Inorganic Chemistry Commons^™

C-H On The Oxo Ferryl Wheel: Comparison Of Pyridine And Imidazole-Substituted Ligands For C-H Activation And Functionalization, Elizabeth Milem

Electronic Theses and Dissertations

The selective and efficient transformation of hydrocarbon feedstocks is of high value for industry and research. While Shilov-type organometallic methods have facilitated this goal, systems designed after nature’s use of cheap and abundant iron-based enzymes are desired for wider-scale applications. This work establishes hydrocarbon oxidation efficiency of synthetic pyridine-based ligands (BPMEN, BPMPN) compared to commercially available TPA with in situ generated catalysts. Literature studies of traditionally synthesized BPMEN systems and initial in situ studies offered evidence for enhanced reactivity (TON) as compared to TPA. Expansion to a propyl backbone to produce BPMPN tested the increased chelate ring size’s impact on …

Analysis Of The Light Responsive Azobenzene Peptide Nucleic Acid Duplexes, Kat Nguyen

Honors College Theses

Peptide nucleic acids (PNAs) are oligonucleotide analogues in which the sugar-phosphate backbone has been replaced by a pseudopeptide skeleton. Since PNAs use the natural nucleobases (Adenine, Thymine, Cytosine, Uracil, and Guanine) found in either DNA and/or RNA, they are able to hybridize according to Watson-Crick base-pairing to form duplexes. PNA is a promising therapeutic agent because they can function as antigene or antisense chemical agents. To further enhance their utility, we aim to incorporate a photoswitchable moiety using azobenzene. Here, we report the results of the synthesis and purification of a photoswitchable 11 mer PNA along with initial characterization efforts.

Light Harvesting And Electrically Conducting Metal-Organic Frameworks, Monica Gordillo Varela

All Dissertations

Composed of metal clusters nodes and organic linkers, metal-organic frameworks (MOFs) have emerged as versatile platforms with unparalleled chemical and structural tunability, synthetic facility, permanent porosity, and size-selective guest encapsulation capability. These features make them potential candidates for a variety of applications such as gas storage,drug delivery, catalysis,and sensing. In recent years, the introduction of redox- and photoactive components have yielded stimuli-responsive electronic and photonic MOFs and expanded their utility in molecular electronics and energy storage devices/technologies.

Chapter one describes the light-harvesting ability of a porphyrin-based MOF. Herein, we have demonstrated spontaneous solvothermal growth of [100]-oriented uniform pillared-porphyrin framework-11 (PPF-11) …

Understanding Interfacial Reactions Initiating On Electrode Materials For Energy Storage Technologies, Jingnan Li

Graduate Theses and Dissertations

Since the first generation of lithium-ion batteries featured lithium cobalt oxide cathode and carbon anode commercialized in the 1990s, the high-capacity materials with lower cost are in demand to further increase the battery energy density. Lithium metal and silicon anode are promising high-capacity anode materials to achieve next-generation lithium batteries. However, both the materials actively react in electrolytes and suffer from dramatic volume change. Therefore, a reliable passivation layer at the electrolyte/electrode interphase (i.e., solid electrolyte interphase, or “SEI”) is required to support the long-term cycling of both materials. Cetrimonium hydro fluoride (CTAHF2) has been proposed and synthesized as an …

Valorization Of Biopolymers And Biomass To Produce Materials For A More Circular Economy, Moira Lauer

All Dissertations

With a globally increasing population and largely unchecked consumption of raw materials, human society is on track for devastating consequences. Two industries responsible for utilizing massive amounts of raw materials and generating equally gargantuan quantities of waste are the packaging and infrastructure sectors. In 2017 in Europe, for example, packaging reached a record 173 kg of packaging waste per capita. One of the largest packaging consumers is the food industry, in which 40% of packaging is made of petroleum-derived single-use plastic, leading to a massive carbon imbalance. “The Built Environment,” on the other hand, is responsible for about 50% of …

Comparing And Contrasting Therapeutic Drugs Vs. Lifestyle Changes That Combattype-Ii Diabetes, Alexander Cline Helmuth

Chemistry & Biochemistry Student Projects

In this thesis, I will be presenting various preventive approaches to combat type-II diabetes. The focus of this paper will be comparing and contrasting therapeutic drug targets such as Metformin and Sulfonylureas that are prescribed for type-II diabetic patients versus taking preventative steps such as making lifestyle changes including weight management, physical activity, and having a balanced diet that prevents onset of type-II diabetes or helps patients manage type-II diabetes. From this paper, one will gain insight on how there are multiple approaches to combat type-II diabetes that are not in the form of the pill.

