Chemistry Commons^™

Biological Materials: Part A. Temperature-Responsive Polymers And Drug Delivery And Part B. Polymer Modification Of Fish Scale And Their Nano-Mechanical Properties, Xu Xiang

Dissertations, Master's Theses and Master's Reports - Open

This research has three parts. Two parts deal with novel nanoparticle assemblies for drug delivery, and are described in Part A, while the third part looks at properties of fish scales, an abundant and little-used waste resource, that can be modified to have value in medical and other areas.

Part A describes fundamental research into the affects of block sequence of amphiphilic block copolymers prepared from on a new and versatile class of monomers, oligo(ethylene glycol) methyl ether acrylate (OEGA) and the more hydrophobic di(ethylene glycol) methyl ether methacrylate (DEGMA). Polymers from these monomers are biologically safe and give polymers …

Thermal Degradation Of Amines For Co2 Capture, Quanzhen Huang

Theses and Dissertations--Chemistry

In the selection of candidates for CO₂ absorption, solvent thermal degradation has become a general concern due to the significant impact on operational cost and the intention to use thermal compression from high temperature stripping to minimize the overall process energy. In this research, the impact of flue gas contaminants on Monoethanolamine (MEA) thermal degradation was investigated at elevated temperatures consistent with those in the CO₂ stripper. Nitrite, fly ash, sulfate and thiosulfate were each added to 5.0 M MEA and the contaminant-containing MEA solutions were degraded at 125 °C, 135 °C and 145 °C. MEA degrades significantly …

Development Of An Extraction Method For The Mass Spectral Analysis Of Organic Gunshot Residue From Clothing, Brent Casper

Theses and Dissertations--Chemistry

This dissertation will focus on the extraction of volatile organic compounds associated with gunshot residue from articles of clothing, followed by analysis with mass spectrometry. During the discharge of a weapon, a cloud of volatile organic gunshot residue (OGSR) is dispersed around a firearm. This will create a high probability of transfer between the OGSR and the clothing of individuals who are near a discharged weapon.

The first part of this dissertation will be the development of a method for removal of volatile OGSR from articles of clothing. Extraction of OGSR will be completed by solid phase microextraction (SPME), followed …

Spectroscopic Characterization Of Lanthanum-Mediated Hydrocarbon Activation, Dilrukshi C. Hewage

Theses and Dissertations--Chemistry

Lanthanum (La)-promoted hydrocarbon activation reactions were carried out in a laser vaporization metal cluster beam source. Reaction products were identified by time-of-flight mass spectrometry, and the approximate ionization thresholds of La-hydrocarbon complexes were located with photoionization efficiency spectroscopy. The accurate ionization energies and vibrational frequencies of the La complexes were measured using mass analyzed threshold ionization (MATI) spectroscopy. Their molecular structures and electronic states were investigated by combing the MATI spectroscopic measurements with quantum chemical and Franck-Condon factor calculations.

In this dissertation, La-mediated C-H and C-C bond activation reactions were investigated for several small alkynes (acetylene, propyne) and alkenes (propene, …

Unhindered Triangulene Salt Pairs: Substitution-Dependent Contact Ion Pairing And Complex Solvent-Separated Discotic Ions In Solution, Subrahmanyam Modekrutti

Theses and Dissertations--Chemistry

This work sought to enforce aromatic interactions between compatible π-molecular orbital systems with ionic bonding. In this case the interacting partners are oppositely charged discotic triangulene derivatives. The observed properties of the heterodimeric ion-pairs likely arise due to a hypothetical synergy between electrostatics and π-interactions. The work presented here describes investigation of putative covalency arising from this hypothetical synergy in the electrostatics driven π-stacking. In order to probe this, various hypotheses were made and experiments were designed to test their validity. The results from the experiments show existence of contact ion-pairs and complex solvent-separated discotic ions in solution. The formation …

