ACS Publications. Most Trusted. Most Cited. Most Read
Evaluation of the Separate Equilibrium Processes That Dictate the Upper Detection Limit of Neutral Ionophore-Based Potentiometric Sensors

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Anal. Chem. 2002, 74, 13, 3134-3141
    Article

    Evaluation of the Separate Equilibrium Processes That Dictate the Upper Detection Limit of Neutral Ionophore-Based Potentiometric Sensors
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Chemistry, Auburn University, Auburn, Alabama 36849
    Other Access Options

    Analytical Chemistry

    Cite this: Anal. Chem. 2002, 74, 13, 3134–3141
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ac0156159
    Published May 9, 2002
    Copyright © 2002 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!

    The upper detection limit of polar ionophore-based ion-selective electrode membranes is predicted by utilizing the coextraction constant of dissociated electrolyte, the stability constant of the ionophore, and the membrane composition. The coextraction constant of dissociated electrolytes into the polar poly(vinyl chloride) membrane plasticized with o-nitrophenyl octyl ether (PVC−NPOE) is here measured by a novel approach. The sandwich membrane technique is utilized, with one membrane segment containing a lipophilic cation exchanger and the other containing an anion exchanger. This yields information about the coextraction constant and the free ion concentrations of the electrolyte in the two segments. Predictions correlate quantitatively with the upper detection limit observed for ion-selective electrodes based on the ionophores valinomycin, tert-butylcalix[4]arene tetraethyl ester, and calcimycin. The difficulties of the prediction of the upper detection limit for nonpolar poly(vinyl chloride) membranes plasticized with bis(2-ethylhexyl sebacate) (PVC−DOS) due to ion association are discussed in detail. A thermodynamic cycle experiment with a series of sandwich membranes shows that the principal processes governing the upper detection limit of PVC−DOS membranes are identical to those for the PVC−NPOE membranes. However, the stability of the ion pairs between the ionophore−metal ion complexes and the extracted anion are different from that of ion pairs formed between the same anion and the lipophilic anion exchanger. This makes it difficult to quantitatively predict the upper detection limit on the basis of simple apparent coextraction and complexation data alone. The approach reported herein is useful not only for mechanistic purposes but also to shed light onto the many cases where coextraction effects need to be understood but are not directly experimentally accessible.

    Copyright © 2002 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 27 publications.

