Chemistry Commons^™

Structure-Property Relationship Studies Of Electrically Conductive Metal-Organic Framework Materials, Shiyu Zhang

All Dissertations

Electrically conductive metal-organic frameworks (EC-MOFs) are among the most promising materials due to their tunable structures, properties, and diverse functions. However, the lack of comprehensive understanding of their structure-property relationship hinders the development of EC-MOFs. My dissertation focuses on the design, construction, and structure-property relationship studies of EC-MOFs.

Chapter 1 describes how MOFs' structural features and compositions affect the electronic properties and demonstrates conductive mechanisms and the corresponding design strategies to develop EC-MOFs.

Chapter 2 describes the synthesis, characterization, electronic and optical properties of four novel alkali-metal-based (Na, K, Rb, and Cs) 3D-MOFs with continuous tetrathiafulvalene tetracarboxylate (TTFTC) π-stacks, systematicly …

Carbon "Quantum" Dots: Structures, Properties, And Issues, Weixiong Liang

All Dissertations

Carbon dots (CDots) are small carbon nanoparticles (CNPs) with effective surface passivation. The effective passivation has been achieved by the surface functionalization of pre-existing CNPs with organic molecules, mostly molecules containing primary or secondary amine moieties. In the studies highlighted in this dissertation, CNPs were functionalized by selected organic molecules, including especially the use of radical addition reactions, to generate CDots with strong absorption and bright fluorescence emissions. A good demonstration of the approach was the N-ethylcarbazole (NEC) radical addition to CNPs under microwave irradiation. Spectroscopy and microscopy methods were employed to characterize the resulting NEC-CDots, and the results …

Characterizing The Role Of Chemo-Mechanical Couplings In The Activation Process Of Proteins That Undergo Conformational Changes, Ugochi Isu

Graduate Theses and Dissertations

Proteins are not static entities; rather, they are dynamic macromolecules that undergo conformational changes to perform their biological functions. These structural transitions are often coupled to chemical events such as lipid interactions, or changes in the cellular environment. Understanding the intricate interplay between chemical perturbations and the resulting mechanical response is crucial for elucidating the activation mechanisms of proteins. This dissertation aims to characterize the role of chemo-mechanical couplings in the activation process of two G protein-coupled receptors (GPCRs): Cannabinoid Receptor 1 (CB1) and Metabotropic Glutamate Receptor 1 (mGluR1). We employ molecular dynamics simulations to investigate the conformational landscapes of …

Molybdenum Alkylidyne Complexes With Phenoxide Ligands For Alkyne Metathesis, Marvin L. Stewart Jr

LSU Doctoral Dissertations

Abstract

Alkyne metathesis is a powerful synthetic tool, which provides easy access to complex organic molecules in a single-step. It is a dynamic covalent reaction that scrambles alkynes, carbon-carbon triple bonds (C≡C). Molybdenum- or tungsten-alkylidyne (Mo≡C, W≡C) complexes are typically used as catalyst to cleave and reform alkyne bonds. Our goal has been to gain a deeper understanding of the intrinsic differences between functional ligands by the development of novel phenoxide ligands.

In chapter 2 we explore the detailed synthesis of novel phenoxide podand ligands in an effort to identify their mo-alkylidyne complexes. We were able to synthesize a variety …

Killing Cancer: Manipulating Hydrophobic Vanadium Complexes To Improve Anti-Cancer Activity, Levi Ausherman, Debbie C. Crans, Peter A. Lay, Maggi Braasch-Turi

SACAD: Scholarly Activities

Hydrophobic vanadium complexes have recently shown improved anti-cancer activities compared to cisplatin. The hydrophobicity and anti-proliferative activity of [VO(Hshed)(dtb)] ([Hshed= N-(salicylideneaminato)-N’-(2-hydroxyethyl)-1,2-ethanediamine and dtb= 3,5-di(tert-butyl)catechol)]) have inspired the development of a library of hydrophobic vanadium complexes. Increasing the steric bulk of the catechol ligand has been shown to have a direct impact on hydrophobicity and anti-proliferative activities. Currently at Fort Hays State University, the Braasch-Turi group is synthesizing VO(HSHED)(dtb) to build up material to support the chemical analysis and biological assay performed by our collaborators at Colorado State University and the University of Sydney, Australia, respectively. In the future, we plan …

