An Electrochemiluminescence-Based Arsenic (III) Sensor using Luminol on Screen-Printed Gold Electrodes

Harmesa Harmesa , Isnaini Rahmawati , Andrea Fiorani , Yasuaki Einaga , Eny Kusrini , A'an Johan Wahyudi , Asep Saefumillah , Tribidasari A Ivandini

Journal of Electrochemistry ›› 2026, Vol. 32 ›› Issue (2) : 2507092

PDF (1241KB)
Journal of Electrochemistry ›› 2026, Vol. 32 ›› Issue (2) :2507092 DOI: 10.61558/2993-074X.3593
Articles
research-article
An Electrochemiluminescence-Based Arsenic (III) Sensor using Luminol on Screen-Printed Gold Electrodes
Author information +
History +
PDF (1241KB)

Abstract

Electrochemiluminescence (ECL) of luminol has been studied on a screen-printed gold electrode for a simple and sensitive detection of arsenic ions (As(III)). Cyclic voltammetry (CV) was applied as the proposed technique to study luminol's electrochemical behavior and to evaluate the arsenic’s effect in the ECL system, while hydrogen peroxide (H2O2) served as a co-reactant to enhance luminol’s light emission under alkaline conditions. To achieve optimal electrode performance, key parameters including pH, scan rate, and the concentrations of H2O2 and luminol were carefully optimized. The presence of As(III) induced a quenching effect on the luminol/H2O2 ECL system, leading to a linear decrease in ECL signal across the wide concentration range of 1 nmol·L-1 to 150 µmol·L-1. The system demonstrated a low detection limit of 1.21 nmol·L-1 and exhibited excellent repeatability with a relative standard deviation of 2.27%, highlighting its sensitivity and reliability for As(III) detection. A key advantage of this study was the successful use of commercial bare electrodes, which were readily available and required no modifications, proving their effectiveness for ECL-based arsenic sensing. The optimized buffer solution pH of 10 played a critical role in enhancing arsenic detection selectivity, as it facilitated the optimal deprotonation of luminol and ensured arsenic remained in its dissolved state, whereas other potential metal ion interferences were more likely to form solid metal (hydro)oxides. Furthermore, the developed sensor was successfully applied for As(III) detection in a seawater matrix, demonstrating its potential as a robust and effective ECL-based arsenic sensor for environmental applications.

Keywords

Arsenic (III) detection / Electrochemiluminescence / Gold electrode / Hydrogen peroxide / Quenching effect

Cite this article

Download citation ▾
Harmesa Harmesa, Isnaini Rahmawati, Andrea Fiorani, Yasuaki Einaga, Eny Kusrini, A'an Johan Wahyudi, Asep Saefumillah, Tribidasari A Ivandini. An Electrochemiluminescence-Based Arsenic (III) Sensor using Luminol on Screen-Printed Gold Electrodes. Journal of Electrochemistry, 2026, 32(2): 2507092 DOI:10.61558/2993-074X.3593

登录浏览全文

4963

注册一个新账户 忘记密码

Author Contributions

Harmesa Harmesa: Data curation, Formal analysis, Investigation, Writing - original draft. Isnaini Rahmawati: Formal analysis, Investigation, Andrea Fiorani: Supervision, Validation, Yasuaki Einaga: Conceptualization, Supervision, Eny Kusrini: Funding acquisition, Methodology, A'an Johan Wahyudi: Conceptualization, Supervision, Writing - review & editing. Asep Saefumillah: Supervision, Writing - review & editing. Tribidasari A. Ivandini: Conceptualization, Formal analysis, Funding acquisition, Methodology, Supervision, Validation, Writing - review & editing.

Conflicts of Interest

The authors declare that they have no known competing interests.

Supporting Information

Supporting information for this article is available.

Data Availability

Data will be made available on request.

Acknowledgements

This research was funded by Directorate of Research and Development, Universitas Indonesia under Bilateral Strategic Alliance (UI-UTM BISA) Research Collaboration Agreement (Matching Fund) 2023 (Grant No. NKB-1181/UN2.RST/HKP.05.00/2023).

