Chemistry Commons^™

Synthesis Of N-Heterocyclic Molecules And Their Applicability Towards Ion Sensing: Polymeric Chemosensors, Aikohi M. Ugboya

College of Graduate Studies: Theses & Dissertations

Critical to biological and environmental processes are anions because often times their relative concentration in our body can be an indicator of one’s well-being. Therefore, highly sensitive and cost-efficient methods for ions recognition is necessary for human health. In recent times, polymeric chemosensors have become a vital tool for sensing ions because of its higher sensitivity and good mechanical properties compared to their monomeric counterparts. These sensors are designed to produce a measurable response in the presence of a targeted ion such as an electrochemical or optical signal. The unique structure and the photophysical properties of the 1,2,3-triazole core coupled …

Nanomaterials For Double-Stranded Rna Delivery, Stuart Lichtenberg

Theses and Dissertations--Plant and Soil Sciences

RNA interference has enormous potential as a potent, specific, and environmentally friendly alternative to small molecule pesticides for crop protection. The use of exogenous double-stranded RNA offers flexibility in targeting and use in crops in which transgenic manipulation is not an option. The combination of RNAi with nanotechnology offers further advantages that are not available with dsRNA alone. In this work, I have evaluated several different combinations of nanomaterials and polymers for use in RNAi-based pest control systems. First, I have characterized the use of chitosan/dsRNA polyplex nanoparticles for gene knockdown using the model nematode Caenorhabditis elegans. Though chitosan/dsRNA …

Water Dispersible Α-Mangostin By Self-Assembly Process, Jutamad Bumrung

Chulalongkorn University Theses and Dissertations (Chula ETD)

α-Mangostin, major bioactive compounds in Garcinia mangostana Linn, displays various interesting biological activities. However, the poor water solubility of α-mangostin has limited its use in the cosmetics and pharmaceutics. Here, we solve α-mangostin's solubility by creating water dispersible α-mangostin particles through self-assembly process with no need of any auxiliary agents such as polymers or surfactants. The simple and upscalable process gives 100% pure α-mangostin spherical particles with nanometer sizes. FT-IR result suggests that intermolecular interaction among α-mangostin molecules in the nanoparticles is weaker than that of the original α-mangostin solid. The lower thermal stability of the particles as compared to …

การสังเคราะห์พรีเคอร์เซอร์เชื้อเพลิงชีวภาพผ่านแอลดอลคอนเดนเซชันของเฟอร์ฟิวรัลและ 2-บิวทาโนนบนตัวเร่งปฏิกิริยา Srtio3/Sba-15, ธนัทย์ชัย มีมานะ

Chulalongkorn University Theses and Dissertations (Chula ETD)

งานวิจัยนี้ศึกษาการสังเคราะห์พรีเคอร์เซอร์เชื้อเพลิงชีวภาพจากเฟอร์ฟิวรัลและ 2-บิวทาโนนผ่านแอลดอลคอนเดนเซชัน ตัวเร่งปฏิกิริยาที่ใช้ในแอลดอลคอนเดนเซชันเป็นโลหะออกไซด์ผสมที่ได้จากสตรอนเทียมไททาเนต (SrTiO3) ที่มีปริมาณสตรอนเทียมไททาเนตบนตัวรองรับ SBA15 ที่แตกต่างกัน (10%, 15%, 20% and 25%) และอัตราส่วนโดยโมลของ Sr : Ti ในช่วง 0.5 ถึง 2 ซึ่งเตรียมด้วยวิธีอิมเพรค จากนั้นนำมาเผาที่อุณหภูมิ 600 องศาเซลเซียส เป็นเวลา 4 ชั่วโมง จากการศึกษาสมบัติกายภาพและเคมีของตัวเร่งปฏิกิริยาที่เตรียมได้ พบว่า 20STO(2:1)/SBA15 (ที่มีปริมาณสตรอนเทียมไททาเนตบนตัวรองรับร้อยละ 20 โดยน้ำหนัก และ อัตราส่วนโดยโมลของ Sr : Ti เท่ากับ 2) ซึ่งเตรียมด้วยวิธีอิมเพรค มีการกระจายตัวของสตรอนเทียมไททาเนตบนตัวรองรับ SBA15 ที่มีพื้นที่ผิวจำเพาะที่สูงและมีปริมาณตำแหน่งเบสรวมมากที่สุด แอลดอลคอนเดนเซชันของเฟอร์ฟิวรัลและ 2-บิวทาโนนเพื่อสังเคราะห์สารประกอบคาร์บอนิลไม่อิ่มตัวโซ่กิ่งทำในเครื่องปฏิกรณ์ออโตเคลฟภายใต้ความดันไนโตรเจน (10 บาร์) เมื่อวิเคราะห์ผลิตภัณฑ์ด้วยเทคนิคแก๊สโครมากราฟี-แมสสเปกโตสโกปี พบว่า ผลิตภัณฑ์หลักที่เกิดขึ้นเป็นสารประกอบคาร์บอนิลไม่อิ่มตัวที่มีโครงสร้างแบบโซ่ตรง และโซ่กิ่ง นอกจากนี้ยังพบผลิตภัณฑ์ C14 และ C13 ที่อุณหภูมิสูงและเวลาในการทำปฏิกิริยาที่นาน 20STO(2:1)/SBA15 เป็นตัวเร่งปฏิกิริยาที่เหมาะสม โดยให้การเปลี่ยนของเฟอร์ฟิวรัลร้อยละ 53 โดยโมล และ ผลได้ของ C9B ร้อยละ 41 โดยโมล เมื่อใช้ภาวะที่เหมาะสม คือ ปริมาณตัวเร่งปฏิกิริยา 5% โดยน้ำหนัก, อัตราส่วนโดยโมลของเฟอร์ฟิวรัลต่อ 2-บิวทาโนน 1:5, อุณหภูมิในการทำปฏิกิริยา 100 องศาเซลเซียส และเวลาในการทำปฏิกิริยา 5 ชั่วโมง