Ferrocene-Fused Derivatives Of Acenes, Tropones And Thiepins, Bidhya L. Maharjan

Theses and Dissertations--Chemistry

This research project is concentrated on tuning the properties of small organic molecules, namely polyacenes, tropones and thiepins, by incorporating redox-active transition metal centers π-bonded to terminal cyclopentadienyl ligands. Organometallic-fused acenequinones, tropones, thiepins and cyclopentadiene-capped polyacenes were synthesized and characterized. This work was divided into three parts: first, the synthesis of ferrocene-fused acenequinones, cyclopentadiene-capped acenequinones and their subsequent aromatization to polyacenes; second, the synthesis of ferrocene-fused tropones, thiotropones and tropone oxime; and third, the synthesis of ferrocene-fused thiepins. Ferrocene-fused quinones are the precursors to our target complexes. Our synthetic route to ferrocenequinones involved two-fold aldol condensation between 1,2-diformylferrocene and naphthalene-1,4-diol …

Plasma Treated Mesoporous Tio2 Thin Films For Energy Storage Applications, Allen D. Reed

Theses and Dissertations--Chemistry

Mesoporous TiO₂ films treated with N₂/argon plasma or H₂ plasma were studied for use in photoelectrochemical water splitting and electrochemical supercapacitors, respectively. Cubic-ordered mesoporous thin films were prepared by a templated sol-gel method. UV-Vis absorbance spectra indicated that nitrogen plasma treatment significantly reduced the band gap of the TiO₂. XPS analysis showed that nitrogen atoms are incorporated into substitutional sites, rather than interstitial. Photocatalytic activity of nitrogen-doped TiO₂ films was evaluated by chronoamperometry and linear sweep voltammetry. Compared to pristine TiO₂, plasma-treated films showed remarkable photocurrent enhancement (up to 240 times) …

Investigation Into The Competitive Partitioning Of Dissociated H2 And D2 On Activated Fischer-Tropsch Catalysts, Wilson D. Shafer

Theses and Dissertations--Chemistry

The Fischer-Tropsch process, discovered in the early to mid-1920s, still has researchers disputing the C₁ monomer, and the rate-determining step. A tremendous amount of work, over the years, has focused on how hydrogen plays a role in the pseudo-polymerization of chain initiation and propagation, in an attempt to reveal the mechanism. These investigations attempted to elucidate the debated issues through studying the kinetic isotopic effect (KIE) for CO hydrogenation by switching the syngas from CO/H₂ to CO/D₂ during a steady-state period. Applying this switching step could result in a deviation in the rate of CO hydrogenation, indicating …

Folate Conjugated Hyperbranched Polyester Nanoparticles For Prostate Tumor-Targeted Delivery Of A Cytotoxic Peptide Via Prostate Specific Membrane Antigen, Orielyz Flores-Fernandez

Electronic Theses and Dissertations

Prostate Cancer is the second most deadly cancer in men, after lung cancer. The need for new and effective therapeutics that can constrain prostate cancer progression are challenged by the lack of suitable delivery strategies that target prostate cancer tissue. To study CT20p as potential chemotherapeutic agent in the treatment of prostate cancer we proposed the use of targetable hyperbranched polyester (HBPE) based nanoparticles as delivery system. Folic acid was conjugated to the nanocarrier to improve the selectivity of the nanoparticle towards specific cell surface targets in prostate cancer cell lines. Specifically we evaluated LNCaP that up-regulated the PSMA receptor. …

Selective Solid Phase Extraction Of Uranium Using An Aminophosphonic Acid Functionalized Composite Material, Ranalda Tsosie

Graduate Student Theses, Dissertations, & Professional Papers

Uranium is an element of interest because it is an abundant source of concentrated energy. In 1948 the US offered money for uranium ore mined in the US, which created a mining boom in the southwest that included the Navajo Reservation. During the late 1960s the demand for uranium decreased and many mining operations shutdown and left behind a legacy of contamination. As a result many Navajo communities have numerous water sources that exceed established maximum contamination levels for uranium and other toxic metals. These contaminations are a direct result of abandoned Cold War uranium mines and mill waste sites …

