Browsing by Author "Billiot, Fereshteh"
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Item Biomimetic iron complexes for the oxidation of C-H bonds in hydrocarbons(2021-12) Le, Uyen; Prakash, Jai; Billiot, Fereshteh; Holubowitch, NicolasWith the rapid growth in transportation and industry, petroleum and other types of fossil fuels (coal, heavy oil) are heavily used for energy production. The consumption of these types of energy resources pose a serious environmental concern because of the production of greenhouse gases such as carbon dioxide, methane, nitrous oxide, and chlorofluorocarbons (CFCs) which are the primary reasons for climate change. This makes the development of cheaper and cleaner energy more important in modern society. Conversion of methane into liquid fuel such as methanol has become a promising goal for future petrochemical derivatives and decreasing petroleum dependence. Methane is the primary component of natural gas which is highly abundant on earth. Methane is used as a raw material to produce methanol which is further used as fuel to generate electricity. However, the conversion of methane into methanol is carried out at high temperature and pressure and this process is energy consuming. This makes methane oxidation catalysts high in demand. In recent decades, transition metal complexes have proven to be efficient and powerful catalysts for various oxidative transformations. Specifically, mononuclear and di-nuclear metal complexes now are widely applied as catalysts for the oxidation of organic substrates and water. Transition metals such as Mn, Fe, Co, Ni and Cu have been recognized as cheap, environmentally friendly and effective catalysts for C-H activation. Specifically, iron is the most attractive metal because it’s very inexpensive (most earth-abundant transition metal), displays high oxidation states (required in catalysis), and is relatively non-toxic. In this research, we will design and develop routes for synthesizing iron complexes that can serve as cheap and efficient catalysts for methane oxidation (or C-H activation). This is the foundation for future research aiming at converting inert hydrocarbons into useful petrochemical derivatives.Item Characterization of green surfactants with Dicarboxylate Polar Head(2023-08) Fritz, Shayden; Billiot, Fereshteh; Xu, Wei; Billiot, Eugene; Olson, MarkThere has been a growing emphasis on developing biodegradable and environmentally friendly surfactants. One such relatively new class of surfactants that fall into this category are amino acid-based surfactants. This research focused on studying the physical properties (critical micelle concentration [CMC] and hydrodynamic radius) of aspartic and glutamic amino acid-based surfactants with two different types of hydrophobic tails (saturated hydrophobic chain with 13 carbons and an unsaturated hydrophobic tail containing 11 carbons). In addition to the varying types of hydrophobic tails and polar headgroups, this study also examined what effect different types of diamine counterions had on the physical properties examined. It is interesting to note that the type of diamine counterion or the amino acid head group, for the most part, had little effect on the physical properties examined. The major factor affecting significant changes in the physical properties was the type of hydrophobic tail. The CMC value obtained for saturated 13 carbon surfactants was significantly lower compared to the surfactant with an unsaturated hydrophobic tail containing 11 carbon chains. The range for the CMC values of saturated 13 carbon surfactant was 6 to 12 mM, while the range of the CMC values of unsaturated 11 carbon surfactant was found to have a value of 33 to 52 mM. The surfactant with the unsaturated 11 carbon chain had a significantly smaller hydrodynamic radius in comparison to the saturated 13 carbon surfactant. The range of the hydrodynamic radius for the unsaturated 11 carbon surfactant had a hydrodynamic range from 1 to 5 nm and the saturated 13 carbon surfactant was between 5 to 8 nm. However, there was one exception to this trend and that was the saturated 13 carbon glutamic surfactant in the presence of 1,2 diaminoethane counterion. It had a significantly larger size than all other surfactants measured. The hydrodynamic radius that was measured from saturated 13 carbon surfactant in the presence of 1,2 diaminoethane had a value of 106.47 nmItem Characterization of single amino acid based surfactants undecanoic L-Isoleucine and undecanoic L-Norleucine in the presence of diamine counterions with varying chain lengths(2019-08) Maynard-Benson, Amber; Billiot, Eugene; Billiot, Fereshteh; Causgrove, TimothyTo understand chiral recognition and discrimination, single amino-acid-based surfactants undecanoic L-isoleucine and L-norleucine were synthesized and examined