ผลของตัวเร่งปฏิกิริยาต่อคุณภาพของน้ำมันชีวภาพจากไพโรไลซิสชิ้นไม้ยูคาลิปตัสและซังข้าวโพดในเครื่องปฏิกรณ์เบดนิ่ง, วรเวช ศรีปราโมช

Chulalongkorn University Theses and Dissertations (Chula ETD)

งานวิจัยนี้ศึกษาภาวะที่เหมาะสมสำหรับการไพโรไลซิสไม้ยูคาลิปตัสและซังข้าวโพดในเครื่องปฏิกรณ์แบบเบดนิ่ง พบว่าภาวะที่เหมาะสมสำหรับชีวมวลทั้งสองชนิดคือ เวลาทำปฏิกิริยาที่ 30 นาที อุณหภูมิ 500 องศาเซลเซียส และขนาดอนุภาคของชีวมวลระหว่าง 0.50-0.71 มิลลิเมตร ส่วนอัตราการไหลแก๊สไนโตรเจนสำหรับไม้ยูคาลิปตัสคือ 120 มิลลิลิตรต่อนาที และสำหรับ ซังข้าวโพดคือ 80 มิลลิลิตรต่อนาที ให้ผลได้น้ำมันชีวภาพสูงสุดของไม้ยูคาลิปตัสและซังข้าวโพดที่ร้อยละ 31.69 และ 22.01 โดยน้ำหนัก ตามลำดับ โดยน้ำมันชีวภาพจากชีวมวลทั้งสองชนิดให้ค่าความร้อนสูงขึ้นและใกล้เคียงกันคือ 23.14 และ 23.27 เมกะจูล/กิโลกรัม ตามลำดับ สอดคล้องกับอัตราส่วน H/C และ O/C ของน้ำมันชีวภาพจากชีวมวลทั้งสองชนิดที่มีค่าต่ำกว่าในชีวมวล เมื่อวิเคราะห์องค์ประกอบของน้ำมันชีวภาพพบว่าส่วนใหญ่เป็นสารในกลุ่มฟีนอล รองลงมาคือสารในกลุ่มกรดคาร์บอกซิลิก แอลดีไฮด์ อีเทอร์ คีโทน ไฮโดรคาร์บอน แซ็กคาไรด์ และสารที่มีปริมาณน้อยสุดคือสารในกลุ่มฟูแรน และจากการศึกษาผลของตัวเร่งปฏิกิริยาโดโลไมต์และเอฟซีซีใช้แล้ว พบว่าปริมาณตัวเร่งปฏิกิริยาที่เหมาะสมสำหรับชีวมวลทั้งสองชนิดคือร้อยละ 5 โดยน้ำหนัก และตัวเร่งปฏิกิริยาทั้งสองชนิดไม่มีผลอย่างมีนัยสำคัญต่อการลดออกซิเจนในน้ำมันชีวภาพ

