Physical Sciences and Mathematics Commons^™

C(Sp2)-C(Sp3) Cross-Coupling Of Aryl Halides And Active C(Sp3)-H Bonds Via Dual Catalysis: Organic Photocatalysis/Nickel Redox Catalysis, Nicholas Armada

Department of Chemistry: Dissertations, Theses, and Student Research

Convenient catalytic methodologies that can facilitate the formation of C-C bonds are undoubtedly of great interest in synthetic organic chemistry. Recent reports in literature have showcased hybrid catalytic methods that couple Ni-redox catalysis and photocatalysis to enable C-H activation of tetrahydrofuran (THF) and subsequent cross-coupling with aryl halides in appreciable yields and under relatively mild reaction conditions.^1-2 However, these studies used expensive, heavy metal-containing photocatalysts and both report difficulty obtaining low-specificity across their scopes of aryl-halides. The following report will shed light on a class of photo-excitable small organic molecules that – in conjunction with a catalytic Ni-redox cycle …

Synthesis And Study Of Hydroxytyrosol Derivatives, Ebenezer Ametsetor

Electronic Theses and Dissertations

Hydroxytyrosol is one of the most powerful known antioxidants. It is a naturally occurring polyphenol, most commonly produced in olive trees, (Olea europaea). The remarkable antioxidant and pharmacological properties of hydroxytyrosol has made it an outstanding compound in the polyphenol family and of great interest to many researchers. Hydroxytyrosol can scavenge free radicals produced during cellular oxidative stress and helps to protect the integrity of cells in living systems. Despite its numerous biological and pharmacological uses, it is found in very low concentration in olive oil, this limits its availability for biomedical applications. This work reports a novel and effective …

A Study In Molecular Recognition: Synthesis Of A Β-Sheet Mimic & Quantitation Of Metal Ions In Aqueous Solutions Through Solid Supported Semi-Selective Chemosensors, Tyler G. Fenske

Theses and Dissertations

From the hydrophobic effect, which is responsible for the organization of amphipathic molecules into cellular membranes, to the highly specific hydrogen binding patterns found in DNA base pairs that keeps our genetic material “zipped up”, non-covalent and reversible interactions are critical to properly functioning biological processes. Molecular recognition is an area of study that seeks to better understand these observed phenomena. In a general sense, association of “Host” and “Guest” molecules are based on ionic forces, hydrophobic interactions, cation-π effects, π-π stacking, conformational restriction, and many others. This dissertation will primarily focus on two projects that have an emphasis on …

Synthesis And Characterization Of Gd-Doped Inp/Zns Quantum Dots For Use In Multimodal Imaging Probes, Molly Erin Duszynski

MSU Graduate Theses

Quantum dots (QDs), which are intensely fluorescent nanocrystals ranging 2-10 nanometers in diameter, have shown promise in fluorescence imaging. However, in vivo applications of QDs are limited due to the opaque surrounding of tissue and bones. In this study, InP/ZnS QDs were doped with a paramagnetic atom in an attempt to render them MRI-active. We have further bioconjugated these nanoprobes to develop highly specific MRI-active probes that can be used for detection of neurodegenerative diseases. These bioconjugated nanoprobes detect a mutated form of alpha-synuclein that forms oligomers that are a hallmark of Parkinson’s disease andother alpha-synucleinopathies. Here, we have optimized …

Development Of Ni-Catalyzed Alkene Dicarbofunctionalization Reactions, Shekhar Kc

Chemistry and Chemical Biology ETDs

Alkenes serve as one of the most important feedstocks for organic synthesis, having two vicinal sites for bond formation. In alkenes, both vicinal sites can be functionalized with two reagents in a process commonly known as alkene difunctionalization, which results in the formation of two new bonds. A number of alkenes difunctionalization reactions, such as diamination, dioxygenation, carboamination and carbooxygenation, are known. However, difunctionalization of alkenes with two carbon-based entities, termed alkene dicarbofunctionalization, is relatively less common. Development of such a process could provide a powerful method to introduce two different carbon fragments across an alkene in a regioselective manner, …

Acid-Mediated N-Iodosuccinimide-Based Thioglycoside Activation For The Automated Solution-Phase Synthesis Of Α-1,2-Linked-Rhamnopyranosides, Victoria R. Kohout, Alyssa L. Pirinelli, Nicola L.B. Pohl

