Dynamic cyclen-metal complexes for molecular sensing and chirality signaling.

Structural dynamism plays important roles in artificial and biological systems, because it controls structures and functions of various molecules and assemblies. In this review, molecular recognition and self-assembling behavior of dynamic armed cyclen-metal complexes are discussed at the molecular and supramolecular levels. These metal complexes provide useful platforms for molecular receptors, supramolecules, and molecular assemblies that can respond rapidly to guest molecules and environments. Since armed cyclens have many structural and geometrical variations, they form a wide variety of metal complexes having specific sensing and signaling functions. The Lewis acidity of the metal cations plays an essential role in anion binding and in hydrolytic catalysis of phosphate esters. Characteristic luminescence and magnetic properties of lanthanides also enable techniques for effective bio-imaging. They also serve as chiral building blocks for self-assembled architectures, which offer chirality integration effective for chirality sensing and signaling at the supramolecular level.

[1]  D. Parker,et al.  Lanthanide complexes as chiral probes exploiting circularly polarized luminescence. , 2012, Chemical Society reviews.

[2]  Hiroshi Ito,et al.  Molecular recognition: from solution science to nano/materials technology. , 2012, Chemical Society reviews.

[3]  A. Sherry,et al.  Europium(III) DOTA-tetraamide complexes as redox-active MRI sensors. , 2012, Journal of the American Chemical Society.

[4]  J. Lehn.  Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry. , 2013, Topics in current chemistry.

[5]  B. König,et al.  Vesicles and micelles from amphiphilic zinc(II)-cyclen complexes as highly potent promoters of hydrolytic DNA cleavage. , 2011, Journal of the American Chemical Society.

[6]  O. Blacque,et al.  Alfred Werner's coordination chemistry: new insights from old samples. , 2011, Angewandte Chemie.

[7]  S. Aoki,et al.  11B NMR sensing of d-block metal ions in vitro and in cells based on the carbon-boron bond cleavage of phenylboronic acid-pendant cyclen (cyclen = 1,4,7,10-tetraazacyclododecane). , 2011, Inorganic chemistry.

[8]  T. Meade,et al.  Reporter protein-targeted probes for magnetic resonance imaging. , 2011, Journal of the American Chemical Society.

[9]  M. Schabel,et al.  Towards the rational design of MRI contrast agents: δ-substitution of lanthanide(III) NB-DOTA-tetraamide chelates influences but does not control coordination geometry. , 2011, Chemistry.

[10]  D. Woessner,et al.  Investigations into whole water, prototropic and amide proton exchange in lanthanide(III) DOTA-tetraamide chelates. , 2011, Dalton transactions.

[11]  J. Morrow,et al.  Eu(III) complexes as anion-responsive luminescent sensors and paramagnetic chemical exchange saturation transfer agents. , 2011, Inorganic chemistry.

[12]  M. Yoneda,et al.  Mixed-metal complexes incorporating platinum and lanthanide centers for selective binding and chirality sensing of succinates. , 2011, Inorganic chemistry.

[13]  T. Zuchner,et al.  Lanthanide-based time-resolved luminescence immunoassays , 2011, Analytical and bioanalytical chemistry.

[14]  C. Rao,et al.  Ion and molecular recognition by lower rim 1,3-di-conjugates of calix[4]arene as receptors. , 2011, Chemical reviews.

[15]  Katsuhiko Ariga,et al.  Langmuir monolayers of a cholesterol-armed cyclen complex that can control enantioselectivity of amino acid recognition by surface pressure. , 2011, Physical chemistry chemical physics : PCCP.

[16]  D. Jin,et al.  Time-gated luminescence microscopy allowing direct visual inspection of lanthanide-stained microorganisms in background-free condition. , 2011, Analytical chemistry.

[17]  Cunyuan Zhao,et al.  Dinuclear Zn(II) complex catalyzed phosphodiester cleavage proceeds via a concerted mechanism: a density functional theory study. , 2011, Journal of the American Chemical Society.

[18]  H. Kalbitzer,et al.  Cu2+-cyclen as probe to identify conformational states in guanine nucleotide binding proteins. , 2011, Journal of the American Chemical Society.

[19]  M. Shionoya,et al.  Chiral recognition of α-amino acids by an optically active (2S,5S,8S,11S)-2,5,8,11-tetraethyl cyclen cobalt(III) complex. , 2011, Inorganic chemistry.

[20]  S. Kubik.  Anion recognition in water. , 2010, Chemical Society reviews.

[21]  Katsuhiko Ariga,et al.  Mechanical tuning of molecular recognition to discriminate the single-methyl-group difference between thymine and uracil. , 2010, Journal of the American Chemical Society.

[22]  I. Kuprov,et al.  Probing the structure, conformation, and stereochemical exchange in a family of lanthanide complexes derived from tetrapyridyl-appended cyclen. , 2010, Inorganic chemistry.

