X-ray spectroscopy of dilute metalloproteins with a transition-edge sensor

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Abstract/Contents

Abstract
Proteins are some of the most complex and finely tuned molecules found in chemistry, responsible for critical tasks such as oxygen delivery, photosynthesis, or nitrogen fixation in cells. Although proteins are mostly composed of hydrogen, carbon, nitrogen, and oxygen, the active site is often a metal. Hemoglobin, responsible for carrying oxygen to the cells, utilizes iron to bond to O2. In order to understand these proteins, it is critical to understand the behavior of the bonding electrons of the metal center. Core-level X-ray spectroscopy is a set of techniques that can yield deep insight into electronic structure. By exciting electrons to the unoccupied orbitals, we can probe the oxidation state, symmetry, and spin of a target element. However, for the most important proteins, the signal of interest is faint, and the samples prone to damage upon exposure to X-rays. New instruments are required that can collect data more quickly and with less noise, so that proteins and other challenging samples can be measured. In this thesis, I present the development of a new instrument for X-ray spectroscopy at the Stanford Synchrotron Radiation Lightsource (SSRL), based on superconducting transition-edge sensors (TES). First, I will describe the capabilities of this detector, and show that it fills a substantial gap in the experimental capabilities of present X-ray instruments. Then I will detail a series of X-ray spectroscopy experiments that I performed with the TES. Using this instrument, I measured both extremely dilute and extremely damage-sensitive samples. This experience allowed us to obtain the first undamaged soft X-ray spectrum of oxyhemoglobin. This spectrum has allowed us to constrain the electronic structure of hemoglobin. Finally, I describe future instruments that will make such measurements more routine.

Description

Type of resource text
Form electronic resource; remote; computer; online resource
Extent 1 online resource.
Place California
Place [Stanford, California]
Publisher [Stanford University]
Copyright date 2020; ©2020
Publication date 2020; 2020
Issuance monographic
Language English

Creators/Contributors

Author Titus, Charles James
Degree supervisor Irwin, Kent
Thesis advisor Irwin, Kent
Thesis advisor Church, Sarah Elizabeth
Thesis advisor Gaffney, Kelly
Degree committee member Church, Sarah Elizabeth
Degree committee member Gaffney, Kelly
Associated with Stanford University, Department of Physics

Subjects

Genre Theses
Genre Text

Bibliographic information

Statement of responsibility Charles James Titus.
Note Submitted to the Department of Physics.
Thesis Thesis Ph.D. Stanford University 2020.
Location electronic resource

Access conditions

Copyright
© 2020 by Charles James Titus
License
This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).

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