References

[1]

Amen R, Bashir H, Bibi I, Shaheen S M, Niazi N K, Shahid M, Hussain M M, Antoniadis V, Shakoor M B, Al-Solaimani S G, Wang H L, Bundschuh J, Rinklebe J. A critical review on arsenic removal from water using biochar-based sorbents: The significance of modification and redox reactions[J]. Chem. Eng. J., 2020, 396: 125195. https://doi.org/10.1016/j.cej.2020.125195.

[2]

kaur R, Garkal A, Sarode L, Bangar P, Mehta T, Singh D P, Rawal R. Understanding arsenic toxicity: Implications for environmental exposure and human health[J]. J. Hazard. Mater. Lett., 2024, 5: 100090. https://doi.org/10.1016/j.hazl.2023.100090.

[3]

Rahaman M S, Rahman M M, Mise N, Sikder M T, Ichihara G, Uddin M K, Kurasaki M, Ichihara S. Environmental arsenic exposure and its contribution to human diseases, toxicity mechanism and management[J]. Environ. Pollut., 2021, 289: 117940. https://doi.org/10.1016/j.envpol.2021.117940.

[4]

Sharma V K, Sohn M. Aquatic arsenic: Toxicity, speciation, transformations, and remediation[J]. Environ. Int., 2009, 35(4): 743-759. https://doi.org/10.1016/j.envint.2009.01.005.

[5]

Alka S, Shahir S, Ibrahim N, Ndejiko M J, Vo D V N, Manan F A. Arsenic removal technologies and future trends: A mini review[J]. J. Clean. Prod., 2021, 278: 123805. https://doi.org/10.1016/j.jclepro.2020.123805.

[6]

Sevak P, Pushkar B. Arsenic pollution cycle, toxicity and sustainable remediation technologies: A comprehensive review and bibliometric analysis[J]. J. Environ. Manage., 2024, 349: 119504. https://doi.org/10.1016/j.jenvman.2023.119504.

[7]

Raju N J. Arsenic in the geo-environment: A review of sources, geochemical processes, toxicity and removal technologies[J]. Environ. Res., 2022, 203: 111782. https://doi.org/10.1016/j.envres.2021.111782.

[8]

Aktar S, Mia S, Makino T, Rahman M M, Rajapaksha A U. Arsenic removal from aqueous solution: A comprehensive synthesis with meta-data[J]. Sci. Total Environ., 2023, 862: 160821. https://doi.org/10.1016/j.scitotenv.2022.160821.

[9]

Herath I, Kumarathilaka P, Bundschuh J, Marchuk A, Rinklebe J. A fast analytical protocol for simultaneous speciation of arsenic by ultra-high performance liquid chromatography (UHPLC) hyphenated to inductively coupled plasma mass spectrometry (ICP-MS) as a modern advancement in liquid chromatography approaches[J]. Talanta, 2020, 208: 120457. https://doi.org/10.1016/j.talanta.2019.120457.

[10]

PétursdóttirÁ H, Gunnlaugsdóttir H. Selective and fast screening method for inorganic arsenic in seaweed using hydride generation inductively coupled plasma mass spectrometry (HG-ICPMS)[J]. Microchem. J., 2019, 144: 45-50. https://doi.org/10.1016/j.microc.2018.08.055.

[11]

Harmesa H, Wahyudi A J, Saefumillah A, Ivandini T A. Electrochemiluminescence systems for metal-ion detection: a systematic review[J]. ChemistrySelect, 2024, 9(21): 1-24. https://doi.org/10.1002/slct.202401544.

[12]

Ivandini T A, Sato R, Makide Y, Fujishima A, Einaga Y. Electrochemical detection of arsenic(III) using indium-implanted boron-doped diamond electrodes[J]. Anal. Chem., 2006, 78(18): 6291-6298. https://doi.org/10.1021/ac0519514.

