Binding Sites of Quinones in Photosynthetic Bacterial Reaction Centers Investigated by Light-Induced FTIR Difference Spectroscopy: Symmetry of the Carbonyl Interactions and Close Equivalence of the QB Vibrations in Rhodopseudomonas sphaeroides and Rhodobacter viridis Probed by Isotope Labeling

Breton, Jacques; Boullais, Claude; Berger, G.; Mioskowski, Charles; Nabedryk, E.

doi:10.1021/bi00036a037

Cited by 96 publications

(181 citation statements)

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“…sphaeroides and Rp. viridis (35) is shown to be consistent with the different orientation of the methoxy groups proposed for the two sites (35). In the present study, the different conformation of the Ile M260 side chain of Rp.…”

Section: Discussionsupporting

confidence: 90%

“…viridis is different from that observed for Q A in Rb. sphaeroides and is more similar to the constrained conformation found for one methoxy group of ubiquinone in the Q B site of both species (35).…”

Section: Discussionsupporting

confidence: 72%

“…viridis. As discussed previously (35), the differential signal at 1,360͞1,367 cm Ϫ1 (Fig. 4) indicates a conformation of the methyl group attached to C 5 of the quinone ring closer to that of Q B than of Q A .…”

Section: Discussionsupporting

confidence: 68%

“…Furthermore, as previously noticed for reconstitution of ubiquinone in Rb. sphaeroides RCs (16,35), it was found that the isotopic labeling of the carbonyl oxygen atoms of the ubiquinone in the Rp. viridis RCs tends to equilibrate on a time scale of a few days with the 18 O͞ 16 O composition of the water used to prepare the final RC resuspension buffer.…”

Section: Resultsmentioning

confidence: 99%

“…viridis. Comparison with the spectra obtained for cytochrome photooxidation (34) or Q B photoreduction (35) in Rp. viridis shows no indication of contribution from these states, notably to the small additional band appearing at 1,559 cm Ϫ1 in the region of Amide II modes (Fig.…”

Section: Discussionmentioning

confidence: 99%

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Efficient exchange of the primary quinone acceptor Q _A in isolated reaction centers of Rhodopseudomonas viridis

Breton

1997

Proc. Natl. Acad. Sci. U.S.A.

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USA 88, 3491-3495], who were able to extract with detergents the firmly bound ubiquinone Q A from the RC of Rhodobacter sphaeroides and reconstitute the site with extraneous quinones. Up to now a comparable protocol was lacking for the RC of Rhodopseudomonas viridis despite the fact that its Q A site, which contains 2-methyl-3-nonaprenyl-1,4-naphthoquinone (menaquinone-9), has provided the best x-ray structure available. Fourier transform infrared difference spectroscopy, together with the use of isotopically labeled quinones, can probe the interaction of Q A with the RC protein. We establish that a simple incubation procedure of isolated RCs of Rp. viridis with an excess of extraneous quinone allows the menaquinone-9 in the Q A site to be almost quantitatively replaced either by vitamin K 1 , a close analogue of menaquinone-9, or by ubiquinone. To our knowledge, this is the first report of quinone exchange in bacterial photosynthesis. The Fourier transform infrared data on the quinone and semiquinone vibrations show a close similarity in the bonding interactions of vitamin K 1 with the protein at the Q A site of Rp. viridis and Rb. sphaeroides, whereas for ubiquinone these interactions are significantly different. The results are interpreted in terms of slightly inequivalent quinone-protein interactions by comparison with the crystallographic data available for the Q A site of the two RCs.In the reaction center (RC) of photosynthetic purple bacteria, two quinone molecules (Q A and Q B ) play an essential role in coupling the electron-and proton-transfer reactions leading to the conversion of light energy into chemical energy (for a review, see ref. 1). Following absorption of a photon, transmembrane electron transfer occurs between a dimer of bacteriochlorophyll molecules and Q A in Ϸ200 ps and then to Q B in 20-100 s. Q A acts as a one-electron acceptor only, whereas Q B plays the role of a two-electron gate and can accept two protons before leaving the RC.The crystal structure of the RCs of the two species of photosynthetic bacteria that have been investigated the most, namely Rhodobacter sphaeroides and Rhodopseudomonas viridis, has been solved in several laboratories (2-9). The best atomic resolution for which structural data on the Q A binding sites are presently available is 2.65 Å for the former species and 2.3 Å for the latter. For these two highly homologous proteins, the structural models reveal that the bonding interactions of Q A , which are 2-methyl-3-nonaprenyl-1,4-naphthoquinone (menaquinone-9) in Rp. viridis and 2,3-dimethoxy-5-methyl-6-decaprenyl-1,4-benzoquinone (ubiquinone-10) in Rb. sphaeroides, are relatively well defined (within the Ϯ0.25-to 0.5-Å precision on the position of the nonhydrogen atoms in the x-ray data), although the details vary among the various structures. Notably, the identity of some of the residues involved in hydrogen bonding and the relative strength of the hydrogen bonds to the two carbonyls of Q A are still not totally clear (2-9).The precise knowledge of the interac...

