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Investigation Of Spontaneously Patterned Nanoporous Organosilicate Thin Film Channels For Liquid Chromatography Applications., Ashwin Sanjay Bhaskaran

Graduate Research Theses & Dissertations

Microscale devices are attractive options for the advancement of biomedical engineering and life science. They have huge potential in the pharmaceutical and biomedical fields provided the critical factors such as device size, product purity and efficiency are not a hindrance. In most cases, traditional microelectronics fabrication processes are quite costly and complicated. By improving on them, their application in fields such as chemical sensing, detection and analysis is possible. By implementing this on a chip, we can reduce the cost and improve portability. This thesis focuses on the investigation of a novel class of spontaneously patterned nanoporous organosilicate nanoparticle-based films …

Characterization Of Potential Anti-Infective Agents By Targeting Burkholderia Pseudomallei And Escherichia Coli Ispf, Dakota Lane Grote

Graduate Research Theses & Dissertations

With the likelihood of contracting an antibiotic resistant infection increasing, the need for novel anti-infective agents is critical. The development of novel anti-infective agents benefits from the identification of new target pathways necessary for the survival of the pathogen. One such target is the methylerythritol phosphate (MEP) pathway, responsible for the synthesis of the isoprenoid precursors isopentyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP) in bacteria and other pathogenic organisms. The MEP pathway is an attractive target because it is specific to a wide range of pathogenic organisms, while humans have a separate pathway, the mevalonate (MVA) pathway, for the biosynthesis …

Coaxially Electrospun Fibrous Polymer Scaffolds For Tissue Regeneration And Drug Delivery, Matthew Michael Kleszynski

Graduate Research Theses & Dissertations

A biomaterial is a substance that is specifically engineered to take on a role within the body, either alone or in conjunction with other materials, with the purpose of influencing the body. Using Polymers as a biomaterial is an exciting field of study that has the potential to further our abilities to help those in need. Creating composite nanofibrous scaffolds composed of hydrophobic and hydrophilic polymers may outperform structures made of a single polymer in both in vitro and in vivo environments. Hydrophilicity governs the behavior of polymers in the body and has influence over the mechanical properties of the …

Electrochemical Study Of The Performance Of Manganese Vanadium Oxide Cathodes In Zinc Batteries, Sarat Alabidun

Graduate Research Theses & Dissertations

Zinc metal batteries are considered a promising alternative for grid energy storage due to the low redox potential (-0.76V vs SHE) and high theoretical specific capacity (850mAh/g) of zinc metal anode as well as its compatibility with aqueous electrolytes. They however face issues of poor cathode stability and rapid capacity fading. Several methods have been devised to improve the stability of the cathode materials and develop novel cathode materials with better performance including the metal ion doping of intercalation materials.This study investigated the performance of zinc metal batteries with novel manganese vanadium oxide cathodes. Organic structure directing agents have been …

Carborane-Appended Levodopa For Prostate-Specific Membrane Antigen And Boron Neutron Capture Therapy, Alejandra Macias

Graduate Research Theses & Dissertations

A multi-step organic synthetic method to attach carborane cages to biocompatible organic compounds for application in Boron Neutron Capture Therapy (BNCT) was conducted. Boron Neutron Capture Therapy is a form of radiation therapy that promises a new and effective form of cancer treatment that involves the destruction of tumor cells using an isotope of boron (10B). The effectiveness of this therapy depends on the boron content accumulated in cancerous tissue. Carboranes are boron-rich clusters that possess unique physical and chemical properties making them suitable for a wide range of applications including medicinal chemistry. Because of their high boron content, carborane-appended …

Metal Complexes Of Bis(Pyrazolyl)Methane-Based Ditopic Ligands, Pubudu Nuwan Perera Hapuarachchige

Masters Theses

No abstract provided.

Determining Material Structures And Surface Chemistry By Genetic Algorithms And Quantum Chemical Simulations, Josiah Jesse Roberts

Theses and Dissertations--Chemistry

With the advent of modern computing, the use of simulation in chemistry has become just as important as experiment. Simulations were originally only applicable to small molecules, but modern techniques, such as density functional theory (DFT) allow extension to materials science. While there are many valuable techniques for synthesis and characterization in chemistry laboratories, there are far more materials possible than can be synthesized, each with an entire host of surfaces. This wealth of chemical space to explore begs the use of computational chemistry to mimic synthesis and experimental characterization. In this work, genetic algorithms (GA), for the former, and …