at various pHs with different counterions. Analysis was conducted utilizing different analytical instruments and techniques such as NMR and Capillary Electrophoresis (CE). Knowledge gained from this research will later be used to develop a database that will recognize behaviors of micelle systems and determine which parameters and materials will be most effective for enantiomeric separation.1 The focus of this particular study was to determine how varying the chain length of diamine counterions affects the properties of the surfactant. The following six counterions were investigated: 1,2-ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and sodium. Sodium was employed as the standard counterion for comparison. Early work was performed using arginine and lysine as counterions before shifting focus to the diamines; this data is also included as supplemental information. Data from this project has shown that the Critical Micelle Concentration (CMC) of surfactants is dependent upon the chain length of the diamine counterions. As the counterion chain length was increased, the CMC decreased. At pH 9 the CMC decreased from 12.19 mM undecanoic L-isoleucine with 1,2 ethylenediamine to a CMC of 2.00 mM for undecanoic Lisoleucine with 1,6 diaminohexane as the counterion. CE data showed that as the chain length of the counterion was increased, the enantiomers were resolved at a lower surfactant-counterion concentration. There was also improved chiral selectivity of BNA enantiomers in the presence of diamine counterions compared to the standard sodium. Based on previous literature, the micellar size also increased with a decrease in CMC as expected. The average hydrodynamic radius of undecanoic L-norleucine with 1,2-ethylenediamine at pH 10 was 9.17 Å compared to 24.52 Å for L-norleucine with 1,6 diaminohexane at pH 10.Item Characterization of the dipeptide based micellar systems undecanoic alanine-alanine and undecanoic alanine-glycine(2018-12) Maldonado, Savanna; Billiot, Fereshteh; Billiot, Eugene; Abdulla, HussainSurfactant are surface-active-agents, meaning surfactants have the ability to lower surface tension. In this research, two dipeptide surfactants undecanoic alanine-alanine and undecanoic alanine-glycine were studied to better understand their micellar systems. Variations of pH, temperature, surfactant concentration, and counterion type were examined to determine what effect, if any, changing these variables would have on micelle formation and chiral recognition. The counter ions examined in this study were di-amine alkanes with a different number of methyl groups separating the amines. These counter ions are pH dependent and preliminary results have shown that pH effects the interaction of these counter ions with the amino acid polar head, and in turn effects the physical properties of the surfactants and their micellar behavior. Some of the properties examined include: the critical micelle concentration, Krafft temperature, enantiomeric separation of chiral compounds, hydrodynamic radius of the micelles as well as fraction bound of the surfactant and counterions to the micelles. These systems were studied using proton Nuclear Magnetic Resonance (NMR), Diffusion Order Spectroscopy (DOSY), Capillary Electrophoresis (CE) and a LabQuest 2 with attached conductivity and temperature probes. The results here provide a better insight on the behavior of these dipeptide micellar systems which will aid in future research.Item Chiral recognition of binaphthyl derivatives with L-undecyl leucine surfactants in the presence of sodium and lysine counterions(Scientific Research Publishing, 2021-05-31) Billiot, Fereshteh; Garcia, Mauro; Risley, Amanda; Billiot, Eugene; Morris, KevinThis study investigates the effect of counterions on the chiral recognition of 1,1'-Binaphthyl-2,2'-diamine (BNA) and 1,1'-Binaphthyl-2,2'-diyl hydrogenphosphate (BNP) enantiomers when using an amino acid-based surfactant undecanoyl L-leucine (und-Leu) as the chiral pseudostationary phase in capillary electrophoresis. The effects of using two different counterions (sodium and lysine) on the chiral recognition of binaphthyl derivatives were compared at varying pH conditions. The enantiomeric separation of BNA and BNP enantiomers via capillary electrophoresis, using und-Leu as the chiral recognition medium, significantly improved the enantiomeric resolution in capillary electrophoresis at pH 7 when using Lysine counterions as compared to using sodium as the counterion. More specifically, at a surfactant concentration of 45 mM, at pH 7, a significant increase in chiral selectivity was observed when lysine was used as the counterion compared to sodium. The enantiomeric resolution of BNA and BNP increased by 6-fold and 1.1-fold, respectively, in capillary electrophoresis experiments when lysine was utilized as the