Unlocking The Secret To Weight Loss: Discovering The Most Effective Green Tea Products, Seoyeon Kim

SACAD: Scholarly Activities

To find the most effective green tea product that can replace

weight loss drugs, we compared the amount of catechin in six

different green tea products. The result was green tea latte

powder contained a significantly small amount of catechin

compared to other products, and the dried pearl green tea leaves

had the highest amount of catechin. Also, the unexpected result

was that green tea supplements had less amount of catechin

compared to dried leaves or even tea bags that are commonly

sold in markets.

Apigenin Alleviates Autistic-Like Stereotyped Repetitive Behaviors And Mitigates Brain Oxidative Stress In Mice, Petrilla Jayaprakash, Dmytro Isaev, Keun-Hang Susan Yang, Rami Beiram, Murat Oz, Bassem Sadek

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Studying the involvement of nicotinic acetylcholine receptors (nAChRs), specifically α7-nAChRs, in neuropsychiatric brain disorders such as autism spectrum disorder (ASD) has gained a growing interest. The flavonoid apigenin (APG) has been confirmed in its pharmacological action as a positive allosteric modulator of α7-nAChRs. However, there is no research describing the pharmacological potential of APG in ASD. The aim of this study was to evaluate the effects of the subchronic systemic treatment of APG (10–30 mg/kg) on ASD-like repetitive and compulsive-like behaviors and oxidative stress status in the hippocampus and cerebellum in BTBR mice, utilizing the reference drug aripiprazole (ARP, 1 …

Applied Depositional Geosystems Of The Coos Bay Basin, Oregon: Organic Geochemistry, Maturation, Paleoenvironmental Reconstruction And Biostratigraphy Of The Coaledo Delta During The Middle Eocene Climatic Optimum (Meco), Allison K. Barbato

LSU Doctoral Dissertations

The Coos Bay Basin on the southwestern coast of Oregon is a forearc basin that contains exceptionally preserved Eocene to Miocene, tidal to wave-dominated, shallow deltaic to deep marine sediments of the Coaledo Delta. Coastal depositional environments are known to host source, reservoir, and seal rocks. Climate, topographic relief, and geographical position all play an important role in regional vegetation development and oceanic setting. This study assesses 84 outcrop and 12 core samples from Coos Bay for their organic geochemical characteristics and microfossil assemblage to provide source rock characterization information, organofacies descriptions, environmental reconstructions, and age control.

Results indicate the …

Green Oxidation Of Aromatic Hydrazide Derivatives Using An Oxoammonium Salt, Nidheesh Phadnis, Jessica A. Molen, Shannon M. Stephens, Shayne M. Weierbach, Kyle M. Lambert, John A. Milligan

College of Life Sciences Faculty Papers

Aromatic diazenes are often prepared by oxidation of the corresponding hydrazides using stoichiometric quantities of nonrecyclable oxidants. We developed a convenient alternative protocol for the oxidation of aromatic hydrazides using Bobbitt's salt (1), a metal-free, recyclable, and commercially available oxoammonium reagent. A variety of aryl hydrazides were oxidized within 75 min at room temperature using the developed protocol. Computational insight suggests that this oxidation occurs by a polar hydride transfer mechanism.

Efforts Toward Difunctionalization Of (Hetero)Arenes Enabled By Visible Light, Eric Allen

Master's Theses (2009 -)

Functionalized arenes and heteroarenes are ubiquitous motifs in natural products, pharmaceuticals, and functional materials. As such, methods to place multiple functionalities on (hetero)arenes in one synthetic step create molecular complexity quickly and are highly valued. The vast majority of current strategies are metal-mediated, although others such as utilizing aryne intermediates and cycloadditions have also been reported. The premier challenge in this research area is the difficulty in controlling regioselectivity. Strategies of controlling regioselectivity have included tuning the electronic nature of the substrate, the use of directing groups (DGs), steric influences, ligand control, and photochemically initiated methods. Certain strategies tend to …

