title: A Bifunctional Thioether Linked Coumarin Appended Calix[4]arene Acquires Selectivity Toward Cu(2+) Sensing on Going from Solution to SAM on Gold.
abstract: A bifunctional calix[4]arene molecule bearing coumarin moiety on the lower rim and thioether moiety on the upper rim (L1), has been synthesized and well characterized by (1)H, (13)C NMR and mass spectrometry. Suitably functionalized coumarin moieties are well suited for selective recognition of various cations and anions. Among the 10 different metal ions studied, only Cu(2+) and Fe(3+) exhibit appreciable changes in the absorption spectra owing to the availability of functional moieties present at both the lower as well as the upper rim of free L1 in acetonitrile solution. To bring better selectivity, we blocked one of these functional moieties by coating on to a surface so that only the other one is exposed to the environment for sensing. Such a study carried out in the present case using the self-assembled monolayer (SAM) of L1 on Au(111) resulted in selective sensing of Cu(2+) over several other metal ions as studied by surface plasmon resonance (SPR). The SAM of L1 on Au(111) was confirmed by different techniques, such as grazing incidence FT-IR, contact angle measurement, cyclic voltammetry and scanning tunneling microscopy. Thus, L1 is proven to be a suitable sensor for Cu(2+) when attached to gold surface.
authors.affiliation: Bioinorganic Laboratory, Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India.
authors.forename: Kushal
authors.initials: K
authors.lastname: Samanta
authors.affiliation: Bioinorganic Laboratory, Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India.
authors.forename: Chebrolu Pulla
authors.initials: CP
authors.lastname: Rao
keywords: bifunctional calix[4]arene; isothermal titration calorimetry; ratio-metric sensing of Cu2+; scanning tunneling microscopy; self-assembled monolayer on Au(111); surface plasmon resonance