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Electrogenerated Chemiluminescence for Potentiometric Sensors
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Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, Quai E.-Ansermet 30, CH-1211 Geneva, Switzerland
[email protected]
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Journal of the American Chemical Society

Cite this: J. Am. Chem. Soc. 2012, 134, 1, 205–207
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https://doi.org/10.1021/ja210600k
Published December 15, 2011

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Abstract

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We report here on a generic approach to read out potentiometric sensors with electrogenerated chemiluminescence (ECL). In a first example, a potassium ion-selective electrode acts as the reference electrode and is placed in contact with the sample solution. The working electrode of the three-electrode cell is responsible for ECL generation and placed in a detection solution containing tris(2,2′-bipyridyl)ruthenium(II) [Ru(bpy)32+] and the coreactant 2-(dibutylamino)ethanol (DBAE), physically separated from the sample by a bridge. Changes in the sample potassium concentration directly modulate the potential at the working electrode, and hence the ECL output, when a constant-potential pulse is applied between the two electrodes. A linear response of the ECL intensity to the logarithmic potassium concentration between 10 μm and 10 mM was found.

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We present here for the first time a generic approach for observing direct electrogenerated chemiluminescence (ECL) output for potentiometric ion sensors. ECL is an attractive technique that takes advantage of spectroscopic and electrochemical methodologies (1-3) and lends itself well to the design of hand-held sensing devices because the emitted light signal can be observed visually or with conventional cameras. (4)
The general concept introduced here couples the potential generated at the interface of the membrane with the ECL emission. Both the input (perturbation) and output (detection) signals are electrochemically generated, providing a basis for future approaches that would be difficult to achieve with traditional electronics, including the achievement of two-dimensional chemical detection based on imaging tools or arrays of bipolar electrodes with ECL. (5-7) This research draws also some analogy from enzyme logic systems pioneered by Katz, in which logical operations are performed directly at the chemical level to realize integrated sensing systems. (8)
Potentiometric ion sensors are today well-established tools in analytical chemistry and account for billions of measurements each year in clinical diagnostics, environmental sensing, and benchtop measurements. (9, 10) Unfortunately, a direct optical readout for potentiometric sensors normally fails because concentration changes within the membrane are typically negligible within the linear response region of the membrane electrode. (11) Consequently, optical ion sensors operate either on the basis of classical indicator chemistry (embedded in a hydrogel phase) (12, 13) or make use of competitive ion-exchange or coextraction equilibria involving lipophilic sensing phases containing selective receptors that are borrowed from their potentiometric counterparts. (14-16) While the former principle suffers from a limited choice of indicators, the latter always detects the concentration (strictly, activity) of two competing or cooperative ions.
Recent work in our group has demonstrated that the sample compartment can be spatially separated from that of ECL generation if a cation-exchanging liquid membrane is used that transports the ECL reagent Ru(bpy)32+ from the sample to a thin-layer ECL compartment by electrochemical excitation. (17) However, it would be attractive to introduce a generic methodology to provide ECL readout for potentiometric sensors without the need to pass current across the ion-selective membrane.
Direct ECL readout of potentiometric sensors can be achieved in the arrangement shown in Figure 1. The potential is applied at the ECL-generating working electrode (WE) with respect to the reference electrode (RE), which is replaced here by the ion-selective electrode (ISE). This indicator electrode is in contact with the sample solution and physically separated from the location of ECL generation by a bridge. When a constant potential is applied across the cell, the potential at the ECL-generating WE directly depends on the potential at the ion-selective electrode. Ion activity changes in the sample may be monitored by ECL via the resulting potential change at the indicator electrode if the ECL intensity is potential-dependent.

Figure 1

Figure 1. Schematic illustration of the electrochemical setup with two separated compartments (sample and detection) used to demonstrate the ECL readout concept for potentiometric sensors. An applied potential between the gold working electrode (WE) and the K+ ISE reference electrode (RE) produces the oxidation of Ru(bpy)32+ and 2-(dibutylamino)ethanol (DBAE), generating light at the gold electrode. The light is collected with a photomultiplier tube (PMT) placed outside the detection compartment. The reference potential is modulated by the activity of K+ in the sample. The potassium ion-selective membrane is composed of a valinomycin-doped polymeric membrane (see the SI for membrane composition). The counter electrode (CE) is placed in the detection compartment.

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A K+ ISE was chosen as the indicator electrode in this early example. Figure 2A shows linear sweep voltammograms from 0 to 1.6 V for the setup illustrated in Figure 1 as a function of the K+ concentration in the sample compartment. As established, the current flows between the WE and the counter electrode (CE) placed in the ECL compartment. The individual voltammograms are shifted along the potential axis according to the potential change at the indicator electrode. The potential separation agrees with the sample K+ concentration according to the Nernst equation, with an observed slope of −58.3 ± 0.2 mV (the ideal value is −59.2 mV at 25 °C), as shown in the Figure 2A inset. The slope is negative because the indicator electrode assumes the position of the RE in the cell, resulting in a reversal of the sign of the potential. The detection limit observed in the inset is below 1 μM K+ concentration, which is in accordance with other literature reports on similarly formulated membrane electrode systems. (18)

Figure 2

Figure 2. (A) Linear sweep voltammograms (current vs applied potential between the WE and RE) for the configuration shown in Figure 1. Increasing K+ concentrations in a 10 mM LiCl background electrolyte shift the voltammograms to lower potentials. The arrow indicates the direction of increasing K+ concentration (0.1 μM, 1 μM, 10 μM, 100 μM, 1 mM, and 10 mM, with sulfate as the counterion). Inset: Observed potential shift (ΔE) as a function of the logarithmic K+ concentration for the current value indicated by the horizontal arrow in (A). (B) Corresponding ECL signal as a function of the linear sweep potential for different K+ concentrations in the sample compartment. Inset: Observed Nernstian potential shift (ΔE) as a function of the logarithmic K+ concentration for the ECL output indicated by the horizontal line in (B).

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The first voltammetric peak at ∼0.3 V is attributed to the oxidation of the coreactant 2-(dibutylamino)ethanol (DBAE) and does not result in ECL generation (also see refs 19 and 20). The second wave in the range of ∼0.8–1.3 V generates an intense red light emission and is attributed to the concurrent oxidation of Ru(bpy)32+ and DBAE (21) (see Figure 2B). When the K+ concentration increases, the ECL peaks shift to less negative potentials, following the behavior of the current response shown in Figure 2A. The same magnitude of light output is observed for the individual measurements, but the shift is again a function of the K+ concentration in the sample compartment with a near-Nernstian slope of −58.5 ± 0.3 mV.
The potentiometric characteristics of the K+ ISE were evaluated separately with a high-impedance interface. A near-Nernstian slope of 59.7 ± 0.2 mV dec–1 with respect to K+ was observed [see Figure 1S in the Supporting Information (SI)], in agreement with the potential shifts shown in Figure 2 under dynamic electrochemistry conditions. Unbiased selectivity coefficients were estimated with the modified separate solutions method. (22) The resulting values are shown in the SI and confirm that a high concentration of Li+ on the order of 10 mM does not influence the potentiometric response (and hence the ECL output) in the chosen K+ concentration range, with log KK,Li = −6.6 ± 0.1. The lower limit of detection and the linear working range are shown in Figure 2S.
Having established that the potential at the WE can be modulated by the potential at the ISE, we subsequently demonstrated direct ECL detection of the K+ concentration. According to the data in Figure 2B, the largest changes in ECL amplitude should be observed at a constant applied cell potential in the rising edge of the ECL-versus-potential spectrum (i.e., in the range of 0.8 to 1.0 V). Figure 3A demonstrates calibration curves for K+ at three different applied potentials (0.8, 0.9, and 1 V). The experiments were performed by applying potential pulses of 0.1 s duration and collecting the emitted light at the WE with a photomultiplier tube. The maximum sensitivity was found for a potential of 1 V (see Figure 3A). While the data in Figure 2B suggest a roughly sigmoidal response function, a near-linear range from 50 μM to 10 mM K+ concentration was observed (Figure 3A). The response at the lower potentials did not give obvious advantages (also see Figure 3S).

