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RESEARCH ARTICLES
             sequences in order to identify intermediate sequences               that sequences in the non-IGHV1-2*02 cluster are likely              NIH; by grants from the International AIDS Vaccine
             related to mature neutralizing antibodies. We therefore             misassigned and actually of IGHV1-2*02 origin.                       Initiative’s Neutralizing Antibody Consortium; and by
             used well-established maximum likelihood phylogenetic           45. M. Pancera et al., J. Virol. 84, 8098 (2010).                        the Center for HIV AIDS Vaccine Immunology grant AI
             algorithms to analyze antibody sequence data and to             46. E. A. Kabat, T. T. Wu, K. S. Gottesman, C. Foeller,                  5U19 AI 067854-06 from NIH. Use of sector 22
             build rooted trees of antibody sequences that are derived           Sequences of Proteins of Immunological Interest, 5th                 (Southeast Region Collaborative Access Team) at the
             from a common ancestor (i.e., same VH-germline gene).               Edition (U.S. Department of Health and Human Services,               Advanced Photon Source was supported by the U.S.
       38.   Several of the non-neutralizing heavy-chain sequences shown         Washington, DC, 1991).                                               Department of Energy, Basic Energy Sciences, Office
             in the CDR H3 distribution of Fig. 6 are likely the result of   47. E. Krissinel, K. Henrick, J. Mol. Biol. 372, 774 (2007).             of Science, under contract W-31-109-Eng-38. Structure
             PCR template switching. The single heavy chain depicted in      Acknowledgments: X.W., T.Z., J. Z., G.J.N., M.R., L.S., P.D.K.,          factors and coordinates for antibodies VRC03 and
             the CDR H3 class 1 contour plot contains a unique CDR H3            and J.R.M. designed research; B.Z., C.W., X.C., M.L., K.M.,          VRC-PG04 in complex with HIV-1 gp120 have been
             sequence (fig. S15a), but with a V gene that displays high          S.O.D., S.P., S.D.S., W.S., L.W., Y.Y., Z.Y.Y., Z.Y., NISC,          deposited with the Protein Data Bank under accession
             similarity to class 3 sequences (table S23). The same               and J.M. performed experiments; X.W. isolated and                    codes 3SE8 and 3SE9, respectively. We have also
             observation occurs for the two sequences in the class 2             characterized VRC01-like antibodies by RSC3 probe,                   deposited deep sequencing data for donors 45 and 74
             contour plot. Also, the highly divergent (and outlier)              devised and prepared samples for 454 pyrosequencing,                 (Appendices 1 to 4) used in this study to National
             sequence on the CDR H3 class 9 distribution plot contains the       and assisted with functional characterization; T.Z.                  Center for Biotechnology Information Short Reads
             same CDR H3 as the other 140 class 9 sequences, but with a          determined and analyzed structures of VRC-PG04 and                   Archives (SRA) under accession no. SRP006992.
             V gene that closely matches sequences found in class 8              VRC03 with gp120 and assisted with functional                        Information deposited with GenBank includes the
             (table S23b). Because only a few of more than 1500 unique           characterization; J.Z. devised and carried out                       heavy- and light-chain variable region sequences of
             sequences identified by CDR H3 analysis showed dissimilar           computational bioinformatics on the antibodyome; M.B.,               probe-identified antibodies VRC-PG04 and VRC-PG04b
             V genes, and all of these appeared as single or double              J.A.C, S.H.K, N.E.S., and B.F.H. contributed donor 0219              (accession nos. JN159464 to JN159467), VRC-CH30,
             outliers, template switching can occur but appears to be            materials; M.S., D.R.B., and W.C.K contributed Protocol G            VRC-CH31, and VRC-CH32 (JN159434 to JN159439),
             rare. This rarity is also suggested by an analysis of 606,047       materials, including donor 74; N.D.R. and M.C.                       and VRC-CH33 and VRC-CH34 (JN159470 to 159473),
             non-IGHV1-2*02 from donor 74 for sequences with the CDR             contributed donor 45 materials; X.W., T.Z., J.Z, I.G.,               as well as the sequences of genomically identified
             H3s identified in Fig. 6B, which finds less than 100                N.S.L., Z.Z., L.S., P.D.K., and J.R.M. analyzed the data;            neutralizers: 24 heavy chains from donor 74, 2008
             sequences, of which the majority corresponds to the likely          and L.S., G.J.N., P.D.K., and J.R.M. wrote the paper,                (JN159440 to JN159463), two heavy chains from
             misassigned cluster in the non-IGHV1-2*02 sequence of               on which all authors commented. We thank J. Almeida                  donor 45, 2008 (JN159474 and JN159475), two light
             donor 74 in Fig. 4, as described in (44).                           and D. Douek for protocols of PBMC cDNA preparation                  chains from donor 45, 2001 (JN159468 and JN159469),
       39.   A similar accumulation of somatic mutations was shown               and for helpful discussions; J. Stuckey for assistance               and 1561 unique sequences associated with neutralizing
             (45) with the broadly neutralizing antibodies PG9 and               with figures; T. Wrin for sequence information on the                CDR H3 distributions with at least one low divergent
             PG16 to correlate with an increase in neutralization                donor 74 virus; J. Binley, D. Montefiori, L. Morris, and             member shown in Fig. 6B and fig. S16 (JN157873 to
             breadth and potency.                                                G. Tomaras for donor 0219 serum characterization; and                JN159433).
       40.   D. Nemazee, M. Weigert, J. Exp. Med. 191, 1813 (2000).              all of the IAVI Protocol G team members and the Protocol
       41.   E. Edry, D. Melamed, J. Immunol. 173, 4265 (2004).                  G clinical investigators, specifically, G. Miiro, A. Pozniak,   Supporting Online Material
       42.   J. Glanville et al., Proc. Natl. Acad. Sci. U.S.A. 106,             D. McPhee, O. Manigart, E. Karita, A. Inwoley, W. Jaoko,        www.sciencemag.org/cgi/content/full/science.1207532/DC1
             20216 (2009).                                                       J. DeHovitz, L.-G. Bekker, P. Pitisuttithum, R. Paris,          Materials and Methods
       43.   H. Zhou, Y. Zhou, Protein Sci. 11, 2714 (2002).                     J. Serwanga, and S. Allen. We also thank H. Sato,               Figs. S1 to S20
       44.   The peak at ~25% IGHV1-2*02 divergence and 88%                      I. Wilson, and members of the Structural Biology Section        Tables S1 to S23
             identity was also seen in the sequence plot for sequences           and Structural Bioinformatics Core, Vaccine Research            References (48–82)
             of non-IGHV1-2*02 origin. Cross-donor and CDR H3                    Center, for discussions or comments on the manuscript.          Appendices 1 to 4
             analyses shows that these putative non-IGHV1-2*02–                  Support for this work was provided by the Intramural
             derived sequences segregate with VRC01-like antibodies              Research Program of the Vaccine Research Center,                26 April 2011; accepted 15 July 2011
             in dendrograms and have CDR H3s that are identical to               National Institute of Allergy and Infectious Diseases,          Published online 11 August 2011;
             confirmed VRC01-like antibodies (fig. S16), indicating              and the National Human Genome Research Institute,               10.1126/science.1207532




       Kepler-16: A Transiting                                                                                                                   planets based on the timing of stellar eclipses
                                                                                                                                                 [see, e.g., (1–3)], but in no previous case have
                                                                                                                                                 astronomers obtained direct evidence of a cir-
       Circumbinary Planet                                                                                                                       cumbinary planet by observing a planetary transit
                                                                                                                                                 (a miniature eclipse as the planet passes directly
       Laurance R. Doyle,1* Joshua A. Carter,2 Daniel C. Fabrycky,3 Robert W. Slawson,1                                                          in front of a star). Detection of a transit greatly
       Steve B. Howell,4 Joshua N. Winn,5 Jerome A. Orosz,6 Andrej Prˇsa,7 William F. Welsh,6                                                    enhances confidence in the reality of the planet
       Samuel N. Quinn,8 David Latham,8 Guillermo Torres,8 Lars A. Buchhave,9,19 Geoffrey W. Marcy,11                                            and provides unusually precise knowledge of
       Jonathan J. Fortney,12 Avi Shporer,13,14 Eric B. Ford,15 Jack J. Lissauer,4 Darin Ragozzine,2                                             its mass, radius, and orbital parameters (4).
       Michael Rucker,16 Natalie Batalha,16 Jon M. Jenkins,1 William J. Borucki,4 David Koch,4                                                       Here we present the detection of a transiting
       Christopher K. Middour,17 Jennifer R. Hall,17 Sean McCauliff,17 Michael N. Fanelli,18                                                     circumbinary planet around a binary star sys-
       Elisa V. Quintana,1 Matthew J. Holman,8 Douglas A. Caldwell,1 Martin Still,18 Robert P. Stefanik,8                                        tem based on photometric data from the NASA
       Warren R. Brown,8 Gilbert A. Esquerdo,8 Sumin Tang,8 Gabor Furesz,8,10 John C. Geary,8                                                    Kepler spacecraft. Kepler is a 0.95-m space tele-
       Perry Berlind,20 Michael L. Calkins,20 Donald R. Short,21 Jason H. Steffen,22 Dimitar Sasselov,8                                          scope that monitors the optical brightness of
       Edward W. Dunham,23 William D. Cochran,24 Alan Boss,25 Michael R. Haas,4                                                                  about 155,000 stars within a field encompassing
       Derek Buzasi,26 Debra Fischer27                                                                                                           105 square degrees in the constellations Cygnus
                                                                                                                                                 and Lyra (5–8).
       We report the detection of a planet whose orbit surrounds a pair of low-mass stars. Data from the                                             Star number 12644769 from the Kepler Input
       Kepler spacecraft reveal transits of the planet across both stars, in addition to the mutual eclipses                                     Catalog was identified as an eclipsing binary
       of the stars, giving precise constraints on the absolute dimensions of all three bodies. The planet is                                    with a 41-day period, from the detection of its
       comparable to Saturn in mass and size and is on a nearly circular 229-day orbit around its two                                            mutual eclipses (9). Eclipses occur because the
       parent stars. The eclipsing stars are 20 and 69% as massive as the Sun and have an eccentric 41-day                                       orbital plane of the stars is oriented nearly edge-
       orbit. The motions of all three bodies are confined to within 0.5° of a single plane, suggesting that                                     on as viewed from Earth. During primary eclipses,
       the planet formed within a circumbinary disk.                                                                                             the larger star, denoted “A,” is partially eclipsed
                                                                                                                                                 by the smaller star “B,” and the system flux de-
                   planet with two suns is a familiar con-                   binary planets—those that orbit around both mem-                    clines by about 13%. During secondary eclipses,

