Organic Chemistry Commons^™

In Silico Investigation For The Conversion Of Methyl Oleate To Gasoline, Arkanil Roy

Graduate Theses/Dissertations

Petroleum products are found in all walks of life. From the plastic casing on a cell phone to the gasoline that runs most vehicles, a lot is derived from petroleum. Ubiquitous use of petroleum has adversely affected the environment. Toxic substances such as SOx and NOx are released into the atmosphere during the processing and usage of petroleum products, which contributes to global warming. Inevitable oil spills cause devastating effects to marine ecosystems. The rate of regeneration of petroleum is much slower than the rate of usage that would lead to it being exhausted in the recent future. Hence, a …

Visualization Without Vision – How Blind And Visually Impaired Students And Researchers Engage With Molecular Structures, Croix J. Laconsay, Henry B. Wedler, Dean J. Tantillo

Journal of Science Education for Students with Disabilities

This article examines the tools and techniques currently available that enable blind and visually impaired (BVI) individuals to visualize three-dimensional objects used in learning chemistry concepts. How BVI individuals engage with and visualize molecular structure is discussed and recent tactile (or haptic) and auditory methods for visualization of various chemistry concepts are summarized. Remaining challenges for chemistry education researchers are described with the aim of highlighting the potential value of educational research in further enabling BVI students to pursue careers in science, technology, engineering, and mathematics (STEM) fields.

The Development Of A New Entry Point Into Enantiomerically Enriched Sulfinyl Derivatives, Jessica Shaw

Theses and Dissertations

Optical probes may be used as reliable tools for detecting and imagining the inside of cells for medical diagnostics. Among available options, the use of thiol probes is of interest as thiols are present in nearly all cells and their levels are tightly regulated, thus any variation is associated with disease. A proper thiol bioimaging probe must have a thiol cleavage group/reactive group and a fluorophore. It is found that novel sulfinate aryl ester (phenoxysulfinate esters) probes selectively cleave thiols at physiological pH and show much promise as effective tools for bioimaging.

In this context, the synthesis of the related …

Global Atmospheric Budget Of Acetone: Air-Sea Exchange And The Contribution To Hydroxyl Radicals, Siyuan Wang, Eric C. Apel, Rebecca H. Schwantes, Kelvin H. Bates, Daniel J. Jacob, Emily V. Fischer, Rebecca S. Hornbrook, Alan J. Hills, Louisa K. Emmons, Laura L. Pan, Shawn Honomichl, Simone Tilmes, Jean‐François Lamarque, Mingxi Yang, Christa A. Marandino, E. S. Saltzman, Warren J. De Bruyn, Sohiko Kameyama, Hiroshi Tanimoto, Yuko Omori, Samuel R. Hall, Kirk Ullmann, Thomas B. Ryerson, Chelsea R. Thompson, Jeff Peischl, Bruce C. Daube, Róisín Commane, Kathryn Mckain, Colm Sweeney, Alexander B. Thames, David O. Miller, William H. Brune, Glenn S. Diskin, Joshua P. Digangi, Steven C. Wofsy

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Acetone is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere. The oceans impose a strong control on atmospheric acetone, yet the oceanic fluxes of acetone remain poorly constrained. In this work, the global budget of acetone is evaluated using two global models: CAM‐chem and GEOS‐Chem. CAM‐chem uses an online air‐sea exchange framework to calculate the bidirectional oceanic acetone fluxes, which is coupled to a data‐oriented machine‐learning approach. The machine‐learning algorithm is trained using a global suite of seawater acetone measurements. GEOS‐Chem uses a fixed surface seawater concentration of acetone to calculate the oceanic fluxes. Both …

Chemical Variability In Volatile Oils Of Bentong Ginger: A Chemometric Study, Ahmad Jahiddin Farah Syuhaidah

Student Works (2020-2029)

The volatile oil of ginger (Zingiber officinale) possesses various pharmacological properties corresponding to its chemical compositions, which in turn, depends on its source material and preparation method. In this study, preliminary experiments were carried out to investigate the variations in volatile oil of ginger prepared based on different method (dry/fresh samples), extraction duration and size reduction process (grate/slice samples). The ginger volatile oil yield can be quantitatively improved by using a fresh sample with grated form and a longer extraction cycle. Gas Chromatography-Mass Spectrometry (GC-MS) was conducted and the chromatogram profile was subjected to Principal Component Analysis (PCA). Results show …