Figure 3

Figure 3. (A) ECL calibration curves for different K+ levels at three external applied potentials: 0.8 V, 0.9 and 1 V. Error bars have been added for each potassium activity. (B) ECL peaks as a function of time recorded when short chronoamperometric pulses were applied on the cell. The peak width is 0.1 s, and the amplitude depends on the K+ concentration. The reproducibility of the peak maxima (RSD < 2%, n = 3) is somewhat inferior to that for the integrated ECL peaks (error bars in Figure 2A).

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Rapid fixed potential pulses to generate ECL show promising reproducibility, as shown in Figure 3B. The low consumption of reagents during the short pulses reduces any significant attenuation of the ECL signal with time. Figure 3B shows the transient ECL signal at a 1 V applied potential as a function of the concentration of potassium in the sample compartment, demonstrating a relative standard deviation (RSD) of 0.3–0.5% in the ECL output.
In summary, this work has shown how a selective potentiometric sensor can be used to modulate the potential at a working electrode that is placed in a compartment optimized for efficient electrogenerated chemiluminescene detection. For the system explored here, a 1 V applied potential gives rise to large and reproducible changes in ECL intensity, demonstrating a generic approach to yield direct light emission readout for potentiometric sensors. The system introduced here relies on the potential of a second electrode placed in the sample compartment to close the cell circuit (in a final design most appropriately through a liquid junction). This means that an optical readout for ion concentration changes can now be accomplished for the first time with extrathermodynamic assumptions that are no more severe than those for established ion-selective electrodes.

Supporting Information

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Experimental details, potentiometric characterization, and ECL peaks at different applied potentials. This material is available free of charge via the Internet at http://pubs.acs.org.

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Author Information

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  • Corresponding Author
    • Eric Bakker - Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, Quai E.-Ansermet 30, CH-1211 Geneva, Switzerland
  • Authors
    • Gastón A. Crespo - Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, Quai E.-Ansermet 30, CH-1211 Geneva, Switzerland
    • Günter Mistlberger - Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, Quai E.-Ansermet 30, CH-1211 Geneva, Switzerland

Acknowledgment

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The authors thank the Swiss National Science Foundation and the University of Geneva for supporting this research. We also thank S. Jeanneret for electronics support.

References

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This article references 22 other publications.