counterion compared to using sodium. Furthermore, the retention factor of BNA and BNP enantiomers also increased approximately 3.5-fold and 4-fold, respectively, in the presence of lysine counterions as compared to using sodium counterions. When running buffer in capillary electrophoresis was increased to pH 11, the resolution and retention factors were nearly identical when comparing the effects of the sodium and lysine counterions. This signifies the important role of lysine’s positive net charge on chiral recognition. This study provides insight into the potential advantages of using cationic, pH-dependent counterions such as lysine to significantly improve the chiral recognition of binaphthyl derivatives when using chiral anionic surfactants as the pseudostationary phase in capillary electrophoresis.Item Chiral recognition of Dansyl Derivatives with an amino acid-based molecular micelle: A Molecular dynamics investigation(Scientific Research Publishing, 2021-05-26) Billiot, Fereshteh; Garcia, Mauro; Black, Nathan; Billiot, Eugene; Morris, Kevin F.; Fang, YayinIn this study, the chiral separation mechanisms of Dansyl amino acids, including Dansyl-Leucine (Dans-Leu), Dansyl-Norleucine (Dans-Nor), Dansyl-Tryptophan (Dans-Trp) and Dansyl-Phenylalanine (Dans-Phe) binding to poly-sodium N-undecanoyl-(L)-Leucylvalinate, poly (SULV), were investigated using molecular dynamics simulations. Micellar electrokinetic chromatography (MEKC) has previously shown that when separating the enantiomers of these aforementioned Dansyl amino acids, the L-enantiomers bind stronger to poly (SULV) than the D-enantiomers. This study aims to investigate the molecular interactions that govern chiral recognition in these systems using computational methods. This study reveals that the computationally- calculated binding free energy values for Dansyl enantiomers binding to poly (SULV) are in agreement with the enantiomeric order produced in experimental MEKC studies. The L-enantiomers of Dans-Leu, Dans-Nor, Dans-Trp, and Dans-Phe binding to their preferred binding pockets in poly (SULV) yielded binding free energy values of −21.8938, −22.1763, −21.3329 and −13.3349 kJ∙mol−1, respectively. The D-enantiomers of Dans-Leu, Dans-Nor, Dans-Trp, and Dans-Phe binding to their preferred binding pockets in poly (SULV) yielded binding free energy values of −14.5811, −15.9457, −13.6408, and −12.0959 kJ∙mol−1, respectively. Furthermore, hydrogen bonding analyses were used to investigate and elucidate the molecular interactions that govern chiral recognition in these molecular systems.Item Computational chemistry study of iron-based complexes for aqueous redox flow batteries(2021-08) Nguyen, Giang Thi Hoang; Holubowitch, Nicolas; Billiot, Fereshteh; Causgrove, TimothyRedox flow batteries (RFBs) are a new kind of battery with a great potential to store electricity from renewable energy sources like solar, wind, and tidal on a large scale. This project aims to discover new RFB active compounds that are eco-friendly and inexpensive to produce compared to vanadium, which is the current active compound for most commercial RFBs. This research focuses on iron-based organometallic complexes which are promising inexpensive and long-lived catholytes for aqueous RFBs. The long-term goal of this project is to discover new active compounds for aqueous redox flow battery (RFB). When iron binds with bipyridine (a common ligand for organometallic complexes), it gives stability at near-neutral pH and high discharge potential (high energy density) relative to uncompleted ferrous/ferric ions. However, there are two major challenges with Iron tris(2,2’-bipyridine): low aqueous solubility and dimerization. In this research project, computational chemistry, mainly density functional theory (DFT), will be applied to predict properties of Iron tris(2,2’-bipyridine) for RFBs. Redox potentials are best predicted via computation of Gibbs free energies in a Born-Haber thermodynamic cycle. Due to a variety of functionals and basis sets that serve as inputs for quantum chemistry calculations, different approximations including BP89, PBE, PBE0, B3LYP, BHLYP, B3PW91 and CAM-B3LYP were performed to match redox potential and structural determinations from DFT with actual lab data. As a result, PBE0 functional with LANL2DZ/def2-TZVP basis set gave the most accurate information. Hence, it is applied for deeper study about molecular orbitals, electrostatic potential, and the highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) In the pursuit of new RFB compounds, it is critical to understand the relationship of molecular structure, functional group properties, and electronic properties. Redox potential of 13 derivatives of bipyridine were calculated. We were able to plot the effects of substituents on bipyridine ligand on the complex’s redox potentials