       A           cept from science fiction. However, the
                   evidence for the existence of circum-
                                                                             bers of a stellar binary—has been limited. A few
                                                                             good cases have been made for circumbinary
                                                                                                                                                 B is completely occulted by A, and the resulting
                                                                                                                                                 drop in flux is only about 1.6% because B is rel-


1602                                                     16 SEPTEMBER 2011                  VOL 333           SCIENCE            www.sciencemag.org
RESEARCH ARTICLES

                 1.00


                 0.95


                 0.90


                 0.85
 Relative flux




                                      0                 100                            200                         300                            400                          500

                                                       1.005                                           1.005
                        Star B eclipses Star A                 Star A occults Star B                            Planet b transits Star A                 1.0002    Planet b transits Star B

                 1.00                                  1.000                                           1.000                                             1.0000
                                                                                                                                                         0.9998
                                                       0.995                                           0.995
                 0.95                                                                                                                                    0.9996
                                                                                                       0.990                                             0.9994
                                                       0.990
                 0.90
                                                                                                       0.985                                             0.9992
                                                       0.985                                                                                             0.9990
                 0.85                                                                                  0.980
                          170.9 171.0 171.1 171.2                 273.1 273.2 273.3 273.4 273.5                425.0 425.1 425.2 425.3 425.4                      −18.6 −18.5 −18.4 −18.3 −18.2

                                                                                             Time [BJD − 2,455,000]
Fig. 1. Photometry of Kepler-16. (Top) Photometric time series from the                               in Kepler observing, data are missing from one primary eclipse at BJD
Kepler spacecraft of star system Kepler-16 (KIC 12644769, KOI-1611, 2MASS                             2,455,089, and one secondary eclipse at BJD 2,455,232. Note in particular
19161817+5145267, Kepler magnitude = 11.762). Each data point is the                                  the shifting order of the tertiary (green) and quaternary (red) eclipses: The first
relative brightness at a given time [in barycentric Julian days (BJDs)]. The 1%                       and third pairs begin with the tertiary eclipse, whereas the second pair leads
variations on ~10-day time scales are probably due to starspots carried around                        with the quaternary eclipse. This is because the stars’ orbital motion places
by stellar rotation (a periodogram gives a rotation period of about 35 days). The                     them in different positions at each inferior conjunction of the planet. The stars
sharp dips are eclipses, appearing as vertical lines in this 600-day plot. They are                   silhouette the planet as they move behind it. (Bottom) Closeups (narrower
identified as primary (B eclipses A, blue), secondary (A occults B, yellow), tertiary                 scales in time and relative flux) of representative examples of each type of
(b transits A, green), and quaternary (b transits B, red). Because of interruptions                   eclipse, along with the best-fitting model (gray), with parameters from Table 1.

atively small and has a lower surface brightness                        During tertiary eclipses, the total light declines             to be either a planet or a third star with grazing
(Fig. 1).                                                           by 1.7%. Because this is larger than the 1.6% de-                  eclipses. Decisive evidence that it is a planet came
    This target drew further attention when three                   cline during secondary eclipses (when star B is                    from investigation of the timing of the stellar
additional drops in brightness were detected out-                   completely concealed), the tertiary eclipses had                   eclipses. The primary and secondary eclipse times
side of the primary and secondary eclipses, sepa-                   to be transits of the third body across star A. This               were found to depart from strict periodicity by
rated by intervals of 230.3 and 221.5 days (10).                    interpretation was supported by the subsequent                     deviations on the order of 1 min. A third body
These tertiary eclipses could not be attributed to                  detection of weaker 0.1% quaternary eclipses,                      causes timing variations in two ways. First, there
the stars alone, and indicated the presence of a                    which were consistent with the passage of the                      is a light travel-time effect: The third body in-
third body. The differing intervals between the                     third body across star B. The observed time of                     duces a periodic motion of the center of mass
tertiary eclipses are simply explained if the third                 this quaternary eclipse was used to predict two                    of the stellar binary, causing periodic variations
body is in a circumbinary orbit, because stars A                    other times of quaternary eclipses that should                     in the time required for the eclipse signals to
and B would be in different positions in their                      have been present in the data, and these two                       reach Earth (13, 14). Second, there is a dynamical
mutual orbit each time the third body moved in                      events were subsequently detected (Fig. 1).                        effect: The gravitational attraction of each star
front of them (11, 12). In contrast, there would be                     Because the third body covers only 1.7% of                     to the third body varies with time because of
no ready explanation for the shifting times of the                  the area of star A, which was determined to be                     the changing positions of all three bodies, causing
tertiary eclipses if they were produced by a back-                  smaller than the Sun on the basis of its broadband                 perturbations in the stars’ orbital parameters and
ground star system or some other unrelated event.                   colors (10), the circumbinary body was suspected                   therefore in the eclipse times (15, 16). Both effects


1                                                                                                                                          19
  Carl Sagan Center for the Study of Life in the Universe, SETI      University of Copenhagen, DK-2100 Copenhagen, Denmark.                  Konkoly Observatory, Konkoly ut 15-17, Budapest, H-1121,
                                                                     10
Institute, 189 Bernardo Avenue, Mountain View, CA 94043,               Centre for Star and Planet Formation, Natural History               Hungary. 20Fred Lawrence Whipple Observatory, Smithsonian
USA. 2Hubble Fellow, Harvard-Smithsonian Center for Astro-           Museum of Denmark, University of Copenhagen, DK-1350                  Astrophysical Observatory, Amado, AZ 85645, USA. 21De-
physics, 60 Garden Street, Cambridge, MA 02138, USA.                 Copenhagen, Denmark. 11Department of Astronomy, Uni-                  partment of Mathematics, San Diego State University, 5500
3
 Hubble Fellow, Department of Astronomy and Astrophysics,            versity of California, Berkeley, CA 94720, USA. 12Department          Campanile Drive, San Diego, CA 92182, USA. 22Fermilab
University of California, Santa Cruz, CA 95064, USA. 4NASA           of Astronomy and Astrophysics, University of California, Santa        Center for Particle Astrophysics, Post Office Box 500, Batavia,
Ames Research Center, Moffett Field, CA 94035, USA.                  Cruz, Santa Cruz, CA 95064, USA. 13Las Cumbres Observatory            IL 60510, USA. 23Lowell Observatory, Flagstaff, AZ 86001,
5
 Department of Physics and Kavli Institute for Astrophysics          Global Telescope Network, 6740 Cortona Drive, Suite 102,              USA. 24McDonald Observatory, University of Texas at Austin,
and Space Research, Massachusetts Institute of Technology,           Santa Barbara, CA 93117, USA. 14Department of Physics,                Austin, TX 78712, USA. 25Carnegie Institute of Washington,
77 Massachusetts Avenue, Cambridge, MA 02139, USA. 6De-              Broida Hall, University of California, Santa Barbara, CA              Washington, DC 20015, USA. 26Eureka Scientific, 2452
partment of Astronomy, San Diego State University, 5500              93106, USA. 15211 Bryant Space Science Center, Gainesville, FL        Delmer Street, Suite 100, Oakland, CA 94602, USA. 27De-
Campanile Drive, San Diego, CA 92182–1221, USA. 7Depart-             32611–2055, USA. 16Department of Physics, San Jose State              partment of Astronomy, Yale University, New Haven, CT
ment of Astronomy and Astrophysics, Villanova University,            University, San Jose, CA 95192, USA. 17Orbital Sciences               06511, USA.
800 East Lancaster Avenue, Villanova, PA 19085, USA.                 Corporation/NASA Ames Research Center, Moffett Field, CA
8
  Harvard-Smithsonian Center for Astrophysics, 60 Garden             94035, USA. 18Bay Area Environmental Research Institute/              *To whom correspondence should be addressed. E-mail:
Street, Cambridge, MA 02138, USA. 9Niels Bohr Institute,             NASA Ames Research Center, Moffett Field, CA 94035, USA.              ldoyle@seti.org


                                                    www.sciencemag.org              SCIENCE           VOL 333            16 SEPTEMBER 2011                                                                   1603
RESEARCH ARTICLES
                                                                                                                                                             depend on the mass of the third body. Therefore,
                                                                                                                                                             we could constrain the mass of the third body
       Fig. 2. Radial-velocity var-           20
                                                                                                                                                             by fitting the eclipse data with a numerical model
       iations and perturbations of                                                                 Star A