  1. 1
    Miao, W. J. Chem. Rev. 2008, 108, 2506– 2553
    Google Scholar
    1
    Electrogenerated Chemiluminescence and Its Biorelated Applications
    Miao, Wujian
    Chemical Reviews (Washington, DC, United States) (2008), 108 (7), 2506-2553CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. The rapid development of electrogenerated chemiluminescence (ECL) in both fundamentals and applications over the past several years has clearly demonstrated that ECL is a powerful tool for ultrasensitive biomol. detection and quantification. High-throughput, miniaturized biosensors based on ECL technol. capable of multiplexing detection with high sensitivity, low detection limit, and good selectivity and stability will continue to attract the interest of the research community. With further understanding of ECL mechanisms, new highly efficient, tunable ECL systems, both emitters and coreactants, will be developed. Approaches based on ECL enhancement as well as quenching may play an important role in designing new methodologies for sensitive biomol. recognition. Thermodn. and kinetic studies of biomol. interactions using ECL are expected to be further expanded. The combination of ECL with other techniques could lead to the development of new instruments or provide valuable insights into mol. structures and intracellular components of biorelated species. Ultimately, detection of single biomols. will be realized.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXmtlCqurY%253D&md5=53805dc698b191a4fc2ebef17aeefe9b
  2. 2
    Richter, M. M. Chem. Rev. 2004, 104, 3003– 3036
    Google Scholar
    2
    Electrochemiluminescence (ECL)
    Richter, Mark M.
    Chemical Reviews (Washington, DC, United States) (2004), 104 (6), 3003-3036CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Electrochemiluminescence ( ECL) involves the generation of species at electrode surfaces that then undergo electron-transfer reactions to form excited states that emit light. By employing ECL-active species as labels on biol. mols., ECL has found application in immunoassays and DNA analyses. Com. systems have been developed that use ECL to detect many clin. important analytes (e.g., α-fetoprotein, digoxin, protein and steroidal hormones, and various antibodies) with high sensitivity and selectivity.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXitlWmsLw%253D&md5=b30fc3521d1df4e0b0760d5fb3fbb0d3
  3. 3
    Bard, A. J. Electrogenerated Chemiluminescence; Marcel Dekker: New York, 2004.
    Google Scholar
    There is no corresponding record for this reference.
  4. 4
    Delaney, J. L.; Hogan, C. F.; Tian, J. F.; Shen, W. Anal. Chem. 2011, 83, 1300– 1306
    Google Scholar
    4
    Electrogenerated Chemiluminescence Detection in Paper-Based Microfluidic Sensors
    Delaney, Jacqui L.; Hogan, Conor F.; Tian, Junfei; Shen, Wei
    Analytical Chemistry (Washington, DC, United States) (2011), 83 (4), 1300-1306CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
    This paper describes the first approach at combining paper microfluidics with electrochemiluminescent (ECL) detection. Inkjet printing was used to produce paper microfluidic substrates which are combined with screen-printed electrodes (SPEs) to create simple, cheap, disposable sensors which can be read without a traditional photodetector. The sensing mechanism is based on the orange luminescence due to the ECL reaction of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)32+) with certain analytes. Using a conventional photodetector, 2-(dibutylamino)ethanol (DBAE) and NAD (NADH) could be detected to levels of 0.9 μM and 72 μM, resp. Significantly, a mobile camera phone can also be used to detect the luminescence from the sensors. By analyzing the red pixel intensity in digital images of the ECL emission, a calibration curve was constructed demonstrating that DBAE could be detected to levels of 250 μM using the phone.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXosVyktA%253D%253D&md5=16dc1f36ff8d564af792d86105c6bb48
  5. 5
    Chow, K. F.; Mavre, F.; Crooks, R. M. J. Am. Chem. Soc. 2008, 130, 7544– 7545
    Google Scholar
    5
    Wireless Electrochemical DNA Microarray Sensor
    Chow, Kwok-Fan; Mavre, Francois; Crooks, Richard M.
    Journal of the American Chemical Society (2008), 130 (24), 7544-7545CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    We report an electrochem. DNA microarray sensor whose function is controlled with just two wires regardless of the no. of individual sensing electrodes. The bipolar sensing electrode is modified with probe DNA, and the anode end of each electrode is configured to emit light (electrogenerated chemiluminescence) upon hybridization of cDNA labeled with electrocatalytic (oxygen redn.) Pt nanoparticles at the cathode. The important finding is that DNA can be selectively detected at an array of three electrodes. In principle, however, this advance provides a means for controlling the potential of many electrodes using just two wires and then indirectly detg. the current flowing through all of them simultaneously by correlating light emission to current.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXmtlCqtLc%253D&md5=bafd66705383bb524714fada27df0d73
  6. 6
    Chow, K. F.; Mavre, F.; Crooks, J. A.; Chang, B. Y.; Crooks, R. M. J. Am. Chem. Soc. 2009, 131, 8364– 8365
    Google Scholar
    6
    A Large-Scale, Wireless Electrochemical Bipolar Electrode Microarray
    Chow, Kwok-Fan; Mavre, Francois; Crooks, John A.; Chang, Byoung-Yong; Crooks, Richard M.
    Journal of the American Chemical Society (2009), 131 (24), 8364-8365CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The authors report a microelectrochem. array composed of 1000 individual bipolar electrodes that are controlled with just 2 driving electrodes and a simple power supply. The system is configured so that faradaic processes occurring at the cathode end of each electrode are correlated to light emission via electrogenerated chemiluminescence (ECL) at the anode end. This makes it possible to read out the state of each electrode simultaneously. The significant advance is that the electrode array is fabricated on a glass microscope slide and is operated in a simple electrochem. cell. This eliminates the need for microfluidic channels, provides a fabrication route to arbitrarily large electrode arrays, and will make it possible to place sensing chemistries onto each electrode using a robotic spotter.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXmsFWmtbc%253D&md5=27aeaf85c8b7d3742a249adc9f4f7dca
  7. 7
    Mavre, F.; Anand, R. K.; Laws, D. R.; Chow, K. F.; Chang, B. Y.; Crooks, J. A.; Crooks, R. M. Anal. Chem. 2010, 82, 8766– 8774
    Google Scholar
    7
    Bipolar Electrodes: A Useful Tool for Concentration, Separation, and Detection of Analytes in Microelectrochemical Systems
    Mavre, Francois; Anand, Robbyn K.; Laws, Derek R.; Chow, Kwok-Fan; Chang, Byoung-Yong; Crooks, John A.; Crooks, Richard M.
    Analytical Chemistry (Washington, DC, United States) (2010), 82 (21), 8766-8774CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
    A review including bioanal. applications.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtFWlsb7N&md5=52366013fcbc3396037677b3901af18a
  8. 8
    Katz, E.; Privman, V. Chem. Soc. Rev. 2010, 39, 1835– 1857
    Google Scholar
    There is no corresponding record for this reference.
  9. 9
    Bakker, E.; Pretsch, E. Angew. Chem., Int. Ed. 2007, 46, 5660– 5668
    Google Scholar
    There is no corresponding record for this reference.
  10. 10
    Pretsch, E. TrAC, Trends Anal. Chem 2007, 26, 46– 51
    Google Scholar
    There is no corresponding record for this reference.
  11. 11
    Bakker, E.; Buhlmann, P.; Pretsch, E. Chem. Rev. 1997, 97, 3083– 3132
    Google Scholar
    11
    Carrier-Based Ion-Selective Electrodes and Bulk Optodes. 1. General Characteristics
    Bakker, Eric; Buehlmann, Philippe; Pretsch, Ernoe
