Digital Commons Network^™

Cytotoxic Polyketides With An Oxygen-Bridged Cyclooctadiene Core Skeleton From The Mangrove Endophytic Fungus Phomosis Sp. A818, Wei Zhang, Baobing Zhao, Liangcheng Du, Yuemao Shen

Department of Chemistry: Faculty Publications

Plant endophytic microorganisms represent a largely untapped resource for new bioactive natural products. Eight polyketide natural products were isolated from a mangrove endophytic fungus Phomosis sp. A818. The structural elucidation of these compounds revealed that they share a distinct feature in their chemical structures, an oxygen-bridged cyclooctadiene core skeleton. The study on their structure–activity relationship showed that the α,β-unsaturated δ-lactone moiety, as exemplified in compounds 1 and 2, was critical to the cytotoxic activity of these compounds. In addition, compound 4 might be a potential agonist of AMPK (5'-adenosine monophosphate-activated protein kinase).

Chemoselective Alteration Of Fluorophore Scaffolds As A Strategy For The Development Of Ratiometric Chemodosimeters, Xinqi Zhou, Lauren Lesiak, Rui Lai, Jon R. Beck, Jia Zhao, Christian Elowsky, Hui Li, Cliff I. Stains

Department of Chemistry: Faculty Publications

Ratiometric sensors generally couple binding events or chemical reactions at a distal site to changes in the fluorescence of a core fluorophore scaffold. However, such approaches are often hindered by spectral overlap of the product and reactant species. We provide a strategy to design ratiometric sensors that display dramatic spectral shifts by leveraging the chemoselective reactivity of novel functional groups inserted within fluorophore scaffolds. As a proof-of-principle, fluorophores containing a borinate (RF₆₂₀) or silanediol (SiOH2R) functionality at the bridging position of the xanthene ring system are developed as endogenous H₂O₂ sensors. Both …

The Future Of Nmr-Based Metabolomics, John L. Markley, Rafael Bruschweiler, Arthur S. Edison, Hamid R. Eghbalnia, Robert Powers, Daniel Raftery, David S. Wishart

Department of Chemistry: Faculty Publications

The two leading analytical approaches to metabolomics are mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy. Although currently overshadowed by MS in terms of numbers of compounds resolved, NMR spectroscopy offers advantages both on its own and coupled with MS. NMR data are highly reproducible and quantitative over a wide dynamic range and are unmatched for determining structures of unknowns. NMR is adept at tracing metabolic pathways and fluxes using isotope labels. Moreover, NMR is non-destructive and can be utilized in vivo. NMR results have a proven track record of translating in vitro findings to in vivo clinical …

Resolving The Cofactor-Binding Site In The Proline Biosynthetic Enzyme Human Pyrroline-5-Carboxylate Reductase 1, Emily M. Christensen, Sagar M. Patel, David A. Korasick, Ashley C. Campbell, Kurt L. Krause, Donald F. Becker, John J. Tanner

Department of Chemistry: Faculty Publications

Pyrroline-5-carboxylate reductase (PYCR) is the final enzyme in proline biosynthesis, catalyzing the NAD(P)H-dependent reduction of [?]1-pyrroline-5-carboxylate (P5C) to proline. Mutations in the PYCR1 gene alter mitochondrial function and cause the connective tissue disorder cutis laxa. Furthermore, PYCR1 is overexpressed in multiple cancers, and the PYCR1 knock-out suppresses tumorigenic growth, suggesting that PYCR1 is a potential cancer target. However, inhibitor development has been stymied by limited mechanistic details for the enzyme, particularly in light of a previous crystallographic study that placed the cofactor-binding site in the C-terminal domain rather than the anticipated Rossmann fold of the N-terminal domain. To fill this …

Indole-Induced Reversion Of Intrinsic Multiantibiotic Resistance In Lysobacter Enzymogenes, Yong Han, Yan Wang, Yameng Yu, Haotong Chen, Yuemao Shen, Liangcheng Du

