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The structure-function relation in Biology suggests that every biological molecule has evolved its structure to carry out a specific function. However, for many of these processes (such as those with catalytic activity) the structure of the biomolecule changes during the course of a reaction. Understanding the structure-function relation thus becomes

The structure-function relation in Biology suggests that every biological molecule has evolved its structure to carry out a specific function. However, for many of these processes (such as those with catalytic activity) the structure of the biomolecule changes during the course of a reaction. Understanding the structure-function relation thus becomes a question of understanding biomolecular dynamics that span a variety of timescales (from electronic rearrangements in the femtoseconds to side-chain alteration in the microseconds and more). This dissertation deals with the study of biomolecular dynamics in the ultrafast timescales (fs-ns) using electron and X-ray probes in both time and frequency domains.

It starts with establishing the limitations of traditional electron diffraction coupled with molecular replacement to study biomolecular structure and proceeds to suggest a pulsed electron source Hollow-Cone Transmission Electron Microscope as an alternative scheme to pursue ultrafast biomolecular imaging. In frequency domain, the use of Electron Energy Loss Spectroscopy as a tool to access ultrafast nuclear dynamics in the steady state, is detailed with the new monochromated NiON UltraSTEM and examples demonstrating this instrument’s capability are provided.

Ultrafast X-ray spectroscopy as a tool to elucidate biomolecular dynamics is presented in studying X-ray as a probe, with the study of the photolysis of Methylcobalamin using time-resolved laser pump – X-ray probe absorption spectroscopy. The analysis in comparison to prior literature as well as DFT based XAS simulations offer good agreement and understanding to the steady state spectra but are so far inadequate in explaining the time-resolved data. However, the trends in the absorption simulations for the transient intermediates show a strong anisotropic dependence on the axial ligation, which would define the direction for future studies on this material to achieve a solution.
ContributorsSubramanian, Ganesh (Author) / Spence, John (Thesis advisor) / Rez, Peter (Committee member) / Alford, Terry (Committee member) / Weierstall, Uwe (Committee member) / Kirian, Richard (Committee member) / Arizona State University (Publisher)
Created2016
Description

Polyketides are a wide ranging class of natural microbial products highly relevant to the pharmacological industry. As chemical synthesis of polyketides is quite challenging, significant effort has been made to understand the polyketide synthases (PKSs) responsible for their natural production. Native to Streptomyces, the aln biosynthetic gene cluster was recently

Polyketides are a wide ranging class of natural microbial products highly relevant to the pharmacological industry. As chemical synthesis of polyketides is quite challenging, significant effort has been made to understand the polyketide synthases (PKSs) responsible for their natural production. Native to Streptomyces, the aln biosynthetic gene cluster was recently characterized and encodes for an iterative type I polyketide synthase (iT1PKS). This iT1PKS produces both , and ,-double bond polyketides named allenomycins; however, the basis in which one bond is chosen over the other is not yet clear. The dehydratase domain, AlnB_DH, is thought to be solely responsible for catalyzing double bond formation. Elucidation of enzyme programming is the first step towards reprogramming AlnB_DH to produce novel industrially relevant products. The Nannenga lab has worked as collaborators to the Zhao lab at the University of Illinois at Urbana-Champaign to unravel AlnB_DH’s structure and mechanism. Here, mutant constructs of AlnB_DH are developed to elucidate enzyme structure and provide insight into active site machinery. The primary focus of this work is on the development of the mutant constructs themselves rather than the methods used for structural or mechanistic determination. Truncated constructs were successfully developed for crystallization and upon x-ray diffraction, a 2.45 Å resolution structure was determined. Point-mutated constructs were then developed based on structural insights, which identified H49, P58, and H62 as critical residues in active site machinery.

ContributorsBlackson, Wyatt (Author) / Nannenga, Brent (Thesis director) / Nielsen, David (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / School of Molecular Sciences (Contributor)
Created2023-05