Anion induced azo-hydrazone tautomerism for the selective colorimetric sensing of fluoride ion.

The design, synthesis, characterization and their anion sensing properties of two receptors capable of exhibiting azo-hydrazone tautomerism are reported. The anion sensing properties have been investigated using electronic, fluorescence and nuclear magnetic spectral studies in addition to electrochemical and visual detection experiments. Both the receptors selectively bind fluoride ion with >100 nm red-shift in the electronic spectrum and the color changes from yellow to red. The results of the spectral studies revealed that the sensing mechanism involves fluoride ion induced change of chromophore from C=N (hydrazone form) to N=N (azo form) in these receptors leading to the visible color change. Density Functional Theory calculations were conducted to rationalize the optical response of the receptors.

Molecular complexes of l-phenylalanine with substituted 1,4-benzoquinones in aqueous medium: spectral and theoretical investigations.

Various spectral techniques such as UV-Vis, FT-IR, and fluorescence have been employed to investigate the charge transfer interaction of L-phenylalanine (LPA) with substituted 1,4-benzoquinones (MQ(1-4)). Kinetic and thermodynamic properties of the complexes were determined in aqueous medium at physiological condition (pH=7). The interaction of MQ(1-4) with L-phenylalanine (LPA) was found to proceed through the formation of donor-acceptor complex, yielding a radical anion. The stoichiometry of the complexes was determined by Jobs continuous variation method and was found to be 1:1 in all the cases. Fluorescence quenching studies showed that the interaction between the donor and the acceptors is spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The order of the experimentally measured association constant of these complexes was well supported by DFT/B3LYP calculations.

Charge transfer complexes of quinones in aqueous medium: spectroscopic and theoretical studies on interaction of cimetidine with novel substituted 1,4-benzoquinones and its application in colorimetric sensing of anions.

For the first time, the charge transfer (CT) complexes of quinones in aqueous medium have been reported. A series of novel water soluble 1,4-benzoquinones possessing variable number of chloro and methoxy substituents has been employed as electron acceptors (MQ1-4) in the CT complexation with cimetidine (CTD) drug. The mechanism of the interaction has been investigated using various spectral techniques such as UV-Vis, (1)H NMR and FT-IR spectra. The rate of the CT interaction was observed to decrease with progressive replacement of chloro by methoxy substituent in the quinone and this variation is well supported by the formation constant and enthalpy of activation values. Ab initio DFT calculations predicted that the variation in the bond lengths of the carbonyl moieties and the charge densities on the carbonyl oxygen atoms depend largely on the nature of the substituent present in the quinone ring. Also, the HOMO(Donor)-LUMO(Acceptor) energy gaps correlate linearly with the formation constants of the CT complex. The equilibrium, kinetic, electrochemical and theoretical investigations of the CT interaction of these quinones indicated that progressive replacement of electron withdrawing chlorine atom (-I effect) by an electron releasing methoxy group (+M effect) makes these acceptors progressively weaker. The charge-transfer complex, formed between CTD and monomethoxy quinone derivative, has been employed as a new class of chromogenic sensor for the colorimetric sensing of fluoride and acetate ions.

Substituent effect on the electron acceptor property of 1,4-benzoquinone towards the formation of molecular complex with sulfamethoxazole.

UV-Vis, (1)H NMR, FT-IR, LC-MS and fluorescence spectral techniques were employed to investigate the mechanism of interaction of sulfamethoxazole with varying number of methoxy/chloro substituted 1,4-benzoquinones (MQ1-4) and to characterize the reaction products. The interactions of MQ1-4 with sulfamethoxazole (SULF) were found to proceed through the formation of a donor-acceptor complex, containing radical anion and its conversion to the product. Fluorescence quenching studies showed that the interaction between the donor and the acceptors are spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The results of the correlation of experimentally measured binding constants with electrochemical data and ab initio DFT calculations supported these observations.

Spectroscopic investigation on the mechanism of formation of molecular complexes of albendazole and trimethoprim with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

UV-vis, (1)H NMR, FT-IR, mass and fluorescence spectral techniques were employed to investigate the mechanism of interaction of albendazole and trimethoprim with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and to characterize the reaction products. The interaction of DDQ with trimethoprim (TMP) and albenadazole (ALB) were found to proceed through the formation of donor-acceptor complex, containing DDQ radical anion and its conversion to the product. Fluorescence quenching studies indicated that the interaction between the donors and the acceptor are spontaneous and the interaction of TMP-DDQ (binding constant=2.9×10(5)) is found to be stronger than that the ALB-DDQ (binding constant=3×10(3)) system. Also, the binding constant increased with an increase in polarity of the medium indicating the involvement of radical anion as intermediate.