Geometrical Isomerism Directed Electrochemical Sensing
Autor: | Chathakudath P. Vinod, Mruthyunjayachar Chattanahalli Devendrachari, Musthafa Ottakam Thotiyl, Shabbah Begum, Harish Makri Nimbegondi Kotresh, Alagar Raja Kottaichamy, Ravikumar Thimmappa, Zahid Manzoor Bhat |
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Rok vydání: | 2020 |
Předmět: |
Surface Properties
Nitrogen Dioxide Substituent Electrons Electronic structure 010402 general chemistry Electrochemistry Electrocatalyst 01 natural sciences Catalysis Arsenic Analytical Chemistry chemistry.chemical_compound Isomerism Computational chemistry Organometallic Compounds Molecule Particle Size Spectroscopy Molecular Structure Chemistry 010401 analytical chemistry Cobalt Electrochemical Techniques Resonance (chemistry) 0104 chemical sciences Quartz Crystal Microbalance Techniques Oxidation-Reduction |
Zdroj: | Analytical Chemistry. 92:4541-4547 |
ISSN: | 1520-6882 0003-2700 |
Popis: | We report the independent role of isomerism of secondary sphere substituents over their nature, a factor often overlooked in molecular electrocatalysis pertaining to electrochemical sensing, by establishing that isomerism redefines the electronic structure at the catalytic reaction center via geometrical factors. UV-vis spectroscopy and X-ray photoelectron spectroscopy suggest that a substituent's isomerism in molecular catalysts conjoins molecular planarity and catalytic activation through competing field effects and resonance effects. As a classical example, we demonstrate the influence of isomerism of the -NO2 substituents for the electrocatalytic multi electron oxidation of As(III), a potentially important electrochemical pathway for water remediation and arsenic detection. The isomerism dependent oxidative activation of catalytic center leads to a nonprecious molecular catalyst capable for direct As(III) oxidation with an experimental detection limit close to WHO guidelines. This work opens up an unusual approach in analytical chemistry for developing various sensing platforms for challenging chemical and electrochemical reactions. |
Databáze: | OpenAIRE |
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