by applying Hammett equation. In addition, dimerization of Fe(bpy)3SO4, which leads to poor voltage efficiencies in batteries with this catholyte is studied in this research. Due to spin-crossover of the charged (oxidized) Fe (III) complex, it changes structural, vibrational, electronic, and magnetic properties of the molecule. Hence, it forms a dimer during discharge which leads to a drop in voltage efficiency. Preventing dimerization is important in RFB research because it maintain total voltage output of the redox flow battery. Due to spin-crossover phenomenon, broken symmetry was applied to describe the magnetic properties of dimer which is antiferromagnetic. In addition, the dimer undergoes two electron reductions to regenerate two Febpy2+ monomers, thus a modified Born-Haber thermodynamic cycle is applied in discharge reaction to estimate discharge potential of dimer.Item Development and verification of a computational model for the prediction of critical micelle concentrations (CMCs) for monoanionic amino acid-based surfactants(2023-08) Black, Nathan D.; Billiot, Eugene; Billiot, Fereshteh; Olson, MarkIn this research, the critical micelle concentrations (CMCs) of nine novel monoanionic amino acid-based surfactants (AABSs) were experimentally determined and used to validate a CMC prediction model based upon molecular dynamics (MD) simulations. The AABSs were synthesized, purified, and had their CMCs determined via the electrical conductivity method. After parametrizing the AABSs with a hybrid gaff2/ff14SB force field, MD simulations were performed in which they were solvated with various explicit and implicit solvents at concentrations ranging from 0.1 – 100 mM. This produced several parameters which are believed to be representative of the thermodynamics of AABS solutions. A battery of polynomial regression and statistical uncertainty analyses were performed on the concentration-dependent values of each parameter for the AABSs. It was found that using the implicit solvent model IGB8 results in distinct measurement uncertainties before and after specific concentrations that strongly agreed with the experimental CMCs. Utilizing an algorithm based upon the t-test in which these values were identified, the total potential and van der Waal energies were found to be the best predictors of AABS CMCs. This was supplemented by a quantitative structure-property relationship (QSPR) study in which ionization potentials and van der Waal energies were identified as strong predictors for experimental CMCs. It was jointly concluded from the results of MD simulation analysis and QSPR regressions that electrostatic energies restrict the CMCs of this family of AABSs to a particular order of magnitude, while the van der Waal energies distinguish each AABs from one another. This research represents the first documented (and successful) attempt to theoretically predict CMCs for AABSs, as well as a pioneering unification between MD simulation- and QSPR-based theoretical studies.Item Development of bis-bipyridinium and anthracene carboxyimide-based stimuli-responsive soft matter(2023-08) Jakharia, Vandan Paresh; Olson, Mark; Billiot, Fereshteh; Billiot, EugeneThis thesis focuses on the design and synthesis of an array of novel amphiphilic and polymeric molecules as precursors for developing dynamic stimuli-responsive supramolecular materials by harnessing the competency of non-covalent interactions. Over the past decades, bipyridinium-based derivatives have gained tremendous attention due to their applicability as functional units in tunable supramolecular complexes. The innate propensity of functionalized bipyridinium salts to serve as a ?-electron deficient acceptor allows them to undergo ?-? stacking donor-acceptor CT interactions in the presence of ?-electron rich organic molecules. This characteristic feature was employed to develop novel bipyridinium-functionalized amphiphiles and bio-polymeric materials that are capable of engaging in molecular recognition with and facilitating the extraction of melatonin, a neurotransmitter from water. The first project reports the design and development of heptyl and glycol-bridged bis-bipyridinium-based gemini amphiphiles that can undergo template-directed self-assembly. Previous studies indicated that the electrophilic aromatic nature of tetra-cationic bis-bipyridinium gemini amphiphiles can be exploited to form ?-? stacking charge-transfer interactions with ?