Synthesis, Molecular Characteristics, And Antibacterial Assessment Of Marine Hydroid Aqueous Extract-Based Silver Bio-Nanoparticles, Fredryk Mandey, Aulia Rhamdani Arfan, Rugaiyah Andi Arfah

Makara Journal of Science

This investigation aims to synthesize, analyze the molecularity, and test the ability of bacterial inhibition capability of silver nanoparticles that have been synthesized by simply mixing silver nitrate and aqueous extracts of marine natural products with and without the addition of amylum as a stabilizing agent. This research, with and without the addition of amylum as a stabilizing agent, obtained 39.0 and 55.2 mg of solids of round-shaped morphology silver nanoparticles with diameters of 87.9 and 103.0 nm., respectively. In addition, the antibacterial testing assay against Staphylococcus aureus and Escherichia coli showed some considerably good results. S. aureus with the …

Mechanistic Investigation Of C—C Bond Activation Of Phosphaalkynes With Pt(0) Complexes, Roberto M. Escobar, Abdurrahman C. Ateşin, Christian Müller, William D. Jones, Tülay Ateşin

Research Symposium

Carbon–carbon (C–C) bond activation has gained increased attention as a direct method for the synthesis of pharmaceuticals. Due to the thermodynamic stability and kinetic inaccessibility of the C–C bonds, however, activation of C–C bonds by homogeneous transition-metal catalysts under mild homogeneous conditions is still a challenge. Most of the systems in which the activation occurs either have aromatization or relief of ring strain as the primary driving force. The activation of unstrained C–C bonds of phosphaalkynes does not have this advantage. This study employs Density Functional Theory (DFT) calculations to elucidate Pt(0)-mediated C–CP bond activation mechanisms in phosphaalkynes. Investigating the …

Reversible O–H Bond Activation By Tripodal Tris(Nitroxide) Aluminum And Gallium Complexes, Joseph S. Scott , '22, Mika L. Maenaga , '21, Audra J. Woodside , '19, Vivian W. Guo , '26, Alex R. Cheriel , '24, M. R. Gau, Paul R. Rablen, Christopher R. Graves

Chemistry & Biochemistry Faculty Works

Herein, we report the preparation and characterization of the Group 13 metal complexes of a tripodal tris(nitroxide)-based ligand, designated (TriNOx³⁻)M (M = Al (1), Ga (2), In (3)). Complexes 1 and 2 both activate the O–H bond of a range of alcohols spanning a ∼10 pKₐ unit range via an element-ligand cooperative pathway to afford the zwitterionic complexes (HTriNOx²⁻)M–OR. Structures of these alcohol adduct products are discussed. We demonstrate that the thermodynamic and kinetic aspects of the reactions are both influenced by the identity of the metal, with 1 having higher reaction equilibrium constants and proceeding at a …

Group Contribution Revisited: The Enthalpy Of Formation Of Organic Compounds With “Chemical Accuracy” Part V, R. J. Meier, Paul R. Rablen

Chemistry & Biochemistry Faculty Works

Group Contribution (GC) methods to predict thermochemical properties are eminently important in chemical process design. Following our earlier work in which a Group Contribution (GC) model was presented to account for the gas-phase heat of formation of organic molecules which, for the first time, revealed chemical accuracy (1 kcal/mol or 4 kJ/mol), we here present Group Contribution parameters for a range of additional series of molecules allowing the application to a wider range of molecules whilst, mostly, retaining chemical accuracy. The new classes of molecules include amines, alkylesters, and various substituted benzenes, including t-butyl-benzenes, phenols, methoxybenzenes, anilines, benzaldehydes, and acetophenones, …

3-Chloropropylbis(Catecholato)Silicate As A Bifunctional Reagent For The One-Pot Synthesis Of Tetrahydroquinolines From O-Bromosulfonamides, Noah Brodsky, Nidheesh Phadnis, Mohamed Ibrahim, Isabel M. Andino, Inés Blanc Giro, John A. Milligan

College of Life Sciences Faculty Papers

Bis(catecholato)silicate salts are easily accessible reagents that can be used to install alkyl fragments through photoredox-enabled cross-coupling. These reagents can incorporate various functional groups including pendant alkyl halides. A halogenated organosilicate reagent was leveraged to develop a one-pot synthesis of tetrahydroquinolines from o-bromosulfonamides, where the bifunctional reagent participates in a nickel/photoredox cross-coupling followed by intramolecular nucleophilic substitution. The functional group tolerance of this cross-coupling strategy allowed for the preparation of a series of substituted tetrahydroquinolines.