Microfluidic Paper Analytical Devices, Madison Page

Chemistry & Biochemistry Student Projects

Microfluidic paper analytical devices (µPADs) are small, paper-based matrices similar to Lab-on-a-Chip (LOC). They are capable of semi-quantitative analysis, with applications ranging from medical to environmental to food and beverage testing. Important to improving point-of-care devices (POCs), various techniques have been integrated into µPADs to customize analysis and fit different clinical situations.

The Application Of Biological Processes To Increase Energy Potential In Landfills, Ashlyn Eisenhart

Chemistry & Biochemistry Student Projects

There has been a dramatic increase in the amount of waste that we humans have created. This has been due to population growth, an increase in industrial manufacturing, along with urbanization and modernization.⁸ The number of tons of municipal solid waste entering landfills has increased from 82.5 million tons in 1960 to 146.1 million tons in 2018.¹⁷ However, thanks to recycling, composting, and energy recovery from combustion, the percentage of solid waste going to landfills has dramatically decreased, from around 93.6 to about 65.4 percent.¹⁷

Chemistry Of Toothpaste, Kayla Blanche Kirtley

Chemistry & Biochemistry Student Projects

The chemistry of toothpaste is explained, with a description of the chemical components and their mode of action in the role of toothpaste.

Synthetic, Photophysical, And Catalytic Studies Of Light-Harvesting Macrocyclic Complexes, Fox Bratcher

Masters Theses & Specialist Projects

Chromophores are an important class of compounds in Nature and industry, with several hundred thousand tons produced annually as dyes and pigments. Alone, these compounds absorb light unto themselves; however, several of these compounds can be combined to produce a beneficial cascading transfer of energy to a core chromophore.

In this study, photophysical properties of several covalent and axially borondipyrromethene (BODIPY)-conjugated complexes of porphyrin and salphen scaffolds have been evaluated in a series of emission and catalytic studies. In the porphyrin systems, a beneficial excited energy transfer (EET) from the BODIPY moieties to the porphyrin core was observed; however, only …

Synthesis Of Phosphonate-Based Diimide Ligands, Kenya V. Medina

Honors Program Theses and Research Projects

There has been a resurged interest in the synthesis of metal-organic frameworks because of their potential applications in energy production and drug delivery. Although diimides are insoluble in aqueous solutions, the addition of phosphonic acid allows the complex to be water soluble, which greatly increases their application. Therefore, the creation of a hybrid metal-organic complex by the addition of phosphonic groups to diimide ligands can result in a polar porous compound. In this project the ligand design included the use of dianhydrides including pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, and biphenyl-tetracarboxylic acid dianhydride. These dianhydride precursors were refluxed under argon …

Biomimetic Synthesis Of Palladium Nanoparticles For Catalytic Application, Emily A. Groover

College of Graduate Studies: Theses & Dissertations

The synthesis of palladium nanoparticles (Pd NPs) using materials-directed peptides is a novel, nontoxic approach which exerts a high level of control over the particle size and shape. This biomimetic technique is environmentally benign, featuring nonhazardous ligands and ambient conditions. Nanoparticles are extremely reactive catalysts, boasting a large surface-to-volume ratio when compared to their bulk counterparts. The rational design of these nanoparticles using peptides has been very successful in aqueous environments, but no research has been done to apply it in organic systems. As such, the biomimetic synthesis of Pd NPs in an organic system is here investigated, with ethanol …