การเตรียมพีเอ็มเอ็มเอ-ซิลิกานาโนคอมพอสิตผ่านราฟต์อิมัลชันพอลิเมอไรเซชันและไฮบริดเมมเบรนสำหรับเพอร์แวพอเรชัน, เกื้อชนม์ ศรีสัมฤทธิ์

Chulalongkorn University Theses and Dissertations (Chula ETD)

พีเอ็มเอ็มเอ-ซิลิกานาโนคอมพอสิตอิมัลชันถูกสังเคราะห์ผ่านราฟต์อิมัลชันพอลิเมอไรเซชันควบคู่กับเทคนิคดิฟเฟอเรนเชียลไมโครอิมัลชันพอลิเมอไรเซชัน งานวิจัยนี้ศึกษาผลของความเข้มข้นของสารมาโคร-ราฟต์ และปริมาณอนุภาคซิลิกา ต่อร้อยละการเปลี่ยนมอนอเมอร์ ขนาดอนุภาคเฉลี่ย และประสิทธิภาพการห่อหุ้มซิลิกา พบว่า พีเอ็มเอ็มเอ-ซิลิกา นาโนคอมพอสิตมีค่าร้อยละการเปลี่ยนมอนอเมอร์ที่สูง ขนาดอนุภาคเฉลี่ยมีค่า 57.6 นาโนเมตร ที่ภาวะการเติมอนุภาคซิลิการ้อยละ 10 โดยน้ำหนักของมอนอเมอร์ ภาพจากกล้องจุลทรรศน์ อิเล็กตรอนแบบส่องผ่าน แสดงลักษณะทางสัณฐานวิทยาของพีเอ็มเอ็มเอ-ซิลิกานาโนคอมพอสิตแสดง โครงสร้างอนุภาคแกน-เปลือกระดับนาโน จากนั้นเตรียมยางธรรมชาติ/พีเอ็มเอ็มเอ- ซิลิกาไฮบริดเมมเบรนด้วยวิธีผสมโดยตรง ผลที่ได้แสดงให้เห็นความสามารถ ในการพัฒนาสมบัติเชิงกลและสมบัติเชิงความร้อนของพีเอ็มเอ็มเอ-ซิลิกา นาโนคอมพอสิตในไฮบริดเมมเบรน และมากไปกว่านั้นการประยุกต์ใช้ไฮบริด เมมเบรนในกระบวนการเพอร์แวพอเรชัน อนุภาคพีเอ็มเอ็มเอ-ซิลิกานาโนคอมพอสิต สามารถเพิ่มค่าการซึมผ่านของน้ำและประสิทธิภาพการแยกใน ยางธรรมชาติ/พีเอ็มเอ็มเอ-ซิลิกาไฮบริดเมมเบรน โดยการปรับปรุงพื้นผิวของเมมเบรน ยางธรรมชาติให้มีค่าสมบัติชอบน้ำสูงขึ้น ดังนั้นพีเอ็มเอ็มเอ-ซิลิกานาโนคอมพอสิตมี ศักยภาพที่จะนำไปใช้เป็นสารตัวเติมประสิทธิภาพสูงสำหรับเทคโนโลยีการแยกสาร

Chemical Constituents From The Roots Of Cratoxylum Cochinchinense, Peeravat Natrsanga

Chulalongkorn University Theses and Dissertations (Chula ETD)

The phytochemical investigation of the CH2Cl2 extract from the roots of Cratoxylum cochinchinense led to the isolation of four new xanthone derivatives, namely cratochinone A-D (1-4), along with sixteen known xanthones (5-20). Their structures were characterized by spectroscopic methods, especially spectroscopic data (1D and 2D NMR) as well as comparison with those reported in the literature for known xanthones. Moreover, all isolated compounds were evaluated for their cytotoxicity against five human cancer cell lines (KB, HeLa S-3, HT-29, MCF-7 and Hep G2 cell lines). Compounds 2, 7, and 9 showed significant cytotoxic effects against all cell lines with IC₅₀ values …

Investigating Paraben 3,5-Substitution Effects On Estrogen Receptor Binding, Zachary Morgan