Chemistry Publications

Carbohydrate structures are often complex. Unfortunately, synthesis of the range of sugar combinations precludes the use of a single coupling protocol or set of reagents. Adapting known, reliable bench-chemistry reactions to work via automation will help forward the goal of synthesizing a broad range of glycans. Herein, the preparation of di- and tri-saccharides of alpha 1→2 rhamnan fragments is demonstrated using thioglycoside donors with the development for a solution-phase-based automation platform of commonly used activation conditions using N-iodosuccinimide (NIS) with trimethylsilyl triflate. Byproducts of the glycosylation reaction are shown to be compatible with hydrazine-based deprotection conditions, lending broader functionality …

Phenolate Derivatives Of Octanuclear Iron-Oxo-Pyrazolato Complexes; Enantiomeric Resolution Of T-Symmetry Species, Konstantinos Lazarou

FIU Electronic Theses and Dissertations

Octanuclear ferric complexes involving achiral phenolates of the general formula [Fe₈(μ-O)₄(μ-pz)₁₂(R-C₆H₄O)₄], (R = 4-NO₂, 4-CN, 4-F, 4-Cl, 4-I, 4-CH₃O, and 3-NO₃), where synthesized and characterized by single crystal X-ray crystallography, elemental analysis, ¹H-NMR, UV-Vis, IR, ⁵⁷Fe Mössbauer spectroscopy and electrochemical methods (cyclic and differential pulse voltammetry). Results indicate that the nature of the phenolate substituents allows the fine tuning of the spectroscopic data of the compounds.

Subsequently, this project focused on the resolution of the racemic …

Synthesis Of A Protein Based Photocatalytic Hydrogen Production System, Alexander M. Brown

Honors Program Theses and Projects

Anthropogenic climate change is one of the most pressing challenges facing humans today. It is scientifically established that the production of copious amounts of greenhouse gases such as carbon dioxide (CO2) is the primarycause of global warming. Many of these greenhouse gases are produced from the combustion of carbon-based fuels and researchers are investigating promising alternative fuel sources such as hydrogen gas. Hydrogen gas is a clean burning fuel that stores a significant amount of chemical potential energy. The goal of this project was to synthesize a protein based photocatalytic hydrogen production system and to characterize the effects of modifications …

Mild Synthesis Of Perylene Tetracarboxylic Monoanhydrides With Potential Applications In Organic Optoelectronics, Xizhe Zhao

Dissertations, Theses, and Capstone Projects

Perylene tetracarboxylic derivatives are considered good n-type semi-conductors. In past decades, there has been extensive study on their synthesis and electronic properties. Because of the high electron affinity, the ability to form π-π stacks, they have been widely utilized in organic photovoltaic solar cells, field-effect transistors and light-emitting diodes. Many of those applications prefer unsymmetrically substituted perylene tetracarboxylic derivatives. Perylene monoanhydrides are the most versatile intermediates for the preparation of unsymmetrically substituted perylene tetracarboxylic derivatives. In this thesis, I focused on introducing new synthesis methods for perylene monoanhydrides with labile functional group and their potential applications in organic optoelectronics.

In …

Evaluating The Scalability Of Graphene Synthesis, Evan Dexter

Scholar Week 2016 - present

Graphene is a new material, first isolated in 2004, consisting of one to a few atomic layers of carbon in a lattice sheet structure. Graphene has high tensile strength, high surface area, very low electrical resistance, and various other special properties that make it an excellent material for use in emerging technologies in the categories of electrical components, energy systems, and high strength applications. The production scale of graphene sheets and its variations is currently limited to laboratory use, with a great amount of current research going into the development of manufacturing techniques of the material. I conducted experiments to …

Synthesis, Molecular Structure, And 1h Nmr Analysis Of Bis(Tetraphenylcyclopentadienyl)Ruthenium(Ii), Michael P. Castellani, John M. Wright, Steven J. Gelb, Arnold L. Rheingold, William C. Trogler

Michael P. Castellani

Reaction of [Ru(p-cymene)Cl₂]₂ with K(η⁵-C₅HPh₄) in refluxing diglyme yields (η⁵-C₅Ph₄)₂Ru in ca 50% yield. The complex was not susceptible to oxidation or reduction. (C₅HPH₄)₂Ru crystallizes in the triclinic P1 space group with a = 8.549(4), b = 10.793(4), c = 12.842(5) Å, α = 65.98(3), β = 73.10(3), γ = 83.49(3)° and Z = 1. The least-squares data refined to R(F) = 3.53% and R(wF = 3.82% for the …