Pd-Based Photocatalysts For Heck C-C Cross-Coupling Reactions, Suha Ali Alshehri

Masters Theses

Heck C-C cross-coupling reaction has been widely employed in synthetic organic chemistry because of its high efficiency and simplicity, however the conventional Heck C-C cross-coupling reaction conditions involve the use of an expensive toxicant phosphine-ligated palladium complexes, and high temperature. To address these drawbacks, a highly efficient, homogeneous photocatalyst based on BODIPY for the Heck C-C cross-coupling reactions of aryl iodide and methyl acrylate in DMF solvent under inert conditions has been developed. The 4-Py-BDP-Pd, 3-Py-BDP-Pd and, 2-Py-BOD-Pd catalysts were synthesized and purified using column chromatography. The optical properties of products and intermediates were studied by UV/vis absorption and fluorescence …

Characterization Of Landfill Leachate For Enhanced Metal Recovery, Hanna Fulford, Amisha Shah, Inez Hua, Nadezhda Zyaykina, Lori Hoagland, Alejandro Rodriguez Sanchez, Umut Bicim

Discovery Undergraduate Interdisciplinary Research Internship

Landfills contain a trove of valuable materials, such as critical, precious, and rare earth metals, that are integral to the United State’s economy and national security. The leachate that filters through landfills picks up these materials, which allows for the possibility of recovery. For this research, samples will be analyzed from landfills throughout the Midwestern United States to provide a baseline on water quality constituents, elements present, and microbial activity. Preliminary data for this study was acquired by analyzing samples of landfill leachate from a landfill in northern Indiana. pH readings indicate that the leachate is slightly basic. It also …

Synthesis Of Molecular Probes For The Detection Of Toxic Analytes, Rashid Mia

Dissertations

Two different types of molecular probes have been synthesized. The first family of probes is the coumarin class of compounds. These chemodosimters are referred to as Low Molecular Weight Fluorescent probes (LMFP). The other type of molecular probe is a macrocycle known as a pillar[5]arene receptor.

The chemodosimters (2.12a-c and 3.12a) were synthesized in four to five steps. The photophysical properties were extensively studied in various solvent systems (DMSO, CH₃CN, DMF, MeOH, EtOH, Me₂CO, MeCO₂Et, CHCl₃, C₆H₅Me, and C₆H₆). Dimethyl sulfoxide (DMSO) …

Designing Environmentally Responsible And Highly Effective Bioorthogonally Functionalized Chiral Mri Contrast Agents, Karley Breann Maier

Dissertations and Theses

Magnetic resonance imaging (MRI) revolutionized diagnostic imaging and modernized the characterization of numerous diseases. The clinical success of MRI is in large part due to the employment of gadolinium-based contrast agents (GBCAs). Due to sensitivity limitations, GBCAs are indicated at markedly high dosages (~1 g Gd³⁺ per exam). The routine use of such large quantities of gadolinium poses significant health and environmental risks. There are growing concerns over the effects of dechelation of the metal in vivo and the possible effect of resulting gadolinium deposition. Concurrently, there is a rising awareness of gadolinium anomalies borne by GBCAs which undergo …

The Reactivity Of Metal Phosphites: Oxidative Rate Analysis, Jamie Kitchens

Symposium of Student Scholars

Phosphorous compounds are involved in many of the biomolecular processes deemed fundamental for life. DNA, ATP, and phospholipids are a few of the molecules where phosphates can be found in the body. Phosphates are geochemically characterized by their low solubility and poor reactivity. This has led to the investigation of reaction mechanisms that could lead to the formation of the phosphorous compounds found in organisms. The oxidation of phosphite into phosphate could be how phosphates were introduced to life, due to phosphites being more soluble and more reactive than phosphates. We will present the synthesis and oxidation reactivity of four …

Cu-Promoted C-H Bond Hydroxylation Inspired By Cu-Dependent Metalloenzymes, Rachel Trammell