Concept Mapping As A Tool For Enhancing Self-Paced Learning In A Distance Scenario, John Allen Richbourg

Walden Dissertations and Doctoral Studies

Researchers have determined that concept maps serve as effective tools in the traditional science classroom. The purpose of this experimental study was to investigate concept mapping as a tool for student knowledge acquisition in 10th grade science for students in distance learning situations. Research questions were designed to investigate the influence of concept mapping on rate and quality of student knowledge acquisition and retention. This study was a pretest-posttest 2-group comparison study, constructivist in nature and based on the theory of cognitive learning. Participants included 36 students in the 10th grade at an inner-city school in the United States. Control …

Reconfigurable Solid-State Dye-Doped Polymer Ring Resonator Lasers, Hengky Chandrahalim, Xudong Fan

Faculty Publications

This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3′-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G) and 3,3′-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm² per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm² per pulse …

Predicting Aqueous Solubility Of Pharmaceutical Agents By Solid Dispersion Prepared By Solvent Evaporation Method, Karthik Reddy Patlolla

University of the Pacific Theses and Dissertations

Solubility of active pharmaceutical agents is a crucial process that determines drug absorption and ultimately its bioavailability. Many of the new therapeutically beneficial compounds discovered are lipophilic requiring various solubility enhancement strategies to improve their solubility. Among these strategies, solubility enhancement using solid dispersions is a leading method. To obtain a desirable increase in the solubility of a poorly-soluble compound, a good understanding of the molecular descriptors influencing the enhancement of solubility is essential. Therefore, the major research objective was to determine the descriptors which significantly influence the solubility enhancement by solid dispersions. After enhancing the solubility of selected poorly-soluble …

Potential Switchable Circularly Polarized Luminescence From Chiral Cyclometalated Platinum(Ii) Complexes, Xiao-Peng Zhang Zhang, Victoria Chang, Jian Liu, Xiao-Liang Yang, Wei Huan, Yizhi Li, Cheng-Hui Li, Gilles Muller, Xiao-Zeng You

Faculty Publications, Chemistry

A series of chiral cyclometalated platinum(II) complexes, [Pt((−)-L1)(Dmpi)]Cl ((−)-1), [Pt((+)-L1)(Dmpi)]Cl ((+)-1), [Pt((−)-L2)(Dmpi)]Cl ((−)-2), [Pt((+)-L2)(Dmpi)]Cl ((+)-2), [Pt3((−)-L2)2(Dmpi)4](ClO4)4 ((−)-3), and [Pt3((+)-L2)2(Dmpi)4](ClO4)4 ((+)-3) [(−)-L1 = (−)-4,5-pinene-6′-phenyl-2,2′-bipyridine, (+)-L1 = (+)-4,5-pinene-6′-phenyl-2,2′-bipyridine), (−)-L2 = (−)-1,3-bis(2-(4,5-pinene)pyridyl)benzene, (+)-L2 = (+)-1,3-bis(2-(4,5-pinene)pyridyl)benzene, Dmpi = 2,6-dimethylphenyl isocyanide], have been designed and synthesized. In aqueous solutions, (−)-1 and (+)-1 aggregate into one-dimensional helical chain structures through Pt···Pt, π–π, and hydrophobic–hydrophobic interactions. (−)-3 and (+)-3 represent a novel helical structure with Pt–Pt bonds. The formation of helical structures results in enhanced and distinct chiroptical properties as evidenced by circular dichroism spectra. Circularly polarized luminescence (CPL) was observed from the aggregates of (−)-1 and …

Gumbos As Matrices For Matrix-Assisted Laser Desorption Ionization Time Of Flight Mass Spectrometry, Hashim Abdullah Al Ghafly

LSU Doctoral Dissertations

This work involves the investigation of a group of uniform materials based on organic salts (GUMBOS) as matrices for matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF) for analysis of hydrophobic biomolecules. GUMBOS are new class of materials that show great promise as MALDI matrices because they are able to form a thin-layer on the MS target, thereby enhancing the sample homogeneity, signal intensity, and shot-to-shot reproducibility. The detection of hydrophobic peptides using MALDI-TOF MS remains a challenge because the majority of matrices utilized are hydrophilic thereby exhibiting low affinity for hydrophobic molecules. To address this, I …