Purification And Isolation Of Α-Chloro-Β-Lactone Precursor Molecules, Matthew Ellis

ASPIRE 2024

This research investigates the synthesis of α-chloro-β-lactone molecules, focusing on the production, isolation, and purification of two precursor compounds from chloroacetic acid and substituted benzaldehydes. While multiple methods were explored, including EDC, DIC, and DCC catalysis, DCC proved to be most effective in producing higher yields. However, challenges in purification arose due to the formation of byproducts, particularly with DCC, prompting further investigation for efficient extraction and purification techniques. DCC, however, shows a promising route for α-chloro-β-lactone synthesis, despite purification complexities.

Pisa Printing Microneedles With Controllable Aqueous Dissolution Kinetics, Aaron Priester, Jimmy Yeng, Yuwei Zhang, Krista Hilmas, Risheng Wang, Anthony J. Convertine

Chemistry Faculty Research & Creative Works

This study focused on the development of high-resolution polymeric structures using polymer-induced self-assembly (PISA) printing with commercially available digital light-processing (DLP) printers. Significantly, soluble solids could be 3D-printed using this methodology with controllable aqueous dissolution rates. This was achieved using a highly branched macrochain transfer agent (macro-CTA) containing multiple covalently attached CTA groups. In this work, the use of acrylamide as the self-assembling monomer in isopropyl alcohol was explored with the addition of N-(butoxymethyl)acrylamide to modulate the aqueous dissolution kinetics. PISA-printed microneedles were observed to have feature sizes as small as 27 μm, which was close to the resolution limit …

Stereospecific Cross-Coupling Reactions Of Vinyl Triflates And An Investigation Of The Synthesis And Reactivity Of Activated Alkyltricyclohexylstannanes, Pejman Ghaemimohammadi

Dissertations, Theses, and Capstone Projects

Organic chemistry exists in all aspects of everyday life from polymers to pharmaceutics. Formation of carbon-carbon bonds is essential for the synthesis of complex organic compounds. This goal can be achieved by using transition metal catalysts. Second-row transition metals such as Pd, Pt, Rh, and Ir have shown remarkable efficacy in these reactions. Metal-catalyzed cross-coupling reactions form carbon-carbon bonds between electrophiles and nucleophiles using transition metal catalysts. Pd is mainly used in this reaction.

Transition metal-catalyzed cross-coupling reactions that form a bond between two C(sp²) carbons have been widely studied over the past decades. C(sp²)-C(sp^{3 …}

Studies Of Oxidopyrylium Ylide Dimers And Their Utility In The Synthesis Of Densely Functionalized Troponoids, Daniel V. Schiavone

Dissertations, Theses, and Capstone Projects

Herein, we describe our efforts to investigate mechanistic considerations of oxidopyrylium ylides and their use in cycloadditions to form complex bicyclic structures and the advancement of these cycloadducts to the synthesis of densely functionalized tropolones. This work also describes applications of tropolones as biologically relevant structures and dynamic fluorophores.

In Chapter 1, we expand upon previous studies done in the Murelli Lab describing the ability of 3-hydroxy-4-pyrone derived oxidopyrylium dimers to revert back to ylides in situ and as result can be used as a clean oxidopyrylium ylide source in accessing oxabicyclic compounds. Intermolecular cycloadditions of these ylides can be …

The Effect Of Variation Of N-Substituents On Oxidopyridinium Ions In (4+3) Cycloadditions, Zahria Patrick, Madison Clark

Undergraduate Research Symposium

The aim of this research project is to expand the scope of 4 + 3 cycloadduct chemistry by varying functional groups attached to the prerequisite oxidopyridinium ion for each respective cycloadduct product. While N-substitution of the pyridinium precursor is known to proceed smoothly if alkylated by a lone methyl group, we evaluated the effect a larger alkyl group would have on the overall yield of the 4 + 3 cycloadduct product.