                                                Radial Velocity [km s−1]
                                                0                                                   Star B                                                   of three-body gravitational interactions. This mod-
       eclipse times. (Top) Observed
                                                                                                                                                             el, described below in detail, showed that the
       radial-velocity variations of         −20
                                                                                                                                                             third body must be less massive than Jupiter.
       star A as a function of orbital
       phase, based on observations
                                             −40                                                                                                                  Hence, based on the depth of the tertiary
       with the spectrograph of the          −60
                                                                                                                                                             eclipses and on the magnitude of the eclipse
       Tillinghast 1.5-m telescope                                                                                                                           timing variations, the third body was shown to be
                                             −80                                                                                                             a transiting circumbinary planet. The model was
       at the Fred Lawrence Whipple           60
                                                                                                                                                             based on the premise that the three bodies move
                                        Residuals
       Observatory on Mount Hopkins,          40
                                         [m s−1]
                                              20
       Arizona (SOM). Solid dots are            0                                                                                                            under the influence of mutual Newtonian grav-
                                             −20
       the data, and the smooth              −40                                                                                                             itational forces. For this purpose, we modified the
                                             −60
       curve is the best-fitting mod-           0.0             0.2           0.4           0.6       0.8       1.0                                          computer code that was used to model the tri-
       el. Although only the light                                              Orbital Phase                                                                ple star system KOI-126 (17) [supporting online
                                          Deviations of Eclipse Times from Constant−Period Model [min]




       from star A could be detected          1.5                                                                                                            material (SOM)]. The leading-order relativistic
       in the spectra, the model for               Star B eclipses Star A
                                              1.0                                                                                                            correction to the force law was included, although
       star B’s motion is also shown.                                                                                                                        it proved to be unimportant. The bodies’ positions
                                              0.5
       Residuals from the best mod-                                                                                                                          were calculated with a Bulirsch-Stoer algorithm
       el fits are given just below the       0.0
                                                                                                                                                             and corrected for the finite propagation speed
       radial velocity curve. (Middle       −0.5                                                                                                             of light across the system before being compared
       and Bottom) Deviations of            −1.0                                                                                                             to the data. The loss of light due to eclipses was
       the stellar eclipse times from                                                                                                                        calculated by assuming the disks of stars A and B
                                            −1.5
       strict periodicity, as observed          2                                                                                                            to be circular, with a quadratic law describing
       (colored dots) and modeled                  Star A occults Star B
                                                                                                                                                             the decline in intensity toward the limb (18). We
       (open diamonds). As noted                1
                                                                                                                                                             also allowed for an additional time-independent
       previously, one primary eclipse
                                                                                                                                                             source of light to account for any possible back-
       and one secondary eclipse                0
       were missed. The deviations                                                                                                                           ground stars within the Kepler photometric ap-
       are on the order of 1 min for          −1                                                                                                             erture. In practice, this parameter was found to
       both primary and secondary                                                                                                                            be consistent with zero and bounded to be less
                                              −2                                                                                                             than 1.3% of the total light of the system (19).
       stellar eclipses. In the mod-           −100           0          100         200        300      400    500
       el, the effects of dynamical                                        Time [BJD − 2,455,000]                                                                 We fitted all of the photometric data within
       perturbations are dominant,                                                                                                                           6 hours of any eclipse or transit. Before fitting, a
       with light-time variations contributing only at the level of 1 s. If the third body were more massive than a                                          linear trend was removed from each segment, to
       planet (>13 jovian masses), the timing variations would have exceeded 30 min. This would have been off                                                correct for the slow starspot-induced variations
       the scale of the diagram shown here, and in contradiction with the observations.                                                                      evident in Fig. 1. A successful model had to be

       Fig. 3. Scale diagram of the Kepler-16 system. The current orbits of the
       Kepler-16 system are shown as gray curves. The sizes of the bodies
       (including the Sun, Jupiter, and Saturn) are in the correct proportions to




                                                                                                                                                                                                  To Earth
       one another, but they are on a scale 20 times larger than the orbital                                                                                 b
       distance scale. The binary and circumbinary planet orbital planes lie
       within 0.4° of each other (Table 1), so the orbits are essentially flat, as
       drawn. The planet’s orbital eccentricity is nearly zero, whereas the
       orbital eccentricity of the binary star system is presently about 0.16. A
       “+” symbol marks the center of mass of all three bodies.



                                                                                                                                                                       B
                                                                                                                                                         A
                                                                                                                                                                                                 Sa iter
                                                                                                                                                                                                      rn
                                                                                                                                                                                                   tu
                                                                                                                                                                                            n

                                                                                                                                                                                                   p
                                                                                                                                                                                         Su

                                                                                                                                                                                                Ju




                                                                                                                                  0.5 AU
                                                                                                                                           Orbit scale                                          Planet Size scale



1604                                                                                                     16 SEPTEMBER 2011   VOL 333   SCIENCE     www.sciencemag.org
RESEARCH ARTICLES
compatible with the timings, durations, and depths       Figures 1 and 2 show the very good match that             perturbations, with light-time variations contribut-
of the primary and secondary stellar eclipses, as well   was achieved between the model and the data.              ing only at the level of 1 s. The third body’s di-
as the transits of the planet across both stars. The     Uncertainties in the parameters were determined           mensions are well within the planetary regime, with
model also had to account for the slight depar-          with a Differential Evolution Markov Chain Monte          a mass of 0.333 T 0.016 and a radius of 0.7538 T
tures from strict periodicity of the stellar eclipses.   Carlo simulation (20) (SOM).                              0.0025 those of Jupiter. Following the convention
Furthermore, to pin down the stellar masses and              Due to the presence of three-body effects             of (21), we can denote the third body Kepler-16
provide an absolute distance scale, we undertook         (namely, the shifts in eclipse times and transit          (AB)-b, or simply “b” when there is no ambiguity.
spectroscopic observations to track the radial ve-       durations), the masses, radii, and orbital distances          Considering its bulk properties, the planet is
locity variations of star A (Fig. 2, top panel).         of this system are well determined in absolute units,     reminiscent of Saturn but with a higher mean
    The model parameters were adjusted to fit            not just in relative units. The eclipse timing varia-     density (0.964 g cm–3, compared to the Saturnian
the photometric and radial-velocity data (Table 1).      tions are dominated by the effects of dynamical           density of 0.687 g cm–3). This suggests a greater
                                                                                                                   degree of enrichment by heavy elements. With
                                                                                                                   a mass and radius, one can begin to model a
Table 1. Characteristics of the Kepler-16 system. For all parameters except Teff and [m/H] (which are described    planet’s interior structure, which will depend on
in the SOM), the results are based on the photometric-dynamical model. The quoted values and uncertainty           age because planets cool and contract with time.
intervals are based on the 15.85, 50, and 84.15% levels of the cumulative distributions of the marginalized        Usually the stellar age is used as a proxy for the
posteriors for each parameter, making them analogous to 1s intervals for Gaussian statistics. The quoted orbital   planetary age, but in this case the stellar age is
parameters are osculating Jacobian parameters at BJD 2,455,212.12316. The distance from Kepler-16 to Earth         not unambiguous. The primary star (A) is a slow
has not been measured, but is probably about 200 light years, judging from the apparent brightness of star A
                                                                                                                   rotator (with a period of about 35.1 days, judging
and theoretical models of stellar structure that give a crude estimate of its intrinsic luminosity.
                                                                                                                   from the out-of-eclipse variations), which is usu-
Parameter                                                                             Value and uncertainty        ally indicative of old age. In contrast, its level
                                                                                                                   of starspot activity and chromospheric emission
                                                    Star A
                                                                                                                   (Mount Wilson S value = 1.10) are indicative of
Mass, MA (M solar)                                                                          0.6897+0.0035
                                                                                                  –0.0034
                                                                                                                   youth. The spectroscopic determination of star
Radius, RA (R solar)                                                                        0.6489+0.0013
                                                                                                  –0.0013
                                                                                                                   A’s heavy-element fraction ([m/H] = –0.3 T 0.2)
Mean density, rA (g/cm3)                                                                     3.563+0.017
                                                                                                  –0.016
                                                                                                                   is also relatively uncertain, making it more diffi-
Surface gravity, log gA (cgs)                                                               4.6527+0.0017
                                                                                                  –0.0016
                                                                                                                   cult to estimate the age with theoretical evolu-
Effective temperature, Teff (K)                                                              4450 T 150
                                                                                                                   tionary models. Nevertheless, for any age greater
Metallicity, [m/H]                                                                           –0.3 T 0.2
                                                                                                                   than 0.5 billion years, the planet’s interior would
                                                                                                                   include 40 to 60 Earth masses of heavy elements,
                                                    Star B
                                                                                                                   according to standard planetary models (22). This
Mass, MB (M solar)                                                                        0.20255+0.00066
                                                                                                  –0.00065
                                                                                                                   would imply a composition of approximately half
Radius, RB (R solar)                                                                      0.22623+0.00059
                                                                                                  –0.00053
                                                                                                                   gas (hydrogen and helium) and half heavy ele-
Mean density, rB (g/cm3)                                                                     24.69+0.13
                                                                                                  –0.15
                                                                                                                   ments (presumably ice and rock). Saturn, in con-
Surface gravity, log gB (cgs)                                                              5.0358+0.0014
                                                                                                  –0.0017
                                                                                                                   trast, is at least two-thirds gas by mass (23).
                                                                                                                       To investigate the long-term (secular) changes
                                                   Planet b
                                                                                                                   in the orbital parameters, and to check on the
Mass, Mb (MJupiter)                                                                          0.333+0.016
                                                                                                   –0.016
                                                                                                                   system’s stability, we integrated the best-fitting
Radius, Rb (RJupiter)                                                                       0.7538+0.0026
                                                                                                   –0.0023
                                                                                                                   model forward in time by two million years.
Mean density, rb (g/cm3)                                                                     0.964+0.047
                                                                                                   –0.046
                                                                                                                   Within the context of our gravitational three-
Surface gravity, gb (m/s2)                                                                    14.52+0.70
                                                                                                   –0.69
                                                                                                                   body model, secular variations occur on a time
                                                                                                                   scale of about 40 years, without any significant
                                               Binary star orbit
                                                                                                                   excursions in orbital distance that would have
Period, P1 (day)                                                                        41.079220+0.000078
                                                                                                   –0.000077
                                                                                                                   led to instability. The planet’s orbital eccentricity
Semi-major axis length, a1 (AU)                                                           0.22431+0.00035
                                                                                                  –0.00034
                                                                                                                   reaches a maximum of about 0.09. Likewise, the
Eccentricity, e1                                                                          0.15944+0.00061
                                                                                                  –0.00062
                                                                                                                   planet’s line-of-sight orbital inclination changes
Argument of periapse, w1 (deg)                                                             263.464+0.026
                                                                                                   –0.027
                                                                                                                   by 0.2°, which is large enough that transits are
Mean longitude, l1 (deg)                                                                  92.3520+0.0011
                                                                                                  –0.0011
                                                                                                                   only visible from Earth about 40% of the time
Inclination, i1 (deg)                                                                     90.3401+0.0016
                                                                                                  –0.0019
                                                                                         ≡0 (by definition)         (averaged over centuries). In particular, the plan-
Longitude of nodes, W1 (deg)
                                                                                                                   etary transits across star A should cease in early
                                                                                                                   2018, and return sometime around 2042. The
                                          Circumbinary planet orbit
                                                                                                                   planetary transits across star B are already grazing
Period, P2 (day)                                                                           228.776+0.020
                                                                                                   –0.037
                                                                                                                   and are predicted to disappear for 35 years be-
Semi-major axis length, a2 (AU)                                                            0.7048+0.0011
                                                                                                  –0.0011
                                                                                                                   ginning in May 2014.
Eccentricity, e2                                                                           0.0069+0.0010
                                                                                                  –0.0015
                                                                                                                       The planet experiences swings in insolation
Argument of periapse, w2 (deg)                                                                318+10.
                                                                                                  –22.
                                                                                                                   due to the motion of the stars on short time scales
Mean longitude, l2 (deg)                                                                    106.51+0.32
                                                                                                   –0.16
                                                                                                                   and to secular changes in the planet’s orbit on
Inclination, i2 (deg)                                                                      90.0322+0.0022
                                                                                                   –0.0023
                                                                                                                   long time scales. These variations are likely to af-
Longitude of nodes, W2 (deg)                                                                     +0.013
                                                                                            0.003–0.013
                                                                                                                   fect the temperature and structure of the planet’s
                                                                                                                   atmosphere. The planet’s current equilibrium tem-
                                            Other parameters
                                                                                                                   perature, averaged over several orbits, is between
Flux ratio of stars in Kepler bandpass, FB/FA                                             0.01555+0.00010
                                                                                                  –0.00006
                                                                                                                   170 and 200 K, assuming isotropic re-radiation
Upper limit on third light (95% conf.), FX/(FA + FB)                                          <0.013
                                                                                                                   of the stellar flux and a Bond albedo between
Radial velocity parameter of barycenter, g (km s−1)                                        –32.769–0.035
                                                                                                   +0.035
                                                                                                                   0.2 and 0.5 (in the neighborhood of Saturn’s value
Photometric noise parameter, sphot                                                                +0.0000062
                                                                                        0.0002403–0.0000060
                                                                                                                   of 0.34). The orbital motions of the stars and