Department of Chemistry: Faculty Publications

Lysobacter species are a group of environmental bacteria that are emerging as a new source of antibiotics. One characteristic of Lysobacter is intrinsic resistance to multiple antibiotics, which had not been studied. To understand the resistance mechanism, we tested the effect of blocking two-component regulatory systems (TCSs) on the antibiotic resistance of Lysobacter enzymogenes, a prolific producer of antibiotics. Upon treatment with LED209, an inhibitor of the widespread TCS QseC/QseB, L. enzymogenes produced a large amount of an unknown metabolite that was barely detectable in the untreated culture. Subsequent structural elucidation by nuclear magnetic resonance (NMR) unexpectedly revealed that …

Human Serine Racemase Structure/Activity Relationship Studies Provide Mechanistic Insight And Point To Position 84 As A Hot Spot For Β-Elimination Function, David L. Nelson, Greg A. Applegate, Matthew L. Beio, Danielle L. Graham, David B. Berkowitz

Department of Chemistry: Faculty Publications

There is currently great interest in human serine racemase, the enzyme responsible for producing the NMDA co-agonist D-serine. Reported correlation of D-serine levels with disorders including Alzheimer’s disease, ALS, and ischemic brain damage (elevated D-serine) and schizophrenia (reduced D-serine) has further piqued this interest. Reported here is a structure/activity relationship study of position Ser⁸⁴, the putative re-face base. In the most extreme case of functional reprogramming, the S84D mutant displays a dramatic reversal of β-elimination substrate specificity in favor of L-serine over the normally preferred L-serine-O-sulfate (~1200-fold change in k_cat/K_{m …}

Assessment Of Metabolic Changes In Mycobacterium Smegmatis Wild Type And Alr Mutant Strains: Evidence For A New Pathway Of D-Alanine Biosynthesis., Darrell D. Marshall, Steven Halouska, Denise K. Zinniel, Robert J. Fenton, Katie Kenealy, Harpreet K. Chahal, Govardhan Rathnaiah, Raul G. Barletta, Robert Powers

Department of Chemistry: Faculty Publications

In mycobacteria, D-alanine is an essential precursor for peptidoglycan biosynthesis. The only confirmed enzymatic pathway to form D-alanine is through the racemization of L-alanine by alanine racemase (Alr, EC 5.1.1.1). Nevertheless, the essentiality of Alr in Mycobacterium tuberculosis and Mycobacterium smegmatis for cell survivability in the absence of D-alanine has been a point of controversy with contradictory results reported in the literature. To address this issue, we examined the effects of alr inactivation on the cellular metabolism of M. smegmatis. The M. smegmatis alr insertion mutant TAM23 exhibited essentially identical growth to wild type mc²155 in the …

Transcriptional And Antagonistic Responses Of Biocontrol Strain Lysobacter Enzymogenes Oh11 To The Plant Pathogenic Oomycete Pythium Aphanidermatum, Yangyang Zhao, Guoliang Qian, Yuan Chen, Liangcheng Du, Fengquan Liu

Department of Chemistry: Faculty Publications

Lysobacter enzymogenes is a ubiquitous, beneficial, plant-associated bacterium emerging as a novel biological control agent. It has the potential to become a new source of antimicrobial secondary metabolites such as the Heat-Stable Antifungal Factor (HSAF), which is a broad-spectrum antimycotic with a novel mode of action. However, very little information about how L. enzymogenes detects and responds to fungi or oomycetes has been reported. An in vitro confrontation bioassay between the pathogenic oomycete Pythium aphanidermatum and the biocontrol bacterial strain L. enzymogenes OH11 was used to analyze the transcriptional changes in the bacteria that were induced by the oomycetes. Analysis …

Ion Mobility-Resolved Collision-Induced Dissociation And Electron Transfer Dissociation Of N-Glycopeptides: Gathering Orthogonal Connectivity Information From A Single Mass- Selected Precursor Ion Population, Venkata Kolli, Katherine N. Schumacher, Eric Dodds

