Ion-Selective Electrodes Based on Two Competitive Ionophores for Determining Effective Stability Constants of Ion−Carrier Complexes in Solvent Polymeric MembranesClick to copy article linkArticle link copied!
Abstract
A new potentiometric method to determine effective complex formation constants in organic membrane phases is reported in detail. It demands measurements with two different membranes, one containing a highly selective reference ionophore (in this case for H+) and anionic sites and another containing the same components and additionally the lipophilic ionophore to be characterized. The response characteristics of both electrodes can be compared and related to the effective complex formation constant of the ion carrier in the membrane. Potentiometric experiments with membranes containing a series of highly selective H+-ionophores confirm that alkali metal ions are not complexed by these ionophores. The ionophores valinomycin, BME-44, ETH 2120, tert-butylcalix[4]arene tetraethyl ester, and ETH 1810 are characterized using this potentiometric technique with potassium, sodium, and lithium ions in the sample. The complex formation constants are generally large and correspond very well to data obtained with a previously established optical method.
*
In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.
†
Auburn University.
‡
Swiss Federal Institute of Technology.
✗
Abstract published in Advance ACS Abstracts, December 15, 1997.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 54 publications.
- Vladimir V. Egorov, Andrei V. Siamionau, Ekaterina G. Ragoyja. H+-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits. ACS Sensors 2023, 8
(5)
, 2087-2095. https://doi.org/10.1021/acssensors.3c00417
- Yujie Liu, Alexander Wiorek, Gaston A. Crespo, Maria Cuartero. Spectroelectrochemical Evidence of Interconnected Charge and Ion Transfer in Ultrathin Membranes Modulated by a Redox Conducting Polymer. Analytical Chemistry 2020, 92
(20)
, 14085-14093. https://doi.org/10.1021/acs.analchem.0c03124
- Xin V. Chen, Maral P.S. Mousavi, Philippe Bühlmann. Fluorous-Phase Ion-Selective pH Electrodes: Electrode Body and Ionophore Optimization for Measurements in the Physiological pH Range. ACS Omega 2020, 5
(23)
, 13621-13629. https://doi.org/10.1021/acsomega.0c00582
- Xiaojiang Xie and Eric Bakker . Determination of Effective Stability Constants of Ion-Carrier Complexes in Ion Selective Nanospheres with Charged Solvatochromic Dyes. Analytical Chemistry 2015, 87
(22)
, 11587-11591. https://doi.org/10.1021/acs.analchem.5b03526
- Peter J. Greenawalt, Mohammed B. Garada, and Shigeru Amemiya . Voltammetric Characterization of Ion–Ionophore Complexation Using Thin Polymeric Membranes: Asymmetric Thin-Layer Responses. Analytical Chemistry 2015, 87
(16)
, 8564-8572. https://doi.org/10.1021/acs.analchem.5b02355
- Masafumi Miyake, Li D. Chen, Gianluca Pozzi, and Philippe Bühlmann . Ion-Selective Electrodes with Unusual Response Functions: Simultaneous Formation of Ionophore–Primary Ion Complexes with Different Stoichiometries. Analytical Chemistry 2012, 84
(2)
, 1104-1111. https://doi.org/10.1021/ac202761x
- Li D. Chen, Debaprasad Mandal, Gianluca Pozzi, John A. Gladysz, and Philippe Bühlmann . Potentiometric Sensors Based on Fluorous Membranes Doped with Highly Selective Ionophores for Carbonate. Journal of the American Chemical Society 2011, 133
(51)
, 20869-20877. https://doi.org/10.1021/ja207680e
- Elsayed M. Zahran, Yuran Hua, Semin Lee, Amar H. Flood, and Leonidas G. Bachas . Ion-Selective Electrodes Based on a Pyridyl-Containing Triazolophane: Altering Halide Selectivity by Combining Dipole-Promoted Cooperativity with Hydrogen Bonding. Analytical Chemistry 2011, 83
(9)
, 3455-3461. https://doi.org/10.1021/ac200052q
- Kebede L. Gemene and Eric Bakker. Direct Sensing of Total Acidity by Chronopotentiometric Flash Titrations at Polymer Membrane Ion-Selective Electrodes. Analytical Chemistry 2008, 80