Thermotropic And Lyotropic Phase Behaviours Of Spontaneously Self-Assembled Amphiphilic Branched-Chain Glycosides With Various Chain Length, Abdul Hamid Hairul Amani

Student Works (2020-2029)

Lipid polymorphism is a process which illustrates the self-assembly of lipid aggregation depending on the environment. Lipids such as branched-chain glycolipids which are amphiphilic molecules also known as amphitropic tend to generate mesophases in thermotropic (dry) and lyotropic (solvation) conditions. These molecules are capable of self-aggregating into various types of glycolipid self-assemblies offering an interesting insight in relation to their functions in living cells. Hence, this study aims to investigate the mesophases of ꞵ-D-glycosides which are branched-chain synthetic glycolipids, namely, ꞵ-D-glucosides and ꞵ-D-maltosides. The study was carried out on the thermotropic phases of dry glycosides and the lyotropic phases of …

Teaching College Chemistry In The Time Of Covid-19 Pandemic: A Personal Account Of Teaching In The Old Normal Vs. The New Normal, Armando M. Guidote Jr

Chemistry Faculty Publications

The SARS CoV-2 (Severe Acute Respiratory Syndrome CoronaVirus 2), cause of COVID-19 (CoronaVirus Disease 2019) has afflicted close to 10 million people all over the world resulting to almost half a million deaths. This disease is severely contagious and necessitates social or physical distancing between persons. As such, traditional face-to-face learning is not advised and teachers need to shift to online teaching. There are challenges to online teaching and learning for students, teachers, and the higher education institute, e.g. hardware, bandwidth, and software issues. These will be difficult but these can be overcome eventually. This work is a personal account …

Oxadiazinones As Chiral Auxiliaries: Chiral Templates For Asymmetric Conjugate Addition In The Synthesis Of ( R )-( + )-Tolterodine, Fatima Olayemi Obe

Theses and Dissertations

The stereoselective formation of carbon-carbon bonds through the process of conjugate addition has proven to be a very important methodology in synthetic organic chemistry. In this context, oxadiazinones are chiral auxiliaries that have been applied in the asymmetric aldol addition reaction to synthesize valuable synthetic fragments such as the aldol side chain of the multi-drug resistance medicinal agent, hapalosin. This thesis describes efforts that were directed towards employing oxadiazinones as chiral scaffolds for the process of asymmetric conjugate addition with the ultimate objective of using this methodology in the preparation of medicinal agents such as Tolterodine. Preliminary efforts focused on …

Transition Metal-Free Domino Acyl Substitution/Michael Addition Of Alkenyl Grignard Reagents To Lactam Esters: Synthesis Of Lactam-Bearing Homoallylic Ketones, Abdikani Omar Farah, Muhannad Rabah, Timothy K. Beng

All Faculty Scholarship for the College of the Sciences

A solvent-controlled protocol for the direct and transition metal-free addition of alkenyl Grignard reagents to vicinally functionalized sp³-rich morpholinones has been developed, leading to the chemo and regioselective synthesis of lactam-bearing homoallylic ketones. The addition of lithium chloride proved to be essential. In cases where a new stereocenter is generated, the doubly branched homoallylic ketones are obtained in unexpectedly high diastereoselectivities. Efforts to extend the methodology to other heterosubstituted lactams revealed some important reactivity and selectivity differences.

Benzosiloles With Crystallization-Induced Emission Enhancement Of Electrochemiluminescence: Synthesis, Electrochemistry, And Crystallography, Liuqing Yang, Donghyun Koo, Jackie Wu, Jonathan M. Wong, Tyler Day, Ruizhong Zhang, Harshana Kolongoda, Kehan Liu, Jian Wang, Zhifeng Ding, Brian Pagenkopf

Chemistry Publications

Crystallization-induced emission enhancement (CIEE) was demonstrated for the first time for electrochemilunimescence (ECL) with two new benzosiloles. Compared with their solution, the films of the two benzosiloles gave CIEE of 24 times and 16 times. The mechanism of the CIEE-ECL was examined by spooling ECL spectroscopy, X-ray crystal structure analysis, photoluminescence, and DFT calculation. This CIEE-ECL system is a complement to the well-established aggregation-induced emission enhancement (AIEE) systems. Unique intermolecular interactions are noted in the crystalline chromophore. The first heterogeneous ECL system is established for organic compounds with highly hydrophobic properties.