(Η5‐Cyclopentadienyl)Tricarbonylmanganese(I) Complexes, Patrick N. Kirk, Michael P. Castellani

Michael P. Castellani

Since the initial preparation of (η⁵‐C₅H₅)Mn(CO)₃ by Fischer and Jira in 1954, many methods have been developed for the synthesis of this compound (often referred to as “cymantrene”) and its C₅ substituted derivatives. Interestingly, each of these preparations has at least one significant drawback from a preparative perspective (thallium reagents, high pressures, poor yields, or reactants that require significant preparative investment). Surprisingly missing from this collection of preparative methods is the direct reaction between commercially available Mn(CO)₅Br and NaC₅H₅. In 1988, however, Smart and coworkers found …

Low-Valent Synthons Of Titanium : Investigations On Structure-Reactivity Relationships, Rolando Aguilar

Open Access Theses & Dissertations

Strategies for the functionalization of abundant, small molecules into products with added value provide a powerful approach to address environmental sustainability issues. Dinitrogen (N2), and carbon oxides (CO, CO2), are examples of the ample, yet, underutilized atmospheric feedstock of nitrogen and carbon building blocks to produce a variety of chemicals. Although, potentially valuable, small molecules are inert under most conditions, and as such, their industrial activation often requires heterogeneous catalysts operated under high pressures (200 atm) and temperatures (450-600 ºC).

To this end, great efforts in synthetic inorganic chemistry have been devoted to the generation of well-defined and highly reactive …

Antitumor Properties Of Imidazolium Salts, Jenna Frantz

Williams Honors College, Honors Research Projects

This is the final write-up for an honors research project for the University of Akron Williams Honors College. Synthesis of novel imidazolium salts was conducted. Following synthesis of imidazolium salts, the stability of the compound was tested at 37°C over a 72-hour period to give preliminary information about drug stability in vivo. 2D NMR was also conducted to confirm the structure of TPP-1. The student wrote an experimental protocol for the use of C57BL/6 mice and performed the online CITI training by the IRB to prepare to work with animals in a study of the antitumor properties of imidazolium salts …

Synthesis And Antimicrobial Activity Of 1-(Benzo[B]Thiophen-4-Yl)-4-(2-(Oxo, Hydroxyl, And Fluoro)-2-Phenylethyl)Piperazine And 1-(Benzo[D]Isothiazole-3-Yl)-4-(2-(Oxo, Hydroxy, And Fluoro)-2-Phenylethyl)Piperazine Derivatives, Vaibhav Mishra, Tejpal Singh Chundawat

Turkish Journal of Chemistry

Twenty-two compounds in a series of 1-(benzo[$b$]thiophen-4-yl)-4-(2-(oxo, hydroxy, and fluoro)-2-phenylethyl) piperazine and 1-(benzo[$d$]isothiazole-3-yl)-4-(2-(oxo, hydroxy, and fluoro)-2-phenylethyl)-piperazine derivatives were synthesized through nucleophilic substitution reaction of phenacyl bromides with hetero arylpiperazine, reduction, and then fluorination. Compound K2 showed potent activity against gram-negative bacterial stain P. aeruginosa with minimum inhibitory concentration (MIC) value of 12.5 μg/mL. This compound showed better inhibitory activity than the standard drug chloramphenicol. K4 against S. aureus, H2 against P. aeruginosa, and F4 against E. coli showed good inhibitory activity with MIC values of 62.5 μg/mL. Compounds K1, K2, K4, K8, F1, and F3 showed good inhibitory activity against …

Synthesis And Antitumor Activities Of 2-(Piperidin-4-Yl)-Thiazole-4-Carboxamides Analogues Of Tubulysins, Xiangfu Peng, Mingsha Shao, Shuchao Ma, Lei Yao

