Okuno, Y. and S. Cavagnero, Effect of heavy atoms on photochemically induced dynamic nuclear polarization in liquids. Journal of Magnetic Resonance, 2018. 286: p. 172-187.
Given its short hyperpolarization time (~10-6 s) and mostly non-perturbative nature, photo-chemically induced dynamic nuclear polarization (photo-CIDNP) is a powerful tool for sensitivity enhancement in nuclear magnetic resonance. In this study, we explore the extent of 1H-detected 13C nuclear hyperpolarization that can be gained via photo-CIDNP in the presence of small-molecule additives containing a heavy atom. The underlying rationale for this methodology is the well-known external-heavy-atom (EHA) effect, which leads to significant enhancements in the intersystem-crossing rate of selected photosensitizer dyes from photoexcited singlet to triplet. We exploited the EHA effect upon addition of moderate amounts of halogen-atom-containing cosolutes. The resulting increase in the transient triplet-state population of the photo-CIDNP sensitizer fluorescein resulted in a significant increase in the nuclear hyperpolarization achievable via photo-CIDNP in liquids. We also explored the internal-heavy-atom (IHA) effect, which is mediated by halogen atoms covalently incorporated into the photosensitizer dye. Widely different outcomes were achieved in the case of EHA and IHA, with EHA being largely preferable in terms of net hyperpolarization.
[NMR paper] Photochemically Induced Dynamic Nuclear Polarization Observed by Solid-state NMR in a Uniformly (13)C-isotope Labeled Photosynthetic Reaction Center.
Photochemically Induced Dynamic Nuclear Polarization Observed by Solid-state NMR in a Uniformly (13)C-isotope Labeled Photosynthetic Reaction Center.
Related Articles Photochemically Induced Dynamic Nuclear Polarization Observed by Solid-state NMR in a Uniformly (13)C-isotope Labeled Photosynthetic Reaction Center.
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Authors: Paul S, Bode BE, Matysik J, Alia A
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Symmetry Break of Special Pair: Photochemically Induced Dynamic Nuclear Polarization NMR Confirms Control by Nonaromatic Substituents
Symmetry Break of Special Pair: Photochemically Induced Dynamic Nuclear Polarization NMR Confirms Control by Nonaromatic Substituents
Karthick Babu Sai Sankar Gupta, A. Alia, Huub J.M. de Groot and Jo?rg Matysik
http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/0/jacsat.ahead-of-print/ja402238w/aop/images/medium/ja-2013-02238w_0006.gif
Journal of the American Chemical Society
DOI: 10.1021/ja402238w
http://feeds.feedburner.com/~ff/acs/jacsat?d=yIl2AUoC8zA
http://feeds.feedburner.com/~r/acs/jacsat/~4/SoHEJYzuguk
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[NMR paper] Symmetry break of special pair: Photochemically induced dynamic nuclear polarization NMR confirms control by nonaromatic substituents.
Symmetry break of special pair: Photochemically induced dynamic nuclear polarization NMR confirms control by nonaromatic substituents.
Symmetry break of special pair: Photochemically induced dynamic nuclear polarization NMR confirms control by nonaromatic substituents.
J Am Chem Soc. 2013 Jun 6;
Authors: Sai Sankar Gupta KB, Alia A, de Groot HJ, Matysik J
Abstract
Despite the high structural symmetry of cofactor arrangement and protein environment, light-induced electron transfer in photosynthetic reaction centers (RCs) of the purple...
Effect of heavy atoms on photochemically induced dynamic nuclear polarization in liquids
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