                                        www.sciencemag.org             SCIENCE        VOL 333        16 SEPTEMBER 2011                                                     1605
planet are expected to produce seasonal temper-                  addition to a transiting circumbinary planet, this                  22. J. J. Fortney, M. S. Marley, J. W. Barnes, Astrophys. J.
       ature variations of around 30 K.                                 makes Kepler-16 a treasure for both exoplan-                            659, 1661 (2007).
                                                                                                                                            23. T. Guillot, Annu. Rev. Earth Planet. Sci. 33, 493 (2005).
           The planetary orbit is aligned with the stellar              etary and stellar astrophysical investigations.                     24. H. Scholl, F. Marzari, P. Thebault, Mon. Not. R.
       orbit to within 0.4°. This extreme coplanarity sug-                                                                                      Astron. Soc. 380, 1119 (2007).
       gests that the planet was formed along with the                        References and Notes                                          25. D. E. Trilling et al., Astrophys. J. 658, 1289 (2007).
       stars, within a circumbinary protoplanetary disk,                                                                                    26. E. V. Quintana, J. J. Lissauer, Icarus 185, 1 (2006).
                                                                         1.   H.-J. Deeg et al., Astron. Astrophys. 480, 563 (2008).
                                                                                                                                            27. A. Pierens, R. P. Nelson, Astron. Astrophys. 483, 633
       as opposed to being captured from another sys-                    2.   J. W. Lee et al., Astron. J. 137, 3181 (2009).
                                                                                                                                                (2008).
       tem. Planetesimal formation around an eccentric                   3.   K. Beuermann et al., Astron. Astrophys. 521, L60 (2010).
                                                                                                                                            28. N. Haghighipour, Planets in Binary Star Systems
                                                                         4.   J. N. Winn, in Exoplanets, S. Seager, Ed. (Univ. of Arizona
       binary is a theoretical challenge, because of the                      Press, Tucson, AZ, 2010), pp. 55–77.
                                                                                                                                                (Astrophysics and Space Science Library, vol. 366,
       large collision velocities of particles that are stirred                                                                                 Springer, New York, 2010).
                                                                         5.   W. J. Borucki et al., Science 327, 977 (2010).
                                                                                                                                            29. G. Torres, J. Andersen, A. Giménez, Astron. Astrophys.
       by the stellar binary (24), although the detection                6.   D. Koch et al., Astrophys. J. Lett. 713, L79 (2010).
                                                                                                                                                Rev. 18, 67 (2010).
       of debris disks around close binaries has been                    7.   D. A. Caldwell et al., Astrophys. J. Lett. 713, L92 (2010).
                                                                                                                                            30. S. B. Howell, M. E. Everett, W. Sherry, E. Horch, D. Ciardi,
                                                                         8.   J. M. Jenkins et al., Astrophys. J. Lett. 713, L87 (2010).
       interpreted as dust produced by colliding plane-                  9.   A. Prša et al., Astron. J. 141, 83 (2010).
                                                                                                                                                Astron. J. 142, 19 (2011).
       tesimals (25). Subsequent stages of planet forma-                                                                                    Acknowledgments: NASA’s Science Mission Directorate
                                                                        10.   R. W. Slawson et al., Kepler eclipsing binary stars. II.
                                                                                                                                                provided funding for the Kepler Discovery mission. L.R.D.
       tion around binaries have been studied theoretically,                  2166 eclipsing binaries in the second data release;
                                                                                                                                                acknowledges the NASA Kepler Participating Scientist
       both for terrestrial planets (26) and gas giants (27),                 preprint available at http://arxiv.org/abs/1103.1659.
                                                                                                                                                Program (grant no. NNX08AR15G) and helpful
                                                                        11.   H. J. Deeg et al., Astron. Astrophys. 338, 479 (1998).
       but these and other theoretical studies (28) have                12.   L. R. Doyle et al., Astrophys. J. 535, 338 (2000).
                                                                                                                                                discussions with the Kepler Science Team. J.A.C. and
       lacked a well-specified circumbinary planetary sys-                                                                                      D.C.F. acknowledge support for this work provided by
                                                                        13.   J. Irwin, Astrophys. J. 116, 211 (1952).
       tem that could allow such a refinement of models.                                                                                        NASA through Hubble Fellowship grants HF-51267.01-A
                                                                        14.   P. Sybilski, M. Konacki, S. Kozlowski, Mon. Not. R.
                                                                                                                                                and HF-51272.01-A awarded by the Space Telescope
           Finally, the stars themselves are worthy of                        Astron. Soc. 405, 657 (2011).
                                                                                                                                                Science Institute, which is operated by the Association of
       attention, independently of the planet. It is rare               15.   Z. Kopal, Close Binary Systems (Chapman & Hall, London,
                                                                                                                                                Universities for Research in Astronomy for NASA, under
                                                                              1959).
       to measure the masses and radii of such small                    16.   R. Schwarz, N. Haghighipour, S. Eggl, E. Pilat-Lohinger,
                                                                                                                                                contract NAS 5-26555. J.N.W. is grateful for support from
       stars with such high precision, using geometrical                                                                                        the NASA Origins program (grant NNX09AB33G). The
                                                                              B. Funk, Mon. Not. R. Astron. Soc. 414, 2763 (2011).
                                                                                                                                                Kepler data used in this analysis can be downloaded from
       and dynamical methods independent of stellar                     17.   J. A. Carter et al., Science 331, 562 (2011).
                                                                                                                                                http://archive.stsci.edu/prepds/kepler_hlsp.
       evolutionary models. In particular, star B, with                 18.   K. Mandel, E. Agol, Astrophys. J. 580, L171 (2002).
                                                                        19.   Speckle interferometric imaging with the WIYN telescope
       only 20% the mass of the Sun, is the smallest                          also restricted any contaminating stars separated by          Supporting Online Material
       main-sequence star for which such precise mass                                                                                       www.sciencemag.org/cgi/content/full/333/6049/1602/DC1
                                                                              >0.02 arc sec to have a flux less than 3% of the system.
                                                                                                                                            SOM Text
       and radius data are available (29) (Fig. 3). The                       For the methodology, see (30).
                                                                        20.   C. J. F. Ter Braak, Stat. Comput. 16, 239 (2006).             Figs. S1 to S3
       mass ratio of 0.29 is also among the smallest                                                                                        Tables S1 to S5
                                                                        21.   F. V. Hessman et al., “On the naming convention used for
       known for binaries involving fully convective                          multiple star systems and extrasolar planets,” open letter
                                                                                                                                            References (31–41)
       stars at the low-mass end of the main sequence                         to the stellar and exoplanet communities, available at        8 July 2011; accepted 18 August 2011
       (28). With well-characterized low-mass stars, in                       http://arxiv.org/abs/1012.0707.                               10.1126/science.1210923