Department of Chemistry: Faculty Publications

Glycopeptide-level mass spectrometry (MS) and tandem mass spectrometry (MS/MS) analyses are commonly performed to establish site-specific protein glycosylation profiles that are of central importance to gaining structure-function insights on glycoproteins. Confoundingly, the complete characterization of glycopeptide connectivity usually requires the acquisition of multiple MS/MS fragmentation spectra. Complementary ion fragmentation techniques such as collision-induced dissociation (CID) and electron transfer dissociation (ETD) are often applied in concert to address this need. While structurally informative, the requirement for acquisition of two MS/MS spectra per analyte places considerable limitations upon the breadth and depth of large-scale glycoproteomic inquiry. Here, a previously developed method of …

Quantifying The Interactions Of Nickel With Marine Dissolved Organic Matter Using Fluorescence, Elissa Dow

Theses and Dissertations (Comprehensive)

Nickel (Ni) is a versatile metal with an abundance of applications, namely its role in stainless steel, electronics, and batteries, making it a popular choice in industry. Unfortunately, with increasing demand and production comes higher amounts of Ni pollution. Nickel enters ocean waters - either directly or indirectly - and can have profound effects on marine life. Nickel has been established as a toxicant to a variety of aquatic biota, with the divalent cation (Ni²⁺) thought to be the most bioavailable fraction and thus the most toxic. Having a reliable means of quantifying free Ni ion is pertinent …

การขจัดสีย้อมในน้ำเสียจากอุตสาหกรรมกระดาษไหว้เจ้าโดยการดูดซับบนคอมพอสิตแร่ดิน-ไคโตซาน, วิศรุต ม่วงรักษ์

Chulalongkorn University Theses and Dissertations (Chula ETD)

งานวิจัยนี้มีจุดประสงค์เพื่อศึกษาการขจัดสีย้อมรีแอคทีฟเรด 120 ในน้ำ โดยการดูดซับบนตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซาน และเปรียบเทียบกับตัวดูดซับไคโตซาน ซึ่งการทดลองนี้จะศึกษาการดูดซับแบบกะ โดยตัวแปร ที่ศึกษาในการทดลอง คือ ปริมาณตัวดูดซับ ความเข้มข้นเริ่มต้นของสารละลายสีย้อม ค่าความเป็นกรดด่าง โดยเวลาที่ใช้ในการดูดซับ ตั้งแต่ 15 นาทีถึง 420 นาที จากการวิเคราะห์คุณลักษณะของตัวดูดซับโดยใช้ใช้เทคนิคฟูเรียร์ทรานส์ฟอร์มอินฟราเรดสเปกโทรสโกปี (FTIR) พบว่าตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซานจะมีลักษณะสเปกตรัมเฉพาะที่สะท้อนถึงตัวดูดซับไคโตซานและตัวดูดซับแร่ดินอย่างชัดเจน เมื่อพิจารณาพื้นที่ผิวการดูดซับโดยใช้เทคนิคการดูดซับ/การคายซับไนโตรเจน พบว่าแนวโนมของการเพิ่มสัดส่วนของแร่ดินจะช่วยเพิ่มพื้นที่ผิวให้กับตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซาน ส่งผลให้ตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซาน มีพื้นที่ผิวที่สูงกว่าตัวดูดซับไคโตซาน เนื่องจากไคโตซานเข้าไปแทรกในโครงสร้างของแร่ดิน สามารถอธิบายด้วยเทคนิคเอกซเรย์ฟลูออเรสเซนต์ (XRF) ทำให้โครงสร้างของแร่ดินเกิดการขยายขนาดขึ้น สำหรับผลจากการศึกษาตัวแปรต่างๆ พบว่า ตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซาน มีประสิทธิภาพในการกำจัดสีย้อมได้ดีกว่าตัวดูดซับไคโตซานและตัวดูดซับแร่ดิน ถึง 1.17 เท่า และ 1.88 เท่า ตามลำดับ การเพิ่มปริมาณตัวดูดซับจะช่วยลดระยะเวลาในการดูดซับให้เร็วยิ่งขึ้น สำหรับตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซาน พบว่าสามารถกำจัดสีย้อมได้หมดสมบูรณ์ทุกความเข้มข้น และสามารถกำจัดสีย้อมได้ดีสำหรับทุกช่วงของค่าความเป็นกรดด่างที่ได้ศึกษาในงานวิจัย แบบจำลองสมดุลการดูดซับของตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซาน สอดคล้องกับแบบจำลองการดูดซับของโกเบิลคอร์ริแกน จลนพลศาสตร์การดูดซับของตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซาน มีอัตราเร็วของปฏิกิริยาการดูดซับสารละลายสีย้อมเป็นปฏิกิริยาอันดับสองเทียม นอกจากนี้ยังพบว่ากลไกในการควบคุมขั้นตอนการดูดซับคือ ขั้นตอนการของการแพร่ผ่านชั้นฟิล์ม และขั้นตอนของการแพร่ภายในรูพรุน สำหรับการศึกษาอุณหพลศาสตร์ของการดูดซับพบว่าตัวดูดซับคอมพอสิตแร่ดิน-ไคโตซาน สามารถเกิดขึ้นได้เองและเกิดขึ้นได้ดีที่อุณหภูมิสูง