(10)
, 3743-3750. https://doi.org/10.1021/ac701983x
- Martin Telting-Diaz and, Eric Bakker. Effect of Lipophilic Ion-Exchanger Leaching on the Detection Limit of Carrier-Based Ion-Selective Electrodes. Analytical Chemistry 2001, 73
(22)
, 5582-5589. https://doi.org/10.1021/ac010526h
- Eric Bakker,, Ernö Pretsch, and, Philippe Bühlmann. Selectivity of Potentiometric Ion Sensors. Analytical Chemistry 2000, 72
(6)
, 1127-1133. https://doi.org/10.1021/ac991146n
- Yanming Mi and, Eric Bakker. Determination of Complex Formation Constants of Lipophilic Neutral Ionophores in Solvent Polymeric Membranes with Segmented Sandwich Membranes. Analytical Chemistry 1999, 71
(23)
, 5279-5287. https://doi.org/10.1021/ac9905930
- Mathias Nägele,, Eric Bakker, and, Ernö Pretsch. General Description of the Simultaneous Response of Potentiometric Ionophore-Based Sensors to Ions of Different Charge. Analytical Chemistry 1999, 71
(5)
, 1041-1048. https://doi.org/10.1021/ac980962c
- Yanming Mi,, Christopher Green, and, Eric Bakker. Polymeric Membrane pH Electrodes Based on Electrically Charged Ionophores. Analytical Chemistry 1998, 70
(24)
, 5252-5258. https://doi.org/10.1021/ac980678l
- Kwangrok R. Choi, Madeline L. Honig, Philippe Bühlmann. Covalently attached ionophores extend the working range of potentiometric pH sensors with poly(decyl methacrylate) sensing membranes. The Analyst 2024, 149
(4)
, 1132-1140. https://doi.org/10.1039/D3AN02047A
- Andrei V. Siamionau, Ekaterina G. Ragoyja, Vladimir V. Egorov. A feasible, fast and reliable method for estimating ion-site association constants in plasticized PVC ion-selective electrode membranes. Analytica Chimica Acta 2023, 1239 , 340556. https://doi.org/10.1016/j.aca.2022.340556
- Yujie Liu, Gaston A. Crespo, Maria Cuartero. Semi-empirical treatment of ionophore-assisted ion-transfers in ultrathin membranes coupled to a redox conducting polymer. Electrochimica Acta 2021, 388 , 138634. https://doi.org/10.1016/j.electacta.2021.138634
- Julia Ashina, Vasily Babain, Dmitry Kirsanov, Andrey Legin. A Novel Multi-Ionophore Approach for Potentiometric Analysis of Lanthanide Mixtures. Chemosensors 2021, 9
(2)
, 23. https://doi.org/10.3390/chemosensors9020023
- Canwei Mao, Dajing Yuan, Lu Wang, Eric Bakker. Separating boundary potential changes at thin solid contact ion transfer voltammetric membrane electrodes. Journal of Electroanalytical Chemistry 2021, 880 , 114800. https://doi.org/10.1016/j.jelechem.2020.114800
- N. V. Pokhvishcheva, M. A. Peshkova. Ionic Liquids as Plasticizers for Optodes. Moscow University Chemistry Bulletin 2020, 75
(2)
, 115-120. https://doi.org/10.3103/S002713142002011X
- Andrey V. Kalinichev, Ana Frosinyuk, Maria A. Peshkova, Konstantin N. Mikhelson. The impact of ion association in the optode phase to the dynamic range and the sensitivity of the response of ion-selective bulk optodes. Sensors and Actuators B: Chemical 2017, 249 , 123-130. https://doi.org/10.1016/j.snb.2017.03.088
- Y. Zhu, C. Guéguen. Evaluation of free/labile concentrations of trace metals in Athabasca oil sands region streams (Alberta, Canada) using diffusive gradient in thin films and a thermodynamic equilibrium model. Environmental Pollution 2016, 219 , 1140-1147. https://doi.org/10.1016/j.envpol.2016.09.018
- Gastón A. Crespo, Majid Ghahraman Afshar, Noelia Barrabés, Marcin Pawlak, Eric Bakker. Characterization of Salophen Co(III) Acetate Ionophore for Nitrite Recognition. Electrochimica Acta 2015, 179 , 16-23. https://doi.org/10.1016/j.electacta.2015.03.180
- Tatiana V. Shishkanova, Vladimir Král, Přemysl Fitl, Martin Vrňata, Pavel Matějka. Smart Design for Potentiometric Detection. Electroanalysis 2015, 27
(3)
, 713-719. https://doi.org/10.1002/elan.201400553
- Shuping Han, Wataru Naito, Yoshimichi Hanai, Shigeki Masunaga. Evaluation of trace metals bioavailability in Japanese river waters using DGT and a chemical equilibrium model. Water Research 2013, 47
