, Volume 25, Issue 11, pp 5537–5550 | Cite as

Simultaneous detection of glutathione, threonine, and glycine at electrodeposited RuHCF/rGO–modified electrode

  • Saranya S
  • Jency Feminus J
  • Geetha B
  • Deepa P NEmail author
Original Paper


Ruthenium hexacyanoferrate/reduced graphene oxide (RuHCF/rGO) electrode was fabricated by electrochemical deposition of RuHCF on a rGO-modified electrode. Electrocatalytic oxidation and determination of glutathione, threonine, and glycine were carried out simultaneously using the modified electrode. The electrochemical sensor showed a wide linear response in the concentration range of 5.12–25.58 μM for glutathione, 1.98–15.86 μM for threonine, and 1.25–7.49 μM for glycine. The RuHCF/rGO–modified electrode showed minimal interference in the presence of related compounds. The limit of detection observed for glutathione, threonine, and glycine was 1.70, 0.66, and 0.4 μM respectively. Saliva samples were used for checking the analytical utility of the RuHCF/rGO–modified electrode for sensing the three analytes, and the recovery percentages were between 95.80 and 98.03. The electrode also exhibited long-term stability and shelf life.


Electrochemical Ruthenium hexacyanoferrate Reduced graphene oxide Glutathione Threonine Glycine 


Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Yun L, Lili Y, Xiaoxia M, Mengjia L, Jing Z, Yongmei Y (2016) Electrochemical detection of glutathione based on Hg2 þ-mediated strand displacement reaction strategy. Biosens Bioelectron 85:664–668Google Scholar
  2. 2.
    Nesakumar N, Berchmans S, Alwarappan S (2018) Chemically modified carbon based electrodes for the detection of reduced glutathione. Sensors Actuators B 264:448–466Google Scholar
  3. 3.
    Oztekin Y, Ramanaviciene A, Ramanavicius A (2011) Electrochemical glutathione sensor based on electrochemically deposited poly-m-aminophenol. Electroanalysis 23:701–709Google Scholar
  4. 4.
    Zhao L, Zhao L, Miao Y, Zhang C (2016) Selective electrochemical determination of glutathione from the leakage of intracellular GSH contents in HeLa cells following doxorubicin-induced cell apoptosis. Electrochim Acta 206:86–98Google Scholar
  5. 5.
    Jahan Bakhsh R, Nader T, Mohammad AK, Reza O (2015) A high sensitive electrochemical nanosensor for simultaneous determination of glutathione, NADH and folic acid. Mater Sci Eng C 47:77–84Google Scholar
  6. 6.
    Qian W, Hongchang P, Yongqiang D, Yuwu C, Fengfu F (2018) Colorimetric determination of glutathione by using a nanohybrid composed of manganese dioxide and carbon dots. Microchim Acta 185:291Google Scholar
  7. 7.
    Lee PT, Goncalves LM, Compton RG (2015) Electrochemical determination of free and total glutathione in human saliva samples. Sensors Actuators B 221:962–968Google Scholar
  8. 8.
    Liu X, Wang Q, Zhang Y, Zhang LC, Su YY, Lv Y (2013) Colorimetric detection of glutathione in human blood serum based on the reduction of oxidized TMB. New J Chem 37:2174–2178Google Scholar
  9. 9.
    McDermott GP, Francis PS et al (2011) Determination of intracellular glutathione and glutathione disulfide using high performance liquid chromatography with acidic potassium permanganate chemiluminescence detection. Analyst 136:2578–2585PubMedGoogle Scholar
  10. 10.
    Zhiqiang W, Yongjian S, Qianwen Y et al (2018) Electrochemical determination of tyrosine in human serum based on glycine polymer and multi-walled carbon nanotubes modified carbon paste electrode. Int J Electrochem Sci 13:7478–7488Google Scholar
  11. 11.
    Elahe M, Ali M, Hadi B (2014) First report for voltammetric determination of methyldopa in the presence of folic acid and glycine. Mater Sci Eng C 36:168–172Google Scholar
  12. 12.
    Vandana B, Sharanjeet K, Kumar M (2012) Fluorescent supramolecular metal assemblies as ‘no quenching’ probe for detection of threonine in nanomolar range. Chem Commun 00:1–3Google Scholar
  13. 13.