Chemistry Theses and Dissertations

From 2003 to 2015, Schӧnecker and Baran proposed a dinuclear Cu/O₂ species in their mechanistic proposal for the hydroxylation of sp³ C-H bonds within their systems (proposed based on yields). Inspired from the site selectivity of this methodology and poor analysis of the mechanism, the first project was inspired to re-examine the sp³ C-H bond hydroxylation by Schrӧnecker and Baran and perform an intensive investigation into understanding how Cu/O₂ interact which led us to propose a new mechanism based on the evidence collected (i.e., LCu^II-hydroperoxide species that undergoes homolytic O-O bond cleavage). From there …

Synthesis Of A Zinc Dipyrrin Complex For Photocatalytic Reduction Of Co2, Sylvia Meredith

Undergraduate Honors Theses

Zinc dipyrrin complexes have the potential to act as cheap, effective photosensitizers. Synthesizing and studying different types could lead to more efficient solar energy harvesting processes, especially the production of solar fuel. Here, two attempts to synthesize 1,3,7,9-tetraphenyl-5-mesityldipyrromethene are reported and discussed. According to ¹H NMR, the first synthesis attempt was not successful. The second synthesis attempt was not purified effectively, so ¹H NMR produced inconclusive results. Further purification strategies or alternate synthesis methods are required.

Visible Light Generation And Mechanistic Investigation Of High-Valent Metal-Oxo Species Supported By Different Ligands, Seth Ellis Klaine

Masters Theses & Specialist Projects

Numerous transition metal catalysts have been designed as biomimetic model compounds for the active site of metalloenzymes found throughout Nature, most notably cytochrome P450 monooxygenases that carry out the oxidative transformations of organic substrates with near-perfect chemo-, regio-, and stereo-selectivity. The primary active oxidants in catalytic and enzymatic cycles are fleeting high-valent metal-oxo intermediates where the oxo ligand can transfer to an organic substrate in a process known as oxygen atom transfer (OAT).

In the present work, porphyrin-manganese(III), salen-chromium(III), and salenmanganese( III) derivatives were successfully synthesized and spectroscopically characterized using 1H NMR and UV-Vis spectroscopies. A facile photochemical approach was …

Synthesis And Catalytic Oxidation Of Organic Substrates By Light-Harvesting Metalloporphyrins, Christian Alcantar

Masters Theses & Specialist Projects

note: Some notation in this abstract may not appear exactly as formatted in the thesis.

In this work, ruthenium, iron, and manganese light-harvesting metalloporphyrins have been successfully synthesized to serve as biomimetic models of the active site of Cytochrome P450 for the development of a green and efficient oxidation catalyst. The covalent introduction of light-harvesting boron-dipyrrin (BODIPY) fluorophores on the porphyrin macrocycle allows for the absorption of a broader range of visible light in addition to that captured by the porphyrin aromatic system alone. It is expected that this core-antenna system will increase the absorbed light energy and transfer it …

Interactions Of Organic Fluorophores With Plasmonic Surface Lattice Resonances, Robert J. Collison

Dissertations, Theses, and Capstone Projects

It is common knowledge that metals, alloys and pure elements alike, are lustrous and reflective, the more so when a metal surface is flat, polished, and free from oxidation and surface fouling. However, some metals reflect visible light, in the 380 nm to 740 nm range of wavelengths, much more strongly than others. In particular, some metals reflect wavelengths in certain portions of the ultraviolet (UV), visible, and near-infrared (NIR) regime, let us say 200 nm to 2000 nm, while absorbing light strongly in other segments of this range. There are several factors that account for this difference between various …

Synthesis Of A Series Of Ag(I)-Nhc Complexes For Future Antibacterial Studies, Alyssa Malto

Honors Program Theses

For thousands of years, silver (Ag) has been widely used for medicinal purposes due to its broad-spectrum antimicrobial properties. While medicinal silver usage declined with the advent of antibiotics, there has been a renewed interest in therapeutic silver coordination compounds to combat the spread of antibiotic resistance. N-heterocyclic carbenes (NHCs) are promising ligands for silver metallodrugs due to their wide structural variety that allows for tunability of the complex’s overall steric and electronic properties and previously established bioactivity against various pathogens and cancer cell lines. There is potential for efficacy against biofilms, a type of microbial growth pattern that is …

A Novel Palladium Bodipy Photocatalyst For Sonogashira Carbon-Carbon Cross-Coupling, Prahadeesh Nagaretnam

Masters Theses

No abstract provided.

