๐”– Bobbio Scriptorium
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Cover of Pulled to the Alpha: Alphas in Heat Book Five

Pulled to the Alpha: Alphas in Heat Book Five

โœ Scribed by Turner, Olivia T.


Book ID
100385756
Year
2020
Tongue
English
Weight
179 KB
Category
Fiction

No coin nor oath required. For personal study only.

โœฆ Synopsis


Chapter 1 focuses on the fundamental methods we use to perform computational chemistry research. The chapter begins with a discussion of molecular force fields and the Schrodinger equation before moving to a discussion of density functional theory (DFT), molecular optimizations, and the self-consistent field. The aim of this chapter is to provide a concise but detailed overview of the methods used. The chapter ends with a discussion of why I chose to study computational chemistry. Chapter 2 focuses on the hydration propensities of biologically relevant [alpha] -ketoamides. Quantum mechanical (QM) calculations were used to predict the hydration propensities of [alpha] ketoamides. These computationally-determined hydration equilibrium constants were compared to experimental hydration equilibrium constants for six [alpha]-ketoamides synthesized in house. The agreement of computational and experimental results led to a computational method that can be used to quickly and accurately predict hydration equilibria of [alpha]-ketoamides and other similar carbonyl compounds computationally. [alpha]-ketoamides are of increasing pharmaceutical interest because of their high electrophilicity at the keto carbonyl. Results from this project are presented herein. Chapter 3 provides an in-depth discussion of both a computational and experimental investigation of a 1,3 bromide migration where bromine migrates from a carbon in a phenyl ring to the benzylic position; these carbons are in a 1,3 relationship. QM calculations were performed on a copper-mediated 1,3 bromide migration in a styrene system. In this project, we were contacted by an experimental group who wanted our assistance understanding the mechanism of the 1,3 bromide shift they observed experimentally. I worked with my colleague, Dr. Brandi Hudson, to elucidate the mechanism. The reaction took place over a series of several steps: First, the copper migrates from the benzylic position to C2 of the benzene ring. Then, bromine migrates from its original place to the copper. The copper then delivers the bromine to the benzylic carbon which completes the 1,3 bromide shift. These results are reported on herein. Experimental results are also provided. Chapter 4 presents my results from a purely computational study using QM to elucidate the mechanism of the isomerization of 24 methylenecycloartanol, a sterol found in olive oil. This project interests me particularly because the isomerization of 24-methylenecycloartanol could be used as an indicator of thermally-treated olive oil. Most of the olive oil imported to the United States claims to be extra virgin, meaning never heated above room temperature, but investigations have demonstrated that some oils imported as extra virgin actually undergo thermal processing. 24-methylenecycloartanol is a triterpenoid and isomerizes under heat via protonation and a 1,2 hydride shift. Because of difficulty finding a suitable transition state structure for protonation, I calculated proton transfer energies responsible for transferring a proton from acetic acid to a base in a variety of solvents. These do not define the barrier of protonation but they are a lower bound of the energy required for protonation. We found that as the solvent dielectric increased, the proton transfer energy decreased. Unfortunately, we do not yet have a method of detecting 24-methylenecycloartanol or its isomerized product experimentally in olive oil samples but we hope to develop an experimental method in the future. Chapter 5 focuses on a computational study performed on the isomerization of isozizanoic acid (present in vetiver oil) to 12-norisoziza-5-ene through nigritene and 6 epinigritine. Vetiver oil is typically extracted from plant matter via steam distillation and it was observed that isozizanoic acid concentrations decreased and nigritene and 12 norisoziza 5 ene were produced. The mechanism we propose involves two alkyl shifts and, most notably, a push-pull decarboxylation reaction where rearrangements must occur before and after the decarboxylation. This type of push-pull decarboxylation is rare and of sincere interest to me. The results from this investigation are presented here. Chapter 6 is all about wine and terpenes found in both red and white wine grapes. Wine is among the most complex liquids on earth containing thousands of natural products. Terpenes and terpenoids are one class of organic compound highly prevalent in wine. A review on key terpenes and terpenoids found in wine that affect flavor, aroma, color and texture is presented herein. We also show how terpenes can be biosynthesized. Organic chemistry is inherently visual in nature. However, computational chemistry can be made accessible to the blind or visually impaired. Numerous results are presented expressing how computational organic chemistry can be made accessible to the blind or visually impaired community throughout Chapters 7 and 8. Chapter 7 discusses many in-house techniques used to make computational chemistry more accessible to the blind or visually impaired, including a preliminary discussion of 3-D printing, several computer scripts written in house to make computational chemistry more accessible, and a variety of non computer related techniques used to make tactile figures used by BVI scientists. Chapter 8 focuses on the development and analysis of several computer scripts that enhance accessibility written in collaboration with the Center for Molecular and Biomolecular Informatics in The Netherlands. The software discussed is called AsteriXBVI and allows us to perform many tasks including but not limited to extracting images from PDF files that can be made tactile, creating 3-D printable files of output structures from calculations, and braille annotations indicating bond length on all 3-D printable structures. A newly-developed Molecular Fabricator is also discussed; the Molecular Fabricator allows anyone to create molecular structures using a QWERTY keyboard (with no graphical user interface). The Molecular Fabricator utilizes five straightforward commands and a working knowledge of Simplified Molecular Input Line Entry Specification (SMILES) strings in order to build structures. Chemistry laboratory spaces can be dangerous if not treated properly. In particular, teaching labs where most people working are relatively inexperienced can be dangerous if safety is not at the forefront. Students with disabilities can safely complete lab courses and Chapter 9 presents several measures that should be taken to ensure a safe lab space for all. Chapter 11 presents four key scripts that a colleague, Dr. Ryan Pemberton, and I created to make computational chemistry doable without sighted assistance. Incidentally, we discovered that these scripts aid all computational chemists, not just those of us who are blind. The utility of these scripts is presented in Chapter 11 and the actual code is presented in Appendix A11. Teaching is and has always been very important to me. Chapters 10 and 12 present a medley of teaching experiences and teaching philosophies. Chapter 12 closes with some thoughts from my graduate career.


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โœ Olivia T. Turner ๐Ÿ“‚ Fiction ๐Ÿ“… 2020 ๐Ÿ› Olivia T. Turner Publishing ๐ŸŒ English โš– 254 KB

Iโ€™ve always been fiercely independent. A working girl with a promising career in the FBI. No time for love and definitely no time for a boyfriend. Who has time for any of that when there are outlaw dragons to catch? Iโ€™m in this small mountain town in Montana for two days tops. Get in, grab that