    Noedson de JB, Cristina ARL, Ronner JMB et al (2018) Digestible threonine for slow-growing broilers: performance, carcass characteristics, intestinal mucin, and duodenal morphometry. R Bras Zootec 47:20170193.
  14. 14.
    Selvakumar P, Kokulnathan T, Shen MC, Vijayalakshmi V, Sayee KR (2017) Voltammetric determination of Sudan I in food samples based on platinum nanoparticles decorated on graphene-β-cyclodextrin modified electrode. J Electroanal Chem S1572–6657:30225–30224Google Scholar
  15. 15.
    Lanlan W, Yuan S, Ping L, Xuejun K (2018) Polystyrene nanofibers capped with copper nanoparticles for selective extraction of glutathione prior to its determination by HPLC. Microchim Acta 185:321Google Scholar
  16. 16.
    Singh VK, Yadav PK, Chandra S, Bano D, Talat M, Hasan SH (2018) Peroxidase mimetic activity of fluorescent NS-carbon quantum dots and its application for colorimetric detection of H2O2 and glutathione in human blood serum. J Mater Chem B 6:5256–5268. CrossRefGoogle Scholar
  17. 17.
    Shuyun Z, Lei H, Fang Z et al (2016) Fluorimetric evaluation of glutathione reductase activity and its inhibitors using carbon quantum dots. Talanta 161:769–774Google Scholar
  18. 18.
    Selvakumar P, Kokulnathan T, Shen MC, Xiao HL (2016) Preparation and characterisation of gold nanoparticles decorated on graphene oxide @ polydopamine composite : application for sensitive and low potential detection of catechol. Sensors Actuators B 233:298–306Google Scholar
  19. 19.
    Thangavelu K, Tata SKS, Shen MC, Tse WCBD (2018) Ex-situ decoration of graphene oxide with palladium nanoparticles for the highly sensitive and selective electrochemical determination of chloramphenicol in food and biological samples. J Taiwan Inst Chem Eng 000:1–13Google Scholar
  20. 20.
    Kokulnathan T, Nehru R, Shen-MC, Wei CL (2017) Nanomolar electrochemical detection of caffeic acid in fortified wine samples based on gold/palladium nanoparticles decorated graphene flakes (Au/PdNPsGRF). J Colloid Interface Sci 501:77–85Google Scholar
  21. 21.
    Pan L, Suqin L, Gaopeng D, Yuting L, Liang Y (2013) Enhancement in detection of glucose based on a nickel hexacyanoferrate–reduced graphene oxide-modified glassy carbon electrode. Aust J Chem 66:983–988Google Scholar
  22. 22.
    Paulo RO, Cristian K, Antonio SM et al (2018) Copper hexacyanoferrate nanoparticles supported on biochar for amperometric determination of isoniazid. Electrochim Acta 285:373–380Google Scholar
  23. 23.
    Paulo RO, Arthur FS, Eduardo GCN, Aldo JGZ, Luiz HMJ, Marcio FB (2018) Nickel hexacyanoferrate supported at nickel nanoparticles for voltammetric determination of rifampicin. Sensors Actuators B 260:816–823Google Scholar
  24. 24.
    Dias IARB, Costa WM, Cervini P, Cavalheiro ETG, Marques ALB (2016) Ruthenium hexacyanoferrate (III) modified glassy carbon electrode for determination of captopril. Electroanalysis 28:1–8Google Scholar
  25. 25.
    Xiaoli L, Jianbin P, Kemei P et al (2015) An electrochemical sensor for hydrazine and nitrite based on graphene–cobalt hexacyanoferrate nanocomposite: toward environment and food detection. J Electroanal Chem 745:80–87Google Scholar
  26. 26.
    Hung YL Tzu C, Liao WHC, Chia HC, Lin CC (2016) Molybdate hexacyanoferrate (MoOHCF) thin film: a brownish red Prussian blue analog for electrochromic window application. Sol Energy Mater Sol Cells 145:8–15Google Scholar
  27. 27.
    SulingY GL, Guifang W, Junhong Z, Zhihui Q, Lingbo Q (2015) Decoration of chemically reduced graphene oxide modified carbon paste electrode with yttrium hexacyanoferrate nanoparticles for nanomolar detection of rutin. Sensors Actuators B Chem 206:126–132Google Scholar
  28. 28.
