Shakespeare - Hamlet - 1600 2D or not 2D??? Han-sur-Lesse 2009 - - - PowerPoint PPT Presentation

shakespeare hamlet 1600 2d or not 2d
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Shakespeare - Hamlet - 1600 2D or not 2D??? Han-sur-Lesse 2009 - - - PowerPoint PPT Presentation

Multi-dimensional spectroscopy Thomas la Cour Jansen Zernike Institute for Advanced Materials University of Groningen Shakespeare - Hamlet - 1600 2D or not 2D??? Han-sur-Lesse 2009 - Thomas la Cour Jansen Outline Why do multi-dimensional


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Multi-dimensional spectroscopy

Thomas la Cour Jansen

Zernike Institute for Advanced Materials University of Groningen

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Shakespeare - Hamlet - 1600 2D or not 2D???

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Outline

Why do multi-dimensional spectroscopy? Examples from the real world. Phenomena: Spectral diffusion Rotation Population transfer Structure: Peptides/Proteins Dynamics: Chemical exchange Water

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Motional narrowing

Time Frequency

cos(ωt) exp(−t2/τ 2)

cos(ωt) exp(−t/τ) Kubo, J. Math. Phys., 4:174 (1963)

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Spectral diffusion

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Rotational dynamics

Anisotropy:

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Peptides/Proteins

  • Amide CO stretch in every

peptide unit.

  • Coupling depends on the

conformation

  • Probe global structure and it’s

dynamics.

  • Require treatment of the local

environment

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Proteins/Peptides

Tokmakoff et al. J. Am. Chem. Soc. 126:7981 (2004)

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Proteins/Peptides

Dijkstra and Knoester, J. Phys. Chem. B 109:9787 (2005)

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Peptides/Proteins

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Peptides/Proteins

Jansen and Knoester, Biophys. J. 94:1818 (2008)

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Chemical Exchange

Structural rearrangement in Fe(CO)5

Harris et al. Science 319:1820 (2008)

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Chemical Exchange

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Chemical Exchange

Tokmakoff, Cho et al. J. Phys. Chem. B 109:11016 (2005)

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Three-dimensional infrared spectroscopy

  • S. Garrett-Roe and P. Hamm, Acc. Chem. Res. 42:1412 (2009)

CO2 dissolved in water

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Bulk water

Miller et al., Nature, 434:199 (2005) Woutersen and Bakker, Nature, 402:507 (1999)

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Han-sur-Lesse 2009 - Thomas la Cour Jansen

Electronic spectroscopy

Freming, Cho et al. Nature 434:625 (2005)