Colloidal Crystals, Natalya Khanina

Open Access Theses

Capillaries packed with a silica colloidal crystal (SCC) of 470 nm nonporous particles have recently been shown to offer significant improvements in the peak width, resolution, and speed of protein analysis due to the reduction of the A and C term broadening contributions of the Van Deemter equation. While protein separations using this technology have shown vast improvements, small molecules remain largely unexplored. As the SCC allows for an approximately diffusion limited system, extremely high plate numbers are expected for small molecule separations. The research presented herein studies the feasibility of pressure-driven small molecule separation using SCCs and commercial instrumentation. …

Aircraft-Based Measurements For The Identification And Quantification Of Sources And Sinks In The Carbon Cycle, Dana R Caulton

Open Access Dissertations

Improved quantification of carbon-cycle sources and sinks is an important requirement for determining mitigation strategies and modeling future climate interactions. Analytically robust measurements require high-precision instrumentation and thoughtful experimental design to produce rigorous and reproducible results despite complex and quickly changing meteorological and environmental conditions. Here, an aircraft platform equipped with a high-precision cavity ring-down spectrometer for CO₂, CH₄ and H₂O quantification was used to acquire data from previously un-sampled sources. The aircraft mass-balance technique was used to quantify CH4 emissions from natural gas well pads in the drilling stage, which were 2-3 orders of …

Syntheses Of Aminyl Diradicals And Nitroxide Tetra- And Octaradicals, Arnon Olankitwanit

Department of Chemistry: Dissertations, Theses, and Student Research

This dissertation comprises of two main research projects: aminyl diradicals and calix[4]arene nitroxide tetra- and octaradicals. The design, multi-step synthesis and characterization, including NMR, EPR spectroscopy, magnetic measurements and X-ray crystallography of precursors and target compounds will be discussed.

Aminyl radicals, nitrogen-centered radicals, are typically short-lived and considered as reactive intermediates. Because of their unique magnetic properties, aminyls are attractive building blocks for high-spin di-and polyradicals. The challenge is in the design and synthesis of aminyls with increased stability. In this chapter, we have prepared triplet (S = 1) ground state aminyl diradicals, which are derivatives of aza-m …

Resonant Two-Photon Ionization Studies Of Non Covalent Interactions In Halo Aromatic Clusters And Spin-Orbit Coupling Modeling In Mono-Halocarbenes, Silver Nyambo

Dissertations (1934 -)

Non-covalent interactions in halobenzenes (PhX) (X=F, Cl, Br) and phenylamine (C₆ H₅ NH₂ ) have been studied here using resonance two-photon ionization (R2PI) spectroscopy combined with a linear TOF-mass spectrometer. Their interaction with polar molecules in form of ammonia (NH ₃ ) and trifluorohalomethanes (CF₃ X) has also been studied. DFT and TD-DFT calculations using M06-2X functionals were carried out on different cluster conformations to compliment experimental results. A general trend of broadness in homogenous dimers (PhX)₂ , has been attributed to mainly the presence of multiple cluster isomers and Frank-Condon activity in the low …

Electrochemical And Surface Enhanced Raman Spectroscopic Studies Of Benzimidazole On Nickel Electrode, Ping-Jie Wei, Ya-Xian Yuan, Min-Min Xu, Jian-Lin Yao, Ren-Ao Gu

Journal of Electrochemistry

By measuring cyclic voltammograms and polarization curves, the inhibition effects of benzimidazole (BMIH) concentration in acetonitrile system on a nickel electrode were investigated. It was found that the oxidation and the corrosion potentials shifted positively, and the oxidation current decreased with the increase in the concentration of BIMH. Potential dependent adsorption and film formation behavior of BMIH on the nickel electrode were investigated by in situ SERS spectroscopy. With the potential moving from negative direction to positive direction, the complexes made of BIMH and nickel were formed, preventing the nickel electrode from corrosion. In addition, the 0.001 mol·L^-1 of …

In-Situ Afm Force Curve Investigations On Layered Structures Of Au(111)-Ionic Liquid Interfaces And Temperature Dependence, Xiao Zhang, Yun-Xin Zhong, Jia-Wei Yan, Bing-Wei Mao

Journal of Electrochemistry

By utilizing in-situ AFM force curve measurements systematic investigations have been carried out on Au(111)-ionic liquid interface in BMIPF₆ and OMIPF₆ of imidazolium-based ionic liquids with different lengths of alkyl side chains. The temperature dependence of the number, thickness and stability of the layered structures of each system are studied by performing AFM force curve measurements at potentials far negative of the PZC. The layered structures at Au (111)/BMIPF₆ interface are composed of two charged interior layers and two neutral exterior layers at -1.0 V, while those at Au (111)/OMIPF₆ interface only one charged interior layer …

Investigation Of The Dynamics Of Photocarriers During Photoelectrochemical Water Splitting By Combination Of Photoelectrochemistry And Transient Absorption Spectroscopy, Wen-Hua Leng

Journal of Electrochemistry

Semiconductor photoelectrochemical hydrogen production is an important and promising technology for utilizing solar energy. The efficiency of hydrogen production depends on the efficiencies of separation and transport of photo-generated carriers. A deep understanding of the behavior of these processes has guiding significance for designing efficient solar hydrogen device. photoelectrochemical and transient absorption spectroscopy methods are powerful tool for studying the microscopic dynamics and mechanism of photocatalytic reaction. This review describes the part of the latest results of the author regarding the semiconductor photoelectrochemical hydrogen production obtained by these methods,and the problems and future research priorities in this field are proposed.

