Tailored flavoproteins acting as light-driven spin machines pump nuclear hyperpolarization

Tailored flavoproteins acting as light-driven spin machines pump nuclear hyperpolarization Full article

Journal

Scientific Reports
ISSN: 2045-2322

Output data

Year: 2020, Volume: 10, Number: 1, Article number : 18658, Pages count : 13 DOI: 10.1038/s41598-020-75627-z

Authors

Ding Yonghong ¹ , Kiryutin Alexey S. ^2,3 , Zhao Ziyue ¹ , Xu Qian-Zhao ^1,4 , Zhao Kai-Hong ⁴ , Kurle Patrick ¹ , Bannister Saskia ⁵ , Kottke Tilman ⁵ , Sagdeev Renad Z. ^2,3 , Ivanov Konstantin L. ^2,3 , Yurkovskaya Alexandra V. ^2,3 , Matysik Jörg ¹

Affiliations

1	Institut für Analytische Chemie, Universität Leipzig, Linnéstr. 3, 04103 Leipzig, Germany
2	International Tomography Center, Siberian Branch of Russian Academy of Sciences, Institutskaya, 3a, Novosibirsk 630090, Russia
3	Novosibirsk State University, Pirogova 1, Novosibirsk 630090, Russia
4	State Key Laboratory of Agricultural Microbiology, Huazhong Agricultural University, Wuhan 430070, China
5	Physikalische und Biophysikalische Chemie, Universität Bielefeld, Universitätsstr. 25, 33615 Bielefeld, Germany

The solid-state photo-chemically induced dynamic nuclear polarization (photo-CIDNP) effect generates non-Boltzmann nuclear spin magnetization, referred to as hyperpolarization, allowing for high gain of sensitivity in nuclear magnetic resonance (NMR). Well known to occur in photosynthetic reaction centers, the effect was also observed in a light-oxygen-voltage (LOV) domain of the blue-light receptor phototropin, in which the functional cysteine was removed to prevent photo-chemical reactions with the cofactor, a flavin mononucleotide (FMN). Upon illumination, the FMN abstracts an electron from a tryptophan to form a transient spin-correlated radical pair (SCRP) generating the photo-CIDNP effect. Here, we report on designed molecular spin-machines producing nuclear hyperpolarization upon illumination: a LOV domain of aureochrome1a from Phaeodactylum tricornutum, and a LOV domain named 4511 from Methylobacterium radiotolerans (Mr4511) which lacks an otherwise conserved tryptophan in its wild-type form. Insertion of the tryptophan at canonical and novel positions in Mr4511 yields photo-CIDNP effects observed by 15N and 1H liquid-state high-resolution NMR with a characteristic magnetic-field dependence indicating an involvement of anisotropic magnetic interactions and a slow-motion regime in the transient paramagnetic state. The heuristic biomimetic design opens new categories of experiments to analyze and apply the photo-CIDNP effect.

Ding Y. , Kiryutin A.S. , Zhao Z. , Xu Q-Z. , Zhao K-H. , Kurle P. , Bannister S. , Kottke T. , Sagdeev R.Z. , Ivanov K.L. , Yurkovskaya A.V. , Matysik J.
Tailored flavoproteins acting as light-driven spin machines pump nuclear hyperpolarization
Scientific Reports. 2020. V.10. N1. 18658 :1-13. DOI: 10.1038/s41598-020-75627-z WOS OpenAlex

Submitted:	Jul 6, 2020
Accepted:	Oct 15, 2020
Published online:	Oct 29, 2020

Web of science:	WOS:000587692300055
OpenAlex:	W3097202085

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OpenAlex	20