Longwood Senior Theses

Paraben, a compound formerly found in cosmetics, has been found to bind the Estrogen Receptor Alpha (ERα), a receptor found primarily in reproductive tissues. In paraben binding the ERα, the risk of breast cancer increases. In order to better understand how 3,5-substituted paraben derivatives bind the ER, Molecular Operating Environment was used to calculate the interaction energy associated with binding these substrates to the ER. It was found that substituted paraben molecules exhibit a weaker binding to the ER, whereas paraben molecules with varying alkyl chains bind stronger to the ER. Further, in comparing molecular and bimolecular docking data, it …

Copper-Mediated N1-Arylation Of Benzotriazoles, Magdalena R. Andrzejewska

Dissertations and Theses

Benzotriazoles are group of bicyclic heterocyclic compounds that contain three nitrogen atoms fused to a benzene ring. Along with their derivatives, they possess a wide range of properties. They are used in medical field, as they exhibit such properties as antibacterial,antiplasmoidal,antiprotozoal, antifungal and anti-inflammatory activities, among others. They are also used in various industries as herbicides, UV absorbers, deicing and antiicing agents and corrosion inhibitors, to list a few. Because of their wide range of applications, we designed a new two-step synthesis for the formation of N-1-aryl benzotriazoles. 1-Hydroxy-1H-benzotriazole N-oxides were synthesized using phenylboronic acid (PhB(OH) …

Nanostructured Materials For Photocatalysis, Water Treatment And Solar Desalination, Hiran D. Kiriarachchi

Theses and Dissertations

Maintaining a constant supply of clean drinking water is among the most pressing global challenges in our time. About one-third of the population is affected by the water scarcity and it can only get worse with climate change, rapid industrialization, and the population growth. Even though nearly 70 percent of the planet is covered by water, the consumable freshwater content is only 2.5 percent of it. Unfortunately, the accessible portion of it is only 1 percent. Even so, most of the freshwater bodies are choked with pollution. Considering the vast availability of saline water on the planet and the increasing …

Expansion Of The Genetic Code To Include Acylated Lysine Derivatives And Photocaged Histidine, William D. Kinney

Theses and Dissertations

The genetic code of all known organisms is comprised of the 20 proteinogenic amino acids that serve as building blocks on a peptide chain to form a vast array of proteins. Proteins are responsible for virtually every biological process in all organisms; however, the 20 amino acids contain a limited number of functional groups that often leaves much to be desired. The lack of diversity addresses the need to increase the genetic repertoire of living cells to include a variety of amino acids with novel structural, chemical, and physical properties not found in the common 20 amino acids. In order …

Development And Characterization Of Stationary Phase Gradients For High Performance Liquid Chromatography, Anna Forzano

Theses and Dissertations

Choosing a stationary phase is the first step in developing a liquid chromatography (LC) separation method, where the selectivity is governed by the differential interactions of the analytes with the stationary and mobile phases. Introducing a gradient in stationary phase functionality allows for tuning of analyte retention, translating to a possible improvement in selectivity and an increase in resolution versus that offered by uniform stationary phases.

In this work, C₁₈-silica, phenylbutyl-silica, and phenylbutyl-ammonium opposed continuous stationary phase gradients were fabricated using controlled rate infusion (CRI) on particle packed LC columns. Characterization of the stationary phase was carried out …

Biometal-Induced Structural Consequences Of Α-Synuclein – The Parkinson’S Disease Protein, Dinendra L. Abeyawardhane

Theses and Dissertations

The pre-synaptic protein α-Synuclein (αS) is often linked to the pathology of Parkinson’s disease (PD), an age-related neurodegenerative disorder. Lewy bodies, the cytopathological hallmarks of PD, are found to be rich in aggregates of misfolded αS protein. Metal dyshomeostasis has also been linked to PD due to the accumulation of iron in the substantia nigra pars compacta, and diminished copper levels reported in this same region. Metal dyshomeostasis in the brain coupled with oxidative stress can enhance the aggregation of αS. Recently, it was confirmed that mammalian αS is universally acetylated at the N-terminus, a common post-translational modification in …

The Development Of Intrinsically Cell-Permeable Peptide Libraries Using Mrna Display, Nicolas A. Abrigo

Theses and Dissertations

Peptides are emerging as promising therapeutics due to their inhibitory affinity towards protein-protein interactions (PPI). However, peptides have been limited mainly by their poor bio-stability and lack of cell permeability. Efforts to generate drug-like peptides have led to the development of macrocyclic peptides, which exhibit improved stability. Yet, most macrocyclic peptides still require the assistance of a cell penetrating peptide (CPP) for cellular entry.