    Chemical Reviews (Washington, D. C.) (1997), 97 (8), 3083-3132CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review, with 322 refs., is given on the relation of the response of carrier-based ion-selective electrodes and bulk optodes.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXnsFSiu74%253D&md5=8719f01e08a2f5172d4aa95586fa5242
  12. 12
    Citterio, D.; Takeda, J.; Kosugi, M.; Hisamoto, H.; Sasaki, S.; Komatsu, H.; Suzuki, K. Anal. Chem. 2007, 79, 1237– 1242
    Google Scholar
    There is no corresponding record for this reference.
  13. 13
    Clark, H. A.; Kopelman, R.; Tjalkens, R.; Philbert, M. A. Anal. Chem. 1999, 71, 4837– 4843
    Google Scholar
    There is no corresponding record for this reference.
  14. 14
    Morf, W. E.; Seiler, K.; Rusterholz, B.; Simon, W. Anal. Chem. 1990, 62, 738– 742
    Google Scholar
    There is no corresponding record for this reference.
  15. 15
    Suzuki, K.; Tohda, K.; Tanda, Y.; Ohzora, H.; Nishihama, S.; Inoue, H.; Shirai, T. Anal. Chem. 1989, 61, 382– 384
    Google Scholar
    There is no corresponding record for this reference.
  16. 16
    Wolfbeis, O. S. Anal. Chem. 2008, 80, 4269– 4283
    Google Scholar
    There is no corresponding record for this reference.
  17. 17
    Crespo, G. A.; Mistlberger, G.; Bakker, E. Chem. Commun. 2011, 47, 11644– 11646
    Google Scholar
    There is no corresponding record for this reference.
  18. 18
    Bakker, E. J. Electrochem. Soc. 1996, 143, L83– L85
    Google Scholar
    18
    Determination of improved selectivity coefficients of polymer membrane ion-selective electrodes by conditioning with a discriminated ion
    Bakker, Eric
    Journal of the Electrochemical Society (1996), 143 (4), L83-L85CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
    A new method for detg. selectivity coeffs. of carrier based ion-selective electrodes toward highly discriminated ions is proposed. For each sep. measured ion soln., the interfacial layer of the membrane contacting the sample must contain only the ion to be measured for the exptl. detn. of Nikolskii coeffs. that reflect the true ion-exchange selectivity of the membrane. For this reason, it is recommended here that the electrode membrane is conditioned in a soln. of a discriminated ion that, preferably, is the cation of the tetraphenylborate salt incorporated in the membrane. The selectivity of valinomycin based plasticized poly(vinyl chloride) membrane electrodes was characterized by using this new method and logarithmic Nikolskii coeffs. for K+ over Na+, Mg2+, and Ca2+ were detd. as -4.5, -7.5, and -6.9, resp. All measured ions showed near-Nernstian electrode slopes.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XisVyrsro%253D&md5=91094cbc2412478d79c42a443245d837
  19. 19
    Zu, Y. B.; Bard, A. J. Anal. Chem. 2000, 72, 3223– 3232
    Google Scholar
    There is no corresponding record for this reference.
  20. 20
    Zu, Y. B.; Bard, A. J. Anal. Chem. 2001, 73, 3960– 3964
    Google Scholar
    There is no corresponding record for this reference.
  21. 21
    Liu, X. Q.; Shi, L. H.; Niu, W. X.; Li, H. J.; Xu, G. B. Angew. Chem., Int. Ed. 2007, 46, 421– 424
    Google Scholar
    21
    Environmentally friendly and highly sensitive ruthenium(II) tris(2,2'-bipyridyl) electrochemiluminescent system using 2-(dibutylamino)ethanol as co-reactant
    Liu, Xiaoqing; Shi, Lihong; Niu, Wenxin; Li, Haijuan; Xu, Guobao
    Angewandte Chemie, International Edition (2007), 46 (3), 421-424CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Elec. light orchestra: The electrochemiluminescence (ECL) intensity of the [Ru(bpy)3]2+/2-(dibutylamino)ethanol (DBAE) system at Au and Pt electrodes are ∼10 and 100 times, resp., greater than that of the commonly used [Ru(bpy)3]2+/tripropylamine (TPA) system. Thus, DBAE is a promising co-reactant for [Ru(bpy)3]2+ ECL immunoassays and DNA probe assays.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXotVGjug%253D%253D&md5=69332cbc5a3d8c8b02911c43580c46b7
  22. 22
    Bakker, E.; Pretsch, E.; Buhlmann, P. Anal. Chem. 2000, 72, 1127– 1133
    Google Scholar
    22
    Selectivity of Potentiometric Ion Sensors
    Bakker, Eric; Pretsch, Ernoe; Buehlmann, Philippe
    Analytical Chemistry (2000), 72 (6), 1127-1133CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
    A review, with 29 refs., is given. Selectivities of solvent polymeric membrane ion-selective electrodes (ISEs) are quant. related to equil. at the interface between the sample and the electrode membrane. However, only correctly detd. selectivity coeffs. allow accurate predictions of ISE responses to real-world samples. also, they are also required for the optimization of ionophore structures and membrane compns. Best suited for such purposes are potentiometric selectivity coeffs. as defined already in the 1960s. This paper briefly reviews the basic relations and focuses on possible biases in the detn. of selectivity coeffs. The traditional methods to det. selectivity coeffs. (sep. soln. method, fixed interference method) are still the same as those originally proposed by IUPAC in 1976. However, several precautions are needed to obtain meaningful data. For example, errors arise when the response to a weakly interfering ion is also influenced by the primary ion leaching from the membrane. Wrong selectivity coeffs. may be also obtained when the interfering agent is highly preferred and the electrode shows counterion interference. Recent advances show how such pitfalls can be avoided. A detailed recipe to det. correct potentiometric selectivity coeffs. unaffected by such biases is presented.
    >> More from SciFinder ®
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  5. Sutida Jansod, Eric Bakker. Tunable Optical Sensing with PVC-Membrane-Based Ion-Selective Bipolar Electrodes. ACS Sensors 2019, 4 (4) , 1008-1016. https://doi.org/10.1021/acssensors.9b00179
  6. Wenyue Gao, Stéphane Jeanneret, Dajing Yuan, Thomas Cherubini, Lu Wang, Xiaojiang Xie, Eric Bakker. Electrogenerated Chemiluminescence for Chronopotentiometric Sensors. Analytical Chemistry 2019, 91 (7) , 4889-4895. https://doi.org/10.1021/acs.analchem.9b00787
  7. Jia-Dong Zhang, Lei Lu, Xiu-Fang Zhu, Li-Jing Zhang, Shan Yun, Chuan-Song Duanmu, Lei He. Direct Observation of Oxidation Reaction via Closed Bipolar Electrode-Anodic Electrochemiluminescence Protocol: Structural Property and Sensing Applications. ACS Sensors 2018, 3 (11) , 2351-2358. https://doi.org/10.1021/acssensors.8b00736
  8. Jingying Zhai, Liyuan Yang, Xinfeng Du, Xiaojiang Xie. Electrochemical-to-Optical Signal Transduction for Ion-Selective Electrodes with Light-Emitting Diodes. Analytical Chemistry 2018, 90 (21) , 12791-12795. https://doi.org/10.1021/acs.analchem.8b03213
  9. Zdeňka Jarolímová, Tingting Han, Ulriika Mattinen, Johan Bobacka, Eric Bakker. Capacitive Model for Coulometric Readout of Ion-Selective Electrodes. Analytical Chemistry 2018, 90 (14) , 8700-8707. https://doi.org/10.1021/acs.analchem.8b02145
  10. Andrew S. Danis, Karlie P. Potts, Samuel C. Perry, Janine Mauzeroll. Combined Spectroelectrochemical and Simulated Insights into the Electrogenerated Chemiluminescence Coreactant Mechanism. Analytical Chemistry 2018, 90 (12) , 7377-7382. https://doi.org/10.1021/acs.analchem.8b00773
  11. Yan-Mei Lei, Rui-Xin Wen, Jia Zhou, Ya-Qin Chai, Ruo Yuan, Ying Zhuo. Silver Ions as Novel Coreaction Accelerator for Remarkably Enhanced Electrochemiluminescence in a PTCA–S2O82– System and Its Application in an Ultrasensitive Assay for Mercury Ions. Analytical Chemistry 2018, 90 (11) , 6851-6858. https://doi.org/10.1021/acs.analchem.8b01018
  12. Sutida Jansod, Maria Cuartero, Thomas Cherubini, Eric Bakker. Colorimetric Readout for Potentiometric Sensors with Closed Bipolar Electrodes. Analytical Chemistry 2018, 90 (11) , 6376-6379. https://doi.org/10.1021/acs.analchem.8b01585
  13. Jiawang Ding, Enguang Lv, Liyan Zhu, and Wei Qin . Optical Ion Sensing Platform Based on Potential-Modulated Release of Enzyme. Analytical Chemistry 2017, 89 (6) , 3235-3239. https://doi.org/10.1021/acs.analchem.7b00072
