A Chemiluminescent Ion Sensing Platform Based on Ionophores

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A Chemiluminescent Ion Sensing Platform Based on Ionophores Li Deng, Jingying Zhai, and Xiaojiang Xie Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.9b02113 • Publication Date (Web): 05 Jun 2019 Downloaded from http://pubs.acs.org on June 5, 2019

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Analytical Chemistry

A Chemiluminescent Ion Sensing Platform Based on Ionophores Li Deng , Jingying Zhaià, and Xiaojiang Xie

*

Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China à

SUSTech Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen, 518055, China

*

E-mail: [email protected]

Abstract. We report here an ionophore-based chemiluminescent platform for the selective detection of ions. This method functions on the basis of the ion-exchange between the target ion and the divalent organic cation lucigenin, which luminesces after reacting with hydrogen peroxide in alkaline conditions. Using the K+ ionophore valinomycin, chemiluminescent detection of K+ (from 10 nM to 1 M) was performed on both dichloromethane solutions and polymeric films. While the ionophores ensured excellent selectivity, the detection range could be adjusted with the ratio between the aqueous and the organic phases, and the divalent lucigenin ions also made the sensitivity for divalent target ions higher than conventional ionophore-based ion-selective optodes. The generalizability of the method was shown by changing the K+ ionophore into a Pb2+ ionophore, which successfully realized the highly selective detection of Pb2+ from 0.1 nM to 0.1 mM. Preliminary application of the method was demonstrated with the determination of K+ in diluted human blood serum (5 samples) and the results agreed well with those obtained from potentiometric ion-selective electrodes. clinical electrolytes. The optical counterpart was also coined ionophore-based ion-selective optodes and functions on the basis of ion-exchange for cations.21-22 Typically, ion-selective optodes are formed with an ionophore, an ion-exchanger and a signal transducer molecule (chromoionophore), all incorporated in an organic environment. Extraction of the target ions by the ionophores forces the transfer of positively charged species from the organic phase to the aqueous solution, hence resulting in the changes in the optical properties of the signal transducer. In addition to measurements in the absorbance and fluorescence mode, our group also reported ionophore-based detection of ions based on distance change and dye release that could be analyzed even by the naked eye.23-24 Photoacoustic interrogations of ionselective optodes were also reported several times by Clark and Kopelman.25-26 Bakker and co-workers previously coupled electrochemiluminescence (ECL) to potentiometric ISEs and chronopotentiometry.27-28 Compared with ECL, CL does not require additional electrochemical controls and is instrumentally less demanding. To the best of our knowledge, ionophore-based sensors with CL as signal readout were not yet reported. In this work, we present for the first time an ionophore-based CL approach for the detection of metal ions. The analytical principle was demonstrated by using K+ and Pb2+ as the model ions and lucigenin (LG2+) as the CL reagent. LG2+ is among the most wellknown CL molecules with well-established chemiluminescent mechanism since 1935.29 The ionophore, ion-exchanger, and LG2+ were combined in an organic solvent or a plasticized poly (vinyl chloride) (PVC) film. Ion-exchange between the target ions and LG2+ defines the amount of LG2+ released and the CL intensity. Experimental CL responses induced by the analytes agreed very well with the ion-change model. The excellent selectivity of the platform was ensured by valinomycin as the potassium ionophore and a calixarene derivative as the lead ionophore, respectively. The CL detection was successfully used to determine K+ levels in human blood serum samples and the results were quite satisfactory compared with those from ISEs.

The chemiluminescent technology has opened an enormous global market that continues to grow in forensic science, immunoassays, pharmaceutical R&D, and rapid chemical analyses.1-4 Since chemiluminescence (CL) is generated after chemical reactions, there is no need for additional light sources in the setup. Unlike fluorescence and light absorption measurements, most samples do not emit CL. Therefore, the background signal in CL measurements is often extremely low as well. The simplicity of detection and no background signal rendered CL a very attractive tool in analytical chemistry. Amongst various target analytes, metal ions form an important family for which their vital connection with biology, food, natural environments and human health is well recognized. CL-based instrumentation can be much more compact, cost-effective and portable than the conventional instrumental analysis tools for ions such as atomic spectrometers, ion chromatography, and ICP mass spectrometers. CL can be directly enhanced or quenched by certain metal ions or indirectly as a consequence of the chemical reaction with the ions.5-7 This phenomenon lays the foundation of several previous work on the CL detection of metal ions. For instance, the famous luminol CL was reported to be sensitive to Cu2+ in the presence of thiourea.8 DNAzyme-enhanced CL of luminol could serve as a tool for the detection of K+.9 CL-based detection of Hg2+ was also reported by Lu and co-workers by utilizing the thymineHg2+-thymine chemistry.10 Other approaches to detect ions including Fe2+, Pb2+, Co2+, Hg2+, Cu2+, F-, and so on were also reported.11-19 While each method has its own merits, a systematic platform for the detection of ions with CL remains lacking. Moreover, given the chemical complexity of certain real samples, the selectivity of the methods remains a great challenge. On the other hand, ionophore-based electrochemical and optical sensors were demonstrated to be highly selective and robust for the detection of various ions.20-21 Using ionophores to develop ion sensors is attractive because in this way the methodology can cover a range of analytes simply by choosing different ionophores. So far, classical ionophore-based sensors were interrogated in electrochemical, light absorption, or fluorescence mode. The potentiometric ion-selective electrodes (ISEs) are probably the most well-known since their success in measuring ³