Single Molecule Electrophoresis And Optical Detection Using Thermoplastic Nanofluidic Devices: An Experimental And Simulation Study, Kumuditha Madushanka Weerakoon Ratnayake

LSU Doctoral Dissertations

Nanofludic devices provide a great platform for single molecular analysis. The unique phenomena in nanoscale gained such interest in investigating the single molecular behavior in nanochannels. Sizes less than 200 nm in one or two-dimensional structures have lead to fascinating observations not accessible in microscale. When a single molecule translocates through a nanotube it interacts with channel walls by adsorption/ desorption, van der Waals interactions and hydrophilic interactions providing a mechanism for separation without any extra additives. Moreover, double layer thickness governed by the background electrolyte plays a vital role. We report single molecular electrophoresis phenomena in nanochannels and nanoslits …

Constitutive Activity In Orphan G Protein Coupled Receptors, Adam Lee Martin

Doctoral Dissertations

"The goal of this research was to use a distal signaling pathway analysis to evaluate the extent of agonist independent constitutive signaling among orphan class-A G protein coupled receptors (GPCRs). These receptors translate extracellular signals via conformational change into intracellular activation of different G proteins and subsequent second messenger synthesis. These small molecules regulate cellular biochemistry, eventually leading to nuclear signaling that results in changes in gene expression. Some GPCRs are capable of signaling in the absence of an activating ligand, a phenomenon called constitutive activity that is inhibited via an "inverse-agonist". The use of cAMP dependent Luciferase expression is …

Synthesis, Characterization And Application Of Acrylic Colloidal Unimolecular Polymer (Cup), Ameya Manohar Natu

Doctoral Dissertations

"Colloidal Unimolecular Polymer (CUP) particles were prepared by the process of water reduction on amphiphilic acrylic copolymers prepared via free radical polymerization technique. The formation of CUP particles was driven by the polymer-polymer interaction being greater than the polymer-solvent interaction and entropically favored by release of the water. It was demonstrated by Dynamic Light Scattering technique that CUP particles based on copolymers below 13,000 MW were unstable and the particles aggregated to a higher particle size. For the polymers with molecular weight (MW) above 13,000, a good correlation between the theoretical and experimental CUP particle size was observed. The rheology …

Synthesis And Characterization Of Vanadium Oxide Nanomaterials, Tyler M. Fears

Doctoral Dissertations

"This dissertation focuses on the synthesis and characterization of vanadium oxide nanomaterials and neutron-transparent Li-ion battery electrolytes.

Vanadium oxide gels were synthesized via the epoxide-assisted gelation of VOCl₃ using epichlorohydrin in ethanol. This represents the first epoxide-assisted gelation developed for vanadium oxide gels and serves as a potential economical replacement for the fabrication of vanadium oxide gels via the hydrolysis of vanadium alkoxides. Though epoxide-assisted gelation has been demonstrated for a number of transition metal oxides, the gelation mechanism observed here for VOCl₃ appears to be unique.

While investigating the electrochemical and structural properties of lithium vanadates, it …

Mechanical Characteristics Of Organically Modified Fly Ash-Kaolinite Mixtures, Xin Kang

Doctoral Dissertations

"Fly ash is a hazardous waste material to the environment. Beneficial reuse of fly ash, however, brings economic and environmental benefits, i.e., decreases the cost of disposal, reduces greenhouse gas emission, and improves mechanical properties of construction materials. Due to the lack of pozzolanic properties, the reuse rate of Class F fly ash in geotechnical engineering is relatively low (ACAA 2013). In order to promote the effectiveness and sustainability of high volume reuse of class F fly ash in geotechnical engineering, biopolymers (Chitosan, and Xanthan gum) and synthetic polymers (Polyethylene Oxide, PEO) were used instead of the traditional stabilizers to …