        REPORTS
                                                                                                                                            triazole products is that simple chemical or
       Unclicking the Click: Mechanically                                                                                                   thermal treatments capable of cleanly reverting
                                                                                                                                            the coupling reactions into their constituent
       Facilitated 1,3-Dipolar Cycloreversions                                                                                              azides and alkynes are unknown. We envi-
                                                                                                                                            sioned that mechanical force could be used to
                                                                                                                                            surmount the otherwise inaccessible barrier to
       Johnathan N. Brantley, Kelly M. Wiggins, Christopher W. Bielawski*                                                                   triazole cycloreversion; that is, under the appro-
                                                                                                                                            priate mechanical stress, triazoles might not
       The specific targeting of covalent bonds in a local, anisotropic fashion using mechanical methods
                                                                                                                                            retain their structural integrity. Such a retro-
       offers useful opportunities to direct chemical reactivity down otherwise prohibitive pathways. Here,
                                                                                                                                            cycloaddition would also indicate that triazoles
       we report that embedding the highly inert 1,2,3-triazole moiety (which is often prepared using the
                                                                                                                                            are not necessarily orthogonal to chemical trans-
       canonical “click” coupling of azides and alkynes) within a poly(methyl acrylate) chain renders it
                                                                                                                                            formations and would provide a method by
       susceptible to ultrasound-induced cycloreversion, as confirmed by comprehensive spectroscopic and
                                                                                                                                            which reactive azide or alkyne intermediates
       chemical analyses. Such reactivity offers the opportunity to develop triazoles as mechanically labile
                                                                                                                                            could be selectively unmasked to effect desired
       protecting groups or for use in readily accessible materials that respond to mechanical force.
                                                                                                                                            transformations (Scheme 1).
                                                                                                                                                Recent advances in mechanochemistry (12)—
              he 1,3-dipolar cycloaddition of azide and                 the past decade because it exhibits rapid kinetics                  wherein exogenous forces can be directed to

       T      alkyne moieties (1, 2), which allows ac-
              cess to a variety of substituted triazoles, is
       included under the umbrella of “click” chemistry.
                                                                        under mild conditions, high functional group and
                                                                        solvent tolerance, and good atom economy, and
                                                                        it has a propensity to generate relatively chem-
                                                                                                                                            mechanophores, or small molecules possessing
                                                                                                                                            mechanically labile bonds, through the judicious
                                                                                                                                            attachment of polymer chains—have demon-
       This reaction has found broad applicability over                 ically inert and thermally stable products. In                      strated that formally disallowed pericyclic reac-
                                                                        addition to finding compelling use in molecu-                       tions and thermally inaccessible isomerizations
                                                                        lar and polymer functionalizations, this cou-                       can be readily induced through site-specific me-
       Department of Chemistry and Biochemistry, The University of
       Texas at Austin, 1 University Station A1590, Austin, TX 78712,   pling motif has been applied to robust,                             chanical activation (13–18). Such forces can be
       USA.                                                             chemically orthogonal ligations for the study of                    harnessed through the application of ultrasound
       *To whom correspondence should be addressed. E-mail:             biological systems (3–11). However, a conse-                        to polymer solutions, whereby cavitation induces
       bielawski@cm.utexas.edu                                          quence of the high kinetic stability of these                       velocity gradients and attendant stress to the


1606                                                 16 SEPTEMBER 2011                  VOL 333           SCIENCE           www.sciencemag.org

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Kepler 16- a transiting circumbinary planet

