Abstract

We report on the UV-induced photochemistry of the biologically relevant sulfur-containing thiol group and the disulfide bond in solution using picosecond X-ray absorption spectroscopy at the sulfur K-edge. This study provides element-specific insight into the 267-nm induced photo-chemistry of two model compounds, an aromatic thiol and an aliphatic disulfide. Our transient spectra point to two primary and several secondary photoproducts, and our analysis may aid in understanding UV damage in proteins.

Highlights

  • Sulfur is of great importance in all fields of chemistry ranging from material science to biochemistry due to its electronic versatility and high natural abundance

  • We have investigated two model compounds in solution with time-resolved X-ray absorption spectroscopy (TRXAS) at the sulfur K-edge to establish the early timescale photochemistry of the thiol group and the disulfide bond and address long-standing open questions

  • We investigated an aromatic thiol (4-MTP, 1) which has previously been studied by the Bradforth and Ashfold groups using ultrafast optical, vibrational, and TKER spectroscopy [1,2,3]

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Summary

Introduction

Sulfur is of great importance in all fields of chemistry ranging from material science to biochemistry due to its electronic versatility and high natural abundance. We have investigated two model compounds in solution with TRXAS at the sulfur K-edge to establish the early timescale photochemistry of the thiol group and the disulfide bond and address long-standing open questions.

Results
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