    Caroline M, Yves B, Caroline DD, Agnes G, Laurent DW (2015) Cs ion exchange by a potassium nickel hexacyanoferrate loaded on a granular support. Chem Eng Sci 137:904–913Google Scholar
  29. 29.
    Lusheng C, Fenghua Z, Sue L, Chunting L, Hua Z, Huaixiang L (2018) Lead(II) ion detection in purified drinking water by nickel hexacyanoferrate-modified n-Si electrode in presence of dihydroxybenzene. J Solid State Electrochem 1–9Google Scholar
  30. 30.
    Vidhisha J, Uma S, Kaitha BS, Shiv S (2015) Green synthesis of potassium zinc hexacyanoferrate nanocubes and its potential application in photocatalytic degradation of organic dyes. RSC Adv 5:26141–26149Google Scholar
  31. 31.
    Li ZC, Qing SC, Cui JZ, Pei XL, Ming SW, Guo CG (2015) Photochromism and photomagnetism of a 3d−4f Hexacyanoferrate at room temperature. J Am Chem Soc 137:10882–10885PubMedGoogle Scholar
  32. 32.
    Magdalenda F, Helena PG, Pawel C et al (2017) Magnetic and magneto-optical properties of nickel hexacyanoferrate/ chromate thin films. RSC Adv 7:1382–1386Google Scholar
  33. 33.
    Phil N, Robin P, John PH (2018) Development of a simple, low cost chronoamperometric assay for fructose based on a commercial graphite-nanoparticle modified screen-printed carbon electrode. Food Chem 241:122–126Google Scholar
  34. 34.
    Wendell MC, Aldale LBM, Edmar PM et al (2010) Hydrazine oxidation catalyzed by ruthenium hexacyanoferrate-modified glassy carbon electrode. J Appl Electrochem 40:375–382Google Scholar
  35. 35.
    Chen S-M, Lu M-F, Lin K-C (2005) Preparation and characterization of ruthenium oxide/hexacyanoferrate and ruthenium hexacyanoferrate mixed films and their electrocatalytic properties. J Electroanal Chem 579:163–174Google Scholar
  36. 36.
    Emily AH, Rasa P, Samo BH, Bozidar O, Malcolm RS (2010) Amperometric microsensor for direct probing of ascorbic acid in human gastric juice. Anal Chim Acta 678:176–182Google Scholar
  37. 37.
    Kuo CL, Chuen-PH, Shen MC (2012) Electrocatalytic oxidation of alcohols, sulfides and hydrogen peroxide based on hybrid composite of ruthenium hexacyanoferrate and multi-walled carbon nanotubes. Int J Electrochem Sci 7:11426–11443Google Scholar
  38. 38.
    Leila S, Anjali AA (2014) Graphene oxide synthesized by using modified hummers approach. Renew Energy Environ Eng 02:2348–0157Google Scholar
  39. 39.
    Toh SY, Loh KS, Kamarudin SK, Daud WRW (2014) Graphene production via electrochemical reduction of graphene oxide synthesis and characterization. Chem Eng J 251:422–434Google Scholar
  40. 40.
    Paolo B, Giovanni F, Daniela S et al (2017) A glucose/oxygen enzymatic fuel cell based on gold nanoparticles modified graphene screen-printed electrode. Proof-of-concept in human saliva. Sensors Actuators B Chem 256:921–930Google Scholar
  41. 41.
    Fumiyuki S, Ryosuke F, Takashi K, Yusuke O (2012) Preparation of monodisperse cobalt(II) hexacyanoferrate(III) nanoparticles using cobalt ions released from a citrate complex. J Phys Chem C 116:3394–3399Google Scholar
  42. 42.
    Xingxing W, Yun Z, Shan J, Xiaobo J, Yong L, Craig EB (2011) Cubic copper hexacyanoferrates nanoparticles: facile template free deposition and electrocatalytic sensing towards hydrazine. Int J Electrochem 5:1–5Google Scholar
  43. 43.
    Youning G, Delong L, Qiang F, Chunxu P (2015) Influence of graphene microstructures on electrochemical performance for supercapacitors. Prog Nat Sci Mater Inter 22:379–385Google Scholar
  44. 44.
    Hu Y, Yu B, Li W, Manigandan CY (2019) W2C nanodots decorated CNT networks as highly efficient and stable electrocatalyst for hydrogen evolution in acidic and alkaline media. Nanoscale 11:4876–4884. CrossRefPubMedGoogle Scholar
  45. 45.
