Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 133, Issue 16, Pages 6440-6448Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja200849g
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Funding
- Air Force Office of Scientific Research [FA-9550-09-1-0139]
- U.S. National Science Foundation [CHE-091199]
- National Institute of Health [R01-GM068649]
- National Science Foundation [CHE-0239800]
- Yale University Faculty of Arts and Sciences High Performance Computing facility
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [911199] Funding Source: National Science Foundation
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We present infrared photodissociation spectra of two protonated peptides that are cooled in a similar to 10 K quadrupole ion trap and tagged with weakly bound H-2 molecules. Spectra are recorded over the range of 600-4300 cm(-1) using a table-top laser source, and are shown to result from one-photon absorption events. This arrangement is demonstrated to recover sharp (Delta v similar to 6 cm(-1)) transitions throughout the fingerprint region, despite the very high density of vibrational states in this energy range. The fundamentals associated with all of the signature N-H and C=O stretching bands are completely resolved. To address the site-specificity of the C=O stretches near 1800 cm(-1), we incorporated one C-13 into the tripeptide. The labeling affects only one line in the complex spectrum, indicating that each C=O oscillator contributes a single distinct band, effectively reporting its local chemical environment. For both peptides, analysis of the resulting band patterns indicates that only one isomeric form is generated upon cooling the ions initially at room temperature into the H-2 tagging regime.
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