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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
Halogen Bonding Ionophore for Potentiometric Iodide Sensing
Georgina E K K Seah1, Angeline Y X Tan1, Zhi Hao Neo1
1Institute of Material Research and Engineering, A*STAR (Agency for Science, Technology and Research) Research Entities, 2 Fusionopolis Way, Innovis #08-03, Singapore 138634, Singapore.
Insights
We developed a novel sensor for detecting iodide (I-), an essential nutrient for thyroid health. This sensor utilizes halogen bonding interactions for selective and rapid iodide quantification in various samples.
Area of Science:
- Supramolecular Chemistry
- Analytical Chemistry
- Chemical Sensing
Background:
- Iodide (I-) is a crucial micronutrient vital for thyroid hormone synthesis.
- Accurate and rapid quantification of iodide is essential in food and biological matrices.
- Existing methods for iodide detection may lack portability or selectivity.
Purpose of the Study:
- To report the first halogen bonding (XB) tripodal ionophore (XB1) for selective iodide anion sensing.
- To investigate the role of XB interactions in ionophore-analyte binding.
- To develop and evaluate an iodide-selective potentiometric sensor based on XB1.
Main Methods:
- Synthesis and characterization of the XB tripodal ionophore XB1.
- Nuclear Magnetic Resonance (NMR) spectroscopy to study binding interactions with iodide.
- Fabrication and electrochemical evaluation of iodide-selective electrodes using XB1 and the phase boundary model.
Main Results:
- XB1 demonstrated selective binding with iodide, primarily driven by halogen bonding interactions.
- The developed iodide-selective electrode showed a near-Nernstian response (-51.9 mV/decade) over a wide dynamic range (10-1 to 10-6 M).
- The sensor exhibited anti-Hofmeister selectivity for iodide over thiocyanate, enabling *in situ* determination in complex samples.
Conclusions:
- Halogen bonding is a viable supramolecular interaction for designing selective anion sensors.
- The XB1 ionophore enables the development of robust and selective potentiometric sensors for iodide.
- This work advances the field of anion sensing through the application of XB interactions.
Abstract:
Iodide (I-) is an essential micronutrient for thyroid function. Hence, rapid and portable sensing is important for I- quantification in food and biological samples. Herein, we report the first example of a halogen bonding (XB) tripodal ionophore (XB1) which is selective for the I- anion. NMR binding studies of XB1 and its H-triazole analog HB2 with I- demonstrated the dominant influence of XB interactions between the ionophore and the I- analyte. The phase boundary model was applied to formulate iodide-selective electrodes with the ionophore XB1. The optimal electrode exhibited a near-Nernstian response of -51.9 mV per decade within a large dynamic range (10-1 to 10-6 M) and notably anti-Hofmeister selectivity for I- over thiocyanate (SCN-), enabling the in situ determination of I- in complex samples. This work establishes XB as a viable supramolecular interaction in the potentiometric sensing of anions.
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