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Section: Discussionsupporting

confidence: 90%

Section: Discussionsupporting

confidence: 72%

Section: Discussionsupporting

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Efficient exchange of the primary quinone acceptor Q _A in isolated reaction centers of Rhodopseudomonas viridis

Breton

1997

Proc. Natl. Acad. Sci. U.S.A.

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Synthesis of [3-D3]-, [3-13C]-, and [1,2-13C2]Propynes and Their Use for the Synthesis of [5-D3-Methyl]-, [5-13C-Methyl]-, and [5,6-13C2-2,5-Cyclohexadienyl]ubiquinones 3

Boullais¹,

Rannou

Réveillère

et al. 2000

Eur. J. Org. Chem.

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Three selectively labeled propynes were prepared either with deuterium or carbon‐13 at position 3 and doubly labeled with carbon‐13 at positions 1 and 2 by an alkylation reaction from the corresponding labeled or unlabeled monolithio acetylides and dimethylsulfates. Their lithiation with nBuLi gave the corresponding propynyllithium derivatives which reacted with dimethyl squarate to afford the corresponding propargylic alcohols. These were thermolysed in p‐xylene to furnish [5‐D3‐methyl]‐, [5‐13C‐methyl]‐, and [5,6‐13C2‐2,5‐cyclohexadienyl]ubiquinone. The farnesyl side chain was introduced onto the labeled quinones with farnesyl trimethyltin under BF3 catalysis to provide [5‐D3‐methyl]‐, [5‐13C‐methyl]‐, and [5,6‐13C2‐2,5‐cyclohexadienyl]ubiquinone 3 (6c, 6b, 6a, respectively).

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Synthesis of [2,3-13C2-2,5-cyclohexadienyl] ubiquinone 3

Falcou¹,

Boullais²

1998

J Label Compd Radiopharm

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Diethyl [2,3‐13C2] succinate was prepared by the oxidative dimerization of ethyl lithio [2‐13C] acetate in the presence of CuBr2. Its dienolate was generated with lithium diisopropylamide (LDA) and methylated with CH3I to afford diethyl 2‐methyl [2,3‐13C2] succinate which by acid hydrolysis gave the corresponding labelled acid. Treatment of the latter with SOCl2 provided 2‐methyl [2,3‐13C2] succinic anhydride. This anhydride upon treatment with Et3N, ZnCl2 and trimethylchlorosilane in acetonitrile afforded 2,5‐bis (trimethylsilyloxy)‐3‐methyl [3,4 13C2] furan which was subjected to a Diels Alder reaction with trichloroethylene giving rise to 2,3‐dichloro‐5‐methyl [5,6‐13C2] 1,4‐benzoquinone which, in turn, was transformed by a known procedure to [2,3‐13C2‐2,5‐cyclohexadienyl] ubiquinone 3. © 1998 John Wiley & Sons, Ltd.

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Binding Sites of Quinones in Photosynthetic Bacterial Reaction Centers Investigated by Light-Induced FTIR Difference Spectroscopy: Symmetry of the Carbonyl Interactions and Close Equivalence of the QB Vibrations in Rhodopseudomonas sphaeroides and Rhodobacter viridis Probed by Isotope Labeling

Cited by 96 publications

References 35 publications

Efficient exchange of the primary quinone acceptor Q _A in isolated reaction centers of Rhodopseudomonas viridis

Efficient exchange of the primary quinone acceptor Q _A in isolated reaction centers of Rhodopseudomonas viridis

Synthesis of [3-D3]-, [3-13C]-, and [1,2-13C2]Propynes and Their Use for the Synthesis of [5-D3-Methyl]-, [5-13C-Methyl]-, and [5,6-13C2-2,5-Cyclohexadienyl]ubiquinones 3

Synthesis of [2,3-13C2-2,5-cyclohexadienyl] ubiquinone 3

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Binding Sites of Quinones in Photosynthetic Bacterial Reaction Centers Investigated by Light-Induced FTIR Difference Spectroscopy: Symmetry of the Carbonyl Interactions and Close Equivalence of the QB Vibrations in Rhodopseudomonas sphaeroides and Rhodobacter viridis Probed by Isotope Labeling

Cited by 96 publications

References 35 publications

Efficient exchange of the primary quinone acceptor Q A in isolated reaction centers of Rhodopseudomonas viridis

Efficient exchange of the primary quinone acceptor Q A in isolated reaction centers of Rhodopseudomonas viridis

Synthesis of [3-D3]-, [3-13C]-, and [1,2-13C2]Propynes and Their Use for the Synthesis of [5-D3-Methyl]-, [5-13C-Methyl]-, and [5,6-13C2-2,5-Cyclohexadienyl]ubiquinones 3

Synthesis of [2,3-13C2-2,5-cyclohexadienyl] ubiquinone 3

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Efficient exchange of the primary quinone acceptor Q _A in isolated reaction centers of Rhodopseudomonas viridis

Efficient exchange of the primary quinone acceptor Q _A in isolated reaction centers of Rhodopseudomonas viridis