-electron rich molecules. Thus, in an effort to establish structure-property relationships and understand the effect of the bridging unit, varied bridged bis-bipyridinium gemini amphiphiles were synthesized. They were investigated for their use of melatonin as a template for directed self-assembly processes. The charge-transfer interactions between the units lead to absorption band formation in the visible region of the electromagnetic radiation that can be exploited for various material applications. Upon comparing, the two derivatives in detail, their micellization behavior, surface properties, thermodynamic parameters, UV-Vis absorption, and micellar size exhibited similar characteristics. However, the heptyl-bridged gemini amphiphile responded to templation much more strongly, while the glycol-bridged gemini amphiphile exhibited higher solubility, they both portrayed excellent amphiphile and surface-active characteristics. The second part of this work focuses on employing ?-electron deficient bipyridinium units to design and process functional lipoic ester-based polymeric materials for the indole-base molecular targets from water. A series of lipoic-ester based-bipyridinium functionalized polymers with varying alkyl tail lengths were developed and studied to determine structure-property correlations and analyze their material characteristics. Out of the eight-novel functionalized polymeric materials, bipyridinium-bridged lipoic ester polymer (BLEP) formed polymeric sheets while nonyl-bipyridinium-functionalized lipoic ester polymer (9C-BFLEP) formed coacervates in water. Both materials showed comparable and acceptable efficiency in adsorbing melatonin out of solution by harnessing ?-? stacking charge-transfer interactions in conjugation with the hydrophobic effect. This approach provided a quick and promising method for the remediation of indole-cored molecules from water. Lastly, an anthracene carboxyimide derivative was synthesized with the ability to undergo a photo-induced [4+4] cycloaddition dimerization process. The dimerization can easily be reversed upon heating. The compound was found to be able to have a special feature that allows them to undergo single crystal-to-single crystal photo-dimerization upon exposure to UV light. This controlled switchable characteristic property of anthracene carboxyimide are unique and can be utilized for developing tunable molecular switches with applications where stimuli-responsive materials are required.Item Experimental-computational investigation of chiral separations with amino acid-based surfactants(2021-05) Garcia, Mauro; Billiot, Eugene; Billiot, Fereshteh; Causgrove, TimothyThis thesis research investigates the use of amino acid-based micelles to separate enantiomeric compounds. These are investigated using both, experimental and computational methods. The experimental portion of my thesis research investigates the effect of counterions on the chiral recognition of 1,1′-Binaphthyl-2,2′-diamine (BNA) and 1,1′-Binaphthyl-2,2′-diyl hydrogen phosphate (BNP) enantiomers when using an amino acid-based surfactant as the chiral pseudo stationary phase in capillary electrophoresis. The effects of sodium counterions on the chiral recognition of binaphthyl derivatives were compared to that of using pH-dependent Lysine counterions at varying pH conditions. The enantiomeric separation of BNP and BNA enantiomers via capillary electrophoresis, using L-Undecyl-Leucine (und-Leu) as the chiral recognition medium, significantly improved the enantiomeric resolution in capillary electrophoresis at pH 7 when using Lysine counterions as compared to using sodium counterions. Therefore, this experimental project provides insight into the advantages of using cationic, pH-dependent counterions such as Lysine to significantly improve the chiral recognition of binaphthyl derivatives in capillary electrophoresis studies. The computational portion of my thesis research focused on developing computational methodology to study the binding interactions between amino acid-based molecular micelles and chiral enantiomers. The computational method development plays a crucial role in helping the research advance towards the development of a predictive database. After developing a set of protocols for the computational research, the methods were then used to study the chiral separation mechanisms of Dansyl amino acids, including Dansyl-Leucine, Dansyl-Norleucine, Dansyl- Tryptophan and Dansyl-Phenylalanine binding to poly-sodium N-undecanoyl-(L)-Leucylvalinate, poly(SULV). This study reveals that the computationally-calculated binding free energy values for Dansyl enantiomers binding to poly(SULV) are in agreement with the enantiomeric order produced in experimental MEKC studies. Furthermore, hydrogen bonding analyses was used to investigate and elucidate the molecular interactions that govern chiral recognition in these molecular systems.Item The influence of diamine counterion use and surfactant counterion ratio on chiral selectivity of amino acid-based surfactants(2022-04) Montoya, Sara; Black, Nathan; Billiot, Eugene; Billiot, Fereshteh; Morris, KevinIn this study, the effects of counterion type and surfactant-to-counterion ratio on the chiral