Developing Synthetic Strategies For Multifaceted Applications Of Stable Gold-Based Complexes, Randall Tyler Mertens

Theses and Dissertations--Chemistry

Development of stable gold-based complexes has been a rapidly advancing field due to the popularity of gold complexes, particularly for use in biomedical research and catalytic transformations. Given that auranofin, a gold(I) complex with FDA approval for the treatment of rheumatoid arthritis is used in the clinic, the development of stable gold-based molecules of clinical relevance is urgently needed. Herein are reported, synthetic strategies used for the development of new classes of gold(I) and gold(III) complexes for advancement in mitochondrial modulation for use as chemotherapeutics as well as application to gold catalysis due to the unique geometry of complexes presented …

Computational Insights On Medicinal Chemistry Targeting Cyp450s, Alexander D. Fenton

Theses and Dissertations--Chemistry

Modern-day medicinal chemistry has provided researchers with a wide variety of tools to not only gather greater insight from their data, but also to generate data in new ways. One such tool is the construction of computational protein models from crystallographic datasets, and their subsequent use to understand the structure-activity relationships of protein-ligand complexes. These models can be utilized for their predictive power to inform the synthesis of, and improvement of, lead compounds. It is the goal of this work to employ such models to the CYP450 enzyme system such that potent and selective inhibitors can be designed, evaluated biologically, …

Plasmon Enhanced Single Molecule Fluorescence In Zero Mode Waveguides (Zmws), Abdullah Masud

Theses and Dissertations--Chemistry

Plasmonic nanostructures are an extensive research focus due to their ability to modify the photophysical properties of nearby fluorophores. Surface plasmons (SP), defined as the collective oscillation of delocalized electrons, are the fundamental characteristic primarily responsible for altering those photophysical properties. Studying fluorophores at the single-molecule level has received significant attention since more specific information can be extracted from single molecule-based studies, which otherwise could be obscured in ensemble studies. However, single-molecule studies are inherently challenging because the signal from a single molecule is usually dim, making it difficult to detect. The situation is even worse in a crowded environment …

Mass Spectrometry Method Development For The Discovery And Characterization Of Secondary Metabolites, Zachary Kelley

Theses and Dissertations--Chemistry

Secondary metabolites are organic compounds produced by an organism for reasons other than growth and development. In plants, secondary metabolites generally act as defense agents produced to deter predators and inhibit other competitive species. For humans, these compounds can often have a beneficial effect and are pursued and utilized as natural pharmaceuticals. The development of sensitive, high-throughput analytical screening methods for plant derived metabolites is crucial for natural pharmaceutical product discovery and plant metabolomic profiling. Here, metabolomic profiling methods were developed using a microfluidic capillary zone electrophoresis device and evaluated against traditional separation approaches. An alkaloid screening assay was constructed …

Flavin Modification And Redox Tuning In The Bifurcating Electron Transfer Flavoprotein From Rhodopseudomonas Palustris: Two Arginines With Different Roles, Nishya Mohamed-Raseek

Theses and Dissertations--Chemistry

Electron bifurcation is considered as a third fundamental mode of energy conservation mechanism in addition to two well-known mechanisms, substrate level phosphorylation and Oxidative phosphorylation, in electron bifurcation endergonic and exergonic redox reactions are coupled. The newly discovered flavin based electron bifurcation in electron transfer flavoproteins (ETFs) helps to reduce low potential ferredoxin, which provides electrons to drive biologically demanding reactions such as atmospheric dinitrogen fixation in diazotroph and methane production in methanogens.

Current research demonstrates the capacity for electron bifurcation in the Rhodopseudomonas palustris ETF (RpalETF) system. RpalETF contains two chemically identical but functionally different FADs: …

Elucidation Of The Structure Of Supramolecular Polymorphs In Peptide Nanofibres Using Raman Spectroscopy, Sian Sloan-Dennison, Ayala Lampel, Eileen Raßlenberg, Rein V. Ulijn, Ewen Smith, Karen Faulds, Duncan Graham

Advanced Science Research Center

Peptide fibre formation via molecular self-assembly is a key step in a range of cellular processes and increasingly considered as an approach to produce supramolecular biomaterials. We previously demonstrated the self-assembly of the tripeptide lysine-dityrosine (KYY) as a substrate for the formation of proton-conducting melanin-like materials. Point based Raman scattering is one of several techniques which were used to characterise the secondary structure of the KYY nanofibre but as is often the case with this type of fibre, the spectra are rather complex and in addition there were variations in intensity between samples making interpretation difficult. Using Raman mapping we …