Isobutyl triflate, generated from the known reaction between isobutyl alcohol and triflic anhydride, was reacted with ethyl 5-hydroxy-nicotinate to generate the respective N-isobutyl oxidopyridinium ion in quantitative …

Etherification Of Propargylic Alcohol Using Ferrocenium Ions, Cody Amann, Sai Anvesh Bezawada, Eike B. Bauer

Undergraduate Research Symposium

Etherification of Propargylic Alcohol using Ferrocenium Ions

Cody Amann, Sai Anvesh Bezawada and Eike B. Bauer*

Department of Chemistry and Biochemistry, University of Missouri-St.Louis, MO 63121

Our research efforts are directed toward the improvement of iron-based catalyst systems. The Bauer research group recently found that the ferrocenium cation is a catalytically active in the etherification of propargylic alcohols. My research was to compare the effect of two different counteranions of the ferrocenium cation on the catalytic activity. Etherification test reactions were performed using 2-methyl-2-phenol-propargylic alcohol and n-butanol to afford the corresponding propargylic ether substitution products. The complexes used …

Adapting Chiral Gas Chromatography Into Existing Undergraduate Laboratories To Emphasize The Importance Of Stereochemistry, Ken Overway, Barnabas Otoo, Nicholas Griffin, Marshall Ritchie, Tyler Lynn, Kate Dear, Tyler Deutsch, Leigha Dillard

Chemistry Faculty Scholarship

Owing to the critical role of stereochemistry in biotechnology, medicine, and industry, it must be well represented in undergraduate lab curricula. To achieve these stereochemical laboratory requirements without sacrificing existing lab techniques, we modified two standard laboratory experiments to include chiral GC analysis as follows. (1) The extraction of carvone from spearmint leaves and caraway seeds via steam-distillation or other extraction methods is widely used in laboratories for analyzing the stereochemistry of the extracted products. The experiment was modified to include a GC method using a β-DEX 225 column. This allowed the students to compare the retention times of the …

Fluorescent Ph Indicators For Classroom Demonstration Of Buffer Action, Mark Muyskens, Mariana Dykstra, Yejin Chung

University Faculty Publications and Creative Works

We report an attractive update to the demonstration of acid−base buffer action that is appropriate for ease of use and getting attention in the classroom. The twist is based on new fluorophore information and the recent availability of UV flashlights serving as an ideal, portable excitation light source. The pH-dependent fluorescence comes from a choice among three natural sources, namely narra tree wood extract, kidneywood extract, and scopoletin, which is a purchasable coumarin, that all perform equally well. We provide practical details for performing the buffer demonstration at scales of 100 and 1000 mL and give background information for context

Research Trends And Impact Report On Aggregation-Induced Emission (Aie), 2001-2021, Elsevier Analytical Services

Public Reports

Since the concept of AIE was first proposed in China in 2001, it has gradually grown to a field of science that attracts dedicated researchers from around the world. Elsevier's data analytics team used AIE experts' interpretation of current theoretical, technological, and industrial development trends in the field for reference to collect AIE-related global scientific publications (from the Scopus database) to serve as a publication set in the field of AIE. This was undertaken to present, accurately and objectively, the development of AIE research over the past two decades and the latest scientific advancements in the field; to facilitate the …

Chemoselective Reduction Of Dicarboxylic Acids Via Iridium Catalyzed Hydrosilylation, Linda Lallawmsangi

Chemistry & Biochemistry Theses - Archive

Reduction of esters to aldehydes poses a challenge since the resulting aldehydes are often more reactive than the initial esters toward nucleophilic hydride-reducing agents. Although bulky, more controllable reducing agents such as lithium tri-tert-butoxyaluminum hydride or diisobutylaluminum hydride (DIBAL-H) have been developed, they are hazardous, sensitive to moisture and air, needing strict reaction conditions, and unsuitable with a wide range of functional groups. We present the design of an iridium-catalyzed chemoselective hydrosilylation method for dicarboxylic imides, followed by hydrolysis to eliminate the amide and yield aldehydes. This approach offers versatility in general reduction chemistry, holds promise for application …

