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ndltd-OhioLink-oai-etd.ohiolink.edu-osu1180128001
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ndltd-OhioLink-oai-etd.ohiolink.edu-osu11801280012021-08-03T05:52:04Z Computational investigations of hydroxyl radical addition to aromatics and alkenes in the presence of solvent, conformational preferences of dendrimers, and theoretical studies of arabinofuranosides and aeptanosides DeMatteo, Matthew P. Computational studies, at the B3LYP and CBS-QB3 levels, confirmed the experimental rate enhancement of hydroxyl radical addition to benzene via calculation of the transition states in the presence of explicit solvent molecules as well as a continuum dielectric field. Using computational methods at the BH&HLYP and CBS-QBH&H levels, it was determined that there was correlation between the activation barrier for hydroxyl radical addition to various alkenes and the ionization potential of the substrate. Investigations of the G2 2-methoxyisophthalamide and 2,6-pyridinedicarboxamide dendrons through a Monte Carlo conformational search followed by volume calculations indicated that both 2-OMe-IPA and 2,6-pydic dendrons would show noticeable differences in volume as a function of solvent polarity. Computational investigations were also used to determine the conformational preferences of pyridine-2,6-dicarboxamide repeat units with two different chiral subunits attached at the periphery (N-H and N-Me amides). The N-H amide dendrons were capable of transferring chirality to biphenol cores, while the N-Me amide dendrons were capable of transferring chirality to tetraphenol cores. Computational investigations at the B3LYP level of the transition states for a regioselective epoxide ring opening of an arabinofuranoside precursor were performed. It was found that the only model able to account for the regioselectivity was that which involved two explicit lithium cations. Another analysis was performed on the prior step of the synthesis that involves formation of a triflate intermediate. In all of the examined triflates it was found that the most stable species was that in which the triflate functional group is trans to the epoxide ring. A Monte Carlo protocol was better suited to cover all of conformational space and determine the conformational preference of the C-glycoside than the fixed envelope approach. The C-glycoside was found to prefer northern conformers in the <sup>3</sup>T<sub>2</sub> or <sup>3</sup>E family in good agreement with the experimentally observed <sup>1</sup>H-NMR coupling constants. The preferred solution conformations of methyl α-D-glycero-D-idoseptanoside and methyl β-D-glycero-D-guloseptanoside were examined by computational approaches and <sup>1</sup>H NMR <sup>3</sup><i>J</i><sub>H,H</sub> coupling constant analysis. The correlation between calculated and observed values suggest that septanose carbohydrates are not so flexible and should generally prefer one twist-chair (TC) conformation. 2007-06-22 English text The Ohio State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=osu1180128001 http://rave.ohiolink.edu/etdc/view?acc_num=osu1180128001 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
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NDLTD
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| language |
English
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NDLTD
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| author |
DeMatteo, Matthew P.
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| spellingShingle |
DeMatteo, Matthew P.
Computational investigations of hydroxyl radical addition to aromatics and alkenes in the presence of solvent, conformational preferences of dendrimers, and theoretical studies of arabinofuranosides and aeptanosides
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| author_facet |
DeMatteo, Matthew P.
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| author_sort |
DeMatteo, Matthew P.
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| title |
Computational investigations of hydroxyl radical addition to aromatics and alkenes in the presence of solvent, conformational preferences of dendrimers, and theoretical studies of arabinofuranosides and aeptanosides
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| title_short |
Computational investigations of hydroxyl radical addition to aromatics and alkenes in the presence of solvent, conformational preferences of dendrimers, and theoretical studies of arabinofuranosides and aeptanosides
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| title_full |
Computational investigations of hydroxyl radical addition to aromatics and alkenes in the presence of solvent, conformational preferences of dendrimers, and theoretical studies of arabinofuranosides and aeptanosides
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| title_fullStr |
Computational investigations of hydroxyl radical addition to aromatics and alkenes in the presence of solvent, conformational preferences of dendrimers, and theoretical studies of arabinofuranosides and aeptanosides
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| title_full_unstemmed |
Computational investigations of hydroxyl radical addition to aromatics and alkenes in the presence of solvent, conformational preferences of dendrimers, and theoretical studies of arabinofuranosides and aeptanosides
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| title_sort |
computational investigations of hydroxyl radical addition to aromatics and alkenes in the presence of solvent, conformational preferences of dendrimers, and theoretical studies of arabinofuranosides and aeptanosides
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The Ohio State University / OhioLINK
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| publishDate |
2007
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| url |
http://rave.ohiolink.edu/etdc/view?acc_num=osu1180128001
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AT dematteomatthewp computationalinvestigationsofhydroxylradicaladditiontoaromaticsandalkenesinthepresenceofsolventconformationalpreferencesofdendrimersandtheoreticalstudiesofarabinofuranosidesandaeptanosides
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1719426859494539264
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