Effects Of N-Acetylcysteine Amide In Preventing/Treating Cataracts, Sri Krishna Yasaswi Maddirala

Doctoral Dissertations

"Cataract, the opacification of an eye lens, is a common pathological abnormality of the lens accounting for approximately 50% of all blindness. The only effective treatment currently available for a cataract is the surgical removal of the affected lens and replacement with an artificial lens for the restoration of vision. Although, cataract surgery is considered to be a very successful procedure in terms of visual outcome, the cost of surgery, need for trained personnel and surgeons, and postsurgical complications, limit the worldwide availability and accessibility of this procedure. Hence, alternative preventive and treatment procedures are worthy of investigation. The lens …

The Synthesis And Characterization Of Water-Reducible Nanoscale Colloidal Unimolecular Polymer (Cup) Particles, Cynthia J. Riddles

Doctoral Dissertations

"The coatings industry has adapted to more stringent guidelines in paint formulations. Current VOC (volatile organic compound) limits placed by the federal government have pushed the industry toward the development of paint formulations which have very little to no VOC's. The development of Colloidal Unimolecular Polymer (CUP) particles is a step in the direction of providing a resin system which exists in zero VOC aqueous dispersion.

The CUP particles are a part of the polymer field of Single Chain Nano Particles (SCNP) and ranged in diameters of 3-9 nm. The research presented in this dissertation describes the synthesis and design …

Long-Term Litter Decomposition Controlled By Manganese Redox Cycling, Marco Keiluweit, Peter Nico, Mark E. Harmon, Jingdong Mao, Jennifer Pett-Ridge, Markus Kleber

Chemistry & Biochemistry Faculty Publications

Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter …

Occurrence, Monitoring And Removal Of Drinking Water Contaminants By Advanced Technologies, Danielle Marie West

Doctoral Dissertations

"In order to maintain drinking water primary standards compliance under the USEPA Stage 2 Disinfectant Disinfection Byproducts Rule, drinking water treatment plants (DWTPs) are switching from free chlorine (FC) to chloramines (MCA). Concerns are raised as MCA disinfection has been linked N-nitrosamine formation. N-nitrosamines are a group of nitrogenous DBPs (N-DBPs) which are highly carcinogenic in comparison to regulated DBPs (THMs and HAAs, generated by FC disinfection). Also in the forefront of drinking water concerns are other emerging drinking water contaminants such as perchlorate. Perchlorate is a contaminant which can enter drinking water from natural deposits or through introduction by …

Characterization Of Terrestrial Dissolved Organic Matter Fractionated By Ph And Polarity And Their Biological Effects On Plant Growth, Rachel L. Sleighter, Paolo Caricasole, Kristen M. Richards, Terry Hanson, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Background: Humic substances are ubiquitous in the environment, complex mixtures, and known to be beneficial to plant growth. To better understand and identify components responsible for plant growth stimulation, a terrestrial aquatic DOM sample was fractionated according to pH and polarity, obtaining acid-soluble and acid-insoluble portions, as well as acid-soluble hydrophobic and hydrophilic fractions using C18. The various fractions were characterized then evaluated for their biological effects on plant growth using bioassays with corn at two carbon rates.

Results: Approximately 43% and 57% of the carbon, and 31% and 69% of the iron, was found in the acid-insoluble and acid-soluble …

Synthesis, Characterization, And Evaluation Of Small Molecule-Based Fluorogenic Probes For The Detection Of Cellular Thiols, Rasika Ranatunga Nawimanage

LSU Doctoral Dissertations

Fluorescence methods for disease diagnosis and detection of important analytes are becoming popular route as a technique, as they offer a simple non-invasive approach. Recently, many novel fluorophores and probes have been reported for selectively and sensitively detecting low abundance biological species in disease pathways. Biological thiols, such as glutathione, cysteine, and homocysteine, along with the smallest member hydrogen sulfide, are key thiol analytes in biological environments, and they play a vital role in living systems by maintaining the redox homeostasis of cells. Alteration of their ratios can cause cellular dysfunction and cell death. Furthermore, thiol levels in cells and …