  • 1. RESEARCH ARTICLES sequences in order to identify intermediate sequences that sequences in the non-IGHV1-2*02 cluster are likely NIH; by grants from the International AIDS Vaccine related to mature neutralizing antibodies. We therefore misassigned and actually of IGHV1-2*02 origin. Initiative’s Neutralizing Antibody Consortium; and by used well-established maximum likelihood phylogenetic 45. M. Pancera et al., J. Virol. 84, 8098 (2010). the Center for HIV AIDS Vaccine Immunology grant AI algorithms to analyze antibody sequence data and to 46. E. A. Kabat, T. T. Wu, K. S. Gottesman, C. Foeller, 5U19 AI 067854-06 from NIH. Use of sector 22 build rooted trees of antibody sequences that are derived Sequences of Proteins of Immunological Interest, 5th (Southeast Region Collaborative Access Team) at the from a common ancestor (i.e., same VH-germline gene). Edition (U.S. Department of Health and Human Services, Advanced Photon Source was supported by the U.S. 38. Several of the non-neutralizing heavy-chain sequences shown Washington, DC, 1991). Department of Energy, Basic Energy Sciences, Office in the CDR H3 distribution of Fig. 6 are likely the result of 47. E. Krissinel, K. Henrick, J. Mol. Biol. 372, 774 (2007). of Science, under contract W-31-109-Eng-38. Structure PCR template switching. The single heavy chain depicted in Acknowledgments: X.W., T.Z., J. Z., G.J.N., M.R., L.S., P.D.K., factors and coordinates for antibodies VRC03 and the CDR H3 class 1 contour plot contains a unique CDR H3 and J.R.M. designed research; B.Z., C.W., X.C., M.L., K.M., VRC-PG04 in complex with HIV-1 gp120 have been sequence (fig. S15a), but with a V gene that displays high S.O.D., S.P., S.D.S., W.S., L.W., Y.Y., Z.Y.Y., Z.Y., NISC, deposited with the Protein Data Bank under accession similarity to class 3 sequences (table S23). The same and J.M. performed experiments; X.W. isolated and codes 3SE8 and 3SE9, respectively. We have also observation occurs for the two sequences in the class 2 characterized VRC01-like antibodies by RSC3 probe, deposited deep sequencing data for donors 45 and 74 contour plot. Also, the highly divergent (and outlier) devised and prepared samples for 454 pyrosequencing, (Appendices 1 to 4) used in this study to National sequence on the CDR H3 class 9 distribution plot contains the and assisted with functional characterization; T.Z. Center for Biotechnology Information Short Reads same CDR H3 as the other 140 class 9 sequences, but with a determined and analyzed structures of VRC-PG04 and Archives (SRA) under accession no. SRP006992. V gene that closely matches sequences found in class 8 VRC03 with gp120 and assisted with functional Information deposited with GenBank includes the (table S23b). Because only a few of more than 1500 unique characterization; J.Z. devised and carried out heavy- and light-chain variable region sequences of sequences identified by CDR H3 analysis showed dissimilar computational bioinformatics on the antibodyome; M.B., probe-identified antibodies VRC-PG04 and VRC-PG04b V genes, and all of these appeared as single or double J.A.C, S.H.K, N.E.S., and B.F.H. contributed donor 0219 (accession nos. JN159464 to JN159467), VRC-CH30, outliers, template switching can occur but appears to be materials; M.S., D.R.B., and W.C.K contributed Protocol G VRC-CH31, and VRC-CH32 (JN159434 to JN159439), rare. This rarity is also suggested by an analysis of 606,047 materials, including donor 74; N.D.R. and M.C. and VRC-CH33 and VRC-CH34 (JN159470 to 159473), non-IGHV1-2*02 from donor 74 for sequences with the CDR contributed donor 45 materials; X.W., T.Z., J.Z, I.G., as well as the sequences of genomically identified H3s identified in Fig. 6B, which finds less than 100 N.S.L., Z.Z., L.S., P.D.K., and J.R.M. analyzed the data; neutralizers: 24 heavy chains from donor 74, 2008 sequences, of which the majority corresponds to the likely and L.S., G.J.N., P.D.K., and J.R.M. wrote the paper, (JN159440 to JN159463), two heavy chains from misassigned cluster in the non-IGHV1-2*02 sequence of on which all authors commented. We thank J. Almeida donor 45, 2008 (JN159474 and JN159475), two light donor 74 in Fig. 4, as described in (44). and D. Douek for protocols of PBMC cDNA preparation chains from donor 45, 2001 (JN159468 and JN159469), 39. A similar accumulation of somatic mutations was shown and for helpful discussions; J. Stuckey for assistance and 1561 unique sequences associated with neutralizing (45) with the broadly neutralizing antibodies PG9 and with figures; T. Wrin for sequence information on the CDR H3 distributions with at least one low divergent PG16 to correlate with an increase in neutralization donor 74 virus; J. Binley, D. Montefiori, L. Morris, and member shown in Fig. 6B and fig. S16 (JN157873 to breadth and potency. G. Tomaras for donor 0219 serum characterization; and JN159433). 40. D. Nemazee, M. Weigert, J. Exp. Med. 191, 1813 (2000). all of the IAVI Protocol G team members and the Protocol 41. E. Edry, D. Melamed, J. Immunol. 173, 4265 (2004). G clinical investigators, specifically, G. Miiro, A. Pozniak, Supporting Online Material 42. J. Glanville et al., Proc. Natl. Acad. Sci. U.S.A. 106, D. McPhee, O. Manigart, E. Karita, A. Inwoley, W. Jaoko, www.sciencemag.org/cgi/content/full/science.1207532/DC1 20216 (2009). J. DeHovitz, L.-G. Bekker, P. Pitisuttithum, R. Paris, Materials and Methods 43. H. Zhou, Y. Zhou, Protein Sci. 11, 2714 (2002). J. Serwanga, and S. Allen. We also thank H. Sato, Figs. S1 to S20 44. The peak at ~25% IGHV1-2*02 divergence and 88% I. Wilson, and members of the Structural Biology Section Tables S1 to S23 identity was also seen in the sequence plot for sequences and Structural Bioinformatics Core, Vaccine Research References (48–82) of non-IGHV1-2*02 origin. Cross-donor and CDR H3 Center, for discussions or comments on the manuscript. Appendices 1 to 4 analyses shows that these putative non-IGHV1-2*02– Support for this work was provided by the Intramural derived sequences segregate with VRC01-like antibodies Research Program of the Vaccine Research Center, 26 April 2011; accepted 15 July 2011 in dendrograms and have CDR H3s that are identical to National Institute of Allergy and Infectious Diseases, Published online 11 August 2011; confirmed VRC01-like antibodies (fig. S16), indicating and the National Human Genome Research Institute, 10.1126/science.1207532 Kepler-16: A Transiting planets based on the timing of stellar eclipses [see, e.g., (1–3)], but in no previous case have astronomers obtained direct evidence of a cir- Circumbinary Planet cumbinary planet by observing a planetary transit (a miniature eclipse as the planet passes directly Laurance R. Doyle,1* Joshua A. Carter,2 Daniel C. Fabrycky,3 Robert W. Slawson,1 in front of a star). Detection of a transit greatly Steve B. Howell,4 Joshua N. Winn,5 Jerome A. Orosz,6 Andrej Prˇsa,7 William F. Welsh,6 enhances confidence in the reality of the planet Samuel N. Quinn,8 David Latham,8 Guillermo Torres,8 Lars A. Buchhave,9,19 Geoffrey W. Marcy,11 and provides unusually precise knowledge of Jonathan J. Fortney,12 Avi Shporer,13,14 Eric B. Ford,15 Jack J. Lissauer,4 Darin Ragozzine,2 its mass, radius, and orbital parameters (4). Michael Rucker,16 Natalie Batalha,16 Jon M. Jenkins,1 William J. Borucki,4 David Koch,4 Here we present the detection of a transiting Christopher K. Middour,17 Jennifer R. Hall,17 Sean McCauliff,17 Michael N. Fanelli,18 circumbinary planet around a binary star sys- Elisa V. Quintana,1 Matthew J. Holman,8 Douglas A. Caldwell,1 Martin Still,18 Robert P. Stefanik,8 tem based on photometric data from the NASA Warren R. Brown,8 Gilbert A. Esquerdo,8 Sumin Tang,8 Gabor Furesz,8,10 John C. Geary,8 Kepler spacecraft. Kepler is a 0.95-m space tele- Perry Berlind,20 Michael L. Calkins,20 Donald R. Short,21 Jason H. Steffen,22 Dimitar Sasselov,8 scope that monitors the optical brightness of Edward W. Dunham,23 William D. Cochran,24 Alan Boss,25 Michael R. Haas,4 about 155,000 stars within a field encompassing Derek Buzasi,26 Debra Fischer27 105 square degrees in the constellations Cygnus and Lyra (5–8). We report the detection of a planet whose orbit surrounds a pair of low-mass stars. Data from the Star number 12644769 from the Kepler Input Kepler spacecraft reveal transits of the planet across both stars, in addition to the mutual eclipses Catalog was identified as an eclipsing binary of the stars, giving precise constraints on the absolute dimensions of all three bodies. The planet is with a 41-day period, from the detection of its comparable to Saturn in mass and size and is on a nearly circular 229-day orbit around its two mutual eclipses (9). Eclipses occur because the parent stars. The eclipsing stars are 20 and 69% as massive as the Sun and have an eccentric 41-day orbital plane of the stars is oriented nearly edge- orbit. The motions of all three bodies are confined to within 0.5° of a single plane, suggesting that on as viewed from Earth. During primary eclipses, the planet formed within a circumbinary disk. the larger star, denoted “A,” is partially eclipsed by the smaller star “B,” and the system flux de- planet with two suns is a familiar con- binary planets—those that orbit around both mem- clines by about 13%. During secondary eclipses, A cept from science fiction. However, the evidence for the existence of circum- bers of a stellar binary—has been limited. A few good cases have been made for circumbinary B is completely occulted by A, and the resulting drop in flux is only about 1.6% because B is rel- 1602 16 SEPTEMBER 2011 VOL 333 SCIENCE www.sciencemag.org
  • 2. RESEARCH ARTICLES 1.00 0.95 0.90 0.85 Relative flux 0 100 200 300 400 500 1.005 1.005 Star B eclipses Star A Star A occults Star B Planet b transits Star A 1.0002 Planet b transits Star B 1.00 1.000 1.000 1.0000 0.9998 0.995 0.995 0.95 0.9996 0.990 0.9994 0.990 0.90 0.985 0.9992 0.985 0.9990 0.85 0.980 170.9 171.0 171.1 171.2 273.1 273.2 273.3 273.4 273.5 425.0 425.1 425.2 425.3 425.4 −18.6 −18.5 −18.4 −18.3 −18.2 Time [BJD − 2,455,000] Fig. 1. Photometry of Kepler-16. (Top) Photometric time series from the in Kepler observing, data are missing from one primary eclipse at BJD Kepler spacecraft of star system Kepler-16 (KIC 12644769, KOI-1611, 2MASS 2,455,089, and one secondary eclipse at BJD 2,455,232. Note in particular 19161817+5145267, Kepler magnitude = 11.762). Each data point is the the shifting order of the tertiary (green) and quaternary (red) eclipses: The first relative brightness at a given time [in barycentric Julian days (BJDs)]. The 1% and third pairs begin with the tertiary eclipse, whereas the second pair leads variations on ~10-day time scales are probably due to starspots carried around with the quaternary eclipse. This is because the stars’ orbital motion places by stellar rotation (a periodogram gives a rotation period of about 35 days). The them in different positions at each inferior conjunction of the planet. The stars sharp dips are eclipses, appearing as vertical lines in this 600-day plot. They are silhouette the planet as they move behind it. (Bottom) Closeups (narrower identified as primary (B eclipses A, blue), secondary (A occults B, yellow), tertiary scales in time and relative flux) of representative examples of each type of (b transits A, green), and quaternary (b transits B, red). Because of interruptions eclipse, along with the best-fitting model (gray), with parameters from Table 1. atively small and has a lower surface brightness During tertiary eclipses, the total light declines to be either a planet or a third star with grazing (Fig. 1). by 1.7%. Because this is larger than the 1.6% de- eclipses. Decisive evidence that it is a planet came This target drew further attention when three cline during secondary eclipses (when star B is from investigation of the timing of the stellar additional drops in brightness were detected out- completely concealed), the tertiary eclipses had eclipses. The primary and secondary eclipse times side of the primary and secondary eclipses, sepa- to be transits of the third body across star A. This were found to depart from strict periodicity by rated by intervals of 230.3 and 221.5 days (10). interpretation was supported by the subsequent deviations on the order of 1 min. A third body These tertiary eclipses could not be attributed to detection of weaker 0.1% quaternary eclipses, causes timing variations in two ways. First, there the stars alone, and indicated the presence of a which were consistent with the passage of the is a light travel-time effect: The third body in- third body. The differing intervals between the third body across star B. The observed time of duces a periodic motion of the center of mass tertiary eclipses are simply explained if the third this quaternary eclipse was used to predict two of the stellar binary, causing periodic variations body is in a circumbinary orbit, because stars A other times of quaternary eclipses that should in the time required for the eclipse signals to and B would be in different positions in their have been present in the data, and these two reach Earth (13, 14). Second, there is a dynamical mutual orbit each time the third body moved in events were subsequently detected (Fig. 1). effect: The gravitational attraction of each star front of them (11, 12). In contrast, there would be Because the third body covers only 1.7% of to the third body varies with time because of no ready explanation for the shifting times of the the area of star A, which was determined to be the changing positions of all three bodies, causing tertiary eclipses if they were produced by a back- smaller than the Sun on the basis of its broadband perturbations in the stars’ orbital parameters and ground star system or some other unrelated event. colors (10), the circumbinary body was suspected therefore in the eclipse times (15, 16). Both effects 1 19 Carl Sagan Center for the Study of Life in the Universe, SETI University of Copenhagen, DK-2100 Copenhagen, Denmark. Konkoly Observatory, Konkoly ut 15-17, Budapest, H-1121, 10 Institute, 189 Bernardo Avenue, Mountain View, CA 94043, Centre for Star and Planet Formation, Natural History Hungary. 20Fred Lawrence Whipple Observatory, Smithsonian USA. 2Hubble Fellow, Harvard-Smithsonian Center for Astro- Museum of Denmark, University of Copenhagen, DK-1350 Astrophysical Observatory, Amado, AZ 85645, USA. 21De- physics, 60 Garden Street, Cambridge, MA 02138, USA. Copenhagen, Denmark. 11Department of Astronomy, Uni- partment of Mathematics, San Diego State University, 5500 3 Hubble Fellow, Department of Astronomy and Astrophysics, versity of California, Berkeley, CA 94720, USA. 12Department Campanile Drive, San Diego, CA 92182, USA. 22Fermilab University of California, Santa Cruz, CA 95064, USA. 4NASA of Astronomy and Astrophysics, University of California, Santa Center for Particle Astrophysics, Post Office Box 500, Batavia, Ames Research Center, Moffett Field, CA 94035, USA. Cruz, Santa Cruz, CA 95064, USA. 13Las Cumbres Observatory IL 60510, USA. 23Lowell Observatory, Flagstaff, AZ 86001, 5 Department of Physics and Kavli Institute for Astrophysics Global Telescope Network, 6740 Cortona Drive, Suite 102, USA. 24McDonald Observatory, University of Texas at Austin, and Space Research, Massachusetts Institute of Technology, Santa Barbara, CA 93117, USA. 14Department of Physics, Austin, TX 78712, USA. 25Carnegie Institute of Washington, 77 Massachusetts Avenue, Cambridge, MA 02139, USA. 6De- Broida Hall, University of California, Santa Barbara, CA Washington, DC 20015, USA. 26Eureka Scientific, 2452 partment of Astronomy, San Diego State University, 5500 93106, USA. 15211 Bryant Space Science Center, Gainesville, FL Delmer Street, Suite 100, Oakland, CA 94602, USA. 27De- Campanile Drive, San Diego, CA 92182–1221, USA. 7Depart- 32611–2055, USA. 16Department of Physics, San Jose State partment of Astronomy, Yale University, New Haven, CT ment of Astronomy and Astrophysics, Villanova University, University, San Jose, CA 95192, USA. 17Orbital Sciences 06511, USA. 800 East Lancaster Avenue, Villanova, PA 19085, USA. Corporation/NASA Ames Research Center, Moffett Field, CA 8 Harvard-Smithsonian Center for Astrophysics, 60 Garden 94035, USA. 18Bay Area Environmental Research Institute/ *To whom correspondence should be addressed. E-mail: Street, Cambridge, MA 02138, USA. 9Niels Bohr Institute, NASA Ames Research Center, Moffett Field, CA 94035, USA. ldoyle@seti.org www.sciencemag.org SCIENCE VOL 333 16 SEPTEMBER 2011 1603
  • 3. RESEARCH ARTICLES depend on the mass of the third body. Therefore, we could constrain the mass of the third body Fig. 2. Radial-velocity var- 20 by fitting the eclipse data with a numerical model iations and perturbations of Star A Radial Velocity [km s−1] 0 Star B of three-body gravitational interactions. This mod- eclipse times. (Top) Observed el, described below in detail, showed that the radial-velocity variations of −20 third body must be less massive than Jupiter. star A as a function of orbital phase, based on observations −40 Hence, based on the depth of the tertiary with the spectrograph of the −60 eclipses and on the magnitude of the eclipse Tillinghast 1.5-m telescope timing variations, the third body was shown to be −80 a transiting circumbinary planet. The model was at the Fred Lawrence Whipple 60 based on the premise that the three bodies move Residuals Observatory on Mount Hopkins, 40 [m s−1] 20 Arizona (SOM). Solid dots are 0 under the influence of mutual Newtonian grav- −20 the data, and the smooth −40 itational forces. For this purpose, we modified the −60 curve is the best-fitting mod- 0.0 0.2 0.4 0.6 0.8 1.0 computer code that was used to model the tri- el. Although only the light Orbital Phase ple star system KOI-126 (17) [supporting online Deviations of Eclipse Times from Constant−Period Model [min] from star A could be detected 1.5 material (SOM)]. The leading-order relativistic in the spectra, the model for Star B eclipses Star A 1.0 correction to the force law was included, although star B’s motion is also shown. it proved to be unimportant. The bodies’ positions 0.5 Residuals from the best mod- were calculated with a Bulirsch-Stoer algorithm el fits are given just below the 0.0 and corrected for the finite propagation speed radial velocity curve. (Middle −0.5 of light across the system before being compared and Bottom) Deviations of −1.0 to the data. The loss of light due to eclipses was the stellar eclipse times from calculated by assuming the disks of stars A and B −1.5 strict periodicity, as observed 2 to be circular, with a quadratic law describing (colored dots) and modeled Star A occults Star B the decline in intensity toward the limb (18). We (open diamonds). As noted 1 also allowed for an additional time-independent previously, one primary eclipse source of light to account for any possible back- and one secondary eclipse 0 were missed. The deviations ground stars within the Kepler photometric ap- are on the order of 1 min for −1 erture. In practice, this parameter was found to both primary and secondary be consistent with zero and bounded to be less −2 than 1.3% of the total light of the system (19). stellar eclipses. In the mod- −100 0 100 200 300 400 500 el, the effects of dynamical Time [BJD − 2,455,000] We fitted all of the photometric data within perturbations are dominant, 6 hours of any eclipse or transit. Before fitting, a with light-time variations contributing only at the level of 1 s. If the third body were more massive than a linear trend was removed from each segment, to planet (>13 jovian masses), the timing variations would have exceeded 30 min. This would have been off correct for the slow starspot-induced variations the scale of the diagram shown here, and in contradiction with the observations. evident in Fig. 1. A successful model had to be Fig. 3. Scale diagram of the Kepler-16 system. The current orbits of the Kepler-16 system are shown as gray curves. The sizes of the bodies (including the Sun, Jupiter, and Saturn) are in the correct proportions to To Earth one another, but they are on a scale 20 times larger than the orbital b distance scale. The binary and circumbinary planet orbital planes lie within 0.4° of each other (Table 1), so the orbits are essentially flat, as drawn. The planet’s orbital eccentricity is nearly zero, whereas the orbital eccentricity of the binary star system is presently about 0.16. A “+” symbol marks the center of mass of all three bodies. B A Sa iter rn tu n p Su Ju 0.5 AU Orbit scale Planet Size scale 1604 16 SEPTEMBER 2011 VOL 333 SCIENCE www.sciencemag.org
  • 4. RESEARCH ARTICLES compatible with the timings, durations, and depths Figures 1 and 2 show the very good match that perturbations, with light-time variations contribut- of the primary and secondary stellar eclipses, as well was achieved between the model and the data. ing only at the level of 1 s. The third body’s di- as the transits of the planet across both stars. The Uncertainties in the parameters were determined mensions are well within the planetary regime, with model also had to account for the slight depar- with a Differential Evolution Markov Chain Monte a mass of 0.333 T 0.016 and a radius of 0.7538 T tures from strict periodicity of the stellar eclipses. Carlo simulation (20) (SOM). 0.0025 those of Jupiter. Following the convention Furthermore, to pin down the stellar masses and Due to the presence of three-body effects of (21), we can denote the third body Kepler-16 provide an absolute distance scale, we undertook (namely, the shifts in eclipse times and transit (AB)-b, or simply “b” when there is no ambiguity. spectroscopic observations to track the radial ve- durations), the masses, radii, and orbital distances Considering its bulk properties, the planet is locity variations of star A (Fig. 2, top panel). of this system are well determined in absolute units, reminiscent of Saturn but with a higher mean The model parameters were adjusted to fit not just in relative units. The eclipse timing varia- density (0.964 g cm–3, compared to the Saturnian the photometric and radial-velocity data (Table 1). tions are dominated by the effects of dynamical density of 0.687 g cm–3). This suggests a greater degree of enrichment by heavy elements. With a mass and radius, one can begin to model a Table 1. Characteristics of the Kepler-16 system. For all parameters except Teff and [m/H] (which are described planet’s interior structure, which will depend on in the SOM), the results are based on the photometric-dynamical model. The quoted values and uncertainty age because planets cool and contract with time. intervals are based on the 15.85, 50, and 84.15% levels of the cumulative distributions of the marginalized Usually the stellar age is used as a proxy for the posteriors for each parameter, making them analogous to 1s intervals for Gaussian statistics. The quoted orbital planetary age, but in this case the stellar age is parameters are osculating Jacobian parameters at BJD 2,455,212.12316. The distance from Kepler-16 to Earth not unambiguous. The primary star (A) is a slow has not been measured, but is probably about 200 light years, judging from the apparent brightness of star A rotator (with a period of about 35.1 days, judging and theoretical models of stellar structure that give a crude estimate of its intrinsic luminosity. from the out-of-eclipse variations), which is usu- Parameter Value and uncertainty ally indicative of old age. In contrast, its level of starspot activity and chromospheric