Short communicationColorimetric ‘naked eye’ sensor for fluoride ion based on isatin hydrazones via hydrogen bond formation: Design, synthesis and characterization ascertained by Nuclear Magnetic Resonance, Ultraviolet–Visible, Computational and Electrochemical studies
Graphical abstract
Introduction
The sensing and recognition of various anions are being a hot topic in the field of supramolecular chemistry due to its important roles played in the areas of biological, chemical, environmental areas [1], [2], [3], [4], [5], [6]. Normally sensing of anions is quite difficult on comparing with cations, due to their size, shape, and low stability constants [7]. Many sensors have been developed for the sensing of anions based on the electrostatic interaction and hydrogen bonding [8], [9], [10].
Among the various anions, fluoride is the one having distinctive chemical and biological properties and huge applications in daily life. Fluoride ions having high charge density, electronegativity, small ionic size, and hard Lewis base nature. Many dental problems in humans like osteoporosis can be cured by the vital role played by fluoride ions [11]. According to WHO, F− intake above 2 mg/L in drinking water may lead to serious health problems like bone cancer, thyroid disorder and bone fragility [12], [13]. In the case of flora, excess F− leads to a decrease in growth and yield and consequently affect the surrounding fauna. Besides, F− is being used in microelectronic sensors, computer chip production and television screens [14].
There are several reported techniques for the detection of anions which include mass spectroscopy [15], ion chromatography [16], flow injection distillation method [17], electrochemistry [18] and colorimetry [19]. The development of colorimetric anion sensors/chemosensors is necessary, because of its visual detection which can give qualitative and quantitative information, cost-effective and no major instrument required. Chemosensors interacts with anions through hydrogen bonding, electrostatic and coordinate interactions or sometimes combination of these type. Considerable chemosensors are reported containing amines [20], urea [21], imidazole [22], imines [23], thiourea [24], phenol [25], pyrrole [26] and hydrazones [27] which detects via formation of hydrogen bond. The present study involves the formation of Schiff bases through a reaction between hydrazones of isatin and aromatic aldehyde containing ortho hydroxyl group.
Synthesis of F− sensor (Z)-3-(((E)-5-bromo-2-hydroxybenzylidene)hydrazono)indolin-2-one (R-IND) was attempted through the formation of isatin hydrazones in the first step and condensation of this with an aromatic aldehyde in the second step. The Sensor R-IND can detect F− in 100% ACN and 20% aqua ACN medium without the interference of other anions through the formation of hydrogen bonding between the hydroxy and amine group of the R-IND and F− ion and it was further supported by UV–Vis, NMR titration and electrochemical techniques. A density functional study was also carried out for its computational support.
Section snippets
Materials and methods
All reagents and solvents, all the anions received as tetrabutylammonium salts from Merck (India) and SD Fine Chem Pvt. Limited (India) and used as such without purification. All UV–Visible spectra were carried out in 100% ACN and 20% aqua ACN, NMR spectra of the samples were taken using a JEOL (400 MHz), where tetramethylsilane (TMS) was used as the internal standard and DMSO‑d6 as the solvent. Resonance multiplicities were explained as s (singlet), d (doublet), t (triplet), and m (multiplet).
Synthesis and characterization of sensor R-IND
The design and synthesis of R-IND are expressed in Scheme 1. In typical, by simple condensation reaction between isatin (0.50 g, 0.003 mmol) and hydrazine hydrate (0.2 g, 0.004 mmol) in the presence of methanol as solvent under reflux for 6 h. Soon after, the formed precipitate was filtered through Whatman No. 41 filter paper and washed several times with cold methanol to yield an intermediate compound. The completion of the reaction was monitored by TLC. The R-IND was obtained by the reaction
Conclusion
In conclusion, a fast, inexpensive and simple to use isatin based sensor for the sensing of F− ions has been developed in 100% ACN and 20% aqua ACN media with good sensitivity as well as selectivity. The Sensor R-IND exhibited color change only upon the addition of F− ions with the significant red shift in UV–Vis spectra among the other competitive anions like Cl−, I−, Br−, H2PO4−, AcO−, CN–, NO3–, ClO4− and HSO4−. The hydrogen bond formation between the hydroxyl, amine group of the R-IND and F−
CRediT authorship contribution statement
B.U. Gauthama: Conceptualization, Data curation, Investigation, Methodology, Writing - original draft. B. Narayana: Resources, Project administration, Writing - review & editing. B.K. Sarojini: Writing - review & editing. J.G. Manjunatha: Supervision. N.K. Suresh: Data curation, Methodology.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgment
The authors gratefully acknowledge BSR one time grant to Prof. B. Narayan for purchase of chemicals. Authors thank DST-PURSE, and NMR Facility Mangalore University for helping in the characterization and also thank the Department of Chemistry FMKMC College, Madikeri, Mangalore University Constituent College for the electrochemical study.