(14)
, 4880-4892. https://doi.org/10.1016/j.watres.2013.05.025
- Konstantin N. Mikhelson. Ionophore-Based ISEs. 2013, 51-95. https://doi.org/10.1007/978-3-642-36886-8_4
- Eric Bakker, Ernö Pretsch. Advances in Potentiometry. 2011, 1-74. https://doi.org/10.1201/b11480-2
- Eric Bakker. Generalized selectivity description for polymeric ion-selective electrodes based on the phase boundary potential model. Journal of Electroanalytical Chemistry 2010, 639
(1-2)
, 1-7. https://doi.org/10.1016/j.jelechem.2009.09.031
- Paul G. Boswell, Csongor Szíjjártó, Markus Jurisch, John A. Gladysz, József Rábai, Philippe Bühlmann. Fluorophilic Ionophores for Potentiometric pH Determinations with Fluorous Membranes of Exceptional Selectivity. Analytical Chemistry 2008, 80
(6)
, 2084-2090. https://doi.org/10.1021/ac702161c
- Eric Bakker, Ernö Pretsch. Modern Potentiometry. Angewandte Chemie International Edition 2007, 46
(30)
, 5660-5668. https://doi.org/10.1002/anie.200605068
- Eric Bakker, Ernö Pretsch. Moderne Potentiometrie. Angewandte Chemie 2007, 119
(30)
, 5758-5767. https://doi.org/10.1002/ange.200605068
- Mariusz Pietrzak, Mark E. Meyerhoff, Elżbieta Malinowska. Polymeric membrane electrodes with improved fluoride selectivity and lifetime based on Zr(IV)- and Al(III)-tetraphenylporphyrin derivatives. Analytica Chimica Acta 2007, 596
(2)
, 201-209. https://doi.org/10.1016/j.aca.2007.06.016
- Shigeru Amemiya. Potentiometric Ion-Selective Electrodes. 2007, 261-294. https://doi.org/10.1016/B978-044451958-0.50020-3
- Ernö Pretsch. The new wave of ion-selective electrodes. TrAC Trends in Analytical Chemistry 2007, 26
(1)
, 46-51. https://doi.org/10.1016/j.trac.2006.10.006
- Zsófia Szigeti, Adam Malon, Tamás Vigassy, Viktor Csokai, Alajos Grün, Katarzyna Wygladacz, Nan Ye, Chao Xu, Vincent J. Chebny, István Bitter, Rajendra Rathore, Eric Bakker, Ernö Pretsch. Novel potentiometric and optical silver ion-selective sensors with subnanomolar detection limits. Analytica Chimica Acta 2006, 572
(1)
, 1-10. https://doi.org/10.1016/j.aca.2006.05.009
- Róbert Bereczki, Boglárka Takács, Róbert E. Gyurcsányi, Klára Tóth, Géza Nagy, Jan Langmaier, Ernö Lindner. Simple, Single Step Potential Difference Measurement for the Determination of the Ultimate Detection Limit of Ion Selective Electrodes. Electroanalysis 2006, 18
(13-14)
, 1245-1253. https://doi.org/10.1002/elan.200603521
- Maria Bocheńska, Anna Zielińska, Radosław Pomećko, Véronique Hubscher-Bruder, Françoise Arnaud-Neu. Lower Rim Substituted tert-Butyl calix[4]arene (part VII): Ionophoric Properties of Calix[4]arene-crown-6 Derivatives in Plasticized PVC-Membrane Electrodes and in Solution. Journal of Inclusion Phenomena and Macrocyclic Chemistry 2005, 52
(1-2)
, 129-134. https://doi.org/10.1007/s10847-004-6332-2
- Maria Bocheńska, Anna Zielińska, Radosław Pomećko, Victor Ch. Kravtsov, Maria Gdaniec. Lower Rim Substituted
tert
‐Butyl Calix[4]Arenes (Part IV). Calix[4]Arene‐Crown Ethers as Ionophores in Plasticized PVC‐Membrane Electrodes. Electroanalysis 2003, 15
(15-16)
, 1307-1313. https://doi.org/10.1002/elan.200302813
- Robert Long, Eric Bakker. Spectral Imaging and Electrochemical Study on the Response Mechanism of Ionophore‐Based Polymeric Membrane Amperometric pH Sensors. Electroanalysis 2003, 15
(15-16)
, 1261-1269. https://doi.org/10.1002/elan.200302806
- R. Daniel Johnson, Leonidas G. Bachas. Ionophore-based ion-selective potentiometric and optical sensors. Analytical and Bioanalytical Chemistry 2003, 376
(3)
, 328-341. https://doi.org/10.1007/s00216-003-1931-0
- Elżbieta Malinowska, Łukasz Górski, Dorota Wojciechowska, Marta M. Reinoso-García, Willem Verboom, David N. Reinhoudt. Potentiometric studies of complexation properties of tetrafunctionalized resorcinarene-based cavitands. New J. Chem. 2003, 27
(10)
, 1440-1445. https://doi.org/10.1039/B305032G