Advanced Detection Of Sars-Cov-2 And Omicron Variants Via Mxene-Graphene Hybrid Biosensors Utilizing Nucleic Acid Probes, Jiaoli Li, Yuwei Zhang, Congjie Wei, Yanxiao Li, Zhekun Peng, Hsin Yin Chuang, Logan Pearce, Adrianus Boon, Yue-Wern Huang, Dong Hyun Kim, Risheng Wang, Chenglin Wu

Biological Sciences Faculty Research & Creative Works

Low-cost biosensors that can rapidly and widely detect viruses are critical for faster diagnosis and treatment decision-making, especially for infections. The commonly used field-effect transistor is sensitive to the biomarker's detection but struggles with precise detection, particularly of nontargets such as ions and proteins. To overcome this limitation, we developed a field-effect transistor biosensor design based on MXene-graphene materials to increase the accuracy and sensitivity of virus detection. Based on the hybridization process between two complementary DNA strands, single-stranded nucleic acids were immobilized on the sensing surface via 3-aminopropyltriethoxysilane and glutaraldehyde to capture the nucleic acids of the target virus. …

Phenanthrene Jamboree, Alexander D. Roth

Honors Theses

Using cyclopropanated and cyclobutanated phenanthrene precursors, our hero embarks on a mission to find as many reactive intermediates as possible. Fraught with danger, romance, and mangosteens, Anderson calls this work 'monstrous' and 'alarming.'

Studies Towards High Surface Area Porous Polymers Via Cross-Coupling Methodology, Anthony Lybrand

Wayne State University Theses

Porous polymers, known for their high internal surface area and robust chemical stability, are promising candidates for applications in gas storage, water purification, energy storage, and catalysis. The Yamamoto-type Ullmann reaction, known for yielding high porosity polymers, serves as a benchmark in this study. However, its limitations as a homocoupling reaction restricts the synthesis of ordered A-B type copolymers. This research addresses this challenge by investigating the use of cross-coupling reactions, particularly the Negishi reaction, to synthesize A-B type copolymers with reduced defectivity and enhanced surface area. The synthesis of fully-metalated intermediates and their subsequent polymerization are discussed in detail. …

Design, Synthesis, And Evaluation Of Class Iia Histone Deacetylase (Hdac) Inhibitors, Lauren Nicole Kotsull

Wayne State University Dissertations

Histone deacetylase (HDAC) proteins are linked to disease states, including cancer, and have become important targets for therapeutic development. Many inhibitors have been developed to target HDAC proteins, including FDA-approved inhibitors Vorinostat (SAHA), Belinostat, Romidepsin, and Panobinostat. These inhibitors non-specifically influence most of the 11 metal-dependent HDAC isoforms, which might contribute to the side effects that patients experience during treatment. The lack of selectivity also diminishes the use of HDAC inhibitors as biomedical research tools. To address these drawbacks, the development of selective inhibitors has been heavily studied. Yet, reported inhibitors are predominantly selective for class I HDAC isoforms (HDACs …

Dna Origami-Assisted Regioselective Organization Of Anisotropic Gold Nanotriangle Clusters, Wenyan Liu, Prashant Gupta, Yuwei Zhang, Krishna Thapa, Srikanth Singamaneni, Risheng Wang

Chemistry Faculty Research & Creative Works

The manipulation of anisotropic nanoparticles, such as gold nanorods and nano prisms, has attracted great attention in nanotechnology due to their sensitive geometry-dependent properties. However. traditional synthesis and assembly methods for these particles face challenges in size uniformity and higher-order structuring. To address these limitations, this study presents a strategy using DNA origami triangles, not just as templates, but as encapsulating agents for gold nanotriangles (AuNTs). This method enables the construction of diverse nanoparticle clusters with precisely controlled distance and orientation. The formed clusters exhibit unique optical characteristics, demonstrated by UV-visible spectroscopy and supported by finite-difference time domain (FDTD) simulations. …