  14. Liming Qi, Yong Xia, Wenjing Qi, Wenyue Gao, Fengxia Wu, and Guobao Xu . Increasing Electrochemiluminescence Intensity of a Wireless Electrode Array Chip by Thousands of Times Using a Diode for Sensitive Visual Detection by a Digital Camera. Analytical Chemistry 2016, 88 (2) , 1123-1127. https://doi.org/10.1021/acs.analchem.5b04304
  15. Min Zhao, Ni Liao, Ying Zhuo, Ya-Qin Chai, Ji-Peng Wang, and Ruo Yuan . Triple Quenching of a Novel Self-Enhanced Ru(II) Complex by Hemin/G-Quadruplex DNAzymes and Its Potential Application to Quantitative Protein Detection. Analytical Chemistry 2015, 87 (15) , 7602-7609. https://doi.org/10.1021/acs.analchem.5b01671
  16. Wenjing Qi, Jianping Lai, Wenyue Gao, Suping Li, Saima Hanif, and Guobao Xu . Wireless Electrochemiluminescence with Disposable Minidevice. Analytical Chemistry 2014, 86 (18) , 8927-8931. https://doi.org/10.1021/ac501833a
  17. Yan Cheng, Yin Huang, Jianping Lei, Lei Zhang, and Huangxian Ju . Design and Biosensing of Mg2+-Dependent DNAzyme-Triggered Ratiometric Electrochemiluminescence. Analytical Chemistry 2014, 86 (10) , 5158-5163. https://doi.org/10.1021/ac500965p
  18. Xiaowei Zhang, Yanchao Han, Jing Li, Libing Zhang, Xiaofang Jia, and Erkang Wang . Portable, Universal, and Visual Ion Sensing Platform Based on the Light Emitting Diode-Based Self-Referencing-Ion Selective Field-Effect Transistor. Analytical Chemistry 2014, 86 (3) , 1380-1384. https://doi.org/10.1021/ac403312f
  19. Ying Zhuo, Ni Liao, Ya-Qin Chai, Guo-Feng Gui, Min Zhao, Jing Han, Yun Xiang, and Ruo Yuan . Ultrasensitive Apurinic/Apyrimidinic Endonuclease 1 Immunosensing Based on Self-Enhanced Electrochemiluminescence of a Ru(II) Complex. Analytical Chemistry 2014, 86 (2) , 1053-1060. https://doi.org/10.1021/ac403019e
  20. Honglan Qi, Xiaoying Qiu, Danping Xie, Chen Ling, Qiang Gao, and Chengxiao Zhang . Ultrasensitive Electrogenerated Chemiluminescence Peptide-Based Method for the Determination of Cardiac Troponin I Incorporating Amplification of Signal Reagent-Encapsulated Liposomes. Analytical Chemistry 2013, 85 (8) , 3886-3894. https://doi.org/10.1021/ac4005259
  21. Minghui Yang Jianxiu Wang Feimeng Zhou . Biomarker Detections Using Functional Noble Metal Nanoparticles. 2012, 177-205. https://doi.org/10.1021/bk-2012-1112.ch007
  22. Daifang Wang, Ligong Shen, Wenjun Liu, Xiao Cao, Qianwen Wang. High -Sensitive Detection of Malachite Green Based on Surface-Enhanced Electrochemiluminescence. Journal of Fluorescence 2025, 35 (2) , 887-894. https://doi.org/10.1007/s10895-023-03563-y
  23. Lu Liu, Yuanxin Liu, Tianjia Jiang, Rongning Liang, Wei Qin. Polymeric membrane ion-selective electrode based on potential-modulated ion transfer: ultrasensitive measurement of oceanic pH. Chemical Communications 2024, 60 (91) , 13404-13407. https://doi.org/10.1039/D4CC04807E
  24. Meixue Lai, Lijie Zhong, Siyi Liu, Yitian Tang, Tingting Han, Huali Deng, Yu Bao, Yingming Ma, Wei Wang, Li Niu, Shiyu Gan. Carbon fiber-based multichannel solid-contact potentiometric ion sensors for real-time sweat electrolyte monitoring. Analytica Chimica Acta 2024, 1287 , 342046. https://doi.org/10.1016/j.aca.2023.342046
  25. Magdalena Michalak, Justyna Kalisz, Agata Michalska, Krzysztof Maksymiuk. High resolution electrochemical monitoring of small pH changes. Electrochimica Acta 2023, 468 , 143147. https://doi.org/10.1016/j.electacta.2023.143147
  26. Robin Nussbaum, Andrea Nonis, Stéphane Jeanneret, Thomas Cherubini, Eric Bakker. Ultrasensitive sensing of pH and fluoride with enhanced constant potential coulometry at membrane electrodes. Sensors and Actuators B: Chemical 2023, 392 , 134101. https://doi.org/10.1016/j.snb.2023.134101
  27. Ke Qu, Jinghong Li. Emerging functional materials in solid-contact potentiometric sensing, a field full of vitality. Materials Chemistry Frontiers 2023, 7 (19) , 4177-4183. https://doi.org/10.1039/D3QM00535F
  28. Tingting Han, Tao Song, Yu Bao, Wei Wang, Ying He, Zhenbang Liu, Shiyu Gan, Dongxue Han, Johan Bobacka, Li Niu. Fast and sensitive coulometric signal transduction for ion-selective electrodes by utilizing a two-compartment cell. Talanta 2023, 262 , 124623. https://doi.org/10.1016/j.talanta.2023.124623
  29. Tingting Han, Tao Song, Shiyu Gan, Dongxue Han, Johan Bobacka, Li Niu, Ari Ivaska. Coulometric Response of H + ‐Selective Solid‐Contact Ion‐Selective Electrodes and Its Application in Flexible Sensors †. Chinese Journal of Chemistry 2023, 41 (2) , 207-213. https://doi.org/10.1002/cjoc.202200500
  30. Naela Delmo, Zekra Mousavi, Tomasz Sokalski, Johan Bobacka. Novel Experimental Setup for Coulometric Signal Transduction of Ion-Selective Electrodes. Membranes 2022, 12 (12) , 1221. https://doi.org/10.3390/membranes12121221
  31. Tanji Yin, Xiaotong Sun, Zhibo Liao, Ziping Zhang. Colorimetric and coulometric dual-mode sensing based on electrochromic Prussian blue device for solid-contact ion-selective electrodes. Sensors and Actuators B: Chemical 2022, 371 , 132502. https://doi.org/10.1016/j.snb.2022.132502
  32. Tingting Han, Tao Song, Yu Bao, Zhonghui Sun, Yingming Ma, Ying He, Shiyu Gan, Dechen Jiang, Dongxue Han, Johan Bobacka, Li Niu. Amperometric response of solid-contact ion-selective electrodes utilizing a two-compartment cell and a redox couple in solution. Journal of Electroanalytical Chemistry 2022, 922 , 116683. https://doi.org/10.1016/j.jelechem.2022.116683
  33. Justyna Kalisz, Katarzyna Węgrzyn, Agata Michalska, Krzysztof Maksymiuk. Resolution increase of ion-selective electrodes response by using a reversed amperometric setup. Electrochimica Acta 2022, 427 , 140886. https://doi.org/10.1016/j.electacta.2022.140886
  34. Jingying Zhai, Dajing Yuan, Xiaojiang Xie. Ionophore-based ion-selective electrodes: signal transduction and amplification from potentiometry. Sensors & Diagnostics 2022, 1 (2) , 213-221. https://doi.org/10.1039/D1SD00055A
  35. Xueqing Gao, Tianjia Jiang, Wei Qin. Potentiometric aptasensing of Escherichia coli based on electrogenerated chemiluminescence as a highly sensitive readout. Biosensors and Bioelectronics 2022, 200 , 113923. https://doi.org/10.1016/j.bios.2021.113923
  36. Xiaotong Sun, Tanji Yin, Ziping Zhang, Wei Qin. Redox probe-based amperometric sensing for solid-contact ion-selective electrodes. Talanta 2022, 239 , 123114. https://doi.org/10.1016/j.talanta.2021.123114
  37. Yinghong Tang, Jingying Zhai, Qinghan Chen, Xiaojiang Xie. Ruthenium bipyridine complexes as electrochemiluminescent transducers for ionophore-based ion-selective detection. The Analyst 2021, 146 (22) , 6955-6959. https://doi.org/10.1039/D1AN01355F
  38. Tanji Yin, Hemin Wang, Jinghui Li, Baiqing Yuan, Wei Qin. Translating potentiometric detection into non-enzymatic amperometric measurement of H2O2. Talanta 2021, 232 , 122489. https://doi.org/10.1016/j.talanta.2021.122489
  39. Jingjing Zhang, Yun Chen, Danjun Fang. Electrochemiluminescence in Luminol-based calcium-selective nanoparticles for the determination of calcium ions. Journal of Electroanalytical Chemistry 2020, 878 , 114671. https://doi.org/10.1016/j.jelechem.2020.114671
  40. Yuzhou Shao, Yibin Ying, Jianfeng Ping. Recent advances in solid-contact ion-selective electrodes: functional materials, transduction mechanisms, and development trends. Chemical Society Reviews 2020, 49 (13) , 4405-4465. https://doi.org/10.1039/C9CS00587K
  41. Xu Hun, Xiaoli Xiong, Jiawang Ding, Wei Qin. Photoelectric current as a highly sensitive readout for potentiometric sensors. Chemical Communications 2020, 56 (27) , 3879-3882. https://doi.org/10.1039/D0CC00138D
  42. Jiawang Ding, Wei Qin. Recent advances in potentiometric biosensors. TrAC Trends in Analytical Chemistry 2020, 124 , 115803. https://doi.org/10.1016/j.trac.2019.115803
  43. Nian Cao, Peng Zeng, Faqiong Zhao, Baizhao Zeng. Au@SiO2@RuDS nanocomposite based plasmon-enhanced electrochemiluminescence sensor for the highly sensitive detection of glutathione. Talanta 2019, 204 , 402-408. https://doi.org/10.1016/j.talanta.2019.06.030
