{"title":"Development of pivalic acid conjugated Nafion modified glassy carbon electrode for sensitive detection of Cu(II) by electrochemical approach","authors":"","doi":"10.1016/j.ica.2024.122309","DOIUrl":null,"url":null,"abstract":"<div><p>In this work, pivalic acid (pivH) molecule is employed for an electrochemical sensing of copper cations in an aqueous medium. For sensitive as well as selective potential sensor application, pivH was fabricated onto a glassy carbon electrode (GCE) facilitated by adhesive conducting binder, nafion, so as make it selective and effective electrochemical probe (pivH/Nafion/GCE) towards specific heavy metal cations. This newly fabricated pivH/Nafion/GCE reveals enhance electrochemical activity toward copper ions in the presence of other interfering heavy metal cations in phosphate buffer solution (PBS) of pH=7. The calibration plot was linear (r<sup>2</sup> = 0.9879) across broad linear dynamic range (LDR) spanning Cu<sup>2+</sup> concentration from 0.1 nM to 0.01 M. The sensitivity and detection limit was found to be 0.0212 × 10<sup>−2</sup> µAµM<sup>−1</sup>cm<sup>−2</sup> and 0.014 nM, respectively. So, this newly fabricated GCE as selective electrochemical probe offers a sensitive as well as selective detection of Cu<sup>2+</sup> cations in real environmental samples using a novel electrochemical, current–potential (I-V), approach, for the first time. Further, we explored pivalic acid for the preparation of new di-nuclear copper complex, [Cu<sub>2</sub>(piv)<sub>4</sub>(pivH)<sub>2</sub>] (where piv = pivalate; pivH=pivalic acid) and characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, elemental analysis and single crystal X-ray diffractometry. Density functional theory (DFT) calculations were carried out to confirm the interactions and these calculations well-support to experimental data. In case of deprotonated form of pivH, Molecular Electrostatic Potential (MEP) analysis exhibits electrostatic potential equals to −148.4 kcal/mol which suggest about the strong interaction of –COOH with copper centers. Similarly, interaction energies, the quantum theory of atoms in molecules (QTAIM) study and Natural Bond Orbital (NBO) analysis also favor to experimental work. Thus, this novel study demonstrates an excellent approach for highly selective and sensitive detection of Cu<sup>2+</sup> cations in short response time with low detection limit and good reproducibility by using I-V method based on newly designed pivH/Nafion/GCE as selective Cu<sup>2+</sup> cationic electrochemical sensor. The experimental data was compactable with theoretical calculations.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324004006","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
In this work, pivalic acid (pivH) molecule is employed for an electrochemical sensing of copper cations in an aqueous medium. For sensitive as well as selective potential sensor application, pivH was fabricated onto a glassy carbon electrode (GCE) facilitated by adhesive conducting binder, nafion, so as make it selective and effective electrochemical probe (pivH/Nafion/GCE) towards specific heavy metal cations. This newly fabricated pivH/Nafion/GCE reveals enhance electrochemical activity toward copper ions in the presence of other interfering heavy metal cations in phosphate buffer solution (PBS) of pH=7. The calibration plot was linear (r2 = 0.9879) across broad linear dynamic range (LDR) spanning Cu2+ concentration from 0.1 nM to 0.01 M. The sensitivity and detection limit was found to be 0.0212 × 10−2 µAµM−1cm−2 and 0.014 nM, respectively. So, this newly fabricated GCE as selective electrochemical probe offers a sensitive as well as selective detection of Cu2+ cations in real environmental samples using a novel electrochemical, current–potential (I-V), approach, for the first time. Further, we explored pivalic acid for the preparation of new di-nuclear copper complex, [Cu2(piv)4(pivH)2] (where piv = pivalate; pivH=pivalic acid) and characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, elemental analysis and single crystal X-ray diffractometry. Density functional theory (DFT) calculations were carried out to confirm the interactions and these calculations well-support to experimental data. In case of deprotonated form of pivH, Molecular Electrostatic Potential (MEP) analysis exhibits electrostatic potential equals to −148.4 kcal/mol which suggest about the strong interaction of –COOH with copper centers. Similarly, interaction energies, the quantum theory of atoms in molecules (QTAIM) study and Natural Bond Orbital (NBO) analysis also favor to experimental work. Thus, this novel study demonstrates an excellent approach for highly selective and sensitive detection of Cu2+ cations in short response time with low detection limit and good reproducibility by using I-V method based on newly designed pivH/Nafion/GCE as selective Cu2+ cationic electrochemical sensor. The experimental data was compactable with theoretical calculations.
期刊介绍:
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.