Selective fluorometric detection of pyrophosphate by 3-hydroxyflavone-diphenyltin(iv) complex in aqueous micellar medium

Abstract

3-Hydroxyflavonate-diphenyltin(IV) chloride (Ph(2)Sn(Ofl)Cl) was prepared and characterized structurally by single crystal X-ray diffraction. The compound possesses high fluorescence (λ(max) 464 nm with excitation at 400 nm) in neutral aqueous solutions containing 5 mM cetyltrimethylammonium chloride and does not lose the flavonol ligand even at high dilution. The fluorescence is selectively quenched by pyrophosphate (PPi) (linear range 0-5 μM, detection limit 0.1 μM). Determination of 1 μM PPi tolerates the presence of 100-fold excess of AMP, ADP, inorganic phosphate and acetate, and 10-fold excess of ATP. From concentration profiles of the quenching effect it is concluded that quenching occurs due to formation of the complex (Ph(2)Sn(Ofl))(3)PPi, which is transformed at higher PPi concentrations to a simple 1 : 1 complex Ph(2)Sn(Ofl)(PPi). No flavonol ligand exchange with PPi is observed. A series of related organotin(IV) complexes were prepared in situ by reacting 3-hydroxyflavone with Me(2)SnCl(2), PhSnCl(3) and n-BuSnCl(3). The derivatives of Me(2)SnCl(2) and PhSnCl(3) behave similarly to Ph(2)Sn(Ofl)Cl but with lower sensitivity to PPi. However, the n-butyltin(IV) derivative tentatively of the composition n-BuSn(Ofl)(2) undergoes fluorescence enhancement rather than quenching in the presence of PPi in the μM concentration range. The results of this study demonstrate that the use of metal flavonol complexes as optical sensors for anions is a promising approach.

Fluorescent and colorimetric chemosensors for pyrophosphate

“…In an extension of this work, the Yatsimirsky group employed 3-hydroxyflavonate(Ofl)-diphenyltin(IV) chloride (Ph 2 Sn(Ofl)Cl) as a selective fluorescent chemosensor for PPi. 38 Complex 50 (Fig. 26) showed strong fluorescence in non-aqueous media but a significant decrease in fluorescence was observed in the presence of water above 10% vol.…”

23‐ and 27‐Membered Macrocyclic Diorganotin(IV) Bis‐dithiocarbamates: Synthesis, Spectroscopic Characterization, DFT Calculations, and Physicochemical Analysis as Anion Receptors

“…Organotin complexes have attracted considerable interest because of their applications in phase‐transfer and transesterification catalysis, in pharmaceutical sciences as antifungicidal, antibacterial, and anti‐tumoral agents, in molecular biology as anion ionophores on membranes, and in electrochemistry for the preparation of ion‐selective polymeric membrane electrodes . Diorganotin complexes derived from dicarboxylates and bis‐dithiocarbamates are known to frequently generate macrocyclic and cage‐type structures, which have been examined exhaustively during the past few years ,…”

An Efficient Probe for Rapid Detection of Cyanide in Water at Parts per Billion Levels and Naked‐Eye Detection of Endogenous Cyanide

“…The use of a micellar medium for the detection of cations has been reported 55–67. In contrast, there are fewer reports in which micelles have been used for anion detection 68–72. We used here a nonionic surfactant, Brij‐58 (known for its use in protein chemistry) for the stabilization of probe 1 in aqueous medium.…”

“…[55][56][57][58][59][60][61][62][63][64][65][66][67] In contrast, there are fewer reports in which micelles have been used for anion detection. [68][69][70][71][72] We used here a nonionic surfactant, Brij-58 (known for its use in protein chemistry) for the stabilization of probe 1 in aqueous medium. Use of Brij-58 micelles ( % 1 mm) showed a small increase in the absorption intensity of 1 (see the Supporting Information).…”