Continuing The Metalation And Ring Closure Of Biliazine, Joshua Villers

Williams Honors College, Honors Research Projects

Continuing previous research conducted by Dr. Ziegler and his Graduate Students in which different metals were selected to metalate the compound Biliazine as well as finding metals that could be used to close the ring system in Biliazine.

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

Masters Theses

No abstract provided.

Cobalt, Molybdenum, And Nickel Complexes, Natural Zeolites, Epoxidation, And Free Radical Reactions, Nicholas K. Newberry

Dissertations, Master's Theses and Master's Reports

Chapter 2 is based on the synthesis and study of the compounds of the bidentate ligand ((5-phenyl-1H-pyrazol-3-yl)methyl)phosphine oxide with molybdenum and cobalt as the transition metal. The complexes were analyzed via FTIR, NMR, UV-Vis, Fluorescence Spectroscopy, TGA, DFT, and XRD. Chapter 3 resulted in the synthesis of the complexes [Ni(II)SSRRL](PF6)2 and [Ni(II)SRSRL](Cl)(PF6) of which [Ni(II)SRSRL](Cl)(PF6) had not been previously analyzed. Both products were analyzed via FTIR, NMR, UV-Vis, CV, DFT, and XRD. Chapter 5 contains the results of the characterization and modification of 4 natural zeolites (AZLB-Na, AZLB-Ca, NM-CA, NV-Na) from the United States in an attempt to increase the …

Fluorinated Phthalonitriles And Phthalocyanines: Synthesis And Spectroscopic Properties, Marius Pelmus

Seton Hall University Dissertations and Theses (ETDs)

Since their discovery at the beginning of the 20^th century, phthalocyanines (Pc) have come a long way; today they are replacing the porphyrins (natural products) in most of their applications. The functionalization of the organic macrocycle, the use of different metals, and the change of the axial ligands resulted in Pc applications in a wide range of fields, ranging from photochemistry, paints, catalysis, to fuel cells and cosmetic products.

In Dr. Gorun’s group was developed a series of electron-deficient Pcs that benefit from a Teflon-like chemical shield, meant also to break the π-π interactions, namely the F₆₄PcM …

Design And Synthesis Of Novel No-Drug Hybrid Compound And Green Catalytic Activity Evaluation Of Synthesized Silver Nanoparticles-Halloysite Nanocomposite, Majed Abdullah Bajaber

LSU New Orleans Theses and Dissertations

Acetaminophen is a well-known analgesic that can manage pain and reduce fever. SCP-1 is a derivative of acetaminophen that showed significantly reduced hepatotoxicity and nephrotoxicity comparative to acetaminophen. Nitric oxides have been well known to play a key role in a wide variety of physiological and pathophysiological important processes. It was therefore of interest to synthesize a nitric oxide donor linked to SCP-1 that could have enhanced analgesic and antipyretic activity. A furoxan CAS 1609 as NO-donor was synthesized and linked to SCP-1 successfully. The furoxan CAS 1609 was initially synthesized from tetronic acid to give 1,2- dioxime in 86 …

Covalent Organic Frameworks As An Organic Scaffold For Heterogeneous Catalysis Including C-H Activation, Harsh Vardhan

USF Tampa Graduate Theses and Dissertations

Linking small organic molecules into an extended solid usually afford disordered amorphous polymers. The instigation of order into such a material is of profound interest to induce inherent fine control of the overall structure. Covalent organic frameworks (COFs) are new class of porous crystalline material prepared by connecting organic building blocks via strong covalent bonds. The judicious choice of organic monomers can give rise to highly ordered and predictable frameworks with high crystallinity, surface area, and thermal/chemical stability. The role of connecting linkages such as B─O, C─C, C─N extends the principle of fundamental molecular covalent chemistry to the formation of …