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Full-Text Articles in Physical Sciences and Mathematics
Theoretical Investigation Of The Co-C Bond Activation In Methylcobalamin And Adenosylcobalamin-Dependent Systems: Mechanistic Insights., Arghya Pratim Ghosh
Theoretical Investigation Of The Co-C Bond Activation In Methylcobalamin And Adenosylcobalamin-Dependent Systems: Mechanistic Insights., Arghya Pratim Ghosh
Electronic Theses and Dissertations
The vitamin B12 derivates, otherwise known as cobalamin (Cbl), are ubiquitous organometallic cofactors. The biologically active forms of Cbl, such as methylcobalamin (MeCbl) and adenosylcobalamin (AdoCbl), act as cofactors in different physiological reactions for both prokaryotes and eukaryotes. A crucial aspect of the Cbl-mediated systems is the activation of the organometallic Co-C bond that plays a critical role in its catalytic activity. One of the most remarkable features of this Co-C bond is its unusual activation in AdoCbl-dependent enzymatic reactions, where a trillion-fold rate acceleration of the Co-C bond cleavage is observed inside the enzyme compared to the isolated …
Investigations Into Effects Of Modified Prolines On Cis-Trans Isomers And Polypeptide Secondary Structure & Prediction Of Spectroscopic Properties Of Phthalonitriles For Characterization, Jeffrey Raab
Seton Hall University Dissertations and Theses (ETDs)
Proline is a unique amino acid because it is the only amino acid whose side chain wraps around and bonds back to the peptide backbone. This ring shape helps proteins form conformations which would otherwise not be possible such as hairpin turns. The cis/trans isomerization of the peptide bond between the preceding amino acid (Xaa) and Proline is important in determining how the secondary structure folds. Thus, being able to control the cis/trans isomerization is important when a specific conformation is desired; Proline can be modified to get make the equilibrium shift whichever way is needed. The modifications …
Investigation Of The C—Cn Bond Activation Of Fluorinated Benzonitriles With [Ni(Dmpe)] And Dft Benchmarking Study With [Ni(Dippe)], Dominique C. Gallegos
Investigation Of The C—Cn Bond Activation Of Fluorinated Benzonitriles With [Ni(Dmpe)] And Dft Benchmarking Study With [Ni(Dippe)], Dominique C. Gallegos
Theses and Dissertations
Carbon-carbon bond activation has become a rapidly growing area of research due to its extensive range of applications. Despite the significant progress that has been made in this field, the cleavage of kinetically inert and thermodynamically stable C—C σ-bonds under mild homogeneous conditions remains a challenge. The activation is primarily limited to systems in which either relief of strain or aromatization serves as a driving force. A notable exception to this is the oxidative addition of unstrained C—CN bonds of nitriles. In this study, we are looking at the effect of fluoro substituents. We hypothesized …
Extension Of Restricted Open-Shell Kohn-Sham Methodology To A Density-Functional Tight-Binding Framework, Reuben Szabo
Extension Of Restricted Open-Shell Kohn-Sham Methodology To A Density-Functional Tight-Binding Framework, Reuben Szabo
WWU Graduate School Collection
The restricted open-shell Kohn-Sham (ROKS) approach for singlet excited states provides some advantages over the ∆-self-consistent-field (∆SCF) method, requiring only a single SCF procedure and avoiding the problem of variational collapse. While ROKS is a powerful tool for DFT, its application to density functional tight-binding (DFTB) could offer significant improvements in time complexity when compared to DFT, enabling excited-state simulations of extended molecular systems on longer timescales than ROKS. In this work we discuss the implementation of an RO-DFTB approach in the DFTB+ package, as well as its suitability for the study of organic dyes and photoactive compounds. For benchmarking, …
Computational Study Of Radical Cation Rearrangements, Mi'kayla D. Word
Computational Study Of Radical Cation Rearrangements, Mi'kayla D. Word
Theses and Dissertations
A radical cation is a molecule that has one unpaired electron that holds a positive charge. The unpaired electron within a radical cation causes the molecule to be reactive. The high reactivity of these species allows for radical cations to be commonly studied experimentally using mass spectrometry and other multi-mass imaging techniques. However, these methods often cannot resolve the reaction mechanisms for these fast reactions. Specifically, radical cation rearrangement mechanisms are particularly unresolved within experiments. For this reason, radical cation rearrangements are computationally investigated to explain complex reaction pathways for processes to understand reactions leading to the initiation of detonation …