Transient two-dimensional spectroscopy with linear absorption corrections applied to temperature-jump two-dimensional infrared
Multidimensional spectroscopies provide increased spectral information but time resolution is often limited by the picosecond lifetimes of the transitions they probe. At the expense of additional complexity, transient multidimensional techniques extend the accessible timescales for studying nonequil...
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Optical Society of America
2012
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Online Access: | http://hdl.handle.net/1721.1/73929 |
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author | Jones, Kevin C. Ganim, Ziad Peng, Chunte Tokmakoff, Andrei |
author2 | Massachusetts Institute of Technology. Department of Chemistry |
author_facet | Massachusetts Institute of Technology. Department of Chemistry Jones, Kevin C. Ganim, Ziad Peng, Chunte Tokmakoff, Andrei |
author_sort | Jones, Kevin C. |
collection | MIT |
description | Multidimensional spectroscopies provide increased spectral information but time resolution is often limited by the picosecond lifetimes of the transitions they probe. At the expense of additional complexity, transient multidimensional techniques extend the accessible timescales for studying nonequilibrium chemical and biophysical phenomena. Transient temperature-jump (T-jump) experiments are particularly versatile, since they can be applied to any temperature-dependent change of state. We have developed a method to correct transient nonlinear techniques for distortions resulting from transient linear absorption of the probing pulses, distortions which can lead to false interpretations of the data. We apply these corrections in the collection of T-jump transient two dimensional infrared spectra for the peptides diglycine and the beta-hairpin peptide trpzip2. For diglycine, the T-jump induces changes in H-bonding, a response which is inherent to all aqueous systems. The trpzip2 results probe the hairpin unfolding kinetics and reveal two time scales: <10 ns increased flexibility and 1:1 mus beta-hairpin disordering. |
first_indexed | 2024-09-23T09:08:26Z |
format | Article |
id | mit-1721.1/73929 |
institution | Massachusetts Institute of Technology |
language | en_US |
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publishDate | 2012 |
publisher | Optical Society of America |
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spelling | mit-1721.1/739292022-09-30T13:42:06Z Transient two-dimensional spectroscopy with linear absorption corrections applied to temperature-jump two-dimensional infrared Jones, Kevin C. Ganim, Ziad Peng, Chunte Tokmakoff, Andrei Massachusetts Institute of Technology. Department of Chemistry Tokmakoff, Andrei Tokmakoff, Andrei Jones, Kevin C. Ganim, Ziad Peng, Chunte Multidimensional spectroscopies provide increased spectral information but time resolution is often limited by the picosecond lifetimes of the transitions they probe. At the expense of additional complexity, transient multidimensional techniques extend the accessible timescales for studying nonequilibrium chemical and biophysical phenomena. Transient temperature-jump (T-jump) experiments are particularly versatile, since they can be applied to any temperature-dependent change of state. We have developed a method to correct transient nonlinear techniques for distortions resulting from transient linear absorption of the probing pulses, distortions which can lead to false interpretations of the data. We apply these corrections in the collection of T-jump transient two dimensional infrared spectra for the peptides diglycine and the beta-hairpin peptide trpzip2. For diglycine, the T-jump induces changes in H-bonding, a response which is inherent to all aqueous systems. The trpzip2 results probe the hairpin unfolding kinetics and reveal two time scales: <10 ns increased flexibility and 1:1 mus beta-hairpin disordering. National Science Foundation (U.S.) (Grant CHE-0616575) National Science Foundation (U.S.) (Grant CHE-0911107) 2012-10-12T15:20:41Z 2012-10-12T15:20:41Z 2012-01 2011-09 Article http://purl.org/eprint/type/JournalArticle 0740-3224 1520-8540 http://hdl.handle.net/1721.1/73929 Jones, Kevin C. et al. “Transient Two-dimensional Spectroscopy with Linear Absorption Corrections Applied to Temperature-jump Two-dimensional Infrared.” Journal of the Optical Society of America B 29.1 (2011): 118. Web. en_US http://dx.doi.org/10.1364/JOSAB.29.000118 Journal of the Optical Society of America B Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf Optical Society of America Prof. Tokmakoff via Erja Kajosalo |
spellingShingle | Jones, Kevin C. Ganim, Ziad Peng, Chunte Tokmakoff, Andrei Transient two-dimensional spectroscopy with linear absorption corrections applied to temperature-jump two-dimensional infrared |
title | Transient two-dimensional spectroscopy with linear absorption corrections applied to temperature-jump two-dimensional infrared |
title_full | Transient two-dimensional spectroscopy with linear absorption corrections applied to temperature-jump two-dimensional infrared |
title_fullStr | Transient two-dimensional spectroscopy with linear absorption corrections applied to temperature-jump two-dimensional infrared |
title_full_unstemmed | Transient two-dimensional spectroscopy with linear absorption corrections applied to temperature-jump two-dimensional infrared |
title_short | Transient two-dimensional spectroscopy with linear absorption corrections applied to temperature-jump two-dimensional infrared |
title_sort | transient two dimensional spectroscopy with linear absorption corrections applied to temperature jump two dimensional infrared |
url | http://hdl.handle.net/1721.1/73929 |
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