1068 VOLUME 16 NUMBER 10 OCTOBER 2009 NATURE STRUCTURAL & MOLECULAR BIOLOGY
ARTICLES
ATP is the universal energy currency in living cells, which constantly
powers many and diverse biochemical processes. Across all life
forms, ATP is mainly produced by the F
1
F
o
ATP synthase. The cyto-
plasmic F
1
catalytic domain (subunits α
3
β
3
γδε) converts ADP and
P
i
to ATP. A central and a peripheral stalk formed by subunits γε and
b
2
δ, respectively, links F
1
to the membrane-embedded F
o
domain,
which includes a reversible molecular rotor known as the c-ring. The
transmembrane proton- or sodium-motive force (pmf, smf) drives
ions to pass through the F
o
complex during ATP synthesis, inducing
the rotation of the c-ring. The central stalk enables the transmission
of this mechanical energy from the F
o
to the F
1
domain, by rotating
alongside the c-ring. The inherently asymmetric γ subunit causes
sequential conformational changes within each of the three catalytic
β subunits in the F
1
head. The three different conformations of the
β subunit endow the binding sites with three different nucleotide
affinities at any time point
1
. A complete revolution of the rotor thus
results in the synthesis of three ATP molecules. The structure of the
F
1
complex has been determined
2
and a wealth of biochemical and
biophysical data, including video microscopy
3
, support the rotational
ATP synthesis mechanism.
The F
o
motor consists in its simplest form of the oligomeric assem-
bly of c subunits that constitute the c-ring, and of two neighboring
subunits, namely a and b
2
. Each of the c subunits can reversibly bind
one H
+
(or Na
+
). Together with the γε complex, the c-ring rotor
of the enzyme spins against the stator subunits ab
2
α
3
β
3
δ (ref. 4).
The number of c subunits per ring has been found to vary between
10 (ref. 5) and 15 (ref. 6). The crystal structure of the rotor ring from
the Ilyobacter tartaricus Na
+
-dependent ATP synthase
7
revealed that
its c-ring comprises 11 subunits. Between each pair of adjacent sub-
units a Na
+
-binding site can be clearly identified, within a compact
coordination shell involving four amino acids and a buried struc-
tural water molecule
8
. It follows also from this observation that ion
exchange during enzyme activity is likely to be accompanied by con-
formational changes in the binding site, presumably in the context
of the a subunit interface
7
. A positively charged arginine in the stator
a subunit is believed to be crucial in this regard
9–11
.
To date, only a handful of species, including I. tartaricus, are
known to use Na
+
as a coupling ion for ATP synthesis
12–15
. The vast
majority of all living organisms use the pmf rather than the smf for
generating ATP. Yet our knowledge of the structure of complete
proton-translocating c subunit rotors has been limited to either
low-resolution X-ray data
5,16
or to models derived from solution NMR
measurements of monomeric c subunits in a chloroform-methanol-
water mixture
17
. Current models of H
+
translocation are based on the
notion that the c-ring forms a complex with the a subunit that creates
two access channels for protons from either side of the membrane
4
.
High-resolution structures to support or refute this model would be
of great interest. Therefore, we have determined the structure of the
F
o
rotor ring from the proton-translocating F
1
F
o
ATP synthase of
alkaliphilic cyanobacterium Spirulina platensis
18
strain C1.
RESULTS
The c
15
ring of S. platensis C1
The c-ring of S. platensis C1 is the largest known in the F-ATP syn-
thase family, and so far the only one that has been visually confirmed
to be a pentadecamer
6
. Bipyramidal crystals with a yellowish-golden
color were obtained. Spectroscopic analysis of isolated single crystals
revealed that they contained chlorophyll a (Chl) and carotenoids (CR,
mainly β-CR) in substoichiometric amounts (0.17 ± 0.03 moles of
Chl+CR per mole of c
15
). It is likely that traces of these photosynthetic
1
Department of Structural Biology,
2
Theoretical Molecular Biophysics Group and
3
Cluster of Excellence Macromolecular Complexes, Max-Planck Institute of
Biophysics, Frankfurt am Main, Germany. Correspondence should be addressed to T.M. (thomas.meier@biophys.mpg.de).
Received 28 May; accepted 21 August; published online 27 September 2009; doi:10.1038/nsmb.1678
High-resolution structure of the rotor ring of a
proton-dependent ATP synthase
Denys Pogoryelov
1
, Özkan Yildiz
1
, José D Faraldo-Gómez
2,3
& Thomas Meier
1,3
The crystal structure of the c-ring from the proton-coupled F
1
F
o
ATP synthase from Spirulina platensis is shown at
2.1-Å resolution. The ring includes 15 membrane-embedded c subunits forming an hourglass-shaped assembly. The structure
demonstrates that proton translocation across the membrane entails protonation of a conserved glutamate located near the
membrane center in the c subunit outer helix. The proton is locked in this site by a precise hydrogen bond network reminiscent
of that in Na
+
-dependent ATP synthases. However, the structure suggests that the different coordination chemistry of the bound
proton and the smaller curvature of the outer helix drastically enhance the selectivity of the H
+
site against other cations,
including H
3
O
+
. We propose a model for proton translocation whereby the c subunits remain in this proton-locked state when
facing the membrane lipid. Proton exchange would occur in a more hydrophilic and electrostatically distinct environment upon
contact with the a subunit interface.
© 2009 Nature America, Inc. All rights reserved.