Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Tailored flavoproteins acting as light-driven spin machines pump nuclear hyperpolarization. / Ding, Yonghong; Kiryutin, Alexey S.; Zhao, Ziyue и др.
в: Scientific Reports, Том 10, № 1, 18658, 01.12.2020.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
}
TY - JOUR
T1 - Tailored flavoproteins acting as light-driven spin machines pump nuclear hyperpolarization
AU - Ding, Yonghong
AU - Kiryutin, Alexey S.
AU - Zhao, Ziyue
AU - Xu, Qian Zhao
AU - Zhao, Kai Hong
AU - Kurle, Patrick
AU - Bannister, Saskia
AU - Kottke, Tilman
AU - Sagdeev, Renad Z.
AU - Ivanov, Konstantin L.
AU - Yurkovskaya, Alexandra V.
AU - Matysik, Jörg
PY - 2020/12/1
Y1 - 2020/12/1
N2 - 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.
AB - 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.
KW - ELECTRON-PARAMAGNETIC-RESONANCE
KW - PHOTOSYNTHETIC REACTION CENTERS
KW - SOLID-STATE NMR
KW - CIDNP MAS NMR
KW - LOV2 DOMAIN
KW - MOLECULAR-MECHANISM
KW - CRYSTAL-STRUCTURES
KW - PHOTOSYSTEM-II
KW - RADICAL PAIRS
KW - POLARIZATION
UR - http://www.scopus.com/inward/record.url?scp=85094216212&partnerID=8YFLogxK
U2 - 10.1038/s41598-020-75627-z
DO - 10.1038/s41598-020-75627-z
M3 - Article
C2 - 33122681
AN - SCOPUS:85094216212
VL - 10
JO - Scientific Reports
JF - Scientific Reports
SN - 2045-2322
IS - 1
M1 - 18658
ER -
ID: 25851723