High Sensitive Detection Of Cd(Ii) And Pb(Ii) Based On Antimony-Film Covered Pencil Core Electrodes, Shan Chen, Zhao-Yan Zheng, Yi-Min Fang, Li-Qing Zheng, Jian-Jun Sun

Journal of Electrochemistry

In this paper, a pencil core was used as the substrate for an antimony-film electrode for simultaneous detection of Cd(II) and Pb(II) by square-wave anodic stripping voltammetry (SWASV). With the deposition time of 180 s, the low limit of detection (LOD) for the electrode was determined to be 0.075·g?L-1 for Cd(II), while 0.13·g·L-1 for Pb(II) with good reproducibility in low pH solutions (pH = 2). The results show a much lower LOD than that of bismuth-film pencil core electrode. Finally, this antimony-film electrode was successfully applied to determine Cd(II) and Pb(II) in tap water.

A Sensitive And Label-Free Electrochemical Aptasensor Based On Signal Amplification Of Carbon Nanotubes, Chun-Yan Deng, Hui-Min Fan, Juan Xiang, Yuan-Jian Li

Journal of Electrochemistry

A label-free electrochemical sensing electrode for highly sensitive detection of adenosine was constructed based on the signal amplification of carbon nanotubes (CNTs). The change in the interfacial feature of the modified electrode was characterized by electrochemical impedance spectroscopy. Using [Ru(NH₃)₆]³⁺ as the signaling moiety, adenosine with concentrations as low as 0.027 nmol·L^-1 can be selectively detected. Additionally, the fabrication of this present aptasensor was simple, time-saving and cost-effective. Compared with other reported aptasensors, the proposed aptasensor had advantages of excellent sensitivity, selectivity and simplicity, which plays a potential role in development of aptasensor.

Determining Kinetics For Simulated Sunlight-Exposed Oil Compounds, Dustin D. Kountz

LSU New Orleans Theses and Dissertations

Understanding of the fate of oil in the environment is of utmost importance; however, accurate, predictive models are still in very early stages. To aid in the development of these models, photodegradation of selected polycyclic aromatic hydrocarbons (PAHs) in an n-alkane hydrocarbon matrix was followed for individual PAHs and mixtures of PAHs similar to that found in the Deepwater Horizon spill. Tetracene in tetradecane photodegraded quickest of all observed PAHs, with a loss of 99% after only one hour of irradiation. Binary mixtures of PAHs showed different degradation amounts, including changes in PAH kinetics. These results suggest that the …

Synthesis And Applications Of Mutimodal Hybrid Albumin Nanoparticles For Chemotherapeutic Drug Delivery And Phototherml Therapy Platforms, Donna V. Peralta

LSU New Orleans Theses and Dissertations

Progress has been made in using human serum albumin nanoparticles (HSAPs) as carrier systems for targeted treatment of cancer. Human serum albumin (HSA), the most abundant human blood protein, can form HSAPs via a desolvation and crosslinking method, with the size of the HSAPs having crucial importance for drug loading and in vivo performance. Gold nanoparticles have also gained medicinal attention due to their ability to absorb near-infrared (NIR) light. These relatively non-toxic particles offer combinational therapy via imaging and photothermal therapy (PPTT) capabilities.

A desolvation and crosslinking approach was employed to encapsulate gold nanoparticles (AuNPs), hollow gold nanoshells (AuNSs), …

Mechanisms And Transients Involved In The Solar Conversion Of Petroleum Films In Aquatic Systems, Phoebe Z. Ray

LSU New Orleans Theses and Dissertations

The behavior of Deepwater Horizon crude oil and other sources of oil were investigated when exposed to sunlight in aquatic systems under environmentally relevant conditions. This research decoupled the abiotic and biotic weathering modifications of oil by focusing solely on the photochemical transformations of oil in aquatic systems. Photochemical rates and mechanisms were measured through the determination of reactive transients. Total hydroxyl radical formation was studied using high benzoic acid concentrations and varying exposure time. Titanium dioxide (TiO₂) nanomaterials were added to the system in an effort to determine if the photocatalyst would enhance oil photodegradation. Photochemical production …

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 …

Does A Plastron Improve Heat Transfer?, Madani A. Khan, Jeffrey Alston, Andrew Guenthner

