title: Selective calcium ion sensing with a bichromophoric squaraine foldamer.
abstract: Several squaraine tethered bichromophoric podand systems 1a-d and a monochromophoric analogue 2 were prepared and characterized. Among these, the bichromophore, 1b, containing five oxygen atoms in the flexible podand moiety was found to specifically bind Ca(2+) in the presence of other metal ions such as K(+), Na(+), and Mg(2+). The selective binding of Ca(2+) is clear from the absorption and emission spectral changes as well as by the visual color change of 1b from light-blue to an intense purple-blue. Benesi-Hildebrand and Job plots confirmed a 1:1 binding between 1b and Ca(2+). Signaling of the binding event is achieved by the cation-induced folding of the bichromophore and the resultant exciton coupling between the squaraine chromophores. The monochromophoric squaraine dye 2 failed to give optical signals upon Ca(2+) binding, due to the absence of exciton interaction in the bound complex. Titration of the folded complex 9 with EDTA released the metal ion from the complex, thereby regaining the original absorption and emission properties of the bichromophore. The squaraine foldamer 1b reported here is the first example of a selective chromogenic Ca(2+) sensor, which works on the principle of exciton interaction in the folded Ca(2+) complex of a bichromophore, the optical properties of which are similar to those of the "H"-type aggregates of analogous squaraine dyes.
authors.affiliation: Photosciences and Photonics Division, Regional Research Laboratory (CSIR), Trivandrum - 695019, India.
authors.forename: Easwaran
authors.initials: E
authors.lastname: Arunkumar
authors.forename: Ayyappanpillai
authors.initials: A
authors.lastname: Ajayaghosh
authors.forename: Jörg
authors.initials: J
authors.lastname: Daub
mesh_terms: D015374:Biosensing Techniques / Q000379:methods*; D002118:Calcium / Q000032:analysis* / Q000737:chemistry; D002414:Cations, Monovalent; D003503:Cyclobutanes / Q000737:chemistry*; D004492:Edetic Acid / Q000737:chemistry; D004563:Electrochemistry; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry; D010636:Phenols / Q000737:chemistry*; D013053:Spectrophotometry; D013379:Substrate Specificity
chemical_list: D002414:Cations, Monovalent; D003503:Cyclobutanes; D008670:Metals; D010636:Phenols; C480596:squaraine; D004492:Edetic Acid; D002118:Calcium