Exposing The Effects Of Reaction Cavity In Solid-Phase Reaction Kinetics, Michael Carr

Master's Theses

Reactivity of molecular solids is governed by topochemical considerations, where minimizedmolecular movement dictates both product identity and kinetics. This Thesis explores the central role reaction cavity plays in the topochemical principle by using the highly varied cavities formed by the different facets of a tetracene crystal. The relative rates for ten different reaction cavities were measured via energy dispersive X-ray spectroscopy for the reaction of tetracene with vapors of maleic anhydride. Variance in cavities resulted in Diels-Alder reaction rates that differed by as much as a factor of 2.6. Effects were understood via molecular dynamic simulations which modeled the approach …

Generation, Characterization, And C-H Bond Activation Reactivity By Mononuclear High-Valent Cobalt(Iv) And Nickel(Iv) Non-Oxo Complexes, Yubin Maria Kwon

Graduate Student Theses, Dissertations, & Professional Papers

The study of terminal high-valent transition metal-oxo complexes has increased significantly over the years as it is believed that they are key reactive intermediates for a wide range of biological and industrial catalytic processes. These complexes are powerful oxidants for the activation of strong C-H bonds. The chemical and physical properties of these complexes remain elusive. It is therefore desirable to study the properties and function of these complexes through synthetic models. There have been many efforts and reports of synthetic high-valent metal-oxo complexes of early and middle transition metals (up to group 8 on the Periodic Table of Elements), …

Development Of High-Performance Hydrogels, Buddhabhushan Salunkhe

Doctoral Dissertations

Here, we present a systematic approach to design robust hydrogel compositions. The goal was to achieve excellent properties to open up new opportunities in especially two challenging applications not previously well-served by hydrogels.

The first part of this research will discuss the systematic screening of polymers for their hydrothermal stability under brine, acidic, neutral, and basic pH conditions followed by novel designs of hydrogel compositions. Certain hydrogel compositions withstand temperatures of up to 150 °C for more than 24 months in high salinity brines. This novel hydrogel composition fills a technology gap between the existing polyacrylamide-based preformed particle gels (PPGs) …

Development Of Intelligent Stimuli-Responsive Biomaterials And Nanodevices, Shuo Yang

Doctoral Dissertations

"Structural DNA nanotechnology utilizes DNA molecules as building blocks to fabricate ordered artificial nanostructures at the molecular level. Among all DNA-based techniques, DNA origami has been considered as one of the most powerful tools for constructing artificial nanostructures with excellent programmability and addressability. Currently, most DNA origami nanostructures are static and do not have the ability to response to environmental stimulation. The development of environmental-responsive DNA origami nanostructures is a critical step towards the realization of intelligent dynamic DNA origami-based nanodevices. This research focuses on the design and fabrication process of both static and dynamic DNA origami nanostructures and their …

Development Of Small Molecule Inhibitors Of Therapeutic Target Enzymes: Paths To Discover Novel Antimicrobials, Thahani Shifna Habeeb Mohammad

Dissertations

The rising antimicrobial resistance to antibiotics is a major global problem, which has been exacerbated by the inappropriate use of antibiotics. The effectiveness of frequently prescribed penicillin derivatives and β-lactamase inhibitors are compromised by the evolution of bacterial β-lactamases and antibiotic-resistant bacteria. Consequently, design and synthesis of small-molecule inhibitors of identified novel antibiotic targets is an urgent unmet medical need. We previously demonstrated that N-functionalized α-aminocyclobutanones can act as peptidomimetic enzyme inhibitors, including inhibition of a key esterase in Francisella Tularensis. The carbonyl of a cyclobutanone is electrophilic due to ring strain, therefore cyclobutanone derivatives can serve as transition state …

Synthesis And Characterization Of Redox Non-Innocent Ligand Supported Transition Metal Complexes, Adriana Marie Lugosan

Dissertations

Catalysis is an integral part of society, which is often taken for granted. Over the past few years, there has been an increased effort to develop catalysts that are more environmentally friendly, selective, and energy efficient. This work focuses on the development of novel complexes made from a carefully designed non-innocent ligand together with earth-abundant and cost-effective transition metals that can be used to understand fundamental inorganic chemistry principles and serve as model systems. The work reported within validates the utility of this novel class of redox non-innocent ligand to form metal complexes with interesting properties, such as a non-porphyrin …