New Alkaloids From Selected Malaysian Alstonia And Lycopodium Species And Their Biological Activity, Soon Yee Joanne Yeap

Student Works (2020-2029)

Two Malaysian plants, Alstonia penangiana Sidiyasa (family: Apocynaceae) and Lycopodium platyrhizoma J.H.Wilce (family: Lycopodiaceae), were investigated for their alkaloidal composition. This project represents the first reported phytochemical study on these two plant species. A total of 94 alkaloids (1−94) were isolated and characterized from the leaf and stem-bark extracts of Alstonia penangiana, a plant endemic to Penang Island, Malaysia. Of these, 32 are new alkaloids. The leaf extract of A. penangiana yielded a total of 15 new alkaloids, including a pair of type-A and type-B macroline isomers (1, 2), four macroline oxindoles (20–23), three talpinine-type oxindoles (41–43), two ajmaline alkaloids …

Catalytic Esterification Of Palm-Based Lauric Acid Diethylene Glycol Via Microwave Heating, Abas Noor Azeerah

Student Works (2020-2029)

Diethylene glycol esters of fatty acids are mixtures of diethylene glycol mono- and di-esters of saturated and unsaturated fatty acids derived from edible oils and fats. The products are produced either by direct esterification of diethylene glycol with fatty acids or by transesterification of diethylene glycol with oils or fats. This study involved in maximizing the conversion of lauric acid to glycol ester via esterification with diethylene glycol, aided by calcined Zn-Mg-Al catalyst in a 250-ml reactor using both conventional and microwave heating. Preliminary catalytic screening involving tin (II) oxalate, Amberlyst-15 and calcined Zn-Mg-Al catalysts in esterification of lauric acid …

Pegylated Block Copolymer For Cancer Imaging And Treatment, Sweety Singh

Dissertations

Gene theranostics have emerged as an important tool for the treatment of cancer as well as other diseases. Among the challenges in this field is the lack of effective vectors to chaperone plasmids into cells while the vector itself exhibits minimal toxicity. Herein, the synthesis, cellular uptake, and gene delivery using a biocompatible norbornene-based block copolymer is reported. This block copolymer, bearing polyethylene glycol moieties along with primary amines is functionalized with both a boron dipyrromethene (BODIPY) fluorophore for fluorescence tracking and a folic acid derivative for cancer cell targeting.

Stoichiometry control afforded residual unreacted amine functional groups available to …

Sufex Activation With Ca(Ntf2)2: A Unified Strategy To Access Sulfamides, Sulfamates, And Sulfonamides From S(Vi) Fluorides, Nicholas Ball, Subham Mahapatra, Cristian P. Woroch, Todd W. Butler, Sabrina N. Carneiro, Sabrina C. Kwan, Samuel R. Khasnavis, Junha Gu, Jason K. Dutra, Beth C. Vetelino, Justin Bellenger, Christopher W. Am Ende

Pomona Faculty Publications and Research

A method to activate sulfamoyl fluorides, fluorosulfates, and sulfonyl fluorides with calcium triflimide and DABCO for SuFEx with amines is described. The reaction was applied to a diverse set of sulfamides, sulfamates, and sulfonamides at room temperature under mild conditions. Additionally, we highlight this transformation to parallel medicinal chemistry to generate a broad array of nitrogen-based S(VI) compounds.

Site-Selective, Catalytic, And Diastereoselective Sp3 C–H Hydroxylation And Alkoxylation Of Vicinally Functionalized Lactams, Timothy K. Beng, Victoria Shearer, Rachel Davey, Ivianne Redman

All Faculty Scholarship for the College of the Sciences

The C–H bond functionalization of sp³ carbon centres presents a significant challenge due to the inert nature of hydrocarbons as well as the need to selectively functionalize one of the numerous aliphatic C–H bonds embodied in organic molecules. Here, we describe catalytic, diastereoselective, and site-selective sp³ C–H hydroxylation/alkoxylation protocols featuring dihydroisoquinolones, γ-, and δ-lactams, which bear vicinal stereocenters. The hydroxylation strategy utilizes oxygen, a waste-free oxidant and affords attractive fragments for potential drug discovery. Fe-catalyzed dehydrative coupling of the resulting tertiary alcohols with simple primary alcohols has led to the construction of highly versatile unsymmetrical dialkyl ethers.