Development Of Poly(Aryleneethynylene)S Synthesis And Application As Fluorescent Sensor, Nopparat Thavornsin

Chulalongkorn University Theses and Dissertations (Chula ETD)

In this research, we focus on preparation and sensor application of poly(aryleneethynylene)s. Our work is divided into two parts. The first study relates to the utilization of salicylaldimine-functionalized poly(m-phenyleneethynylene) as a turn-on chemosensor for ferric ion (Fe3+). The second part is the preparation of highly pure poly(aryleneethtnylene)s using Pd/CaCO3 as a heterogeneous catalyst. In the first part, a new turn-on fluorescent probe for ferric ion based on poly(m-phenyleneethynylene salicylaldimine) (PPE-IM) is developed. The preparation of PPE-IM involves post-polymerization functionalization of corresponding polymeric amine, PPE-AM, via condensation with salicylaldehyde. Degree of polymerization of both PPE-AM and PPE-IM are 17 with polydispersity …

Chemical Constituents From The Roots Of Calophyllum Calaba L., Fuengfa Laopian

Chulalongkorn University Theses and Dissertations (Chula ETD)

Phytochemical investigation of the CH2Cl2 extract from the roots of C. calaba let to the isolation of three new xanthone derivatives, namely calaxanthones A-C (1-3), along with twenty nine known xanthones (4-32). The structures of all isolated compounds were fully characterized using spectroscopic data (1D and 2D NMR) as well as comparison with the previous literature data. Moreover, all isolated compounds were assessed for their in vitro cytotoxicity against the KB, HeLa S-3, HT29, MCF-7 and HepG2 human cancer cell lines. The tested compounds mostly showed moderate to inactive against these five cell lines, except compounds 3 showed potent cytotoxicity …

Relationship Of The Fractal And Chemical Characteristics Of Self-Assembled Natural Organic Matter, Dennis K. Gibson

Electronic Theses and Dissertations

Natural Organic Matter (NOM) is a heterogeneous mixture formed by the degradation of organic substances during early diagenesis in surficial environments. It has been shown that the interaction of the components that comprise this mixture has a significant impact on its microbial mineralization to CO₂. The extent of NOM selfassembly is emerging as an important factor in understanding its role in the global geochemical carbon cycle, and it is beginning to appear that it may be more important than the chemical composition of a sample. The overall goal of this research is to establish NOM’s self-assembled “architecture” and …

Infusion Of Essentail Oils In Agarose Gels To Create Antimicrobial Surfaces, Simran Guron

