Molecular design of artificial molecular and ion recognition systems with allosteric guest responses.

Positive or negative allosterisms are ubiquitously seen in nature where the biological events must be efficiently regulated in response to chemical or physical signals from the outside world. The biomimetic design of such allosteric systems is of great significance in order to regulate the complexation ability or the catalytic activity of artificial receptors according to an allosteric manner. Furthermore, the methodology is very useful to amplify and convert weak chemical or physical signals into other signals which are convenient for us to read out and record. Allosteric systems are classified into four different categories: positive heterotropic, negative heterotropic, positive homotropic, and negative homotropic. In this Account, we account for our artificial allosteric systems and discuss the basic concept for molecular design of such allosteric systems and what kinds of new functions come out of such dynamic systems.

[1]  T. Nabeshima Regulation of ion recognition by utilizing information at the molecular level , 1996 .

[2]  J. Changeux,et al.  Allosteric receptors after 30 years , 1998, Neuron.

[3]  Rjm Roeland Nolte,et al.  A molecular clip with allosteric binding properties , 1991 .

[4]  K. Mitsui,et al.  Synthesis of 2,6-diamidopyridine derivatives and their functions as flavin receptors in chloroform , 1994 .

[5]  S. Shinkai,et al.  Allosteric communication between the metal-binding lower rim and the sugar-binding upper rim on a calix[4]crown platform , 1995 .

[6]  A. Costero,et al.  Bis-cyclohexyl-crown-ethers as allosteric carriers , 1992 .

[7]  S. Shinkai,et al.  Diaza-18-crown-6-based Sugar Receptor Bearing Two Boronic Acids. Possible Communication between Bound Sugars and Metal Cations. , 1995 .

[8]  R. Petter,et al.  Cooperative binding by aggregated mono-6-(alkylamino)-.beta.-cyclodextrins , 1990 .

[9]  M Bolognesi,et al.  New structures of allosteric proteins revealing remarkable conformational changes. , 1996, Current opinion in structural biology.

[10]  Y. Kobuke,et al.  Metal‐Assisted Organization rather than Preorganization for the Design of Macrocyclic Hosts , 1991 .

[11]  Masayuki Takeuchi,et al.  A Strong Positive Allosteric Effect in the Molecular Recognition of Dicarboxylic Acids by a Cerium(IV) Bis[tetrakis(4-pyridyl)porphyrinate] Double Decker. , 1998, Angewandte Chemie.

[12]  D. Reinhoudt,et al.  Incorporation of nitrogen-oxygen bonds in metallomacrocycles. Synthesis, x-ray structure, and electrochemistry of heterodinuclear complexes , 1989 .

[13]  S. Shinkai,et al.  Diaza-18-crown-6-based saccharide receptor bearing two boronic acids. Possible communication between bound saccharides and metal cations , 2000 .

[14]  D. Diamond,et al.  A novel calix[4]arene tetraester with fluorescent response to complexation with alkali metal cations , 1993 .

[15]  S. Shinkai,et al.  Inclusion of [60]Fullerene in a Self-assembled Homooxacalix[3]arene-based Dimeric Capsule Constructed by a PdII–pyridine Interaction. The Li+-binding to the Lower Rims can Improve the Inclusion Ability , 2000 .

[16]  S. Shinkai,et al.  Highly Selective and Sensitive “Sugar Tweezer” Designed from a Boronic-Acid-Appended μ-Oxobis[porphinatoiron(III)] , 1996 .

[17]  T. Traylor,et al.  Cooperativity in chemical model systems: Ligand-induced subunit dimerization , 1982 .

[18]  Masayuki Takeuchi,et al.  Allosteric binding of K+ to crown ether macrocycles appended to a lanthanum double decker system , 2001 .

[19]  M. Ikeda,et al.  Ring rotation controversy in cerium(IV) bis(tetraarylporphyrinate) double deckers: HPLC evidence for the question to rotate or not to rotate , 1998 .

[20]  S. Kubik Large Increase in Cation Binding Affinity of Artificial Cyclopeptide Receptors by an Allosteric Effect , 1999 .

[21]  J. Rebek,et al.  Binding forces and catalysis. The use of bipyridyl-metal chelation to enhance reaction rates , 1985 .