selectivity of several binaphthyl derivatives with L,L- undecanoyl leucine-valinate was examined by use of Micellar Electrokinetic Chromatography (MEKC). The chiral separations of 1, 1−𝑏𝑖−2−𝑛𝑎𝑝ℎ𝑡ℎ𝑦𝑙−2, 2−𝑑𝑖𝑦𝑙ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛(𝐵𝑁 𝑃 )1, 1′−𝑏𝑖−2−𝑛𝑎𝑝ℎ𝑡ℎ𝑦𝑙−2, 2′−𝑑𝑖𝑎𝑚𝑖𝑛𝑒(𝐵𝑁𝐴)𝑎𝑛𝑑1, 1′−𝑏𝑖−2−𝑛𝑎𝑝ℎ𝑡ℎ𝑜𝑙(𝐵𝑂𝐻 by the dipeptide surfactant varied widely in the presence of three counterions, 1,2 diaminoethyl, 1,2 diamino- propyl, and 1,3 diaminopropyl and with surfactant-to-counterion ratios of 1-to-1 and 1-to-0.5. The results of this study have shown that the selection of 1,2 diaminoethyl in a 1-to-1 surfactant-counterion-ratio provides enhanced baseline separation for enantiomers of BOH in comparison to its 1-to-0.5 counterpart, though no significant difference in separation can be observed for enantiomers of BNP under the same conditions. Despite the observation that every one of the three included counterions engendered some degree of separation for each analyte, enantiomers of BNP exhibited heightened separation in the presence of 1,2 diaminoethyl and 1,2 diaminopropyl at a pH level of 8. Conversely, the comparative Na counterion separates enantiomers of BOH and BNA significantly better than the counterions examined.Item Leadership unscripted: Portraits of female crisis leadership(2023-5) James, Kimberley Donaldson; Hemmer, Lynn; Elliff, Scott; Villarreal, Linda; Billiot, FereshtehThis research afforded three female PK-12 educational leaders space in which to examine, deconstruct, reflect, and build upon sensemaking to?understand how they led their campus out of a crisis, how healing from a crisis happened for the leader, and how they led their school community. Three portraits were used to highlight these female PK-12 educational leaders’ experiences to examine contexts, narrative, practices, and consequences of crisis leadership. The research used two interconnected theoretical frames: feminist standpoint theory (Harding, 1996) and sensemaking (Weick, 1993; 2009). Instead of accepting the adage that effective crisis female leadership can be explained by the traditional lens of a leader’s tactile and relational approaches to preparedness and response (Weeks et al., 2013), a portraiture methodology was used (Lawrence-Lightfoot & Davis, 1997) to illuminate the authenticity of the leaders’ actions and goodness that arose out of lived crisis realities of three female PK-12 educational leaders as they led through crises. The purpose of this study was to explore the intersection of sensemaking, crisis leadership, and leadership authenticity as shared through stories and conversations of three female PK-12?educational leaders. The secondary purpose of the study was to expand upon the space within a privileged setting that has been historically viewed through a male perspective by examining the impact of posttraumatic growth leadership development in women leading through a crisis.? The intended audience for this research is educational leaders, specifically female leaders and leadership preparation program faculty. The portraits presented in this study highlighted the strengths and moral/spiritual compasses these female leaders used to navigate crises. Although Liberty, Karina, and Bella faced many challenges during their crises, they faced them with courage—they used different strategies to overcome the crises with the support of the people in their lives, and they displayed resilient leadership skills in performing their duties as a leader. Most leaders deal with crises at some point in their career. This research is significant in that it may help to prevent the isolation that is often felt by leaders dealing with crises.Item Metabolomic profiling of human embryo during pre-implantation in vitro fertilization non-invasive approach(2021-05) Al Shaikh, Maryam; Abdulla, Hussain; Billiot, Fereshteh; Gonzales, Xavier FonzIn vitro fertilization (IVF) is a standard protocol used to treat infertility. However, the probability of successful embryo implantation during IVF is very low. Most of the IVF clinics depend on morphological scoring by embryologists to select high-quality embryos capable of implantation. But morphological scoring has only around 30% successful pregnancy rate. In this study, I investigated the potential of a new embryo scoring method based on measuring the change in culture media's metabolomic profiles. I analyzed 71 culture media samples with known pregnancy outcomes from two different culture media by ultraperformance liquid chromatography (UPLC) coupled with ultrahigh-resolution and accuracy mass spectrometer. I used a newly developed on-the-fly dynamic data acquisition technique to increase the percentage of metabolite compounds with MS2 fragmentation spectra. To identify potential metabolomic pregnancy biomarkers, we used a combination