[13]

Agustiany T, Khalil M, Einaga Y, Jiwanti P K, Ivandini T A. Stable iridium-modified boron-doped diamond electrode for the application in electrochemical detection of arsenic (III)[J]. Mater. Chem. Phys., 2020, 244: 1-7. https://doi.org/10.1016/j.matchemphys.2020.122723.

[14]

Rahmawati I, Fiorani A, Sanjaya A R, Irkham, Du J, Saepudin E, Einaga Y, Ivandini T A. Modification of boron-doped diamond electrode with polyaniline and gold particles to enhance the electrochemiluminescence of luminol for the detection of reactive oxygen species (hydrogen peroxide and hypochlorite)[J]. Diam. Relat. Mater., 2024, 144: 110956. https://doi.org/10.1016/j.diamond.2024.110956.

[15]

Rahmawati I, Saepudin E, Fiorani A, Einaga Y, Ivandini T A. Electrogenerated chemiluminescence of luminol at a boron-doped diamond electrode for the detection of hypochlorite[J]. Analyst, 2022, 147(12): 2696-2702. https://doi.org/10.1039/d2an00540a.

[16]

Wang Y R, Zhao X Y, Qu N R, Gu J M. Electrochemiluminescence for high-performance Chiral recognition of enantiomers: Recent advances and future perspectives[J]. Org. Electron., 2023, 122: 106902. https://doi.org/10.1016/j.orgel.2023.106902.

[17]

Husain R A, Barman S R, Chatterjee S, Khan I, Lin Z H. Enhanced biosensing strategies using electrogenerated chemiluminescence: recent progress and future prospects[J]. J. Mater. Chem., B. 2020, 8(16): 3192-3212. https://doi.org/10.1039/c9tb02578b.

[18]

Zanut A, Fiorani A, Canola S, Saito T, Ziebart N, Rapino S, Rebeccani S, Barbon A, Irie T, Josel H P, Negri F, Marcaccio M, Windfuhr M, Imai K, Valenti G, Paolucci F. Insights into the mechanism of coreactant electrochemiluminescence facilitating enhanced bioanalytical performance[J]. Nat. Commun., 2020, 11(1): 2668. https://doi.org/10.1038/s41467-020-16476-2.

[19]

Truong C K P, Nguyen T D D, Shin I S. Electrochemiluminescent chemosensors for clinical applications: a review[J]. Biochip J., 2019, 13(3): 203-216. https://doi.org/10.1007/s13206-019-3301-9.

[20]

Ying X D, Zhou L, Fu W X, Wang Y F, Su B. Electrochemiluminescence devices for point-of-care testing[J]. Sens. Diagn., 2023, 2(3): 480-491. https://doi.org/10.1039/d2sd00232a.

[21]

Hao N, Wang K. Recent development of electrochemiluminescence sensors for food analysis[J]. Anal. Bioanal. Chem., 2016, 408(25): 7035-7048. https://doi.org/10.1007/s00216-016-9548-2.

[22]

Zhou J J, Lv X Q, Jia J L, Din Z U, Cai S Q, He J L, Xie F, Cai J. Nanomaterials-based electrochemiluminescence biosensors for food analysis: recent developments and future directions[J]. Biosensors, 2022, 12(11): 1046. https://doi.org/10.3390/bios12111046.

[23]

Wang X B, Zhao Y Q, Hua Q, Lu J J, Tang F Y, Sun W J, Luan F, Zhuang X M, Tian C Y. An ultrasensitive electrochemiluminescence biosensor for the detection of total bacterial count in environmental and biological samples based on a novel sulfur quantum dot luminophore[J]. Analyst, 2022, 147(8): 1716-1721. https://doi.org/10.1039/d2an00153e.

[24]

Li L L, Che Y, Zhu J J. Recent advances in electrochemiluminescence analysis[J]. Anal. Chem., 2017, 89(1): 358-371. https://doi.org/10.1021/acs.analchem.6b04675.

[25]

Shen Y, Gao X, Lu H J, Nie C, Wang J L. Electrochemiluminescence-based innovative sensors for monitoring the residual levels of heavy metal ions in environment-related matrices[J]. Coord. Chem. Rev., 2023, 476: 214927. https://doi.org/10.1016/j.ccr.2022.214927.