References (39)
- et al.
Synthesis and photophysical characterization of a Schiff base as anion sensor
Sens. Actuators, B
(2009) - et al.
Amide based receptors for anions
Coord. Chem. Rev.
(2003) - et al.
Macrocyclic anion receptors based on directed hydrogen bonding interactions
Coord. Chem. Rev.
(2003) - et al.
Amino-naphthoquinone and its metal chelates for selective sensing of fluoride ions
Sens. Actuators, B
(2015)et al.Using different chemical methods for deposition of CdS on TiO2 surface and investigation of their influences on the dye-sensitized solar cell performance
Electrochim. Acta
(2014) - et al.
Visual detection of fluoride ion based on ICT mechanism
Spectrochim. Acta Part A Mol. Biomol. Spectrosc.
(2019)et al.Magnesium oxide nanocrystals via thermal decomposition of magnesium oxalate
J. Phys. Chem. Solids
(2010) - et al.
Determination of cyanide in blood by electrospray ionization tandem mass spectrometry after direct injection of dicyanogold
Anal. Bioanal. Chem.
(2011)Ship-in-a-bottle synthesis, characterization and catalytic oxidation of styrene by host (nanopores of zeolite-Y)/guest ([bis (2-hydroxyanil) acetylacetonato manganese (III)]) nanocomposite materials (HGNM)
Microporous Mesoporous Mater.
(2006) - et al.
Selective determination of free cyanide in environmental water matrices by ion chromatography with suppressed conductivity detection
J. Liq. Chromatogr. Relat. Technol.
(2015)et al.Synthesis and characterization of spinel-type zinc aluminate nanoparticles by a modified sol–gel method using new precursor
J. Alloy. Compd.
(2011) - et al.
Porphyrin chemodosimeters: synthesis, electrochemical redox properties and selective ‘naked-eye’detection of cyanide ions
RSC Adv.
(2015)Synthesis and characterization of host (nanodimensional pores of zeolite-Y)–guest [unsaturated 16-membered octaaza–macrocycle manganese (II), cobalt (II), nickel (II), copper (II), and zinc (II) complexes] nanocomposite materials
Chem. Lett.
(2005)et al.Star-shaped PbS nanocrystals prepared by hydrothermal process in the presence of thioglycolic acid
Polyhedron
(2012) - et al.
Why, on interaction of urea-based receptors with fluoride, beautiful colors develop
J. Org. Chem.
(2005) - et al.
Dual chemosensing properties of new anthraquinone-based receptors toward fluoride ions
Tetrahedron Lett.
(2007)
Urea and thiourea based efficient colorimetric sensors for oxyanions
Tetrahedron Lett.
A novel colorimetric sensor for anions recognition based on disubstituted phenylhydrazone
J. Incl. Phenom. Macrocycl. Chem.
Highly sensitive and selective colorimetric naked-eye detection of Cu2+ in aqueous medium using a hydrazone chemosensor
Sens. Actuators, B
Colorimetric and NIR fluorescence receptors for F− ion detection in aqueous condition and its Live cell imaging
Sens. Actuators, B
Aminophenol based colorimetric chemosensor for naked-eye detection of biologically important fluoride and acetate ions in organo-aqueous medium: effective and simple anion sensors
J. Photochem. Photobiol., A
Colorimetric anion sensors based on positional effect of nitro group for recognition of biologically relevant anions in organic and aqueous medium, insight real-life application and DFT studies
Spectrochim. Acta Part A Mol. Biomol. Spectrosc.
Fluoride-responsive gelator and colorimetric sensor based on simple and easy-to-prepare cyano-substituted amide
Org. Biomol. Chem.
Novel azo dye-based color chemosensors for fluoride ions
Spectrochim. Acta Part A Mol. Biomol. Spectrosc.
A fluoride-sensing receptor based on 2, 2′-bis (indolyl) methane by dual-function of colorimetry and fluorescence
Spectrochim. Acta Part A Mol. Biomol. Spectrosc.
A highly selective chemosensor derived from benzamide hydrazones for the detection of cyanide ion in organic and organic-aqueous media: design, synthesis, sensing and computational studies
Supramol. Chem.
Fluorogenic and chromogenic chemosensors and reagents for anions
Chem. Rev.
Arylethynyl receptors for neutral molecules and anions: emerging applications in cellular imaging
Chem. Soc. Rev.
Anion receptor chemistry: highlights from 2010
Chem. Soc. Rev.
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