    1. Andrei D. Novakovskii, Vladimir V. Egorov, Danila V. Korostik. Lipophilicity Criteria for Ionic Components Used in Liquid-Junction-Free Reference Electrodes. Analytical Chemistry 2025, Article ASAP.
    2. Andrey V. Kalinichev, Nadezhda V. Pokhvishcheva, Maria A. Peshkova. Influence of Electrolyte Coextraction on the Response of Indicator-Based Cation-Selective Optodes. ACS Sensors 2020, 5 (11) , 3558-3567. https://doi.org/10.1021/acssensors.0c01747
    3. Renjie Wang, Xinfeng Du, Yaotian Wu, Jingying Zhai, Xiaojiang Xie. Graphene Quantum Dots Integrated in Ionophore-Based Fluorescent Nanosensors for Na+ and K+. ACS Sensors 2018, 3 (11) , 2408-2414. https://doi.org/10.1021/acssensors.8b00918
    4. Xiaojiang Xie, Jingying Zhai, and Eric Bakker . Potentiometric Response from Ion-Selective Nanospheres with Voltage-Sensitive Dyes. Journal of the American Chemical Society 2014, 136 (47) , 16465-16468. https://doi.org/10.1021/ja5107578
    5. Xiaojiang Xie, Günter Mistlberger, and Eric Bakker . Reversible Photodynamic Chloride-Selective Sensor Based on Photochromic Spiropyran. Journal of the American Chemical Society 2012, 134 (41) , 16929-16932. https://doi.org/10.1021/ja307037z
    6. Aleksandar Radu,, Amnon J. Meir, and, Eric Bakker. Dynamic Diffusion Model for Tracing the Real-Time Potential Response of Polymeric Membrane Ion-Selective Electrodes. Analytical Chemistry 2004, 76 (21) , 6402-6409. https://doi.org/10.1021/ac049348t
    7. Eric Bakker. Electrochemical Sensors. Analytical Chemistry 2004, 76 (12) , 3285-3298. https://doi.org/10.1021/ac049580z
    8. Aleksandar Radu,, Martin Telting-Diaz, and, Eric Bakker. Rotating Disk Potentiometry for Inner Solution Optimization of Low-Detection-Limit Ion-Selective Electrodes. Analytical Chemistry 2003, 75 (24) , 6922-6931. https://doi.org/10.1021/ac0346961
    9. Adam Malon,, Aleksandar Radu,, Wei Qin,, Yu Qin,, Alan Ceresa,, Magdalena Maj-Zurawska,, Eric Bakker, and, Ernö Pretsch. Improving the Detection Limit of Anion-Selective Electrodes:  An Iodide-Selective Membrane with a Nanomolar Detection Limit. Analytical Chemistry 2003, 75 (15) , 3865-3871. https://doi.org/10.1021/ac026454r
    10. Shane Peper,, Yu Qin,, Philip Almond,, Michael McKee,, Martin Telting-Diaz,, Thomas Albrecht-Schmitt, and, Eric Bakker. Ion-Pairing Ability, Chemical Stability, and Selectivity Behavior of Halogenated Dodecacarborane Cation Exchangers in Neutral Carrier-Based Ion-Selective Electrodes. Analytical Chemistry 2003, 75 (9) , 2131-2139. https://doi.org/10.1021/ac026056o
    11. Nikolai Yu. Tiuftiakov, Elena Zdrachek, Eric Bakker. Ion-exchange and lipophilicity limitations of ionic liquid reference electrodes. Sensors and Actuators B: Chemical 2024, 407 , 135474. https://doi.org/10.1016/j.snb.2024.135474
    12. Zhehao Zhang, Ian Papautsky. Solid Contact Ion‐selective Electrodes on Printed Circuit Board with Membrane Displacement. Electroanalysis 2023, 35 (1) https://doi.org/10.1002/elan.202100686
    13. Andrei V. Siamionau, Vladimir V. Egorov. Determination of Single-Ion Partition Coefficients between Water and Plasticized PVC Membrane Using Equilibrium-Based Techniques. Membranes 2022, 12 (10) , 1019. https://doi.org/10.3390/membranes12101019
    14. Zhehao Zhang, Ian Papautsky. Miniature Ion‐selective Electrodes with Mesoporous Carbon Black as Solid Contact. Electroanalysis 2021, 33 (10) , 2143-2151. https://doi.org/10.1002/elan.202100088
    15. S. Anastasova, P. Kassanos, Guang-Zhong Yang. Electrochemical Sensor Designs for Biomedical Implants. 2018, 19-98. https://doi.org/10.1007/978-3-319-69748-2_2
    16. Anastasiya D. Ivanova, Evgeniya S. Koltashova, Elena V. Solovyeva, Maria A. Peshkova, Konstantin N. Mikhelson. Impact of the Electrolyte Co-Extraction to the Response of the Ionophore-based Ion-Selective Electrodes. Electrochimica Acta 2016, 213 , 439-446. https://doi.org/10.1016/j.electacta.2016.07.142
    17. Lukasz Mendecki, Nicole Callan, Meghan Ahern, Benjamin Schazmann, Aleksandar Radu. Influence of Ionic Liquids on the Selectivity of Ion Exchange-Based Polymer Membrane Sensing Layers. Sensors 2016, 16 (7) , 1106. https://doi.org/10.3390/s16071106
    18. Maria A. Peshkova, Evgeniya S. Koltashova, Galina A. Khripoun, Konstantin N. Mikhelson. Improvement of the upper limit of the ISE Nernstian response by tuned galvanostatic polarization. Electrochimica Acta 2015, 167 , 187-193. https://doi.org/10.1016/j.electacta.2015.03.139
    19. Alexander R. Harris, Jie Zhang, Robert W. Cattrall, Alan M. Bond. Applications of voltammetric ion selective electrodes to complex matrices. Analytical Methods 2013, 5 (16) , 3840. https://doi.org/10.1039/c3ay40769a
    20. Eric Bakker, Ernö Pretsch. Advances in Potentiometry. 2011, 1-74. https://doi.org/10.1201/b11480-2
    21. Debbie S. Silvester, Ewa Grygolowicz-Pawlak, Eric Bakker. Potentiometric determination of coextraction constants of potassium salts in ion-selective electrodes utilizing a nitrobenzene liquid membrane phase. Analytica Chimica Acta 2010, 683 (1) , 92-95. https://doi.org/10.1016/j.aca.2010.10.012
    22. Vladimir V. Egorov, Peter L. Lyaskovski, Irina V. Il'inchik, Vera V. Soroka, Valentine A. Nazarov. Estimation of Ion‐Pairing Constants in Plasticized Poly(vinyl chloride) Membranes Using Segmented Sandwich Membranes Technique. Electroanalysis 2009, 21 (17-18) , 2061-2070. https://doi.org/10.1002/elan.200904639
    23. Pengchao Si, Eric Bakker. Thin layer electrochemical extraction of non-redoxactive cations with an anion-exchanging conducting polymer overlaid with a selective membrane. Chemical Communications 2009, 7 (35) , 5260. https://doi.org/10.1039/b907893b
    24. Maria A. Peshkova, Anton I. Korobeynikov, Konstantin N. Mikhelson. Estimation of ion-site association constants in ion-selective electrode membranes by modified segmented sandwich membrane method. Electrochimica Acta 2008, 53 (19) , 5819-5826. https://doi.org/10.1016/j.electacta.2008.03.030
    25. Shigeru Amemiya. Potentiometric Ion-Selective Electrodes. 2007, 261-294. https://doi.org/10.1016/B978-044451958-0.50020-3
    26. Andrey Legin, Sergey Makarychev-Mikhailov, John Mortensen, Yuri Vlasov. Potentiometric and impedance studies of membranes based on anion-exchanger and lipophilic inert electrolyte ETH 500. Electrochimica Acta 2004, 49 (28) , 5203-5207. https://doi.org/10.1016/j.electacta.2004.07.001
    27. Chung Keung Lo, Martin M.F. Choi. Symmetrical electrochemical cell for determination of coextraction constants of metal salts for ion-selective polymeric membranes. Analytica Chimica Acta 2003, 485 (2) , 253-262. https://doi.org/10.1016/S0003-2670(03)00420-3
    Download PDF
    Go to Analytical Chemistry
    Get e-Alerts
    Get e-Alerts

    Analytical Chemistry

    Cite this: Anal. Chem. 2002, 74, 13, 3134–3141
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ac0156159
    Published May 9, 2002
    Copyright © 2002 American Chemical Society
    Request reuse permissions

    Article Views

    447

    Altmetric

    -

    Citations

    27
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.