High throughput technologies have been exceptional tools for the discovery of peptides to interrupt PPIs. This work details the recent advancements we have made to improve our high throughput technique, mRNA display, to yield more therapeutically …

An Enzymology And Inhibition Study Of A Camp-Dependent Protein Kinase Linked To Acth-Independent Cushing's Syndrome, Nicole Luzi

Theses and Dissertations

Cyclic-AMP dependent protein kinase (PKA) is a key intracellular signal transduction kinase that is modulated by G_s- and G_i-coupled GPCRs. Under normal physiological conditions, PKA exists as an inactive holoenzyme made up of two catalytic subunits and two regulatory subunits. Upon cAMP binding to the regulatory subunits, the catalytic subunits (PKACa) are released to perform various downstream phosphorylation events. However, aberrant PKA activation can cause various diseases including Cushing’s Syndrome, which is an endocrine disorder caused by the overproduction of cortisol by the hypothalamus-pituitary-adrenal hormone system. This disorder can be caused by pituitary adenomas that release …

Adhesion At Solid/Liquid Interfaces, Neda Ojaghlou

Theses and Dissertations

The adhesion at solid/liquid interface plays a fundamental role in diverse fields and helps explain the structure and physical properties of interfaces, at the atomic scale, for example in catalysis, crystal growth, lubrication, electrochemistry, colloidal system, and in many biological reactions. Unraveling the atomic structure at the solid/liquid interface is, therefore, one of the major challenges facing the surface science today to understand the physical processes in the phenomena such as surface coating, self-cleaning, and oil recovery applications. In this thesis, a variety of theory/computational methods in statistical physics and statistical mechanics are used to improve understanding of water adhesion …

Metallic Systems At The Nano And Micro Scale: Bimetallic Nanoparticles As Catalysts And Mcraly Bond Coats In Thermal Barrier Coatings, Kenneth Kane

Theses and Dissertations

The dissertation is split into two parts. The first part will be focused on changes in material properties found at the nanoscale, as miscibility and electronic structure can change significantly with size. The formation of classically-immiscible bimetallic nanoparticles (BNPs) becomes favorable at the nanoscale and novel catalytic properties can emerge from the bimetallic alloying. The formation of alloyed and non-alloyed BNPs is achieved through pulse laser ablation (PLA) and a significant increase in catalytic activity is observed for both. Recently discovered, the increased activity in the non-alloyed BNPs, deemed multicomponent photocatalysis, is examined and the proposed mechanism discussed. The second …

Solvation Properites Of Supercritical Carbon Dioxide Using Chirped-Pulse Fourier-Transform Microwave Spectra Of Carbon Dioxide / 1, 1-Difluoroethene (Dfe) Mixtures, Tulana Ariyaratne Subasinghe Arachchige

Masters Theses

Supercritical carbon dioxide (sc-C0₂) is a highly utilized industrial substance identified as an excellent solvent and a surfactant, which is cheaper and less hazardous than other typical solvents. The higher solubility of fluorinated hydrocarbons than their hydrocarbon (HC) analogs is not well understood and the theory behind the microsolvation of sc-C0₂ cannot be fully explained with the existing chemical information. Microwave spectroscopy is a good method of identifying the structural arrangement of clusters made from fluorinated HCs and C0₂. I n this project, microwave scans of the four different mixtures of 1 , 1-difluoroethene (DFE) …

Metastable-State Photoacids: Synthesis, Properties, And Applications, Parth Patel

Electronic Theses and Dissertations

Reversible photochromic compounds have the ability to reversibly change its color when it absorbs photons of a particular wavelength. This process of color change is a consequence of structural changes within the compound, such as cis-trans photo-isomerization. Some examples of photochromic compounds are spiropyrans, spirooxazines, diarylethenes and azobenzenes. These compounds have been extensively studied for decades, and are used in various applications such as biomedicine, chemical sensors and harvesting solar energy. However, majority of photochromic compounds are initially activated by ultraviolet (UV) light. The use of UV light is harmful for biological applications and photo-degrade the compound over repeated use. …

The Characterization Of Condom Lubricants And Personal Hygiene Products Using Dart-Tofms And Gc- Ms And The Investigation Of Gold Nanoparticle Behavior In Water And The Interaction With Blood Serum Proteins, Yasmine Moustafa

