13C Photo-CIDNP MAS NMR on the Reaction Center of Green Sulphur Bacterium at Two Different Magnetic Fields

Roy, Esha; Alia, A.; Gast, P.; Gorkom, Hans J. van; Jeschke, Gunnar; Matysik, Jörg

doi:10.1007/978-1-4020-6709-9_39

Cited by 4 publications

(3 citation statements)

References 14 publications

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“…Various photosynthetic RCs of plants (Alia et al, 2004;Diller et al, 2005;Diller et al, 2007;Janssen et al, 2018), algae (Janssen et al, 2010;Janssen et al, 2012), diatoms (Zill et al, 2017;Zill et al, 2019), purple bacteria (Prakash et al, 2007;Daviso et al, 2009b;Paul et al, 2019), heliobacteria (Thamarath et al, 2012b), green sulfur bacteria (Roy et al, 2008) as well as flavoproteins (Thamarath et al, 2010;Ding et al, 2019) have been analyzed with the photo-CIDNP MAS NMR method. Previously, the application of 13 C photo-CIDNP MAS NMR has been restricted to the unlabeled and isolated PSI complex due to difficulties in obtaining selective 13C labelling in plants.…”

Section: Discussion Open Accessmentioning

confidence: 99%

Analysis of the electronic asymmetry of the primary electron donor of photosystem I of Spirodela oligorrhiza by photo-CIDNP solid-state NMR

Janssen¹,

Eschenbach²,

Kurle³

et al. 2020

Preprint

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Abstract. The electron donor in photosystem I, the chlorophyll dimer P700, is studied by photo-CIDNP (photochemically induced dynamic nuclear polarization) MAS (magic-angle spinning) NMR on selectively 13C and uniformly 15N labeled PSI core preparations (PSI-100) obtained from the aquatic plant duckweed (Spirodela oligorrhiza). Light-induced signals originate from the isotope labelled nuclei of the cofactors involved in the spin-correlated radical pair forming upon light excitation. Signals are assigned to the two donor cofactors (Chl a and Chl a') and the two acceptor cofactors (both Chl a). Light induced signals originating from both donor and acceptor cofactors demonstrate that electron transfer occurs through both branches of cofactors in the pseudo-C2 symmetric Reaction Center (RC). The experimental results supported by quantum chemical calculations indicate that this functional symmetry occurs in PSI despite similarly sized chemical-shift differences between cofactors of PSI and the functionally asymmetric special-pair donor of the bacterial RC of Rhodobacter sphaeroides. This contributes to converging evidence that local differences in time-averaged electronic ground-state properties, over the donor are of little importance for functional symmetry breaking across photosynthetic RC species.

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Section: Discussion Open Accessmentioning

confidence: 99%

Analysis of the electronic asymmetry of the primary electron donor of photosystem I of Spirodela oligorrhiza by photo-CIDNP solid-state NMR

Janssen¹,

Eschenbach²,

Kurle³

et al. 2020

Preprint

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“…The effect was discovered by Zysmilich and McDermott in 1994 by performing 15 N magic-angle spinning (MAS) NMR studies on an isolated, frozen and quinone-blocked photosynthetic reaction center protein of the purple bacterium Rhodobacter sphaeroides 6 . Since its discovery, the effect has been observed in plenty of other photosynthetic reaction centers (RCs) of plants 7 – 10 , algae 11 , 12 , diatoms 13 , 14 , purple bacteria 15 – 18 , heliobacteria 19 , 20 , and green sulfur bacteria 21 . The spin-chemical machinery pumping nuclear polarization has been probed by field-dependent 22 , 23 , time-resolved 24 – 26 , and preparation-dependent 27 , 28 experiments, and is interpreted by the occurrence of up to three mechanisms running in parallel 22 , 24 , 29 : In the Differential Relaxation (DR) mechanism, also called “cyclic reactions mechanism”, the symmetry between both decay branches is broken due to a difference in relaxation caused by the paramagnetic molecular triplet state 30 – 32 .…”

Section: Introductionmentioning

confidence: 99%

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

Ding

Kiryutin

Zhao

et al. 2020

Sci Rep

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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.