[26]

Liang R P, Yu L D, Tong Y J, Wen S H, Cao S P, Qiu J D. An ultratrace assay of arsenite based on the synergistic quenching effect of Ru(bpy)32+ and arsenite on the electrochemiluminescence of Au-g-C3N4 nanosheets[J]. Chem. Commun., 2018, 54(99): 14001-14004. https://doi.org/10.1039/c8cc08353c.

[27]

Wang R Z, Zhao Y, Jie G F. A novel DNA-quantum dot nanostructure electrochemiluminescence aptamer sensor by chain reaction amplification for rapid detection of trace Cd2+[J]. Analyst, 2023, 148(19): 4844-4849. https://doi.org/10.1039/d3an01247f.

[28]

Huang R F, Liu H X, Gai Q Q, Liu G J, Wei Z. A facile and sensitive electrochemiluminescence biosensor for Hg2+ analysis based on a dual-function oligonucleotide probe[J]. Biosens. Bioelectron., 2015, 71: 194-199. https://doi.org/10.1016/j.bios.2015.04.038.

[29]

Zhao G H, Li X J, Zhao Y B, Li Y Y, Cao W, Wei Q. Electrochemiluminescence assay of Cu2+by using one-step electrodeposition synthesized CdS/ZnS quantum dots[J]. Analyst, 2017, 142(17): 3272-3277. https://doi.org/10.1039/c7an01014a.

[30]

Zhang Y, Xu J M, Zhou S, Zhu L, Lv X, Zhang J, Zhang L, Zhu P H, Yu J H. DNAzyme-triggered visual and ratiometric electrochemiluminescence dual-readout assay for Pb(II) based on an assembled paper device[J]. Anal. Chem., 2020, 92(5): 3874-3881. https://doi.org/10.1021/acs.analchem.9b05343.

[31]

Zakaria N D, Salih I L, Hamzah H H, Sönmez T, Omar M H, Nor N M, Razak K A, Balakrishnan V. Electrochemical and imaging evaluations of electrochemically activated screen-printed gold electrodes[J]. Analyst, 2024, 149(22): 5401-5410. https://doi.org/10.1039/d4an00990h.

[32]

Kozak J, Tyszczuk-Rotko K. Screen-printed gold electrode for ultrasensitive voltammetric determination of the antipsychotic drug thioridazine[J]. Meas. J. Int. Meas. Confed., 2023, 217: 113107. https://doi.org/10.1016/j.measurement.2023.113107.

[33]

Liu Z G, Huang X J. Voltammetric determination of inorganic arsenic[J]. TrAC - Trends Anal. Chem., 2014, 60: 25-35. https://doi.org/10.1016/j.trac.2014.04.014.

[34]

Duan Y, Song Y, Fan N K, Yao Y Z, Deng S X, Ding S J, Shen B, Yin Q F. Self-enhanced luminol-based electrochemiluminescent hydrogels: An ultrasensitive biosensing platform for fusion gene analysis coupled with target-initiated DNAzyme motor[J]. Biosens. Bioelectron., 2022, 197: 113784. https://doi.org/10.1016/j.bios.2021.113784.

[35]

Liu G P, Yuan Y L, Wang J L. Hemin/G-quadruplex DNAzyme nanowires amplified luminol electrochemiluminescence system and its application in sensing silver ions[J]. RSC Adv., 2016, 6(43): 37221-37225. https://doi.org/10.1039/c6ra01809b.

[36]

Hu Y X, Liu Y, Wang S, Guo Z Y, Hu Y F, Xie H Z. A novel surface-tethered double-signal electrochemiluminescence sensor based on luminol@Au and Cds quantum dots for mercury ion detection[J]. ChemistrySelect, 2019, 4(10): 2926-2932. https://doi.org/10.1002/slct.201802150.