  44. Zhenhao Wang, Renzhong Yu, Hui Zeng, Xinxing Wang, Shizong Luo, Weihua Li, Xiliang Luo, Tao Yang. Nucleic acid-based ratiometric electrochemiluminescent, electrochemical and photoelectrochemical biosensors: a review. Microchimica Acta 2019, 186 (7) https://doi.org/10.1007/s00604-019-3514-6
  45. Ewa Jaworska, Agata Michalska, Krzysztof Maksymiuk. Fluorimetric readout of ion-selective electrode potential changes. Electrochimica Acta 2018, 284 , 321-327. https://doi.org/10.1016/j.electacta.2018.07.130
  46. Marson Ady Putra, Muhammad Rivai, Achmad Arifin. Milk Assessment using Potentiometric and Gas Sensors in Conjunction With Neural Network. 2018, 409-412. https://doi.org/10.1109/ISITIA.2018.8710944
  47. Jianrui Sun, Wenyue Gao, Liming Qi, Yufeng Song, Pan Hui, Zhongyuan Liu, Guobao Xu. Detection of 1,3-dihydroxyacetone by tris(2,2′-bipyridine)ruthenium(II) electrochemiluminescence. Analytical and Bioanalytical Chemistry 2018, 410 (9) , 2315-2320. https://doi.org/10.1007/s00216-017-0833-5
  48. Rongning Liang, Jiawang Ding, Shengshuai Gao, Wei Qin. Mussel‐Inspired Surface‐Imprinted Sensors for Potentiometric Label‐Free Detection of Biological Species. Angewandte Chemie 2017, 129 (24) , 6937-6941. https://doi.org/10.1002/ange.201701892
  49. Rongning Liang, Jiawang Ding, Shengshuai Gao, Wei Qin. Mussel‐Inspired Surface‐Imprinted Sensors for Potentiometric Label‐Free Detection of Biological Species. Angewandte Chemie International Edition 2017, 56 (24) , 6833-6837. https://doi.org/10.1002/anie.201701892
  50. Chunling Wang, Hongyan Yuan, Zhijuan Duan, Dan Xiao. Integrated multi-ISE arrays with improved sensitivity, accuracy and precision. Scientific Reports 2017, 7 (1) https://doi.org/10.1038/srep44771
  51. Yinggui Zhu, Min Zhao, Xiaojuan Hu, Xiaofang Wang, Ling Wang. Electrogenerated chemiluminescence behavior of Tb complex and its application in sensitive sensing Cd2+. Electrochimica Acta 2017, 228 , 1-8. https://doi.org/10.1016/j.electacta.2017.01.049
  52. Xiaowei Zhang, Qingfeng Zhai, Li Xu, Jing Li, Erkang Wang. Paper-based electrochemiluminescence bipolar conductivity sensing mechanism: A critical supplement for the bipolar system. Journal of Electroanalytical Chemistry 2016, 781 , 15-19. https://doi.org/10.1016/j.jelechem.2016.07.009
  53. Min Zhao, Dan Huang, Ying Zhuo, Ya-Qin Chai, Ruo Yuan. Novel tri-layer self-enhanced Ru(II) complex-based nanoparicles for signal-on electrochemiluminescent aptasensor construction. Electrochimica Acta 2016, 212 , 734-743. https://doi.org/10.1016/j.electacta.2016.07.048
  54. Yousry M. Issa, Sabrein H. Mohamed, Mohamed Abd-El Baset. Chemically modified carbon paste and membrane sensors for the determination of benzethonium chloride and some anionic surfactants (SLES, SDS, and LABSA): Characterization using SEM and AFM. Talanta 2016, 155 , 158-167. https://doi.org/10.1016/j.talanta.2016.04.043
  55. Daifang Wang, Longhua Guo, Rong Huang, Bin Qiu, Zhenyu Lin, Guonan Chen. Surface Enhanced Electrochemiluminescence of Ru(bpy)32+. Scientific Reports 2015, 5 (1) https://doi.org/10.1038/srep07954
  56. Majid Ghahraman Afshar, Gastón A. Crespo, Eric Bakker. Thin‐Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection. Angewandte Chemie 2015, 127 (28) , 8228-8231. https://doi.org/10.1002/ange.201500797
  57. Majid Ghahraman Afshar, Gastón A. Crespo, Eric Bakker. Thin‐Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection. Angewandte Chemie International Edition 2015, 54 (28) , 8110-8113. https://doi.org/10.1002/anie.201500797
  58. Stefanie E. K. Kirschbaum, Antje J. Baeumner. A review of electrochemiluminescence (ECL) in and for microfluidic analytical devices. Analytical and Bioanalytical Chemistry 2015, 407 (14) , 3911-3926. https://doi.org/10.1007/s00216-015-8557-x
  59. Xinyi Ni, Yuan Zhao, Qijun Song. Electrochemical reduction and in-situ electrochemiluminescence detection of nitroaromatic compounds. Electrochimica Acta 2015, 164 , 31-37. https://doi.org/10.1016/j.electacta.2015.02.174
  60. Lin-Ru Hong, Ya-Qin Chai, Min Zhao, Ni Liao, Ruo Yuan, Ying Zhuo. Highly efficient electrogenerated chemiluminescence quenching of PEI enhanced Ru(bpy)32+ nanocomposite by hemin and Au@CeO2 nanoparticles. Biosensors and Bioelectronics 2015, 63 , 392-398. https://doi.org/10.1016/j.bios.2014.07.065
  61. Shiguo Sun, Wei Sun, Daozhou Mu, Na Jiang, Xiaojun Peng. Ratiometric ECL of heterodinuclear Os–Ru dual-emission labels. Chemical Communications 2015, 51 (13) , 2529-2531. https://doi.org/10.1039/C4CC08394F
  62. Zhouqian Jiang, Chengfei Zhao, Liqing Lin, Shaohuang Weng, Qicai Liu, Xinhua Lin. A label-free electrochemical immunosensor based on poly(thionine)–SDS nanocomposites for CA19-9 detection. Analytical Methods 2015, 7 (11) , 4508-4513. https://doi.org/10.1039/C5AY00576K
  63. Zhongyuan Liu, Wenjing Qi, Guobao Xu. Recent advances in electrochemiluminescence. Chemical Society Reviews 2015, 44 (10) , 3117-3142. https://doi.org/10.1039/C5CS00086F
  64. Chaomin Gao, Min Su, Yanhu Wang, Shenguang Ge, Jinghua Yu. A disposable paper-based electrochemiluminescence device for ultrasensitive monitoring of CEA based on Ru(bpy) 3 2+ @Au nanocages. RSC Advances 2015, 5 (36) , 28324-28331. https://doi.org/10.1039/C5RA00393H
  65. Morteza Hosseini, Mohammad Reza Moghaddam, Farnoush Faridbod, Parviz Norouzi, Mohammad Reza Karimi Pur, Mohammad Reza Ganjali. A novel solid-state electrochemiluminescence sensor based on a Ru(bpy) 3 2+ /nano Sm 2 O 3 modified carbon paste electrode for the determination of l -proline. RSC Advances 2015, 5 (79) , 64669-64674. https://doi.org/10.1039/C5RA06897E
  66. Daifang Wang, Longhua Guo, Rong Huang, Bin Qiu, Zhenyu Lin, Guonan Chen. Surface Enhanced Electrochemiluminescence for Ultrasensitive Detection of Hg2+. Electrochimica Acta 2014, 150 , 123-128. https://doi.org/10.1016/j.electacta.2014.10.121
  67. Günter Mistlberger, Gastón A. Crespo, Eric Bakker. Ionophore-Based Optical Sensors. Annual Review of Analytical Chemistry 2014, 7 (1) , 483-512. https://doi.org/10.1146/annurev-anchem-071213-020307
  68. Qiong Chen, Hong Chen, Yingying Zhao, Fan Zhang, Fan Yang, Jie Tang, Pingang He. A label-free electrochemiluminescence aptasensor for thrombin detection based on host–guest recognition between tris(bipyridine)ruthenium(II)-β-cyclodextrin and aptamer. Biosensors and Bioelectronics 2014, 54 , 547-552. https://doi.org/10.1016/j.bios.2013.11.028
  69. Xinyi Ni, Tongtong Li, Qijun Song. The electrochemiluminescence of an iridium complex induced by hydroxide and ethoxide ions in organic solvents. Journal of Electroanalytical Chemistry 2014, 719 , 30-34. https://doi.org/10.1016/j.jelechem.2014.02.005
  70. Fengyu Liu, Jiantao Shao, Yinqi Zhao. Electrochemiluminescence detection of chlorpromazine hydrochloride at bare and graphene oxide modified glassy carbon electrodes. Anal. Methods 2014, 6 (16) , 6483-6487. https://doi.org/10.1039/C4AY00898G
  71. Kelei Zhuo, Yujing Wei, Jingjing Ma, Yujuan Chen, Guangyue Bai. Response of PVC membrane ion-selective electrodes to alkylmethylimidazolium ionic liquid cations. Sensors and Actuators B: Chemical 2013, 186 , 461-465. https://doi.org/10.1016/j.snb.2013.05.023
  72. Wenjing Qi, Moustafa Tarek Gabr, Zhongyuan Liu, Lianzhe Hu, Moyan Han, Shuyun Zhu, Guobao Xu. Tris(2,2′-bipyridyl) ruthenium(II) electrochemiluminescence of glyoxal, glyoxylic acid, methylglyoxal, and acetaldehyde. Electrochimica Acta 2013, 89 , 139-143. https://doi.org/10.1016/j.electacta.2012.11.051
  73. Gastón A. Crespo, Eric Bakker. Ionophore-based ion optodes without a reference ion: electrogenerated chemiluminescence for potentiometric sensors. The Analyst 2012, 137 (21) , 4988. https://doi.org/10.1039/c2an35516g
  74. Alexander B. Nepomnyashchii, Allen J. Bard, Jonathan K. Leland, Jeff D. Debad, George B. Sigal, James L. Wilbur, Jacob N. Wohlstadter. Chemiluminescence, Electrogenerated. 2000, 1-12. https://doi.org/10.1002/9780470027318.a5302.pub2
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  • Abstract

