Physical Sciences and Mathematics Commons^™

Oxidative C–C And C–Heteroatom Reactivity Of High-Valent Nickel Complexes, Sofia Marie Smith

Arts & Sciences Electronic Theses and Dissertations

ABSTRACT OF THE DISSERTATION

Oxidative C–C and C–Heteroatom Reactivity of High-Valent Nickel Complexes

by

Sofia M. Smith

Doctor of Philosophy in Chemistry

Washington University in St. Louis, 2019

Professor Liviu M. Mirica, Chair

Professor Kevin D. Moeller, Co-Chair

Nickel catalysts are commonly used for cross-coupling reactions such as Negishi, Kumada and Suzuki couplings. While Ni(0), Ni(I), and Ni(II) intermediates are most relevant in these transformations, Ni(III) and Ni(IV) species have also been recently proposed to play a role in catalysis. The formation of C–C and C–heteroatom bonds plays a fundamental role in organic transformations, and today cross-coupling reactions are one …

Use Of Self-Assembled Monolayers To Tailor Surface Properties: From Lubrication To Neuronal Development, Natalie Ann Lafranzo

All Theses and Dissertations (ETDs)

The subsequent work describes advances in modifying the chemical properties of various substrates to tailor the surface properties for specific applications. This is achieved by making use of a molecular assembly known as self-assembled monolayers, or SAMs. SAMs are composed of tightly packed organic molecules that form a well-ordered structure on a substrate. Typically, the head group of the monomer is covalently anchored to the substrate, and monolayer order and self-assembly is achieved through van der Waals interactions between the long alkyl chains of the monomer's tail group. Monolayers containing head groups consisting of thiols, siloxanes, and phosphonates have been …

Discovery And Identification Of New Dna Photoproducts And Investigation Of The Redox Mechanism Of Human Apurinic/Apyrimidinic Endonuclease 1 (Hape1) Protein, Dian Su

All Theses and Dissertations (ETDs)

Exposure of cells to ultraviolet light results in the formation of DNA photoproducts, many of which have been linked to skin cancer. The majority of these photoproducts arise from a photoreaction between two pyrimidines. Irradiation of double stranded B form DNA under physiological conditions mainly produces adjacent dimers. Nonadjacent photodimers of both intrastrand and interstrand types are much rarer. Intrastrand-type nonadjacent dimers form when one or more nucleotides between two pyrimidines become extrahelical owing to the formation of single strand DNA or a slipped structure. This allows the two pyrimidines to photodimerize in a colinear arrangement, as if the intervening …