The Application Of Machine Learning In Analyzing Organic Compounds From Nmr Spectral Data, Nicole Maia Powell

Senior Independent Study Theses

Nuclear magnetic resonance (NMR) is used in organic chemistry to identify unknown organic compounds. The data obtained from an NMR spectrometer are typically shown in the form of a spectrum, which is then analyzed by an analytical chemist. The action of analyzing a spectrum, especially one of a large and complex molecule, is a long and tedious process. In this project, Python is used to implement hierarchical clustering on NMR data obtained from an NMR spectrometer at the College of Wooster to explore its application in NMR analysis. MATLAB is used to build a decision tree from the same data, …

Predicting Material Properties: Applications Of Multi-Scale Multiphysics Numerical Modeling To Transport Problems In Biochemical Systems And Chemical Process Engineering, Tom Pace

Theses and Dissertations--Physics and Astronomy

Material properties are used in a wide variety of theoretical models of material behavior. Descriptive properties quantify the nature, structure, or composition of the material. Behavioral properties quantify the response of the material to an imposed condition. The central question of this work concerns the prediction of behavioral properties from previously determined descriptive properties through hierarchical multi-scale, multiphysics models implemented as numerical simulations. Applications covered focus on mass transport models, including sequential enzyme-catalyzed reactions in systems biology, and an industrial chemical process in a common reaction medium.

Α-Glucosidase Inhibitors From The Stems Of Thunbergia Laurifolia, Khoa Nguyen Anh

Chulalongkorn University Theses and Dissertations (Chula ETD)

Alpha-glucosidase inhibitory assay-guided isolation of Thunbergia laurifolia L. stems yielded a new compound named 5-acetoxyfuranonapthoquinone (1) along with nineteen known compounds (2-20). The structure of the isolated compounds was elucidated by the analysis of multiple spectroscopic data as well as by comparison with the previous reports. The isolated compounds were evaluated for α-glucosidase inhibition. Syringaresinol (6), rosmarinic acid (11), 1,2,8-trihydroxyxanthone (17), and isojacareubin (18) showed the most potent inhibitory activity among isolated compounds. Kinetic study indicated that syringaresinol (6), 1,2,8-trihydroxyxanthone (17), and isojacareubin (18) could inhibit the maltase and sucrase function by non-competitive, and rosmarinic acid (11) was identified as …

Isolation Of Α-Glucosidase Inhibitors And Cytotoxic Compounds From Heartwood Of Mansonia Gagei Drumm, Le Thi Thu Huong

Chulalongkorn University Theses and Dissertations (Chula ETD)

Phytochemical and biological investigations were carried out on the heartwoods of M. gagei. Twelve known compounds (1–11, 29), ten new sesquiterpenoids (12–21), seven novel compounds (22–28) and one new neolignan (30) were isolated. Their structures were elucidated by spectroscopic data analysis (UV-Vis, FTIR, 1D, 2D NMR and HRESIMS), and their absolute configurations were established by calculation of ECD data. Isolated compounds were evaluated for antioxidant, cytotoxic activity and enzyme inhibitory activity against α-glucosidase. Interestingly, mansonialactam (21) showed significant inhibitory activity against α-glucosidase from the yeast with the IC50 value of 0.2 ± 0.05 mM which was 468 times lower than …

Colorimetric Sensors For Formaldehyde Detection And Electrochemiluminescent For Pathogens Detection, Uma Pongkitdachoti

Chulalongkorn University Theses and Dissertations (Chula ETD)

In this work, two methods for the detection of formaldehyde and one assay for detection of Cryptosporidium parvum DNA (C. parvum) in water samples were developed. For the detection of formaldehyde, silver-doped hydroxyapatite (Ag-HAP) was used to extract formaldehyde from high volume samples and the Tollens’ reaction occurred on the solid surface. After the reaction, silver nanoparticles were produced on the material resulting in the material color change from off-white to yellow or brown depending on the concentration of formaldehyde. By using the Ag-HAP, the detection of formaldehyde was achieved by measuring the color intensity. Under the optimized conditions, this …

Mesoporous Carbon/Silica Nanocomposites With Acid And Base Properties For Glucose Conversion Into Value Added Chemicals, Satit Yousatit

Chulalongkorn University Theses and Dissertations (Chula ETD)