[37]

Zhao C L, Ma C Y, Zhang F P, Li W J, Hong C L, Qi Y. Two-dimensional metal-organic framework nanosheets: An efficient two-electron oxygen reduction reaction electrocatalyst for boosting cathodic luminol electrochemiluminescence[J]. Chem. Eng. J., 2023, 466: 1-8. https://doi.org/10.1016/j.cej.2023.143156.

[38]

Huang Y T, Zhang S P, Chen S S, Chen Y J, Cheng L J, Dai H, Gao L H. Electrochemiluminescence enhanced by molecular engineering linear π-conjugated polymer: An ingenious ECL emitter for the construction of exosome sensing platform[J]. Talanta, 2024, 277: 126405. https://doi.org/10.1016/j.talanta.2024.126405.

[39]

Irkham, Rais R R, Ivandini T A, Fiorani A, Einaga Y. Electrogenerated chemiluminescence of luminol mediated by carbonate electrochemical oxidation at a boron-doped diamond, Anal. Chem., 2021, 93(4): 2336-2341. https://doi.org/10.1021/acs.analchem.0c04212.

[40]

Scholz F, Kahlert H. The calculation of the solubility of metal hydroxides, oxide-hydroxides, and oxides, and their visualisation in logarithmic diagrams[J]. ChemTexts, 2015, 1(1): 7. https://doi.org/10.1007/s40828-015-0006-0.

[41]

Ivandini T A, Yamada D, Watanabe T, Matsuura H, Nakano N, Fujishima A, Einaga Y. Development of amperometric arsine gas sensor using gold-modified diamond electrodes[J]. J. Electroanal. Chem., 2010, 645(1): 58-63. https://doi.org/10.1016/j.jelechem.2010.04.012.

[42]

Eikelboom M, Wang Y, Portlock G, Gourain A, Gardner J, Bullen J, Lewtas P, Carriere M, Alvarez A, Kumar A, O’Prey S, Tölgyes T, Omanović D, Bhowmick S, Weiss D, Salaun P. Voltammetric determination of inorganic arsenic in mildly acidified (pH 4.7) groundwaters from Mexico and India[J]. Anal. Chim. Acta., 2023, 1276: 341589. https://doi.org/10.1016/j.aca.2023.341589.

[43]

Giancarla A, Zanoni C, Merli D, Magnaghi L R, Biesuz R. A new cysteamine-copper chemically modified screen-printed gold electrode for glyphosate determination[J]. Talanta, 2024, 269: 125436. https://doi.org/10.1016/j.talanta.2023.125436.

[44]

Steel L, Ward A C, Jeffrey C, Alcorn D, Corrigan D K. Towards simple, rapid point of care testing for clinically important protein biomarkers of sepsis[J]. SCIOL Biotechnol., 2017, 1: 1-8. https://doi.org/10.11648/j.sjbt.20170101.11.

[45]

Mccormick W J, Doran W J. Covalent immobilisation of a nanoporous platinum film onto a gold screen-printed electrode for highly stable and selective[J]. Catalysts, 2021, 11(10): 1161. https://doi.org/10.3390/catal11101161.

[46]

Monnappa A B, Manjunatha J G, Bhatt A S. Design of a sensitive and selective voltammetric sensor based on a cationic surfactant-modified carbon paste electrode for the determination of alloxan[J]. ACS Omega, 2020, 5(36): 23481-23490. https://doi.org/10.1021/acsomega.0c03517.

[47]

Dhaffouli A, Moussaoui Y, Salazar-Carballo P A, Holzinger M, Carinelli S, Barhoumi H. Design of a high-performance electrochemical sensor using ZnO@SiO₂-n-propyl-NH₂-benzothiazole-AuNPs for the selective and sensitive detection of lead ions in environmental samples[J]. J. Electrochem. Soc., 2025, 172(6): 067520. https://doi.org/10.1149/1945-7111/ade47f.

[48]

Yin F, Sun Q, Huang X Z, Wu G Q, Zhang Y J, Shen Y F. Recent progress in signal enhancement of nanomaterials-based electrochemiluminescence systems[J]. TrAC-Trends Anal. Chem., 2023, 169: 117376. https://doi.org/10.1016/j.trac.2023.117376.

