title: Ferrocene-carbohydrate conjugates as electrochemical probes for molecular recognition studies.
abstract: We report two methods that have allowed the attachment of glucose, mannose and lactose to one or both of the cyclopentadienyl rings of ferrocene. The resulting ferrocene-carbohydrate conjugates were synthesised by the reaction of thioglycosides with ferrocenemethanol and 1,1'-ferrocenedimethanol in acidic media. A second method based on the regiospecific copper(I)-catalysed cycloaddition of propargyl glycoside, azidomethyl and bis(azidomethyl)ferrocene as well as azidoethyl glycoside and ethynylferrocene was also used and led to the synthesis of 1,2,3-triazole-containing glycoconjugates. The electrochemical behaviour of the synthesised glycoconjugates was investigated. In addition, their binding interactions with beta-cyclodextrin were studied by means of NMR spectroscopy, isothermal titration calorimetry, and cyclic and differential pulse voltammetric experiments. These techniques allowed the determination of the thermodynamic parameters of the complexes, the stability constants for the complexes formed with both the neutral and the oxidised states of the ferrocenyl glycoconjugates, the mode of inclusion and the diffusion coefficients for both the glycoconjugates and the complexes.
authors.affiliation: Area de Química Orgánica, Universidad de Almería, 04120 Almería, Spain.
authors.forename: Juan M
authors.initials: JM
authors.lastname: Casas-Solvas
authors.forename: Emilia
authors.initials: E
authors.lastname: Ortiz-Salmerón
authors.forename: Juan J
authors.initials: JJ
authors.lastname: Giménez-Martínez
authors.forename: Luís
authors.initials: L
authors.lastname: García-Fuentes
authors.forename: Luís F
authors.initials: LF
authors.lastname: Capitán-Vallvey
authors.forename: Francisco
authors.initials: F
authors.lastname: Santoyo-González
authors.forename: Antonio
authors.initials: A
authors.lastname: Vargas-Berenguel
mesh_terms: D002151:Calorimetry; D003505:Cyclodextrins / Q000737:chemistry; D004563:Electrochemistry; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D000075163:Metallocenes; D008968:Molecular Conformation; D009005:Monosaccharides / Q000138:chemical synthesis / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D003505:Cyclodextrins; D005296:Ferrous Compounds; D000075163:Metallocenes; D009005:Monosaccharides; C004998:ferrocene