of statistical analysis techniques like principal component analysis (PCA), differential analysis (volcano plots), and trend charts. We used Molecular Formula Calculator software, ChemSpider, and mzCloud databases to assign the molecule formula and chemical structure for the detected significant biomarkers. Also, we applied in-silico fragmentation and FISh scoring to validate the chemical structures of the identified biomarkers. Using PCA, we did not find any apparent clustering for pregnant or non-pregnant samples, but we could locate a few outliers' spectra. However, with volcano plots, we were able to identify a set of up-regulated biomarkers that are associated with non-pregnancy and down-regulated biomarkers that are associated with pregnancy in both media. Utilizing the KEGG and Metabolika databases, we recognized two possible metabolomics pathways. This study can improve selecting viable embryos, which will lead to an increase in the success rate of IVF. It will also provide a better understanding of human embryos' metabolomic biochemical pathways during the preimplantation stage.Item A novel di-iron ligand complex for water oxidation catalysis and the development of bis-bipyridinium-based gemini surfactants for template-directed self-assembly(2022-07-22) Tran, Ha Hoang; Olson, Mark; Billiot, Fereshteh; Holubowitch, NicolasThis thesis reports the designs and synthetic routes for a variety of organic molecules that served as the starting materials for the construction of supramolecular complexes via non-covalent interactions. The first project involved the development of a rationally designed dinucleating ligand that would form various stable diiron complexes as potential water oxidation catalysts (WOCs). The WOCs can promote the clean production of hydrogen gas, a green and potential fuel to replace traditional carbon-based fuels, by lowering its cost and increasing its efficiency. The second research project focused on synthesizing novel bis-bipyridinium-based gemini amphiphiles that were capable of self-assembling or co-assembling with a template molecule (the neurotransmitter melatonin) to form ?-? donor-acceptor charge-transfer complexes. This research provided fundamental insights into the structure-property relationships between the amphiphiles and their self-assembly processes which are important for developing methodology that uses self-assembly to construct complex stimuli-responsive functional molecular architectures. The target compounds, which include the ligand and gemini amphiphiles were synthesized using a two-step SN2 route. Supramolecular complexes were formed from the combination of two species (1st: the ligand and an iron salt, and 2nd: the amphiphile and the template). The obtained compounds were characterized by various techniques including 1H-NMR, 13C-NMR, 2D-COSY, 2D-HSQC, and TOF-ESI-MS. The synthesis of the ligand was achieved with a yield of 86% for the 1st step and 45% for the second step. The ligand was later used to form diiron complexes which can be great WOCs due to their ability to form high valent intermediates for O-O bond formation. The synthesis of the gemini amphiphiles had a yield of 62% for 1st step and 62 – 79% for the 2nd step. The formation of ?-? donor acceptor charge transfer complexes were verified by UV-Vis, 1H-NMR, 2D-ROESY NMR, and 2D-DOSY NMR. Melatonin demonstrated its ability to serve as “molecular glue” that can minimize the Coulombic repulsion among positive charged tetracationic gemini amphiphiles as they underwent self-assembly. This resulted in 1) the formation of larger aggregates; 2) a more thermodynamically favorable self-assembly process; and 3) an overall increase in the efficiency of the amphiphiles to self-assemble into micellar superstructures at lower concentrations.Item Synthesis of aspartic acid-based bifurcated tripeptide surfactants(2023-08-29) Swonke, Roslyn; Garcia, Angelina; Billiot, Eugene; Billiot, Fereshteh; Olson, Mark; Azad, ChandraAmino acid-based surfactants (AABS) are amphipathic molecules composed of an amino acid-based polar headgroup and nonpolar hydrocarbon chain. Surfactants, the truncated name for surface-active agents, are molecules that decrease surface tension. It is this property, along with their amphipathic structure, that imbues surfactants with useful properties, such as encapsulating other compounds and emulsifying insoluble phases. AABS are of particular interest, as they incorporate amino acids, which are the building blocks of life. The incorporation of amino acids as the polar headgroup thus improves bioavailability and biodegradability, thereby increasing the applications of this subset of surfactants. The objective of this study is to synthesize and characterize a group of novel tripeptide bifurcated AABS with aspartic acid as the central amino acid at the polar headgroup.