EXPERIMENTAL SECTION Reagents. Tetrahydrofuran (THF), tertbutylcalix[4]arenetetrakis(N,N-dimethylthioacetamide) (lead ionophore IV), Ä³

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Chemiluminescence Sensor for the Highly Selective and Ultrasensitive Detection of Hg2+ Ions Based on Interstrand Cooperative Coordination and Catalytic Formation of Gold Nanoparticles. Anal. Chem. 2011, 83 (24), 9702-9708. 11. Elbaz, J.; Shlyahovsky, B.; Willner, I., A DNAzyme cascade for the amplified detection of Pb2+ ions or L-histidine. Chem. Commun. 2008, 1569-1571. 12. Li, T.; Liang, G.; Li, X., Chemiluminescence assay for the sensitive detection of iodide based on extracting Hg2+ from a TÐ Hg2+ÐT complex. Analyst 2013, 138, 1898-1902. 13. Li, T.; Wang, E.; Dong, S., Lead(II)-Induced Allosteric GQuadruplex DNAzyme as a Colorimetric and Chemiluminescence Sensor for Highly Sensitive and Selective Pb2+ Detection. Anal. Chem. 2010, 82, 1515-1520. 14. Lin, J.-M.; Shan, X.; Hanaoka, S.; Yamada, M., Luminol Chemiluminescence in Unbuffered Solutions with a Cobalt(II)#Ethanolamine Complex Immobilized on Resin as Catalyst and Its Application to Analysis. Anal. Chem. 2001, 73 (21), 5043-5051. 15. Ren, J.; Huang, X., Sensitive and Universal Indirect Chemiluminescence Detection for Capillary Electrophoresis of Cations Using Cobalt(II) as a Probe Ion. Anal. Chem. 2001, 73, 2663-2668. 16. Shah, S. N. A.; Dou, X.; Khan, M.; Uchiyama, K.; Lin, J.M., N-doped carbon dots/H2O2 chemiluminescence system for selective detection of Fe2+ ion in environmental samples. Talanta 2019, 196, 370-375. 17. Turan, I. S.; Akkaya, E. U., Chemiluminescence Sensing of Fluoride Ions Using a Self-Immolative Amplifier. Org. Lett. 2014, 16 (6), 1680-1683. 18. Wang, M.; Kong, Y.; Li, Y.; Huang, Y.; Fan, A., A chemiluminescence method for the determination of mercury(II) ions by tuning the catalytic activity of gold nanoparticles with ethylenediamine. Anal. Methods 2019, 11, 1317-1323. 19. Amjadi, M.; Manzoori, J. L.; Hallaj, T.; Azizi, N., Sulfur and nitrogen co-doped carbon quantum dots as the chemiluminescence probe for detection of Cu2+ ions. J. Lumin. 2017, 182, 246-251. 20. Bakker, E.; Buhlmann, P.; Pretsch, E., Carrier-based ionselective electrodes and bulk optodes. 1. General characteristics. Chem. Rev. 1997, 97 (8), 3083-3132. 21. Mistlberger, G.; Crespo, G. A.; Bakker, E., IonophoreBased Optical Sensors. Annu. Rev. Anal. Chem. 2014, 7, 483-512. 22. Xie, X.; Bakker, E., Ion selective optodes: from the bulk to the nanoscale. Anal. Bioanal. Chem. 2015, 407 (14), 3899-910. 23. Du, X.; Xie, X., Non-equilibrium diffusion controlled ionselective optical sensor for blood potassium determination. ACS Sens. 2017, 2, 1410-1414. 24. Du, X.; Huang, M.; Wang, R.; Zhai, J.; Xie, X., A rapid point-of-care optical ion sensing platform based on targetinduced dye release from smart hydrogels. Chem. Commun. 2019, 55, 1774-1777. 25. Lee, C. H.; Folz, J.; Zhang, W.; Jo, J.; Tan, J. W. Y.; Wang, X.; Kopelman, R., Ion-Selective Nanosensor for Photoacoustic and Fluorescence Imaging of Potassium. Anal. Chem. 2017, 89 (15), 7943-7949. 26. Cash, K. J.; Li, C.; Xia, J.; Wang, L. V.; Clark, H. A., Optical Drug Monitoring: Photoacoustic Imaging of Nanosensors

ASSOCIATED CONTENT Supporting Information Additional information as noted in the text include: influence of H2O2 and NaOH concentrations, selectivity studies, theoretical response curves, supplementary equations. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author * [email protected] ORCID Xiaojiang Xie: 0000-0003-2629-8362 Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENTS The authors thank the National Natural Science Foundation of China (21874063) and the Shenzhen Municipal Science and Technology Innovation Council (JCYJ20170817105950724) for financial support.

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A Chemiluminescent Ion Sensing Platform Based on Ionophores

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