Bachelor of Science, Wittenberg University, 2021, Biology

Insecticide use is steadily increasing in the United States. Of these, the insecticide Sevin™ has the active ingredient carbaryl, which is a xenobiotic. This is a reverse inhibitor of acetylcholinesterase, which prevents nerve excitation causing paralysis and death in insects. Though insects are the target species, carbaryl has many routes of exposure such as run-off, inhalation, and physical contact making it easy to encounter for non-target species like aquatic life and humans. Carbaryl has been studied within in vitro models to test its effects on zebrafish. The insecticide has already been shown to act on the acetylcholinesterase (AChE) pathway, but it also has potential to act on a second pathway: the aryl hydrocarbon receptor (AhR) pathway. Zebrafish genes and genetic pathways are homologous to humans, allowing for insight on how carbaryl could be affecting humans as well. This study set out to use an in vivo model to show how carbaryl is inducing cytochrome P450 or other AhR pathway gene expression. Gene expression of carbaryl treated embryos were compared to untreated embryos to examine this possible relationship. Cyp1a and cyp1b gene expression was increased with an increase in carbaryl concentration suggesting that carbaryl may be causing induction of the AhR pathway.

Committee: Michelle McWhorter (Advisor); Matthew Collier (Committee Member); Daniel Marous (Committee Member) Subjects: Agricultural Chemicals; Biochemistry; Biology; Developmental Biology; Environmental Science; Genetics; Molecular Biology; Toxicology

Master of Science in Chemistry, Youngstown State University, 2020, Department of Chemistry

This thesis reports the attempted synthesis of carbamates from carboxylic acids via Curtius rearrangement of acyl azide intermediates. Successful synthesis of carbamates of some common alcohols such as ethanol, isopropyl alcohol and cholesterol were achieved adopting the use of diphenyl phosphoryl azide as the azide substrate. The products were confirmed by infra-red spectroscopy, proton nuclear magnetic resonance (1H) and carbon-13 nuclear magnetic resonance (13C). A possible double Curtius rearrangement reaction and product was observed using terephthalic acid as the carboxylic acid and this was confirmed with infra-red spectroscopy and nuclear magnetic resonance as well. Less toxic azides used could not be proven to have worked or not due to the insufficient data obtained from their reactions.

Committee: Peter Norris PhD (Advisor); John A. Jackson PhD (Committee Member); Nina Stourman PhD (Committee Member) Subjects: Chemistry; Organic Chemistry

Master of Science in Chemistry, Youngstown State University, 2016, Department of Chemistry

Carbamate chemistry has a wide variety of applications both in synthetic chemistry as well as in biology. This carbon-nitrogen containing functional group is used as a linker in many potential pharmaceutical agents and in numerous biological systems. These linkages are not only found in naturally occurring substances, however, but can be synthesized in the lab under quite facile conditions via different routes. Organic acyl azides are excellent precursors for these types of linkers and in this thesis we have developed an alternative one-pot synthesis to yield the carbamate product.

Committee: Peter Norris PhD (Advisor); John Jackson PhD (Committee Member); Sherri Lovelace-Cameron PhD (Committee Member) Subjects: Chemistry; Organic Chemistry

MS, University of Cincinnati, 2016, Medicine: Industrial Hygiene (Environmental Health)

Acetylcholinesterase (AChE) inhibitors such as organophosphate insecticides and carbamate insecticides have a severe effect on the human nervous system and other functions of the body. It is important to be able to quickly and accurately monitor water sources near agriculture for contamination by these pesticides. This thesis details the early stages of assay development for the detection of AChE inhibitors with a method that utilizes the formation of fluorescent products from the activity of the enzyme. AChE converts 2-naphthyl acetate to form 2-naphthol, a highly fluorescent product, which was detected via high performance liquid chromatography and fluorescence spectrometry (HPLC/FS). The formation of this product is limited as the enzyme activity is inhibited. This inhibition is quantified through the quantification of 2-naphthol formed. Though statistical significance was not analyzed, inhibition percentages of 5.5-70.9% were found for levels of aldicarb, a carbamate pesticide and potent inhibitor of AChE, from 0.0165 to 3.3 ppm. This assay is within an order of magnitude of target sensitivity based on EPA drinking standards, and has room for improvement for sensitivity as well as precision.

Committee: Mary Beth Genter Ph.D. (Committee Chair); Changchun Xie Ph.D. (Committee Member) Subjects: Environmental Health

Master of Science in Chemistry, Youngstown State University, 2014, Department of Chemistry

In this thesis, acyl chlorides were successfully converted to their corresponding carbamates via Curtius rearrangement in a novel "one-pot" synthesis procedure that uses p-nitrobenzenesulfonylazide as the azide nucleophile source. In the process alkyl esters were also synthesized as the associated by-product. The thesis also deals with the "one-pot" synthesis of acyl azides from acyl chlorides.

Committee: Peter Norris PhD (Advisor); John Jackson PhD (Committee Member); Nina Stourman PhD (Committee Member) Subjects: Chemistry; Organic Chemistry