Synthesis Of The Natural Alkaloids Angustureine, Cuspareine, Galipeine, Galipinine Using Α-Aminocycloalkyl Copper Reagents, Zane Bertoli

Master of Science in Chemical Sciences Theses

Tetrahydroquinolines (THQs) are a group of N-heterocyclic molecules derived from natural sources. They show a wide range of interesting biological activity and have been the basis for a variety of different medications including antibacterial and antiparasitic drugs. The Hancock alkaloids, Galipinine, Galipeine, Cuspareine and Angustureine, are natural 1,2,3,4- tetrahydroquinoline compounds that are found in the South American Angostura tree. Extracts containing these alkaloids have been used to treat fever, dysentery and other ailments. Interestingly, These compounds have shows in vitro antimalarial activity. However, it does not appear in the literature that they have been evaluated for their potential antibiotic activity. …

Synthesis And Evaluation Of Novel Biologically Active Compounds, Madhurima Das

LSU New Orleans Theses and Dissertations

SCP-1, a potent derivative of acetaminophen, exhibits significantly diminished hepatotoxicity and nephrotoxicity relative to acetaminophen and nitrate ester derivatives of acetaminophen. It was therefore of interest to explore the development of nitric oxide donor analogs of SCP-1 to identify compounds that could have enhanced analgesic and/or antipyretic activity while taking advantage of the very low liver and kidney toxicity inherent to SCP-1. In this project, a series of nitrate ester analogues of the SCP-1 were prepared as potential nitric oxide donors. The synthesis of SCP analogs was achieved by triflic acid catalyzed O-acylation of SCP-1 with chloroalkanoyl chlorides followed by …

I. Non-Degradable Polysiloxane Networks For Controlled Release Applications, And Ii. Additive Free, Degradable Silyl-Ether Furyl-Maleimide Networks, Caleb M. Bunton

Chemistry Theses and Dissertations

I. Two different series of non–degradable polysiloxane networks were prepared for the encapsulation and controlled release of a small molecule agent. For the first series, hydrosilylation was utilized to prepare networks of varying crosslink densities, as determined from swelling studies, from vinyl terminated and silylhydride functional poly(dimethyl)siloxanes. For the second series, the thiol-ene reaction was utilized to prepare networks of varying crosslink densities, as determined from swelling studies, from vinyl terminated and mercaptopropyl functional poly(dimethyl)siloxanes. Nile red dye was used as an encapsulated agent and dye release from each series of networks was measured using UV–vis spectroscopy to determine controllability …

Influence Of The Spatial Distribution Of Cationic Functional Groups At Nanoparticle Surfaces On Bacterial Viability And Membrane Interactions, Yongqian Zhang, Natalie V. Hudson-Smith, Seth D. Frand, Meghan S. Cahill, Larissa S. Davis, Vivian Feng, Christy L. Haynes, Robert J. Hamers

Faculty Authored Articles

While positively charged nanomaterials induce cytotoxicity in many organisms, much less is known about how the spatial distribution and presentation of molecular surface charge impact nanoparticle–biological interactions. We systematically functionalized diamond nanoparticle surfaces with five different cationic surface molecules having different molecular structures and conformations, including four small ligands and one polymer, and we then probed the molecular-level interaction between these nanoparticles and bacterial cells. Shewanella oneidensis MR-1 was used as a model bacterial cell system to investigate how the molecular length and conformation of cationic surface charges influence their interactions with the Gram-negative bacterial membranes. Nuclear magnetic resonance (NMR) …

Synthesis Of Fluorinated Pyrazoles Via Intra- And Intermolecular Cyclization Reactions, Matthew Saucier

Honors Theses

Pyrazole-based pharmaceuticals treat a wide array of diseases and conditions including obesity, diabetes, cancer, microbial and viral infections, pain and inflammation, and many neurological disorders. Syntheses for this biologically significant substrate have been well developed, but current methods to afford fluorinated pyrazoles are limited by variability and selectivity. By 2013, over 25% of all drugs available on the market contained the element fluorine due to its unique characteristics leading to improved target protein binding, bioavailability, and metabolic stability. In order to harness these pharmaceutical benefits of fluorine and overcome its difficulty in handling and stability, we set out to develop …