Relaxation Dynamics of Hydrated Thymine, Thymidine, and Thymidine Monophosphate Probed by Liquid Jet Time-Resolved Photoelectron Spectroscopy
- Award ID(s):
- 1663832
- PAR ID:
- 10299684
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry A
- Volume:
- 123
- Issue:
- 50
- ISSN:
- 1089-5639
- Page Range / eLocation ID:
- 10676 to 10684
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Irradiation of the major conformation of duplex DNA found in cells (B form) produces cyclobutane pyrimidine dimers (CPDs) from adjacent pyrimidines in a head-to-head orientation (syn) with the C5 substituents in a cis stereochemistry. These CPDs have crucial implications in skin cancer. Irradiation of G-quadruplexes and other non-B DNA conformations in vitro produces, however, CPDs between non-adjacent pyrimidines in nearby loops with syn and head-to-tail orientations (anti) with both cis and trans stereochemistry to yield a mixture of six possible isomers of the T=T dimer. This outcome is further complicated by formation of mixtures of non-adjacent CPDs of dC=dT, dT=dC, and dC=dC, and successful analysis depends on development of specific and sensitive methods. Towards meeting this need, we investigated whether ion mobility mass spectrometry (IMMS) and MS/MS can distinguish the cis,syn and trans-anti T=T CPDs. Ion mobility can afford base-line separation and give relative mobilities that are in accord with predicted cross sections. Complementing this ability to distinguish isomers is MS/MS collisional activation where fragmentation also distinguishes the two isomers and confirms conclusions drawn from ion mobility analysis. The observations offer early support that ion mobility and MS/MS can enable the distinction of DNA photoproduct isomers.more » « less
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