The purpose of this study is to prepare mesoporous carbon/silica (MCS) nanocomposites using natural rubber (NR) as a renewable carbon source. A series of mesoporous nanocomposites based on NR and hexagonal mesoporous silica (HMS), prepared via an in situ sol-gel process, were used as precursors, which were then converted into the MCS materials by carbonization. The sulfonic acid-functionalized mesoporous carbon/silica (MCS-SO3H) was prepared by direct sulfonation with H2SO4 solution. The silica surface of MCS-SO3H were then grafted by 3-aminopropyltrimethoxysilane to produce the acid–base catalysts (MCS-SO3H-NH2) and used as the solid catalysts in glucose conversion. The MCS nanocomposites exhibited enhanced structural, …

Cellulose-Supported Fluorophore As Metal Ion Sensors, Apiwat Promchat

Chulalongkorn University Theses and Dissertations (Chula ETD)

Organic fluorescent ligands are attractive for qualitative and quantitative analysis of metal ions. Cellulose substrates, especially for filter paper, have been demonstrated as one of the most economical and easy to use platform for fluorescent sensors applied in on-site analysis with naked-eye observation. In this work, new series of amidoquinoline derivatives were synthesized and investigated as the fluorescent ligands for developing paper-based sensors. The sensors are used for convenient analysis either by simple naked-eye observation or an image processing software. In the first part of this dissertation, parallel solid-state synthesis on filter paper macroarray was used for rapid discovery and …

Use Of Modified Nay Zeolite As Ionophore For Perchlorate Selective Electrode, Boonyakorn Srisassawatkul

Chulalongkorn University Theses and Dissertations (Chula ETD)

NaY zeolite is well deserved for being employed as a catalyst, adsorbent, and ion exchanger. Therefore, its ion exchange property is used in ion selective electrodes (ISEs). Commercial NaY zeolite was modified with cetyltrimethylammonium bromide (CTAB) in various concentrations (100, 150, and 200 mM), denoted them as 100, 150 and 200 SMZ, respectively. XRD, FT-IR, SEM and TGA/DTG showed good agreement of CTAB adsorption on zeolite surface. Then SMZ is used to fabricate polymeric membrane with polyvinyl chloride (PVC) plasticized with o-nitrophenyl octyl ether (o-NPOE). The best performance of ISE was exhibited at the membrane composition of 200 SMZ: PVC: …

Chemical Constituents Of Fan-Si Abutilon Indicum Stems, Arum Restu Widyasti

Chulalongkorn University Theses and Dissertations (Chula ETD)

This study aimed to isolate secondary metabolites from the stems of Abutilon indicum and to evaluate their α-glucosidase, pancreatic lipase, α-chymotrypsin inhibitory activity. Chromatographic fractionation of the n-hexane crude extracts led to the isolation of three known metabolite (1-3). The crude extract from all parts of the plant were evaluated for inhibitory activity on the alpha-glucosidase enzyme. The DCM-soluble roots were active with 10.2% at 25 μg/mL. The hexane and MeOH-soluble stems were active with 11.0% at 25 μg/mL and 8.0% at 0.25 μg/mL. The hexane, DCM, and MeOH-soluble leaves are active with 20.2% at 0.025 μg/mL; 20.0% at 0.025 …

Modification Of Screen-Printed Carbon Electrode For Detection Of Pesticides, Kansuda Langor

Chulalongkorn University Theses and Dissertations (Chula ETD)

Methyl parathion (MP) is an organophosphate pesticide broadly used in agriculture to protect crops and fruits from the damages caused by insects and pests. However, when it is used in large quantities, it can be potentially toxic to humans and animals, causing many poisoning effects. Moreover, its residues can also penetrate the food chain (via agriculture food products) as well as contaminating the environment, leading to air, water and soil pollution. Therefore, rapid determination and reliable quantification of trace level of MP are crucially needed for food safety and environmental monitoring. In this work, a low-cost and portable electrochemical sensor …

Colorimetric And Fluorescent Detection Of Nucleic Acid By Styryl Dyes, Kotchakorn Supabowornsathit

Chulalongkorn University Theses and Dissertations (Chula ETD)

Nucleic acid staining dyes are essential tools for the analysis and visualizing of DNA/RNA in vitro and in cellular applications. Although there are several commercially available dyes developed during the past few decades, the selection is still relatively limited, and they are often very costly and associated with undesirable characteristics such as toxicity. Consequently, the discovery of nontoxic, readily available dyes, with desirable and controllable optical characteristics remains important. Styryl dyes have recently gained popularity as potential biological staining agents with many desirable properties including a straightforward synthesis procedure, excellent photostability, tunable optical properties, and high responsiveness towards nucleic acid …