Electronic Theses and Dissertations

This dissertation is divided into two independent research projects. First, condom lubricants, sexual lubricants, and personal hygiene products (PHPs) were studied using direct analysis in real time-time-of-flight-mass spectrometry (DART-TOFMS) and gas chromatography-mass spectrometry (GC-MS). The purpose addressed the concern of perpetrators resorting to new tactics, i.e. using condoms to remove seminal fluid that could provide a DNA link to a suspect, leading to the need of the consideration of condom lubricants as pieces of sexual assault evidence. Due to condom lubricants having a chemical composition resembling PHPs, the investigation of both sample groups was analyzed to prevent false positives. Although …

Tumor-Targeted Conjugated Polymer Nanoparticles With Encapsulated Iron And Its Biomedical Application For In Vitro Killing Of Melanoma Cell Lines Through Ferroptosis Assisted Chemodynamic Therapy (Cdt), Khalaf Jasim

Electronic Theses and Dissertations

Melanoma represents one of the most aggressive and lethal forms of skin cancer, with annually rising incidences throughout the world. Although chemotherapy modalities remain the mainstay of treatment, the therapeutic potential of chemotherapy typically is hampered by multidrug resistance (MDR) and nonspecific drug distribution that causes side-effects. To surmount such limitations, novel nanoformulations of low band-gap poly ({4,8-bis [(2-ethylhexyl) oxy] benzo [1,2-b:4,5-b?] dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl}) (PTB7) and poly [2,1,3-benzothiadiazole- 4,7- diyl [4,4-bis (2-ethylhexyl)- 4H-cyclopenta [2,1-b:3,4-b'] dithiophene-2,6-diyl]] (PCPDTBT) were fabricated by a reprecipitation method. These conjugated polymer nanoparticles were functionalized with the polypeptide endothelin-3 (EDN3-CPNPs) to target melanoma. The …

Magnesium-Based Treatment For The Degradation Of Octachlorodibenzofuran And Trinitrotoluene, Amal Mogharbel

Electronic Theses and Dissertations

The aim of the present research is to investigate the efficacy of using ball-milled zero-valent magnesium (ZVMg) with and without activated carbon (AC) for the dechlorination of polychlorinated dibenzofurans. Three different solvent systems are presented here which are ethanol, ethanol/ethyl lactate (90:10), and 2-butoxyethanol. These solvents in combination with ZVMg with and without activated carbon were tested towards the degradation of octachlorodibenzofuran (OCDF, the most highly chlorinated PCDF congener). All the tested systems were very powerful and reductively dechlorinated OCDF to less chlorinated congeners. However, the system of ball-milled ZVMg and ethanol was the only system which converted OCDF and …

Thermo- And Zero-Valent Iron-Activated Persulfate Oxidation Of 3,5,6-Trichloro-2-Pyridinol In An Aquatic System, Roaa Mogharbel

Electronic Theses and Dissertations

The compound 3,5,6-trichloro-2-pyridinol (TCPy), a metabolite of the broad-spectrum organophosphorous insecticide chlorpyrifos, is both more persistent and more water soluble than its parent compound. This difference, which allows TCPy to more readily leach into surface water and groundwater, has led to widespread contamination of TCPy in soils and aquatic environments. In this study, the degradation of TCPy by sulfate radicals was evaluated using zero valent ironactivated persulfate systems and heat activated persulfate system in aqueous media. Response surface methodology coupled with Box-Behnken design was applied in these studies to evaluate the effects of the independent variables on the mineralization of …

Improved System For Fabrication And Characterization Of Nanophotonic Devices By Multi-Photon Lithography, Rashi Sharma

Electronic Theses and Dissertations

A new system for multi-photon lithography (MPL) was developed and used to fabricate three-dimensional (3D) structures with higher aspect ratio, better resolution, improved fidelity, and reduced structural distortion relative to a conventional implementation of MPL. A set of curved waveguides (Rbend = 19 μm, and 38 μm) and straight waveguides (length = 50 μm, Rbend = ∞) were fabricated in an epoxide photopolymer and optically characterized using light having a wavelength in vacuum of λ0 = 2.94 μm. The optical performance of the waveguides was compared to novel spatially-variant photonic crystals (SVPCs) previously studied in the group. The waveguides were …

A Biochemical Nickel(I) State Supports Nucleophilic Alkyl Addition: A Roadmap For Methyl Reactivity In Acetyl Coenzyme A Synthase, A. C. Manesis, B. W. Musselman, Breena C. Keegan, Jason M. Shearer, N. Lehnert, H. S. Shafaat