[49]

Zhou P, Hu S J, Guo W L, Su B. Deciphering electrochemiluminescence generation from luminol and hydrogen peroxide by imaging light emitting layer[J]. Fundam. Res., 2022, 2(5): 682-687. https://doi.org/10.1016/j.fmre.2021.11.018.

[50]

Pettine M, Campanella L, Millero F J. Arsenite oxidation by H2O2 in aqueous solution[J]. Geochim. Cosmochim. Acta, 1999, 63(18): 2727-2735. https://doi.org/10.1139/v01-027.

[51]

Molnár L, Virčíkova E, Lech P. Experimental study of As(III) oxidation by hydrogen peroxide[J]. Hydrometallurgy, 1994, 35(1): 1-9. https://doi.org/10.1016/0304-386X(94)90013-2.

[52]

Pourbaix M, Zhang H, Pourbaix A. Presentation of an atlas of chemical and electrochemical equilibria in the presence of a gaseous phase[J]. Mater. Sci. Forum., 1997, 251-252: 143-148. https://doi.org/10.4028/www.scientific.net/msf.251-254.143.

[53]

Liu Y, Hu Y X, Wang S, Guo Z Y, Hu Y F. A novel surface-tethered analysis method for mercury (II) ion detection via self-assembly of individual electrochemiluminescence signal units[J]. Electroanalysis, 2018, 30(5): 859-867. https://doi.org/10.1002/elan.201700660.

[54]

Guo Z Y, Chen B B, Wang Z B, Jiang X H. An electrochemiluminescence biosensor for mercury ion detection based on gamma-polyglutamic acid-graphene-luminol composite and oligonucleotides[J]. Sens. Actuators B: Chem., 2015, 209: 579-585. https://doi.org/10.1016/j.snb.2014.12.028.

[55]

Xu M, Zhang Y, Li L, Kong Q K, Zhang L N, Ge S G, Yu J H. Colorimetric and electrochemiluminescence dual-mode sensing of lead ion based on integrated lab-on-paper device[J]. ACS Appl. Mater. Interfaces, 2018, 10(4): 3431-3440. https://doi.org/10.1021/acsami.7b18542.

[56]

Yildiz G, Tasdoven U, Menek N. Electrochemical characterization of luminol and its determination in real samples[J]. Anal. Methods, 2014, 6(19): 7809-7813. https://doi.org/10.1039/c4ay01281j.

[57]

Rajendran S, Ramanaiah D V, Kundu S, Bhunia S K. Yellow fluorescent carbon dots for selective recognition of As3+ and Fe3+ ions[J]. ACS Appl. Nano Mater., 2021, 4(10): 10931-10942. https://doi.org/10.1021/acsanm.1c02391.

[58]

Sepúlveda A C, Gatti L M, Kerl C F, Chennu A, Klatt J M. Arsenic speciation analysis in porewater by a novel colorimetric assay[J]. Sci. Total Environ., 2022, 827: 154155. https://doi.org/10.1016/j.scitotenv.2022.154155.

[59]

Cui L, Wu J, Ju H X. Label-free signal-on aptasensor for sensitive electrochemical detection of arsenite[J]. Biosens. Bioelectron., 2016, 79: 861-865. https://doi.org/10.1016/j.bios.2016.01.010.

[60]

Zhang Y F, Li D L, Compton R G. Arsenic (III) detection with underpotential deposition on gold[J]. J. Electroanal. Chem., 2022, 909: 116154. https://doi.org/10.1016/j.jelechem.2022.116154.

[61]

Kaimal R, Maridevaru M C, Dube A, Wu J J, Sambandam A, Ashokkumar M. Borophene nanosheet-based electrochemical sensing toward groundwater arsenic detection[J]. Ind. Eng. Chem. Res., 2023, 62(38): 15418-15427. https://doi.org/10.1021/acs.iecr.3c01922.

PDF (1241KB)

6

Accesses

0

Citation

Detail

Sections
Recommended

/