[22]  Julius Rebek,et al.  ALLOSTERIC EFFECTS. REMOTE CONTROL OF ION TRANSPORT SELECTIVITY , 1980 .

[23]  Masayuki Takeuchi,et al.  Novel Oligosaccharide Binding to the Cerium(IV) Bis(porphyrinate) Double Decker: Effective Amplification of a Binding Signal through Positive Homotropic Allosterism. , 2000, Angewandte Chemie.

[24]  M. Ikeda,et al.  Allosteric silver(I) ion binding with peripheral pi clefts of a Ce(IV) double decker porphyrin. , 2000, Organic letters.

[25]  Al-Sayah,et al.  Metal Ions as Allosteric Inhibitors in Hydrogen-Bonding Receptors This work was supported by a grant from the Natural Sciences and Engineering Research Council of Canada and by Research Corporation (Research Innovation Award). , 2000, Angewandte Chemie.

[26]  S. Shinkai,et al.  Fluorescent calix[4]arene which responds to solvent polarity and metal ions , 1991 .

[27]  Y. Ishimaru,et al.  A new biphenyl-20-crown-6-derived zinc(II) porphyrin dimer with a potentially heterotropic allostery , 1999 .

[28]  Roger Guilard,et al.  The porphyrin handbook , 2002 .

[29]  S. Shinkai,et al.  A new metal sensory system based on intramolecular fluorescence quenching on the ionophoric calix[4]arene ring , 1992 .

[30]  Tony D. James,et al.  Fluorescent saccharide receptors: A sweet solution to the design, assembly and evaluation of boronic acid derived PET sensors , 1996 .

[31]  S. Shinkai,et al.  Allosteric Interaction of Metal Ions with Saccharides in a Crowned Diboronic Acid , 1994 .

[32]  S. Shinkai,et al.  “Cone”–“Partial Cone” Isomerism in Tetramethoxy-p-t-butylcalix[4]arene. Novel Solvent Effects and Metal Template Effects , 1990 .

[33]  S. Shinkai,et al.  A diboronic acid ‘glucose cleft’ and a biscrown ether ‘metal sandwich’ are allosterically coupled , 1995 .

[34]  R. Krämer,et al.  Allosteric Regulation of Artificial Phosphoesterase Activity by Metal Ions This work was funded by the DFG (Gerhard Hess Programm). , 2000, Angewandte Chemie.

[35]  Takuzo Aida,et al.  Enantiomeric Resolution of Chiral Metallobis(porphyrin)s: Studies on Rotatability of Electronically Coupled Porphyrin Ligands , 1997 .

[36]  J. Pierre,et al.  An artificial allosteric system : regulation of a biomimetic reduction (NADH model) by potassium ions , 1992 .

[37]  C. Hunter,et al.  COOPERATIVE INTERACTIONS IN A TERNARY MIXTURE , 1998 .

[38]  T. Konishi,et al.  Artificial allosteric receptors for nucleotide bases and alkali-metal cations , 1993 .

[39]  Jr. Julius Rebek,et al.  Binding forces, equilibria and rates: new models for enzymic catalysis , 1984 .

[40]  Y. Kobuke,et al.  Positive cooperativity in cation binding by novel polyether-bis(.beta.-diketone) hosts , 1992 .

[41]  Masayuki Takeuchi,et al.  The First Example of Positive Allosterism in an Aqueous Saccharide-Binding System Designed on a Ce(IV) Bis(porphyrinate) Double Decker Scaffold , 2000 .

[42]  Yasutaka Tanaka,et al.  Highly cooperative binding of alkyl glucopyranosides to the resorcinol cyclic tetramer due to intracomplex guest-guest hydrogen-bonding: solvophobicity/solvophilicity control by an alkyl group of the geometry, stoichiometry, stereoselectivity, and cooperativity , 1992 .

[43]  B. Perlmutter-Hayman Cooperative binding to macromolecules. A formal approach , 1986 .

[44]  Th. Ackermann,et al.  K. A. Connors: Binding constants — the measurement of molecular complex stability, John Wiley & Sons, New York, Chichester, Brisbane, Toronto, Singapore 1987. 411 Seiten, Preis: £ 64.15 , 1987 .

[45]  K. Ichikawa,et al.  A fluorescent calix[4]arene as an intramolecular excimer-forming Na+ sensor in nonaqueous solution , 1992 .