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“…Various photosynthetic RCs of plants (Alia et al, 2004;Diller et al, 2005Diller et al, , 2007Janssen et al, 2018), algae (Janssen et al, 2010(Janssen et al, , 2012, diatoms (Zill et al, 2017(Zill et al, , 2019, purple bacteria (Prakash et al, 2007;Daviso et al, 2009b;Paul et al, 2019), heliobacteria (Thamarath et al, 2012b), green sulfur bacteria (Roy et al, 2008), and flavoproteins (Thamarath et al, 2010;Ding et al, 2019) have been analyzed with the photo-CIDNP MAS NMR method. Previously, the application of 13 C photo-CIDNP MAS NMR was restricted to the unlabeled and isolated PSI complex due to difficulties in obtaining selective 13 C labeling in plants.…”

Section: Introductionmentioning

confidence: 99%

Analysis of the electronic structure of the primary electron donor of photosystem I of Spirodela oligorrhiza by photochemically induced dynamic nuclear polarization (photo-CIDNP) solid-state nuclear magnetic resonance (NMR)

et al. 2020

Self Cite

View full text Add to dashboard Cite

Abstract. The electron donor in photosystem I (PSI), the chlorophyll dimer P700, is studied by photochemically induced dynamic nuclear polarization (photo-CIDNP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) on selectively 13C and uniformly 15N labeled PSI core preparations (PSI-100) obtained from the aquatic plant duckweed (Spirodela oligorrhiza). Light-induced signals originate from the isotope-labeled nuclei of the cofactors involved in the spin-correlated radical pair forming upon light excitation. Signals are assigned to the two donor cofactors (Chl a and Chl a') and the two acceptor cofactors (both Chl a). Light-induced signals originating from both donor and acceptor cofactors demonstrate that electron transfer occurs through both branches of cofactors in the pseudo-C2 symmetric reaction center (RC). The experimental results supported by quantum chemical calculations indicate that this functional symmetry occurs in PSI despite similarly sized chemical shift differences between the cofactors of PSI and the functionally asymmetric special pair donor of the bacterial RC of Rhodobacter sphaeroides. This contributes to converging evidence that local differences in time-averaged electronic ground-state properties, over the donor are of little importance for the functional symmetry breaking across photosynthetic RC species.

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13C Photo-CIDNP MAS NMR on the Reaction Center of Green Sulphur Bacterium at Two Different Magnetic Fields

Cited by 4 publications

References 14 publications

Analysis of the electronic asymmetry of the primary electron donor of photosystem I of <i>Spirodela oligorrhiza</i> by photo-CIDNP solid-state NMR

Analysis of the electronic asymmetry of the primary electron donor of photosystem I of <i>Spirodela oligorrhiza</i> by photo-CIDNP solid-state NMR

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

Analysis of the electronic structure of the primary electron donor of photosystem I of <i>Spirodela</i> <i>oligorrhiza</i> by photochemically induced dynamic nuclear polarization (photo-CIDNP) solid-state nuclear magnetic resonance (NMR)

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13C Photo-CIDNP MAS NMR on the Reaction Center of Green Sulphur Bacterium at Two Different Magnetic Fields

Cited by 4 publications

References 14 publications

Analysis of the electronic asymmetry of the primary electron donor of photosystem I of &lt;i&gt;Spirodela oligorrhiza&lt;/i&gt; by photo-CIDNP solid-state NMR

Analysis of the electronic asymmetry of the primary electron donor of photosystem I of &lt;i&gt;Spirodela oligorrhiza&lt;/i&gt; by photo-CIDNP solid-state NMR

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

Analysis of the electronic structure of the primary electron donor of photosystem I of &lt;i&gt;Spirodela&lt;/i&gt; &lt;i&gt;oligorrhiza&lt;/i&gt; by photochemically induced dynamic nuclear polarization (photo-CIDNP) solid-state nuclear magnetic resonance (NMR)

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Analysis of the electronic asymmetry of the primary electron donor of photosystem I of <i>Spirodela oligorrhiza</i> by photo-CIDNP solid-state NMR

Analysis of the electronic asymmetry of the primary electron donor of photosystem I of <i>Spirodela oligorrhiza</i> by photo-CIDNP solid-state NMR

Analysis of the electronic structure of the primary electron donor of photosystem I of <i>Spirodela</i> <i>oligorrhiza</i> by photochemically induced dynamic nuclear polarization (photo-CIDNP) solid-state nuclear magnetic resonance (NMR)