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    Figure 1

    Figure 1. Schematic illustration of the electrochemical setup with two separated compartments (sample and detection) used to demonstrate the ECL readout concept for potentiometric sensors. An applied potential between the gold working electrode (WE) and the K+ ISE reference electrode (RE) produces the oxidation of Ru(bpy)32+ and 2-(dibutylamino)ethanol (DBAE), generating light at the gold electrode. The light is collected with a photomultiplier tube (PMT) placed outside the detection compartment. The reference potential is modulated by the activity of K+ in the sample. The potassium ion-selective membrane is composed of a valinomycin-doped polymeric membrane (see the SI for membrane composition). The counter electrode (CE) is placed in the detection compartment.

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    Figure 2

    Figure 2. (A) Linear sweep voltammograms (current vs applied potential between the WE and RE) for the configuration shown in Figure 1. Increasing K+ concentrations in a 10 mM LiCl background electrolyte shift the voltammograms to lower potentials. The arrow indicates the direction of increasing K+ concentration (0.1 μM, 1 μM, 10 μM, 100 μM, 1 mM, and 10 mM, with sulfate as the counterion). Inset: Observed potential shift (ΔE) as a function of the logarithmic K+ concentration for the current value indicated by the horizontal arrow in (A). (B) Corresponding ECL signal as a function of the linear sweep potential for different K+ concentrations in the sample compartment. Inset: Observed Nernstian potential shift (ΔE) as a function of the logarithmic K+ concentration for the ECL output indicated by the horizontal line in (B).

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    Figure 3

    Figure 3. (A) ECL calibration curves for different K+ levels at three external applied potentials: 0.8 V, 0.9 and 1 V. Error bars have been added for each potassium activity. (B) ECL peaks as a function of time recorded when short chronoamperometric pulses were applied on the cell. The peak width is 0.1 s, and the amplitude depends on the K+ concentration. The reproducibility of the peak maxima (RSD < 2%, n = 3) is somewhat inferior to that for the integrated ECL peaks (error bars in Figure 2A).

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  • References

    This article references 22 other publications.