STAR Program Research Presentations

Superamphiphobic surfaces strongly repel both water and oils. In this work, aluminum coupons are processed by sanding with various grit of sand paper to impart microscale roughness. Subsequent submersion of the aluminum substrate in boiling water grows nanoscale grass-like structures. The oxide layer of Al is slightly soluble in water. During a fast diffusion/equilibrium, Al₂O₃ nanograss grows on the surface. A low energy coating is then deposited on the surface. The micro and nanoscale features create re-entrant structures that trap air enabling contact liquid to be in a Cassie-Baxter state. Superamphiphobicity of the samples were confirmed by …

Antimicrobial Nanoparticles: A Green And Novel Approach For Enhancing Bactericidal Efficacy Of Commercial Antibiotics, Monic Shah

Masters Theses & Specialist Projects

On the verge of entering the post-antibiotic era, numerous efforts are in place to regain the waning charm of antibiotics which are proving ineffective against most “Superbugs”. Engineered nanomaterials, especially gold nanoparticles (GNPs) capped with antibacterial agents, are proving to be an effective and novel strategy against multidrug resistant (MDR) bacteria. In this study, we report a one-step synthesis of antibioticcapped GNPs (25 ± 5 nm) utilizing the combined reducing and capping ability of a cephalosporin antibiotic, ceftazidime. No signs of aggregation or leaching of ceftazidime from GNP surface was observed upon its storage. Antibacterial testing showed dosedependent broad spectrum …

Green Synthesis And Evaluation Of Catalytic Activity Of Sugar Capped Gold Nanoparticles, Yogesh A. Kherde

Masters Theses & Specialist Projects

Owing to the importance of gold nanoparticles in catalysis, designing of them has become a major focus of the researchers. Most of the current methods available for the synthesis of gold nanoaprticles (GNPs) suffer from the challenges of polydispersity, stability and use of toxic and harmful chemicals. To overcome these limitations of conventional methods, in our present study, we made an attempt to design a method for the green synthesis of monodispersed and stable gold nanoparticles by sugars which act as reducing and stabilizing agent. Characterization of synthesized nanoparticles was done by using various analytical techniques such as transmission electron …

Selective Oxidations By Iron(Iii) Porphyrins And Iron(Iii) Corroles, Aaron Dalnamath Carver

Masters Theses & Specialist Projects

The selective oxidation of organic compounds represents a leading technology for chemical industries. They are used in chemical synthesis in the pharmaceutical and petrochemicals industries, and possible the decontamination of harmful substances. However, oxidations reaction are among the most challenging processes to control. Many stoichiometric oxidants with heavy metals are expensive, or toxic maybe both, and therefore unfeasible to be utilized. The ideal processes for catalytic oxidation would use molecular oxygen or hydrogen peroxide as the primary oxygen source, with transition metal catalysts to mimic the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes. This study focuses on the …

Heat Release Of Polyurethanes Containing Potential Flame Retardants Based On Boron And Phosphorus Chemistries, Vladimir Benin, Bastien Gardelle, Alexander Morgan

Chemistry Faculty Publications

Using a polyurethane of methylene diphenyl isocyanate and 1,3-propane diol, several new non-halogenated aromatic boron and phosphorus flame retardants were evaluated for heat release reduction potential using the pyrolysis combustion flow calorimeter (PCFC). The polyurethanes were prepared in the presence of the potential flame retardants via solvent mixing and copolymerization methods, and were then analyzed via spectroscopic methods to determine if the flame retardant was still present in the final product. PCFC testing on the resulting products showed that the flame retardant molecule can have different effects on heat release depending upon how it is mixed into the polyurethane. Some …

Modified-Electrodes For Redox-Magnetohydrodynamic (Mhd) Pumping For Microfluidic Applications, Christena Kayl Nash

Graduate Theses and Dissertations

A new microfluidic pumping and stirring technique was demonstrated for lab-on-a-chip applications. Microfluidics was accomplished via redox-MHD, which takes advantage of a body force (F_B) that is generated when there is a net movement of ions in solution (j) in the presence of a perpendicular magnetic field (B), according to the equation F_B = j×B. In this work the movement of ions in solution was generated using electrodes modified with the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) rather than a redox species in solution, which can interfere with analyte detection and with biological species. …

Structural Studies Of Bile Salt Aggregation By Nuclear Magnetic Resonance Spectroscopy And Mass Spectrometry, Nicholas Doyle

Master’s Theses

Bile salts are biomolecules that are produced in the liver and are responsible for a range of functions in the process of digestion, primarily the emulsification of dietary fat and fat-soluble vitamins. Despite their importance in biological chemistry, the structure and dynamics of bile salt aggregation are not well understood. The efforts described herein attempt to enhance the understanding of cholate aggregation numbers (AN), critical micelle concentration (CMC), micellar structure(s), and interactions with a binaphthyl probe molecule. Cholate is the most common bile salt in mammals and is, therefore, a decent model for describing bile salt aggregation. CMC determination is …