Honors College Theses

The current use of antibiotics is very excessive in multiple settings, from treating patients to being present in cleaning products. This overuse of antibiotics is resulting in multiple consequences, ranging from having a negative impact on human health to breeding antibiotic-resistant strains of microorganisms. Antimicrobial surfaces are useful today to aid in sterilization, especially in the medical setting. This would help prevent the spread of infection of microorganisms in these settings. In our research, agarose acts as the antimicrobial surface and essential oils would act as the solution incorporated into the surface that has the antimicrobial properties. Agarose is a …

Comparative Proteomic Analyses Of The Parietal Lobe From Rhesus Monkeys Fed A High-Fat/Sugar Diet With And Without Resveratrol Supplementation, Relative To A Healthy Diet: Insights Into The Roles Of Unhealthy Diets And Resveratrol On Function, Aaron M. Swomley, Judy C. Triplett, Jeriel T. Keeney, Govind Warrier, Kevin J. Pearson, Julie A. Mattison, Rafael De Cabo, Jian Cai, Jon B. Klein, D. Allan Butterfield

Chemistry Faculty Publications

A diet consisting of a high intake of saturated fat and refined sugars is characteristic of a Western-diet and has been shown to have a substantial negative effect on human health. Expression proteomics were used to investigate changes to the parietal lobe proteome of rhesus monkeys consuming either a high fat and sugar (HFS) diet, a HFS diet supplemented with resveratrol (HFS+RSV), or a healthy control diet for 2 years. Here we discuss the modifications in the levels of 12 specific proteins involved in various cellular systems including metabolism, neurotransmission, structural integrity, and general cellular signaling following a nutritional intervention. …

Cloud Point Extraction In Conjunction With Tangential Flow Filtration (Cpe-Tff) For The Enhanced Separation Of Silver Nanoparticles And Silver Ions From Aqueous Colloids And Biological Matrices, Md Ali Akbar

Browse all Theses and Dissertations

The extensive use of silver nanoparticles (AgNPs) in consumer products and research is accompanied by their inevitable release into the environment. While the environmental fate of AgNPs is still under investigation, most in vitro and in vivo studies agree that the main toxicity of AgNPs is directly related to the release of Ag+ ions from AgNPs. In this study, cloud point extraction (CPE) was combined with tangential flow filtration (TFF) for the enhanced separation of AgNPs and Ag+ from aqueous colloids and biological matrices. The feasibility of the CPE-TFF method was demonstrated on four colloidal (borohydride-, PVP-, citrate-capped and uncapped …

Functionalized Bodipy Dyes For Near-Infrared Emission Of Lanthanide Complexes, Rukshani Wickrama Arachchi

Masters Theses

For many decades, fluorophores have been used to investigate natural systems, but autofluorescence and photobleaching diminish the detection capacity. Recently, BODIPY based lanthanide complexes have been synthesized and their photophysical properties have been investigated. These complexes exhibit higher emission efficiencies at NIR region with longer NIR lifetimes upon exciting at longer wavelength.

In this study, two BODIPY based lanthanide complexes were synthesized and their photophysical properties were evaluated. BODIPY based ligands were synthesized with phenanthroline as the ligand binding group. These ligands exhibit strong absorption at 527 nm and 532 nm, fluorescence at 540 nm and 548 nm with 0.55 …

Bodipy-Based Red Sensitizers For Near-Infrared Emission Of Lanthanide Complexes, Priyangika Prasadini Senevirathne

Masters Theses

During the past 20 years there has been a remarkable growth in the use of the fluorescence technique in biological studies. Fluorescence and time-resolved fluorescence spectroscopy are considered primary research tools in the field of biochemistry. Currently, fluorescence spectroscopy is a dominant methodology and used widely in biotechnology and medical diagnosis process. One impediment in using fluorescent probes is the fluorescence of biological substrates and fluorescence of diagnostic probes are significantly overlapped, and it decreases the detection sensitivity. Also, commercially available probes require UV or near-UV light excitation, causing severe degradation of biological substrates. Near-infrared emitting lanthanide complexes can overcome …