Turkish Journal of Chemistry

}Tubulysins are a family of natural products that exhibit potent antitumor activities, which have attracted much attention from synthetic and medicinal chemists. Previous attempts to aromatize the Tuv part of tubulysin analogues led to a loss in antitumor activity, which suggested that the Ile and Tuv fragments of these analogues were adopting different conformations than the natural products. In this study, a series of 2-(piperidin-4-yl)-thiazole-4-carboxamides have been prepared to investigate whether an intramolecular H-bond between key NH and OH groups is responsible for the conformational control. The antitumor activities of these analogues have been screened using MDA-MB-231-breast, Siha-cervical, MCF7-breast, and …

Synthesis And Bioactivity Of Sulfide Derivatives Containing 1,3,4-Oxadiazole And Pyridine, Gang Yu, Shunhong Chen, Feng He, Dexia Luo, Yu Zhang, Jian Wu

Turkish Journal of Chemistry

A series of novel sulfide derivatives containing 1,3,4-oxadiazole and pyridine were synthesized, characterized, and tested for their antibacterial activity against tobacco bacterial wilt and rice bacterial blight and for insecticidal activity toward diamondback moth. The results showed that some compounds had good insecticidal and bactericidal activity, e.g., the activities of compounds 6e and 6g-6j toward tobacco bacterial wilt were much better than those of commercial thiodiazole-copper, and some of the synthesized compounds possessed good insecticidal activity against Plutella xylostella. Compounds 6d, 6h, 6j, 6l, 6p, 6r, and 6p displayed over 93% activity at 500 mg L$^{-1}$.

Synthesis Of Smz Derivatives And Investigation Of Effects On Germination, Root, And Plant Growth Of \Textit{Arabidopsis Thaliana} L., Tuğba Güngör, Ferah Cömert Önder, Fati̇h Sezer, Aslihan Özbi̇len, Kemal Meli̇h Taşkin, Mehmet Ay

Turkish Journal of Chemistry

A series of sulfonamide derivatives were synthesized by reactions with various functional groups containing benzenesulfonyl chlorides and aniline derivatives under different substitution reaction conditions. The structures of SMZ derivatives were confirmed with melting point, FT-IR, $^{1}$H NMR, $^{13}$C NMR, and LC-MS/MS techniques. In order to investigate the cytotoxic effects of these derivatives, we used a model plant species. The synthesized compounds (S1-S5) and sulfamethazine (SMZ) as a positive control were applied to Arabidopsis thaliana seeds. Our results indicated that S3 and S4 induced shorter roots and lower wet weight in plants. Plants treated with S2 and S5 showed no growth …

Synthesis, Characterization, And Nonlinear Optical Properties Of Some New Series Of S-(5-Aryl-1,3,4-Oxadiazol-2-Yl) 2-Chloroethanethioate Derivatives, Zahra Dono Ghezelbash, Hamideh Motiei, Miri Mahmoody, Karim Akbari Delmaghani

Turkish Journal of Chemistry

In the present investigation, some novel S-(5-aryl-1,3,4-oxadiazol-2-yl)2-chloroethanethioate (3a-3e) derivatives were synthesized and their impact on optical properties was studied. They have also been characterized by elemental analysis and various spectroscopic methods including FTIR, $^{1}$H NMR, $^{13}$C NMR, and UV-Vis techniques. The nonlinear refractive indexes of 3a-3e were also measured in dichloromethane via Z-scan method using a continuous wave diode-pumped laser at 532 nm wavelength. The nonlinear refractive coefficient of compounds was obtained from ${10}^{11}\, \, {m}^{{2}}{/W}$ order. Regarding the appropriate nonlinearity of these compounds, they could be considered good candidates for biooptical and photonic applications. All the synthesized compounds (3a-3e) …

Synthesis Of Cadmium Arsenide Semiconductor Nanoparticles, Superatomic Silver Clusters, And Silver Coordination Polymers, Sarthak Jashubhai Patel

Legacy Theses & Dissertations (2009 - 2024)

Nanomaterials have chemical, electronic, optical, and other properties distinct from their bulk counterparts. However, the atom-precise synthesis of these materials remains a challenge, leaving open many scientific questions regarding the size regime between nanoparticulate (quantum confined) and bulk character. In this work, efforts toward the synthesis of nanoparticulate and atom-precise metal and semimetal materials are described. The synthesis of II-V semiconductor Cd3As2 having a near-zero bandgap is discussed. Analysis by UV-Vis absorption spectroscopy and powder X-ray diffraction indicate the formation of material with unexpected crystallinity and absorption properties The interaction between the molecular source of As and the solvent was …