[23]  S. Aoki,et al.  Molecular recognition of inositol 1,4,5-trisphosphate and model compounds in aqueous solution by ditopic Zn(2+) complexes containing chiral linkers. , 2010, Inorganic chemistry.

[24]  Thorsten Graf,et al.  Stabilizing a weak binding state for effectors in the human ras protein by cyclen complexes. , 2010, Angewandte Chemie.

[25]  Ambika Bumb,et al.  Macromolecules, dendrimers, and nanomaterials in magnetic resonance imaging: the interplay between size, function, and pharmacokinetics. , 2010, Chemical reviews.

[26]  M. Komiyama,et al.  Binuclear terbium(III) complex as a probe for tyrosine phosphorylation. , 2010, Chemistry.

[27]  A. Morita,et al.  Design and synthesis of a fluorescent probe for Zn2+, 5,7-bis(N,N-dimethylaminosulfonyl)-8-hydroxyquinoline-pendant 1,4,7,10-tetraazacyclododecane and Zn2+-dependent hydrolytic and Zn2+-independent photochemical reactivation of its benzenesulfonyl-caged derivative. , 2010, Inorganic chemistry.

[28]  L. Spiccia,et al.  OFF-ON fluorescent detection of thymidine nucleotides by a zinc(II)-cyclen complex bearing two diagonal pyrenes. , 2009, Chemistry.

[29]  S. Shinoda,et al.  Asymmetric twisting and chirality probing properties of quadruple-stranded helicates: coordination versatility and chirality response of Na(+), Ca(2+), and La(3+) complexes with octadentate cyclen ligand. , 2009, Inorganic chemistry.

[30]  G. Muller.  Luminescent chiral lanthanide(III) complexes as potential molecular probes. , 2009, Dalton transactions.

[31]  J. Morrow,et al.  Cerium(III), europium(III), and ytterbium(III) complexes with alcohol donor groups as chemical exchange saturation transfer agents for MRI. , 2009, Inorganic chemistry.

[32]  K. Raymond,et al.  Gd-hydroxypyridinone (HOPO)-based high-relaxivity magnetic resonance imaging (MRI) contrast agents. , 2009, Accounts of chemical research.

[33]  K. Kikuchi,et al.  Anion sensor-based ratiometric peptide probe for protein kinase activity. , 2009, Organic letters.

[34]  R. Doyle,et al.  The coordination chemistry of 1,4,7,10-tetraazacyclododecane-N,N′,N″,N′″-tetraacetic acid (H4DOTA): Structural overview and analyses on structure–stability relationships , 2009 .

[35]  Mark D Pagel,et al.  Using two chemical exchange saturation transfer magnetic resonance imaging contrast agents for molecular imaging studies. , 2009, Accounts of chemical research.

[36]  R. Pal,et al.  Cell-penetrating metal complex optical probes: targeted and responsive systems based on lanthanide luminescence. , 2009, Accounts of chemical research.

[37]  Susan J. Quinn,et al.  Recent developments in the field of supramolecular lanthanide luminescent sensors and self-assemblies , 2008 .

[38]  Francesco Selvestrel,et al.  Phosphate diester and DNA hydrolysis by a multivalent, nanoparticle-based catalyst. , 2008, Journal of the American Chemical Society.

[39]  L. Lindoy,et al.  Recent developments in the d-block metallo-supramolecular chemistry of polypyridyls , 2008 .

[40]  H. Nishihara,et al.  Modification of the luminescence spectra of chloro(tetrapyridylcyclotetramine)europium complexes by fine tuning of the Eu-Cl distance with outer-sphere counterions in the solid state, in a polymer matrix and in solution. , 2008, Chemical communications.

[41]  M. Borkovec,et al.  Tuneable intramolecular intermetallic interactions as a new tool for programming linear heterometallic 4f-4f complexes. , 2007, Inorganic chemistry.

[42]  H. Nishihara,et al.  Control of coordination and luminescence properties of lanthanide complexes using octadentate oligopyridine-amine ligands , 2007 .

[43]  E. Constable,et al.  2,2':6',2''-terpyridines: from chemical obscurity to common supramolecular motifs. , 2007, Chemical Society reviews.

[44]  S. Lincoln,et al.  Synthesis and characterization of water-operative cationic and anionic metal-ion activated molecular receptors for aromatic anions. , 2006, Inorganic chemistry.

[45]  Katsuhiko Ariga,et al.  Mechanical control of enantioselectivity of amino acid recognition by cholesterol-armed cyclen monolayer at the air-water interface. , 2006, Journal of the American Chemical Society.

[46]  A. Sherry,et al.  Structural and chiroptical properties of the two coordination isomers of YbDOTA-type complexes. , 2005, Inorganic chemistry.

[47]  S. Shinoda,et al.  Cholesterol-armed cyclens for helical metal complexes offering chiral self-aggregation and sensing of amino acid anions in aqueous solutions. , 2005, The Journal of organic chemistry.