emission Star A (Mount Wilson S value = 1.10) are indicative of Mass, MA (M solar) 0.6897+0.0035 –0.0034 youth. The spectroscopic determination of star Radius, RA (R solar) 0.6489+0.0013 –0.0013 A’s heavy-element fraction ([m/H] = –0.3 T 0.2) Mean density, rA (g/cm3) 3.563+0.017 –0.016 is also relatively uncertain, making it more diffi- Surface gravity, log gA (cgs) 4.6527+0.0017 –0.0016 cult to estimate the age with theoretical evolu- Effective temperature, Teff (K) 4450 T 150 tionary models. Nevertheless, for any age greater Metallicity, [m/H] –0.3 T 0.2 than 0.5 billion years, the planet’s interior would include 40 to 60 Earth masses of heavy elements, Star B according to standard planetary models (22). This Mass, MB (M solar) 0.20255+0.00066 –0.00065 would imply a composition of approximately half Radius, RB (R solar) 0.22623+0.00059 –0.00053 gas (hydrogen and helium) and half heavy ele- Mean density, rB (g/cm3) 24.69+0.13 –0.15 ments (presumably ice and rock). Saturn, in con- Surface gravity, log gB (cgs) 5.0358+0.0014 –0.0017 trast, is at least two-thirds gas by mass (23). To investigate the long-term (secular) changes Planet b in the orbital parameters, and to check on the Mass, Mb (MJupiter) 0.333+0.016 –0.016 system’s stability, we integrated the best-fitting Radius, Rb (RJupiter) 0.7538+0.0026 –0.0023 model forward in time by two million years. Mean density, rb (g/cm3) 0.964+0.047 –0.046 Within the context of our gravitational three- Surface gravity, gb (m/s2) 14.52+0.70 –0.69 body model, secular variations occur on a time scale of about 40 years, without any significant Binary star orbit excursions in orbital distance that would have Period, P1 (day) 41.079220+0.000078 –0.000077 led to instability. The planet’s orbital eccentricity Semi-major axis length, a1 (AU) 0.22431+0.00035 –0.00034 reaches a maximum of about 0.09. Likewise, the Eccentricity, e1 0.15944+0.00061 –0.00062 planet’s line-of-sight orbital inclination changes Argument of periapse, w1 (deg) 263.464+0.026 –0.027 by 0.2°, which is large enough that transits are Mean longitude, l1 (deg) 92.3520+0.0011 –0.0011 only visible from Earth about 40% of the time Inclination, i1 (deg) 90.3401+0.0016 –0.0019 ≡0 (by definition) (averaged over centuries). In particular, the plan- Longitude of nodes, W1 (deg) etary transits across star A should cease in early 2018, and return sometime around 2042. The Circumbinary planet orbit planetary transits across star B are already grazing Period, P2 (day) 228.776+0.020 –0.037 and are predicted to disappear for 35 years be- Semi-major axis length, a2 (AU) 0.7048+0.0011 –0.0011 ginning in May 2014. Eccentricity, e2 0.0069+0.0010 –0.0015 The planet experiences swings in insolation Argument of periapse, w2 (deg) 318+10. –22. due to the motion of the stars on short time scales Mean longitude, l2 (deg) 106.51+0.32 –0.16 and to secular changes in the planet’s orbit on Inclination, i2 (deg) 90.0322+0.0022 –0.0023 long time scales. These variations are likely to af- Longitude of nodes, W2 (deg) +0.013 0.003–0.013 fect the temperature and structure of the planet’s atmosphere. The planet’s current equilibrium tem- Other parameters perature, averaged over several orbits, is between Flux ratio of stars in Kepler bandpass, FB/FA 0.01555+0.00010 –0.00006 170 and 200 K, assuming isotropic re-radiation Upper limit on third light (95% conf.), FX/(FA + FB) <0.013 of the stellar flux and a Bond albedo between Radial velocity parameter of barycenter, g (km s−1) –32.769–0.035 +0.035 0.2 and 0.5 (in the neighborhood of Saturn’s value Photometric noise parameter, sphot +0.0000062 0.0002403–0.0000060 of 0.34). The orbital motions of the stars and www.sciencemag.org SCIENCE VOL 333 16 SEPTEMBER 2011 1605
  • 5. planet are expected to produce seasonal temper- addition to a transiting circumbinary planet, this 22. J. J. Fortney, M. S. Marley, J. W. Barnes, Astrophys. J. ature variations of around 30 K. makes Kepler-16 a treasure for both exoplan- 659, 1661 (2007). 23. T. Guillot, Annu. Rev. Earth Planet. Sci. 33, 493 (2005). The planetary orbit is aligned with the stellar etary and stellar astrophysical investigations. 24. H. Scholl, F. Marzari, P. Thebault, Mon. Not. R. orbit to within 0.4°. This extreme coplanarity sug- Astron. Soc. 380, 1119 (2007). gests that the planet was formed along with the References and Notes 25. D. E. Trilling et al., Astrophys. J. 658, 1289 (2007). stars, within a circumbinary protoplanetary disk, 26. E. V. Quintana, J. J. Lissauer, Icarus 185, 1 (2006). 1. H.-J. Deeg et al., Astron. Astrophys. 480, 563 (2008). 27. A. Pierens, R. P. Nelson, Astron. Astrophys. 483, 633 as opposed to being captured from another sys- 2. J. W. Lee et al., Astron. J. 137, 3181 (2009). (2008). tem. Planetesimal formation around an eccentric 3. K. Beuermann et al., Astron. Astrophys. 521, L60 (2010). 28. N. Haghighipour, Planets in Binary Star Systems 4. J. N. Winn, in Exoplanets, S. Seager, Ed. (Univ. of Arizona binary is a theoretical challenge, because of the Press, Tucson, AZ, 2010), pp. 55–77. (Astrophysics and Space Science Library, vol. 366, large collision velocities of particles that are stirred Springer, New York, 2010). 5. W. J. Borucki et al., Science 327, 977 (2010). 29. G. Torres, J. Andersen, A. Giménez, Astron. Astrophys. by the stellar binary (24), although the detection 6. D. Koch et al., Astrophys. J. Lett. 713, L79 (2010). Rev. 18, 67 (2010). of debris disks around close binaries has been 7. D. A. Caldwell et al., Astrophys. J. Lett. 713, L92 (2010). 30. S. B. Howell, M. E. Everett, W. Sherry, E. Horch, D. Ciardi, 8. J. M. Jenkins et al., Astrophys. J. Lett. 713, L87 (2010). interpreted as dust produced by colliding plane- 9. A. Prša et al., Astron. J. 141, 83 (2010). Astron. J. 142, 19 (2011). tesimals (25). Subsequent stages of planet forma- Acknowledgments: NASA’s Science Mission Directorate 10. R. W. Slawson et al., Kepler eclipsing binary stars. II. provided funding for the Kepler Discovery mission. L.R.D. tion around binaries have been studied theoretically, 2166 eclipsing binaries in the second data release; acknowledges the NASA Kepler Participating Scientist both for terrestrial planets (26) and gas giants (27), preprint available at http://arxiv.org/abs/1103.1659. Program (grant no. NNX08AR15G) and helpful 11. H. J. Deeg et al., Astron. Astrophys. 338, 479 (1998). but these and other theoretical studies (28) have 12. L. R. Doyle et al., Astrophys. J. 535, 338 (2000). discussions with the Kepler Science Team. J.A.C. and lacked a well-specified circumbinary planetary sys- D.C.F. acknowledge support for this work provided by 13. J. Irwin, Astrophys. J. 116, 211 (1952). tem that could allow such a refinement of models. NASA through Hubble Fellowship grants HF-51267.01-A 14. P. Sybilski, M. Konacki, S. Kozlowski, Mon. Not. R. and HF-51272.01-A awarded by the Space Telescope Finally, the stars themselves are worthy of Astron. Soc. 405, 657 (2011). Science Institute, which is operated by the Association of attention, independently of the planet. It is rare 15. Z. Kopal, Close Binary Systems (Chapman & Hall, London, Universities for Research in Astronomy for NASA, under 1959). to measure the masses and radii of such small 16. R. Schwarz, N. Haghighipour, S. Eggl, E. Pilat-Lohinger, contract NAS 5-26555. J.N.W. is grateful for support from stars with such high precision, using geometrical the NASA Origins program (grant NNX09AB33G). The B. Funk, Mon. Not. R. Astron. Soc. 414, 2763 (2011). Kepler data used in this analysis can be downloaded from and dynamical methods independent of stellar 17. J. A. Carter et al., Science 331, 562 (2011). http://archive.stsci.edu/prepds/kepler_hlsp. evolutionary models. In particular, star B, with 18. K. Mandel, E. Agol, Astrophys. J. 580, L171 (2002). 19. Speckle interferometric imaging with the WIYN telescope only 20% the mass of the Sun, is the smallest also restricted any contaminating stars separated by Supporting Online Material main-sequence star for which such precise mass www.sciencemag.org/cgi/content/full/333/6049/1602/DC1 >0.02 arc sec to have a flux less than 3% of the system. SOM Text and radius data are available (29) (Fig. 3). The For the methodology, see (30). 20. C. J. F. Ter Braak, Stat. Comput. 16, 239 (2006). Figs. S1 to S3 mass ratio of 0.29 is also among the smallest Tables S1 to S5 21. F. V. Hessman et al., “On the naming convention used for known for binaries involving fully convective multiple star systems and extrasolar planets,” open letter References (31–41) stars at the low-mass end of the main sequence to the stellar and exoplanet communities, available at 8 July 2011; accepted 18 August 2011 (28). With well-characterized low-mass stars, in http://arxiv.org/abs/1012.0707. 10.1126/science.1210923 REPORTS triazole products is that simple chemical or Unclicking the Click: Mechanically thermal treatments capable of cleanly reverting the coupling reactions into their constituent Facilitated 1,3-Dipolar Cycloreversions azides and alkynes are unknown. We envi- sioned that mechanical force could be used to surmount the otherwise inaccessible barrier to Johnathan N. Brantley, Kelly M. Wiggins, Christopher W. Bielawski* triazole cycloreversion; that is, under the appro- priate mechanical stress, triazoles might not The specific targeting of covalent bonds in a local, anisotropic fashion using mechanical methods retain their structural integrity. Such a retro- offers useful opportunities to direct chemical reactivity down otherwise prohibitive pathways. Here, cycloaddition would also indicate that triazoles we report that embedding the highly inert 1,2,3-triazole moiety (which is often prepared using the are not necessarily orthogonal to chemical trans- canonical “click” coupling of azides and alkynes) within a poly(methyl acrylate) chain renders it formations and would provide a method by susceptible to ultrasound-induced cycloreversion, as confirmed by comprehensive spectroscopic and which reactive azide or alkyne intermediates chemical analyses. Such reactivity offers the opportunity to develop triazoles as mechanically labile could be selectively unmasked to effect desired protecting groups or for use in readily accessible materials that respond to mechanical force. transformations (Scheme 1). Recent advances in mechanochemistry (12)— he 1,3-dipolar cycloaddition of azide and the past decade because it exhibits rapid kinetics wherein exogenous forces can be directed to T alkyne moieties (1, 2), which allows ac- cess to a variety of substituted triazoles, is included under the umbrella of “click” chemistry. under mild conditions, high functional group and solvent tolerance, and good atom economy, and it has a propensity to generate relatively chem- mechanophores, or small molecules possessing mechanically labile bonds, through the judicious attachment of polymer chains—have demon- This reaction has found broad applicability over ically inert and thermally stable products. In strated that formally disallowed pericyclic reac- addition to finding compelling use in molecu- tions and thermally inaccessible isomerizations lar and polymer functionalizations, this cou- can be readily induced through site-specific me- Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A1590, Austin, TX 78712, pling motif has been applied to robust, chanical activation (13–18). Such forces can be USA. chemically orthogonal ligations for the study of harnessed through the application of ultrasound *To whom correspondence should be addressed. E-mail: biological systems (3–11). However, a conse- to polymer solutions, whereby cavitation induces bielawski@cm.utexas.edu quence of the high kinetic stability of these velocity gradients and attendant stress to the 1606 16 SEPTEMBER 2011 VOL 333 SCIENCE www.sciencemag.org