Molecular Recognition Profiles Of Molecular Cocrystals, Ian C. Tinsley

Masters Theses

The manner in which molecules recognize each other holds critical importance to nearly every area of science. This significance stems from the key underpinning of molecular assembly to our most basic understanding of chemical processes. Whether these interactions relate to small-molecule catalytic transformations or complex physiological processes, the structural features responsible for molecular association play into the well-known adage that form follows function where material property arises from the collective structural features of the molecular components. Because the form of chemical systems is derived from a complex blend of covalent and non-bonded contacts, codifying each contributor has become essential for …

Monitoring Crystal Structure Refinements Using Solid-State Nmr Chemical Shift Tensors, Keyton Kalakewich

Electronic Theses and Dissertations

Inclusion of lattice-fields in density functional theory (DFT) methods has enabled the accurate calculation of solid-state nuclear magnetic resonance (SSNMR) chemical shift tensors. Calculated 13C and 15N tensors (i.e. 3 principle values per nucleus) can be used to monitor crystal structure refinements and to select the correct structure from a large population of computationally generated candidates. In this dissertation, chapter 2 describes a methodology to improve established crystal structures from three different diffraction techniques involving geometric refinement monitored using SSNMR tensor values. The calculated 13C tensors for three relatively simple organic compounds (i.e. acetaminophen, naphthalene, and adenosine) are shown to …

Biomimetic Devices To Drive A Thermodynamically Uphill Reaction Using Light And To Degrade Industrial Waste Stream Components, Madison Joanne Sloan

Theses and Dissertations--Chemistry

Given the amount of industrial waste produced each year, as well as the accruing amount of greenhouse gases in our atmosphere produced by the burning of fossil fuels, it is imperative that humanity develop environmentally-sustainable sources of energy and methods of remediation. Nature achieves both of these by use of enzymes as catalysts, inspiring interest in designing biomimetic systems capable of harnessing clean energy and remediating industrial waste. This study examined the ability of enzymes in electrochemical and convective flow systems to achieve these tasks. The first portion studied the incorporation of enzymes into an electrochemical system to drive the …

Oxidative Stress And Proteomic Studies Of Mammalian Models Of Age-Related Metabolic Dysfunction In Neurodegenerative Disorders, Aaron M. Swomley

Theses and Dissertations--Chemistry

Expression proteomics is the field of science wherein proteins that make up the cellular proteome are identified both by name and by fold-change. Depending on the application of proteomics, this change in level could be due to internal cellular stressors or introduction of xenobiotics. Global oxidative stress measures use immunohistochemistry to determine the relative level of oxidative stress of macromolecules within the cell. In this dissertation, both global oxidative stress measures and expression proteomics were used in a variety of mammalian models in order to determine the effects of protein upregulation, intranasal insulin administration, and resveratrol supplementation on the cellular …

Heterogeneous Base Metal Catalyzed Oxidative Depolymerization Of Lignin And Lignin Model Compounds, John Adam Jennings

Theses and Dissertations--Chemistry

With the dwindling availability of petroleum, focus has shifted to renewable energy sources such as lignocellulosic biomass. Lignocellulosic biomass is composed of three main constituents, lignin, cellulose and hemicellulose. Due to the low value of cellulosic ethanol, utilization of the lignin component is necessary for the realization of an economically sustainable biorefinery model. Once depolymerized, lignin has the potential to replace petroleum-derived molecules used as bulk and specialty aromatic chemicals. Numerous lignin depolymerization strategies focus on cleavage of β-aryl ether linkages, usually at high temperatures and under reductive conditions.