[48]  J. Howard,et al.  Structural and NMR investigations of the ternary adducts of twenty alpha-amino acids and selected dipeptides with a chiral, diaqua-ytterbium complex. , 2004, Dalton transactions.

[49]  S. Shinoda,et al.  Armed Cyclen Receptors : From Three Dimensional Cation Recognition to Supramolecular Architecture , 2004 .

[50]  S. Aoki,et al.  Zinc-nucleic acid interaction. , 2004, Chemical reviews.

[51]  H. Puschmann,et al.  Structural analysis of nine-coordinate lanthanide complexes: steric control of the metal-water distance across the series. , 2003, Inorganic chemistry.

[52]  S. Aoki,et al.  A new zinc(II) fluorophore 2-(9-anthrylmethylamino)ethyl-appended 1,4,7,10-tetraazacyclododecane. , 2003, Inorganic chemistry.

[53]  T. Gunnlaugsson,et al.  Delayed lanthanide luminescence sensing of aromatic carboxylates using heptadentate triamide Tb(III) cyclen complexes: the recognition of salicylic acid in water. , 2002, Chemical communications.

[54]  Y. Urano,et al.  A fluorescent anion sensor that works in neutral aqueous solution for bioanalytical application. , 2002, Journal of the American Chemical Society.

[55]  Max R. Taylor,et al.  Metal ion-dependent molecular inclusion chemistry: inclusion of aromatic anions by coordinated 1,4,7,10-tetrakis((S)-2-hydroxy-3-phenoxypropyl)-1,4,7,10-tetraazacyclododecane. , 2002, Inorganic chemistry.

[56]  S. Aoki,et al.  New potent agents binding to a poly(dT) sequence in double-stranded DNA: bis(Zn2+-cyclen) and tris(Zn2+-cyclen) complexes , 2002, JBIC Journal of Biological Inorganic Chemistry.

[57]  S. Shinoda,et al.  Cholesterol-armed cyclen–Na+ complex as a chiral, helicated amphiphile for supramolecular architecture: self-aggregation and chirality induction in aqueous solution , 2001 .

[58]  L. D. Bari,et al.  Effect of Axial Ligation on the Magnetic and Electronic Properties of Lanthanide Complexes of Octadentate Ligands , 2000 .

[59]  M. Botta,et al.  Ternary Gd(III)L-HSA adducts: evidence for the replacement of inner-sphere water molecules by coordinating groups of the protein. Implications for the design of contrast agents for MRI , 2000, JBIC Journal of Biological Inorganic Chemistry.

[60]  M. W. Hosseini,et al.  Cryptands revisited: Design, synthesis, complexation behaviour and structural analysis of borocryptands , 1998 .

[61]  S. Lincoln.  Mechanistic studies of some macrocyclic complexes , 1997 .

[62]  M. Botta,et al.  Conformational and Coordination Equilibria on DOTA Complexes of Lanthanide Metal Ions in Aqueous Solution Studied by (1)H-NMR Spectroscopy. , 1997, Inorganic chemistry.

[63]  J. Howard,et al.  Structural rigidity and luminescence of chiral lanthanide tetraamide complexes based on 1,4,7,10-tetraazacyclododecane , 1997 .

[64]  S. Aoki,et al.  A NOVEL BIOMIMETIC ZINC(II)-FLUOROPHORE, DANSYLAMIDOETHYL-PENDANT MACROCYCLIC TETRAAMINE 1,4,7,10-TETRAAZACYCLODODECANE (CYCLEN) , 1996 .

[65]  T. Koike,et al.  HYDROLYSIS OF LIPOPHILIC ESTERS CATALYZED BY A ZINC(II) COMPLEX OF A LONG ALKYL-PENDANT MACROCYCLIC TETRAAMINE IN MICELLAR SOLUTION , 1996 .

[66]  M. Botta,et al.  NMR study of solution structures and dynamics of lanthanide(III) complexes of DOTA , 1992 .

[67]  J. Desreux,et al.  Crystal and molecular structure of sodium aqua(1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetato)europate(III) tetrahydrate Na+(EuDOTA.H2O)-.4H2O, and its relevance to NMR studies of the conformational behavior of the lanthanide complexes formed by the macrocyclic ligand DOTA , 1984 .

[68]  J. Krane,et al.  1,4,7,10-Tetrakis(2-hydroxyethyl)-1,4,7,10-tetra-azacyclododecane: a strong cation complexer , 1982 .

[69]  Y. Moroi.  Mechanisms of light-initiated redox reactions of copper(II)-cyclic polyamine surfactant assemblies. , 1981 .

[70]  C. Swahn,et al.  Exploratory Calculations of Medium and Large Rings. Part 2. Conformational Interconversions in Cycloalkanes. , 1973 .

[71]  H. Taube.  Rates and Mechanisms of Substitution in Inorganic Complexes in Solution. , 1952 .