Design And Application Of Task-Specific Organic Salts For Chemical And Biochemical Sensing, Waduge Indika Subodha Galpothdeniya

LSU Doctoral Dissertations

There is an increasing demand for development of new sensors and sensor strategies for accurate detection and discrimination of various analytes. In this regard, colorimetric and fluorometric sensor approaches have attracted considerable attention, primarily because they represent facile and inexpensive analytical tools. In this dissertation, I discuss the design and application of sensors and sensor arrays using task specific organic salts: ionic liquids (ILs) and a group of uniform materials based on organic salts (GUMBOS). As compared to typical ionic compounds, these two classes of organic salts exhibit relatively lower melting points due to bulky organic cations and/or anions. Interestingly, …

Scanning Probe Investigations Of Nanopatterned And Thermo-Responsive Polypeptoids And The Design Of A Sample Stage For Force Modulation Microscopy, Lu Lu

LSU Doctoral Dissertations

Protocols for patterning nanostructures of polymers were developed to enable scanning probe microscopy (SPM) studies of surface properties at the molecular level. A chemically selective surface for patterning polymers was generated by combining particle lithography with organosilane immersion. Poly(N-allyl glycine), a biocompatible and backbone degradable polypeptoid, was grown on Si(111) at confined amine sites using surface-initiated polymerization (also known as the “graft from” approach). A thermo-responsive random copolypeptoid, poly[(N-ethyl glycine)32-r-(N-butyl glycine17)], was pre-synthesized and attached onto a patterned organosilane surface using a thiol-ene click reaction (“graft to” approach). The phase transitions of the copolypeptoid nanostructures in an aqueous environment was …

Palladium-Catalyzed C8-Selective C-H Arylation Of Quinoline N-Oxides: Insights Into The Electronic, Steric And Solvation Effects On The Site-Selectivity By Mechanistic And Dft Computational Studies, David E. Stephens, Johant Lakey-Beitia, Abdurrahman Atesin, Tülay A. Ateşin, Gabriel Chavez, Hadi D. Arman, Oleg V. Larionov

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

We report herein a palladium-catalyzed C-H arylation of quinoline N-oxides that proceeds with high selectivity in favor of the C8-isomer. This site-selectivity is unusual for palladium, since all of the hitherto described methods of palladium-catalyzed C-H functionalization of quinoline N-oxides are highly C2-selective. The reaction exhibits a broad synthetic scope with respect to quinoline N-oxides and iodoarenes and can be significantly accelerated to sub-hour reaction times under microwave irradiation. The C8-arylation method can be carried out on gram scale and has excellent functional group tolerance. Mechanistic and Density Functional Theory (DFT) computational studies provide evidence for the …

Imaging, Spectroscopy, Mechanical, Alignment And Biocompatibility Studies Of Electrospun Medical Grade Polyurethane (Carbothane™ 3575a) Nanofibers And Composite Nanofibers Containing Multiwalled Carbon Nanotubes, Faheem A. Sheikh, Javier Macossay-Torres, Travis Cantu, Xujun Zhang, M. Shamshi Hassan, M. Esther Salinas, Chakavak S. Farhangi, Hassan Ahmad, Hern Kim, Gary L. Bowlin

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

In the present study, we discuss the electrospinning of medical grade polyurethane (Carbothane™ 3575A) nanofibers containing multi-walled-carbon-nanotubes (MWCNTs). A simple method that does not depend on additional foreign chemicals has been employed to disperse MWCNTs through high intensity sonication. Typically, a polymer solution consisting of polymer/MWCNTs has been electrospun to form nanofibers. Physiochemical aspects of prepared nanofibers were evaluated by SEM, TEM, FT-IR and Raman spectroscopy, confirming nanofibers containing MWCNTs. The biocompatibility and cell attachment of the produced nanofiber mats were investigated while culturing them in the presence of NIH 3T3 fibroblasts. The results from these tests indicated non-toxic behavior …