- Patrick Reichmuth, Peter D. van der Wal, Martin Püntener, Angela Schöning-Hammer, Werner E. Morf, Nico F. de Rooij, Ernö Pretsch. Reducing the interference from CO2 or organic acids in ion-selective polymer membrane sensors having a field-effect transistor as internal reference element. Analytica Chimica Acta 2002, 464
(1)
, 79-88. https://doi.org/10.1016/S0003-2670(02)00475-0
- Min Hyung Lee, Choong Leol Yoo, Jae Seon Lee, In-Sook Cho, Byeong Hyo Kim, Geun Sig Cha, Hakhyun Nam. Tweezer-Type Neutral Carrier-Based Calcium-Selective Membrane Electrode with Drastically Reduced Anionic Interference. Analytical Chemistry 2002, 74
(11)
, 2603-2607. https://doi.org/10.1021/ac011160b
- Mikhail M. Shultz, Olga K. Stefanova, Sergey B. Mokrov, Konstantin N. Mikhelson. Potentiometric Estimation of the Stability Constants of Ion−Ionophore Complexes in Ion-Selective Membranes by the Sandwich Membrane Method: Theory, Advantages, and Limitations. Analytical Chemistry 2002, 74
(3)
, 510-517. https://doi.org/10.1021/ac015564f
- Martin Krondak, Tatiana V Shishkanova, Roman Holakovsky, Radko Volf, Ivan Stibor, Vladimı́r Král. Molecular recognition of amino acid esters in liquid polymeric membrane ion-selective electrodes. Analytica Chimica Acta 2001, 448
(1-2)
, 19-25. https://doi.org/10.1016/S0003-2670(01)01318-6
- Enju Wang, Carlos Romero, Darran Santiago, Vayia Syntilas. Optical anion sensing characteristics of indium-porphyrin and lipophilic dichlorofluorescein doped polymer films. Analytica Chimica Acta 2001, 433
(1)
, 89-95. https://doi.org/10.1016/S0003-2670(00)01385-4
- Hong-Seok Kim, Hyun Joo Park, Hyun Joon Oh, Young Kook Koh, Jun-Hyeak Choi, Dong-Hoon Lee, Geun Sig Cha, Hakhyun Nam. Thiazole-Containing Benzo-Crown Ethers: A New Class of Ammonium-Selective Ionophores. Analytical Chemistry 2000, 72
(19)
, 4683-4688. https://doi.org/10.1021/ac000177b
- Yu Qin, Yanming Mi, Eric Bakker. Determination of complex formation constants of 18 neutral alkali and alkaline earth metal ionophores in poly(vinyl chloride) sensing membranes plasticized with bis(2-ethylhexyl)sebacate and o-nitrophenyloctylether. Analytica Chimica Acta 2000, 421
(2)
, 207-220. https://doi.org/10.1016/S0003-2670(00)01038-2
- Elizabeth A. Moschou, Nikolas A. Chaniotakis. Ion-Partitioning Membrane-Based Electrochemical Sensors. Analytical Chemistry 2000, 72
(8)
, 1835-1842. https://doi.org/10.1021/ac991313j
- Yanming Mi, Sally Mathison, Roderick Goines, Alicia Logue, Eric Bakker. Detection limit of polymeric membrane potentiometric ion sensors: how can we go down to trace levels?. Analytica Chimica Acta 1999, 397
(1-3)
, 103-111. https://doi.org/10.1016/S0003-2670(99)00396-7
- Eric Bakker, Philippe Bühlmann, Ernö Pretsch. Polymer Membrane Ion-Selective Electrodes-What are the Limits?. Electroanalysis 1999, 11
(13)
, 915-933. https://doi.org/10.1002/(SICI)1521-4109(199909)11:13<915::AID-ELAN915>3.0.CO;2-J
- Alan Ceresa, Ernö Pretsch. Determination of formal complex formation constants of various Pb2+ ionophores in the sensor membrane phase. Analytica Chimica Acta 1999, 395
(1-2)
, 41-52. https://doi.org/10.1016/S0003-2670(99)00311-6
- Ernö Lindner, Robert E. Gyurcsányi, Richard P. Buck. Tailored Transport Through Ion-Selective Membranes for Improved Detection Limits and Selectivity Coefficients. Electroanalysis 1999, 11
(10-11)
, 695-702. https://doi.org/10.1002/(SICI)1521-4109(199907)11:10/11<695::AID-ELAN695>3.0.CO;2-G
- Jean-Pascal Bourgeois, Luis Echegoyen, Monia Fibbioli, Ernö Pretsch, François Diederich. Regioselektive, durch einen Kronenether- Spacer kontrollierte Synthese vontrans-1- Fulleren-Bisaddukten: Alkalimetallionen- abhängige Redoxeigenschaften von Fulleren-Kronenether-Konjugaten. Angewandte Chemie 1998, 110
(15)
, 2203-2207. https://doi.org/10.1002/(SICI)1521-3757(19980803)110:15<2203::AID-ANGE2203>3.0.CO;2-M
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.