Inorganic Chemistry
Article
‡A.J.M.: Otto Diels Institute of Organic Chemistry, University
of Kiel, Otto-Hahn-Platz 4, Kiel 24098, Germany.
E.; Turro, N. J.; Barton, J. K. Characterization of Dipyridophenazine
Complexes of Ruthenium(II): The Light Switch Effect as a Function
of Nucleic Acid Sequence and Conformation. Biochemistry 1992, 31,
10809−10816. (c) Hartshorn, R. M.; Barton, J. K. Novel
Dipyridophenazine Complexes of Ruthenium(II): Exploring Lumines-
cent Reporters of DNA. J. Am. Chem. Soc. 1992, 114, 5919−5925.
(7) Fung, S. K.; Zou, T.; Cao, B.; Chen, T.; To, W.-P.; Yang, C.; Lok,
C.-N.; Che, C.-M. Luminescent platinum(II) complexes with
functionalized N-heterocyclic carbine or diphosphine selectively
probe mismatched and abasic DNA. Nat. Commun. 2016, 7, 10655.
(8) (a) McConnell, A. J.; Lim, M. H.; Olmon, E. D.; Song, H.;
Dervan, E. E.; Barton, J. K. Luminescent Properties of Ruthenium(II)
Complexes with Sterically Expansive Ligands Bound to DNA Defects.
Inorg. Chem. 2012, 51, 12511−12520. (b) Zeglis, B. M.; Barton, J. K.
Binding of Ru(bpy)2(eilatin)2+ to Matched and Mismatched DNA.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We thank the NIH (GM033309) for its financial support. L.M.
thanks the Belgian American Educational Foundation for the
Cabeaux−Jacobs Fellowship. We are grateful to the Beckman
Institute Laser Resource Center (BILRC) at Caltech for
facilities. We also thank Scott Virgil of the Caltech Center for
Catalysis and Chemical Synthesis for his assistance in the BNIQ
ligand synthesis and Shuo Shi for preliminary work on the
ligand synthesis.
Inorg. Chem. 2008, 47, 6452−6457. (c) Ruba, E.; Hart, J. R.; Barton, J.
̈
K. [Ru(bpy)2(L)]Cl2: Luminescent Metal Complexes that Bind DNA
Base Mismatches. Inorg. Chem. 2004, 43, 4570−4578.
(9) Sullivan, B. P.; Salmon, D. J.; Meyer, T. J. Mixed Phosphine 2,2′-
Bipyridine Complexes of Ruthenium. Inorg. Chem. 1978, 17, 3334.
(10) Hughes, R. O.; et al. Design, Synthesis, and Biological
Evaluation of 3-[4-(2-Hydroxyethyl)piperazin-1-yl]-7-(6-methoxypyr-
idin-3-yl)-1-(2-propoxyethyl)pyrido[3,4-b]pyrazin-2(1H)-one, A Po-
tent, Orally Active, Brain Penetrant Inhibitor of Phosphodiesterase 5
(PDE5). J. Med. Chem. 2010, 53, 2656−2600.
REFERENCES
■
(1) (a) Boyle, K. M.; Barton, J. K. Targeting DNA mismatches with
rhodium metalloinsertors. Inorg. Chim. Acta 2016, 452, 3−11.
(b) Granzhan, A.; Kotera, N.; Teulade-Fichou, M.-P. Finding needles
in a basestack: recognition of mismatched base pairs in DNA by small
molecules. Chem. Soc. Rev. 2014, 43, 3630−3665.
(2) (a) Zeglis, B. M.; Pierre, V. C.; Kaiser, J. T.; Barton, J. K. A Bulky
Rhodium Complex Bound to an Adenosine-Adenosine DNA
Mismatch: General Architecture of the Metalloinsertion Binding
Mode. Biochemistry 2009, 48, 4247−4253. (b) Pierre, V. C.; Kaiser, J.
T.; Barton, J. K. Insights into finding a mismatch through the structure
of a mispaired DNA bound by a rhodium intercalator. Proc. Natl. Acad.
Sci. U. S. A. 2007, 104, 429−434. (c) Jackson, B. A.; Barton, J. K.
Recognition of Base Mismatches in DNA by 5,6-Chrysenequinone
Diimine Complexes of Rhodium(III): A Proposed Mechanism of
Preferential Binding in Destabilized Regions of the Double Helix.
Biochemistry 2000, 39, 6176−6182.
(3) (a) Komor, A. C.; Barton, J. K. An Unusual Ligand Coordination
Gives Rise to a New Family of Rhodium Metalloinsertors with
Improved Selectivity and Potency. J. Am. Chem. Soc. 2014, 136,
14160−14172. (b) Komor, A. C.; Schneider, C. J.; Weidmann, A. G.;
Barton, J. K. Cell-Selective Biological Activity of Rhodium Metal-
loinsertors Correlates with Subcellular Localization. J. Am. Chem. Soc.
2012, 134, 19223−19233. (c) Ernst, R. J.; Komor, A. C.; Barton, J. K.
Selective Cytotoxicity of Rhodium Metalloinsertors in Mismatch
Repair-Deficient Cells. Biochemistry 2011, 50, 10919−10928.