Alternatively, selective benzylic oxidation strategies have recently been explored for …

Characterization And Application Of Hybrid Nanostructures For Enhanced Biological Imaging Using Fluorescence Microscopy Techniques, William E. Martin

Theses and Dissertations--Chemistry

Fluorescence microscopy is a powerful tool for interpreting the structure and function of biomolecules, and their interactions with one another. Understanding fundamental biological mechanisms is important to the development of improved treatments for a variety of diseases. Fluorescent tags are used to track the motion and longevity of such events, with the ability to monitor several biomolecules at once. Currently, many of these studies are conducted using bulk measurements, or several biological events at the same time, because the added light from several emitters can more easily overcome the high fluorescence background inherent to biological systems. Although important in their …

Interactions Of Compounds Containing Group 12 And 16 Elements, Daniel Burriss

Theses and Dissertations--Chemistry

The focus of this dissertation is on the interactions of compounds containing group 12 and 16 elements. This work is presented in three major parts. First, the interaction of the synthetic dithiol N,N’-bis(2-mercaptoethyl)isophthalamide), abbreviated BDTH₂, with selenite. Second, the interaction of cysteine with Cd(II) and the biologically relevant Cd-Cysteine crystal structure. Third, the green synthesis of CdSe quantum dots (QDs).

The interaction of BDTH₂ with selenite is different from the interactions with other metals and metalloids previously studied. Under ambient conditions, BDTH₂ is oxidized to the disulfide, BDT(S-S), while selenite is reduced to elemental selenium. However, …

Epigenetic Modifications To Cytosine And Alzheimer’S Disease: A Quantitative Analysis Of Post-Mortem Tissue, Elizabeth M. Ellison

Theses and Dissertations--Chemistry

Alzheimer’s disease (AD) is the most common form of dementia and the sixth leading cause of death in the United States, with no therapeutic option to slow or halt disease progression. Development of two characteristic pathologic lesions, amyloid beta plaques and neurofibrillary tangles, in the brain are associated with synaptic dysfunction and neuron loss leading to memory impairment and cognitive decline. Although mutations in genes involved in amyloid beta processing are linked to increased plaque formation in the inherited familial form of AD, the more common idiopathic form, termed sporadic AD, develops in the absence of gene mutations. In contrast, …

Formation Of The Ether Bridge In The Loline Alkaloid Biosynthetic Pathway, Minakshi Bhardwaj

Theses and Dissertations--Chemistry

Lolines are specialized metabolites produced by endophytic fungi, such as Neotyphodium and Epichloë species, that are in symbiotic relationships with cool-season grasses. Lolines are vital for the survival of the grasses because their insecticidal and antifeedant properties protect the plant from insect herbivory. Although lolines have various bioactivities, they do not have any concomitant antimammalian activities.

Lolines have complex structures that are unique among naturally occurring pyrrolizidine alkaloids. Lolines have four contiguous stereocenters, and they contain an ether bridge connecting C(2) and C(7) of the pyrrolizidine ring. An ether bridge connecting bridgehead C atoms is unusual in natural products and …

Photoluminescence Mechanism And Applications Of Graphene Quantum Dots, Yiyang Liu

Theses and Dissertations--Chemistry

Graphene quantum dots (GQDs) are small pieces of graphene oxide whose physical dimensions are so confined (a few to a few tens nm) that they have a finite bandgap due to a quantum confinement effect. The finite bandgap of GQDs grants them pronounced absorption bands and a substantial photoluminescence. These optical properties are rarely observed in traditional carbon materials, since most of carbon materials are metallic with a near-zero bandgap and thus have broad absorption spectra with no photoluminescence. The unique optical properties of GQDs, along with GQDs’ inherited advantages from carbon material family (cheap, abundant, non-toxic), make GQDs an …

Arsenic Removal With A Dithiol Ligand Supported On Magnetic Nanoparticles, John Hamilton Walrod Ii

Theses and Dissertations--Chemistry

Exposure to arsenic (As) in water, the ubiquitous toxin that poses adverse health risks to tens of millions, is the result of both anthropogenic and geochemical mobilization. Despite recent publicity and an increased public awareness, the dangers associated with arsenic exposure rank among the top priorities of public health agencies globally. Existing sequestration applications mainly include reductions and adsorption with zero-valent metals and their oxides. The performance of adsorption media is known to preferentially favor aqueous As(V) over As(III) due to the charge of the dissolved oxyanion. Magnetic nanoparticles (MNP) have been the focus of multidisciplinary research efforts for the …