    1. 1
      Miao, W. J. Chem. Rev. 2008, 108, 2506– 2553
      1
      Electrogenerated Chemiluminescence and Its Biorelated Applications
      Miao, Wujian
      Chemical Reviews (Washington, DC, United States) (2008), 108 (7), 2506-2553CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. The rapid development of electrogenerated chemiluminescence (ECL) in both fundamentals and applications over the past several years has clearly demonstrated that ECL is a powerful tool for ultrasensitive biomol. detection and quantification. High-throughput, miniaturized biosensors based on ECL technol. capable of multiplexing detection with high sensitivity, low detection limit, and good selectivity and stability will continue to attract the interest of the research community. With further understanding of ECL mechanisms, new highly efficient, tunable ECL systems, both emitters and coreactants, will be developed. Approaches based on ECL enhancement as well as quenching may play an important role in designing new methodologies for sensitive biomol. recognition. Thermodn. and kinetic studies of biomol. interactions using ECL are expected to be further expanded. The combination of ECL with other techniques could lead to the development of new instruments or provide valuable insights into mol. structures and intracellular components of biorelated species. Ultimately, detection of single biomols. will be realized.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXmtlCqurY%253D&md5=53805dc698b191a4fc2ebef17aeefe9b
    2. 2
      Richter, M. M. Chem. Rev. 2004, 104, 3003– 3036
      2
      Electrochemiluminescence (ECL)
      Richter, Mark M.
      Chemical Reviews (Washington, DC, United States) (2004), 104 (6), 3003-3036CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Electrochemiluminescence ( ECL) involves the generation of species at electrode surfaces that then undergo electron-transfer reactions to form excited states that emit light. By employing ECL-active species as labels on biol. mols., ECL has found application in immunoassays and DNA analyses. Com. systems have been developed that use ECL to detect many clin. important analytes (e.g., α-fetoprotein, digoxin, protein and steroidal hormones, and various antibodies) with high sensitivity and selectivity.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXitlWmsLw%253D&md5=b30fc3521d1df4e0b0760d5fb3fbb0d3
    3. 3
      Bard, A. J. Electrogenerated Chemiluminescence; Marcel Dekker: New York, 2004.
      There is no corresponding record for this reference.
    4. 4
      Delaney, J. L.; Hogan, C. F.; Tian, J. F.; Shen, W. Anal. Chem. 2011, 83, 1300– 1306
      4
      Electrogenerated Chemiluminescence Detection in Paper-Based Microfluidic Sensors
      Delaney, Jacqui L.; Hogan, Conor F.; Tian, Junfei; Shen, Wei
      Analytical Chemistry (Washington, DC, United States) (2011), 83 (4), 1300-1306CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
      This paper describes the first approach at combining paper microfluidics with electrochemiluminescent (ECL) detection. Inkjet printing was used to produce paper microfluidic substrates which are combined with screen-printed electrodes (SPEs) to create simple, cheap, disposable sensors which can be read without a traditional photodetector. The sensing mechanism is based on the orange luminescence due to the ECL reaction of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)32+) with certain analytes. Using a conventional photodetector, 2-(dibutylamino)ethanol (DBAE) and NAD (NADH) could be detected to levels of 0.9 μM and 72 μM, resp. Significantly, a mobile camera phone can also be used to detect the luminescence from the sensors. By analyzing the red pixel intensity in digital images of the ECL emission, a calibration curve was constructed demonstrating that DBAE could be detected to levels of 250 μM using the phone.
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    5. 5
      Chow, K. F.; Mavre, F.; Crooks, R. M. J. Am. Chem. Soc. 2008, 130, 7544– 7545
      5
      Wireless Electrochemical DNA Microarray Sensor
      Chow, Kwok-Fan; Mavre, Francois; Crooks, Richard M.
      Journal of the American Chemical Society (2008), 130 (24), 7544-7545CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      We report an electrochem. DNA microarray sensor whose function is controlled with just two wires regardless of the no. of individual sensing electrodes. The bipolar sensing electrode is modified with probe DNA, and the anode end of each electrode is configured to emit light (electrogenerated chemiluminescence) upon hybridization of cDNA labeled with electrocatalytic (oxygen redn.) Pt nanoparticles at the cathode. The important finding is that DNA can be selectively detected at an array of three electrodes. In principle, however, this advance provides a means for controlling the potential of many electrodes using just two wires and then indirectly detg. the current flowing through all of them simultaneously by correlating light emission to current.
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    6. 6
      Chow, K. F.; Mavre, F.; Crooks, J. A.; Chang, B. Y.; Crooks, R. M. J. Am. Chem. Soc. 2009, 131, 8364– 8365
      6
      A Large-Scale, Wireless Electrochemical Bipolar Electrode Microarray
      Chow, Kwok-Fan; Mavre, Francois; Crooks, John A.; Chang, Byoung-Yong; Crooks, Richard M.
      Journal of the American Chemical Society (2009), 131 (24), 8364-8365CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The authors report a microelectrochem. array composed of 1000 individual bipolar electrodes that are controlled with just 2 driving electrodes and a simple power supply. The system is configured so that faradaic processes occurring at the cathode end of each electrode are correlated to light emission via electrogenerated chemiluminescence (ECL) at the anode end. This makes it possible to read out the state of each electrode simultaneously. The significant advance is that the electrode array is fabricated on a glass microscope slide and is operated in a simple electrochem. cell. This eliminates the need for microfluidic channels, provides a fabrication route to arbitrarily large electrode arrays, and will make it possible to place sensing chemistries onto each electrode using a robotic spotter.
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    7. 7
      Mavre, F.; Anand, R. K.; Laws, D. R.; Chow, K. F.; Chang, B. Y.; Crooks, J. A.; Crooks, R. M. Anal. Chem. 2010, 82, 8766– 8774
      7
      Bipolar Electrodes: A Useful Tool for Concentration, Separation, and Detection of Analytes in Microelectrochemical Systems
      Mavre, Francois; Anand, Robbyn K.; Laws, Derek R.; Chow, Kwok-Fan; Chang, Byoung-Yong; Crooks, John A.; Crooks, Richard M.
      Analytical Chemistry (Washington, DC, United States) (2010), 82 (21), 8766-8774CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
      A review including bioanal. applications.
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    8. 8
      Katz, E.; Privman, V. Chem. Soc. Rev. 2010, 39, 1835– 1857
      There is no corresponding record for this reference.
    9. 9
      Bakker, E.; Pretsch, E. Angew. Chem., Int. Ed. 2007, 46, 5660– 5668
      There is no corresponding record for this reference.
    10. 10
      Pretsch, E. TrAC, Trends Anal. Chem 2007, 26, 46– 51
      There is no corresponding record for this reference.
    11. 11
      Bakker, E.; Buhlmann, P.; Pretsch, E. Chem. Rev. 1997, 97, 3083– 3132
      11
      Carrier-Based Ion-Selective Electrodes and Bulk Optodes. 1. General Characteristics
      Bakker, Eric; Buehlmann, Philippe; Pretsch, Ernoe
      Chemical Reviews (Washington, D. C.) (1997), 97 (8), 3083-3132CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review, with 322 refs., is given on the relation of the response of carrier-based ion-selective electrodes and bulk optodes.
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    12. 12
      Citterio, D.; Takeda, J.; Kosugi, M.; Hisamoto, H.; Sasaki, S.; Komatsu, H.; Suzuki, K. Anal. Chem. 2007, 79, 1237– 1242
      There is no corresponding record for this reference.
    13. 13
      Clark, H. A.; Kopelman, R.; Tjalkens, R.; Philbert, M. A. Anal. Chem. 1999, 71, 4837– 4843
      There is no corresponding record for this reference.
    14. 14
      Morf, W. E.; Seiler, K.; Rusterholz, B.; Simon, W. Anal. Chem. 1990, 62, 738– 742
      There is no corresponding record for this reference.
    15. 15
      Suzuki, K.; Tohda, K.; Tanda, Y.; Ohzora, H.; Nishihama, S.; Inoue, H.; Shirai, T. Anal. Chem. 1989, 61, 382– 384
      There is no corresponding record for this reference.
    16. 16
      Wolfbeis, O. S. Anal. Chem. 2008, 80, 4269– 4283
      There is no corresponding record for this reference.
    17. 17
      Crespo, G. A.; Mistlberger, G.; Bakker, E. Chem. Commun. 2011, 47, 11644– 11646
      There is no corresponding record for this reference.
    18. 18
      Bakker, E. J. Electrochem. Soc. 1996, 143, L83– L85
      18
      Determination of improved selectivity coefficients of polymer membrane ion-selective electrodes by conditioning with a discriminated ion
      Bakker, Eric
      Journal of the Electrochemical Society (1996), 143 (4), L83-L85CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
      A new method for detg. selectivity coeffs. of carrier based ion-selective electrodes toward highly discriminated ions is proposed. For each sep. measured ion soln., the interfacial layer of the membrane contacting the sample must contain only the ion to be measured for the exptl. detn. of Nikolskii coeffs. that reflect the true ion-exchange selectivity of the membrane. For this reason, it is recommended here that the electrode membrane is conditioned in a soln. of a discriminated ion that, preferably, is the cation of the tetraphenylborate salt incorporated in the membrane. The selectivity of valinomycin based plasticized poly(vinyl chloride) membrane electrodes was characterized by using this new method and logarithmic Nikolskii coeffs. for K+ over Na+, Mg2+, and Ca2+ were detd. as -4.5, -7.5, and -6.9, resp. All measured ions showed near-Nernstian electrode slopes.
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    19. 19
      Zu, Y. B.; Bard, A. J. Anal. Chem. 2000, 72, 3223– 3232
      There is no corresponding record for this reference.
    20. 20
      Zu, Y. B.; Bard, A. J. Anal. Chem. 2001, 73, 3960– 3964
      There is no corresponding record for this reference.
    21. 21
      Liu, X. Q.; Shi, L. H.; Niu, W. X.; Li, H. J.; Xu, G. B. Angew. Chem., Int. Ed. 2007, 46, 421– 424
      21
      Environmentally friendly and highly sensitive ruthenium(II) tris(2,2'-bipyridyl) electrochemiluminescent system using 2-(dibutylamino)ethanol as co-reactant
      Liu, Xiaoqing; Shi, Lihong; Niu, Wenxin; Li, Haijuan; Xu, Guobao
      Angewandte Chemie, International Edition (2007), 46 (3), 421-424CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Elec. light orchestra: The electrochemiluminescence (ECL) intensity of the [Ru(bpy)3]2+/2-(dibutylamino)ethanol (DBAE) system at Au and Pt electrodes are ∼10 and 100 times, resp., greater than that of the commonly used [Ru(bpy)3]2+/tripropylamine (TPA) system. Thus, DBAE is a promising co-reactant for [Ru(bpy)3]2+ ECL immunoassays and DNA probe assays.
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    22. 22
      Bakker, E.; Pretsch, E.; Buhlmann, P. Anal. Chem. 2000, 72, 1127– 1133
      22
      Selectivity of Potentiometric Ion Sensors
      Bakker, Eric; Pretsch, Ernoe; Buehlmann, Philippe
      Analytical Chemistry (2000), 72 (6), 1127-1133CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)
      A review, with 29 refs., is given. Selectivities of solvent polymeric membrane ion-selective electrodes (ISEs) are quant. related to equil. at the interface between the sample and the electrode membrane. However, only correctly detd. selectivity coeffs. allow accurate predictions of ISE responses to real-world samples. also, they are also required for the optimization of ionophore structures and membrane compns. Best suited for such purposes are potentiometric selectivity coeffs. as defined already in the 1960s. This paper briefly reviews the basic relations and focuses on possible biases in the detn. of selectivity coeffs. The traditional methods to det. selectivity coeffs. (sep. soln. method, fixed interference method) are still the same as those originally proposed by IUPAC in 1976. However, several precautions are needed to obtain meaningful data. For example, errors arise when the response to a weakly interfering ion is also influenced by the primary ion leaching from the membrane. Wrong selectivity coeffs. may be also obtained when the interfering agent is highly preferred and the electrode shows counterion interference. Recent advances show how such pitfalls can be avoided. A detailed recipe to det. correct potentiometric selectivity coeffs. unaffected by such biases is presented.
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  • Supporting Information

    Supporting Information

    Experimental details, potentiometric characterization, and ECL peaks at different applied potentials. This material is available free of charge via the Internet at http://pubs.acs.org.


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