(4) (a) Gill, M. R.; Thomas, J. A. Ruthenium(II) polypyridyl
complexes and DNA − from structural probes to cellular imaging and
therapeutics. Chem. Soc. Rev. 2012, 41, 3179−3192. (b) Baggaley, E.;
Weinstein, J. A.; Williams, J. A. Lighting the way to see inside the live
cell with luminescent transition metal complexes. Coord. Chem. Rev.
2012, 256, 1762−1785. (c) Lo, K. Luminescent Rhenium(I) and
Iridium(III) Polypyridine Complexes as Biological Probes, Imaging
Reagents, and Photocytotoxic Agents. Acc. Chem. Res. 2015, 48, 2985−
2995. (d) Ji, L.-N.; Zou, X.-H.; Liu, J.-G. Shape- and enantioselective
interaction of Ru(II)/Co(III) polypyridyl complexes with DNA.
Coord. Chem. Rev. 2001, 216−217, 513−536. (e) Li, G.; Sun, L.; Ji, L.;
Chao, H. Ruthenium(II) Complexes with dppz: from molecular
photoswitch to biological applications. Dalton Trans. 2016, 45,
13261−13276. (f) McKinley, A. W.; Lincoln, P.; Tuite, E. M.
Environmental effects on the photophysics of transition metal
complexes with dipyrido[2,3-a:3′,2′-c]phenazine (dppz) and related
ligands. Coord. Chem. Rev. 2011, 255, 2676−2692. (g) Lo, L.; Choi, A.;
Law, W. Applications of luminescent inorganic and organometallic
transition metal complexes as biomolecular and cellular probes. Dalton
Trans. 2012, 41, 6021−6047.
(11) Dempsey, J. L.; Winkler, J. R.; Gray, H. B. Kinetics of Electron
Transfer Reactions of H2-Evolving Cobalt Diglyoxime Catalysts. J. Am.
Chem. Soc. 2010, 132, 1060−1065.
(12) Qiujiang, D. Preparation of 2-bromopyridine from 2-
chloropyridine by halogen exchange. Chem. Ind. Times 2005, 2, 39−40.
(13) Luzung, M. R.; Patel, J. S.; Yin, J. A Mild Negishi Cross-
Coupling of 2-Heterocyclic Organozinc Reagents and Aryl Chlorides.
J. Org. Chem. 2010, 75, 8330−8332.
(14) Milne, J. E.; Buchwald, S. L. An Extremely Active Catalyst for
the Negishi Cross-Coupling Reaction. J. Am. Chem. Soc. 2004, 126,
13028−13032.
(15) Van Houten, J.; Watts, R. J. The Effect of Ligand and Solvent
Deuteration on the Excited State Properties of the Tris(2,2′-
bipyridyl)ruthenium(II) Ion in Aqueous Solution. Evidence for the
Electron Transfer to Solvent. J. Am. Chem. Soc. 1975, 97, 3843−3844.
(16) Van Houten, J.; Watts, R. J. Temperature Dependence of the
Photophysical and Photochemical Properties of the Tris(2,2′-
bipyridyl)ruthenium(II) Ion in Aqueous Solution. J. Am. Chem. Soc.
1976, 98, 4853−4858.
(17) Barton, J. K.; Danishefsky, A. T.; Goldberg, J. M. Tris-
(phenanthroline)ruthenium(II): Stereoselectivity in Binding to DNA.
J. Am. Chem. Soc. 1984, 106, 2172−2176.
(18) Lim, M. H.; Song, H.; Olmon, E. D.; Dervan, E. E.; Barton, J. K.
Sensitivity of Ru(bpy)2dppz2+ Luminescence to DNA Defects. Inorg.
Chem. 2009, 48, 5392−5397.
(19) Peyret, N.; Seneviratne, A.; Allawi, H. T.; SantaLucia, J. Nearest-
Neighbor Thermodynamics and NMR of DNA Sequences with
Internal A·A, C·C, G·G, and T·T Mismatches. Biochemistry 1999, 38,
3468−3477.
(20) SantaLucia, J.; Hicks, D. The Thermodynamics of DNA
Structural Motifs. Annu. Rev. Biophys. Biomol. Struct. 2004, 33, 415−
440.
(21) Zeglis, B. M.; Boland, J. A.; Barton, J. K. Recognition of Abasic
Sites and Base Bulges in DNA by a Metalloinsertor. Biochemistry 2009,
48, 839−849.
(22) Sigman, D. S.; Chen, C.-H. B. Chemical Nucleases: New
Reagents in Molecular Biology. Annu. Rev. Biochem. 1990, 59, 207−
236.
(5) Boynton, A. N.; Marcelis, L.; Barton, J. K. [Ru-
(Me4phen)2(dppz)]2+, a Light Switch for DNA Mismatches. J. Am.
Chem. Soc. 2016, 138, 5020−5023.
(6) (a) Friedman, A. E.; Chambron, J. C.; Sauvage, J. P.; Turro, N. J.;
Barton, J. K. Molecular “Light Switch” for DNA: Ru(bpy)2(dppz)2+. J.
Am. Chem. Soc. 1990, 112, 4960−4962. (b) Jenkins, Y.; Friedman, A.
(23) Sigman, D. S.; Mazumder, A.; Perrin, D. M. Chemical
Nucleases. Chem. Rev. 1993, 93, 2295−2316.
(24) Lim, M. H.; Lau, I. H.; Barton, J. K. DNA Strand Cleavage Near
a CC Mismatch Directed by a Metalloinsertor. Inorg. Chem. 2007, 46,
9528−9530.
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