An ultrasensitive and highly selective fluorescent and colorimetric chemosensor for citrate ions based on rhodamine B and its application as the first molecular security keypad lock based on phosphomolybdic acid and citrate inputs

Rhodamine B (Rh-B) has been developed as novel and efficient colorimetric and fluorometric chemosensor for citrate ions (Cit(3-)) in an absolutely aqueous media. The UV-vis absorption and fluorescent emission titrations experiments have been employed to study the sensing process. RhB could act as an efficient ON-OFF fluorescent chemosensor for phosphomolybdic acid (PMA) based on an electron transfer (ET) process. Also (Rh-B(+))(3 center dot)PMA(3-) could operate as an OFF-ON fluorescent chemosensor for citrate ions based on a ligand substitution process. The chemosensor RhB shows excellent fluorescence sensitivity and selectivity toward citrate in aqueous media, and displays ON-OFF-ON type fluorescence change with alternately adding PMA and citrate to the media along with reversible association-dissociation of the complex. The (Rh-B(+))(3 center dot)PMA(3-) can be applied to the quantification of citrate with a linear ranges covering from 0.053 to 0.83 and 0.08 to 1.6 mu M by detection limits of 6.0 and 9.1 nM for fluorescence and calorimetric methods respectively. The keypad lock operation is particularly important, as the output of the system depends not only on the proper combination but also on the order of input signals, creating the correct password that can be used to open this molecular keypad lock through strong fluorescence emission at 575 nm. As a whole, its various logic gate properties may improve its impact for the development of new-generation intelligence digital devices. The ionic PMA and Cit(3-) inputs to (Rh-B(+))(3 center dot)PMA(3-) have been mimicked as a superimposed electronic molecular keypad lock. Also indicates that RhB is suitable for the detection of Cit(3-) ions in the biological environment. (C) 2014 Elsevier B.V. All rights reserved.