Chemistry Faculty Research

Nickel-containing enzymes such as methyl coenzyme M reductase (MCR) and carbon monoxide dehydrogenase/acetyl coenzyme A synthase (CODH/ACS) play a critical role in global energy conversion reactions, with significant contributions to carbon-centered processes. These enzymes are implied to cycle through a series of nickel-based organometallic intermediates during catalysis, though identification of these intermediates remains challenging. In this work, we have developed and characterized a nickel-containing metalloprotein that models the methyl-bound organometallic intermediates proposed in the native enzymes. Using a nickel(I)-substituted azurin mutant, we demonstrate that alkyl binding occurs via nucleophilic addition of methyl iodide as a methyl donor. The paramagnetic Ni …

Removal Of Antimony And Bismuth From Copper Electrorefining Electrolyte By Two Proprietary Solvent Extraction Extractants, Andrew Artzer

Masters Theses

"Antimony and bismuth are two of the most problematic impurities in copper electrorefining (ER). Because of this, much research has been done investigating the ways to remove them. Processes that are currently being used industrially include anode additions, liberators, ion exchange (IX), and solvent extraction (SX). Of these, liberators and anode additions are the most common while SX is the least, mostly being used for arsenic removal. There are other methods that have been evaluated, but are not in commercial use. These include the use of various electrolyte additives, and adsorbents such as bentonite clay and heavy metal sulfates.

Two …

Oxidative Degradation Of Lignin And Investigation Of Utilization Of Lignin-Derived Materials As Building Blocks For Epoxy Resins, Zhen Fang

Theses and Dissertations--Chemistry

Lignin, the second most abundant biopolymer on earth, is potentially a replaceable source for bulky fuels and chemical feedstocks. There have been numerous reports on methods for the oxidative cleavage of β-O-4 linkages but relatively few reports of how those methods affect other linkages that are present in lignin. We investigated how the β-1 and β-5 linkages respond under oxidative conditions proposed for lignin deconstruction based on their effect on β-O-4 linkages. Mechanochemical treatment of lignin can greatly improve the yield of monomer products and we applied a mechanochemical approach, using powerful ring-and-puck milling to promote lignin degradation. Along with …

Oxidative Depolymerization Of Lignin To Low Molecular Weight Aromatics, Yang Song

Theses and Dissertations--Chemistry

To date, most lignocellulosic biorefinery strategies have focused on optimizing conversion of cellulose to ethanol, leaving lignin as an underutilized biomass constituent. Lignin is engineered by nature with the intent to protect plants from chemical and biological attack; this leaves lignin with high structural irregularity and recalcitrance, rendering conversion of the lignin macromolecule to valuable products particularly challenging. Nevertheless, given that the economics of cellulosic ethanol production are strongly dependent on the value that can be obtained for the lignin co-product, the successful valorization of lignin is a crucial step in the transition towards a bio-based economy.

This thesis focuses …

Bottom-Up Lignomics: Towards The Development Of Adduct Electrospray Ionization Mass Spectrometric Methods To Characterize And Sequence Lignin Oligomers, Shardrack O. Asare

Theses and Dissertations--Chemistry

Lignin, the second most abundant naturally occurring polymer found in plant cell wall has the potential of becoming an alternative source for the production of chemical synthons for the pharmaceuticals and other chemical industries. While much gain has been made towards the development of degradation methods to break down lignin, effective analytical methods are still required to rapidly and accurately identify the products of lignin breakdown experiments. The goal of this work was to develop mass spectrometric methods for the characterization of lignin oligomers based on the study of model lignin compounds.

Unlike peptides and oligosaccharides, lignin model compounds that …

Synthesis And Characterization Of Carbonaceous Particles From Xylose And Soybean Residuals, Shanshan Wang

Theses and Dissertations--Chemistry

Carbonaceous materials, especially in micro and nanoscale, are useful in optical, energy storage, electronic, and biomedical devices or technologies. Techniques have been developed for preparation and modification of the carbonaceous materials, while it is still challenging to tailor the properties of carbonaceous materials effectively and economically. Laser is a powerful tool in academic and industrial laboratories, which also plays important roles in the preparation and modification of high-performance carbonaceous nanomaterials.

In this study low-cost hydrothermal synthesis, high-temperature annealing, and Laser ablation (LAL) methods are developed to prepare functionalized carbon nanomaterials and modify their electrochemical and optical properties.

Sub-micro hollow carbon …