    Maria W, Maximilian B, Jurgen P, Benjamin D (2013) Mechanism of protonation induced changes in Raman spectra of trisheteroleptic ruthenium complex revealed by DFT calculations. RSC Adv 3:5597–5606Google Scholar
  46. 46.
    Ke L, Dan L, Xiang G, Hongxiu D, Nan W, Houyi M (2015) An advanced sodium-ion supercapacitor with a manganous hexacyanoferrate cathode and a Fe3O4/rGO anode. J Mater Chem A 3:16013Google Scholar
  47. 47.
    Philippe S, Faqiang L, Iann CG (2017) Fullerene adduct-mediated covalent assembly of ruthenium nanoparticles and their catalytic properties. Chem Eur J 23:13379–13386. CrossRefGoogle Scholar
  48. 48.
    Rahul K, Elby T, Costa LC et al (2012) Facile synthesis of hydrogenated reduced graphene oxide via hydrogen spillover mechanism. J Mater Chem 22(21):10457–10459Google Scholar
  49. 49.
    Wendell MC, William SC, Edmar PM et al (2013) Electrochemical behavior of ruthenium-hexacyanoferrate modified glassy carbon electrode and catalytic activity towards ethanol electrooxidation. J Braz Chem Soc 24:651–656Google Scholar
  50. 50.
    Devis DT, Samuel AF, Antonio ZG et al (2008) Computational study of the factors controlling enantioselectivity in ruthenium(II) hydrogenation catalysts. Inorg Chem 47:2674–2687Google Scholar
  51. 51.
    Lucimara BP, Elisangela ADO, Ricardo ADMF et al (2014) Electrochemical properties of the hexacyanoferrate(II)-ruthenium(III) complex immobilized on silica gel surface chemically modified with zirconium(IV) oxide. Mater Sci Eng B 188:78–83Google Scholar
  52. 52.
    Ramalingam M, Deepa PN, Sangilimuthu SN (2017) Fabrication and characterization of poly 2-napthol orange film modified electrode and its application to selective detection of dopamine. J Solid State Electrochem 21:3567–3578Google Scholar
  53. 53.
    Manigandan R, Dhanasekaran T, Padmanaban A et al (2019) Bifunctional hexagonal Ni/NiO nanostructures: influence of core-shell phase on magnetism, electrochemical sensing of serotonin and catalytic reduction of 4nitrophenol. Nanoscale Adv 1:1531–1540Google Scholar
  54. 54.
    Yesuraj J, Austin SS, Padmaraj O (2019) Synthesis, characterization and electrochemical performance of DNA-templated Bi2MoO6 nanoplates for supercapacitor applications. Mater Sci Semicond Process 90:225–235Google Scholar
  55. 55.
    Krishnamoorthy G, Ranganathan S, Ramadoss M et al (2013) Nanomolar determination of 4-nitrophenol based on a poly(methylene blue)-modified glassy carbon electrode. Analyst 138:5811Google Scholar
  56. 56.
    Nekrassova O, White PC, Threlfell S et al (2002) An electrochemical adaptation of Ellman’s test. Analyst 127:797–802PubMedGoogle Scholar
  57. 57.
    Abiman P, Wildgoose GG, Compton RG (2007) Electroanalytical exploitation of nitroso phenyl modified carbon-thiol interactions: application to the low voltage determination of thiols. Electroanalysis 19:437–444Google Scholar
  58. 58.
    Antwi C, Johnson AS, Selimovic A, Martin RS (2011) Use of microchip electrophoresis and a palladium/mercury amalgam electrode for the separation and detection of thiols. Anal Methods 3:1072–1078Google Scholar
  59. 59.
    Meliha C, Fatma NE, Ulku A (2013) Centri-Voltammetric determination of glutathione. Microchim Acta 180:93–100Google Scholar
  60. 60.
    Mao Xiao M, Li Yuan Y, Wang Peng Y, Liu Xian (2009) Study on voltammetric determination of threonine by using carbon paste electrode based on the activity effect of surfactant. App Chem Ind 12:1771–1773Google Scholar
  61. 61.
    Marcio V, Susana ICTL, Lauro TK (2008) Electrochemical oxidation of glycine by doped nickel hydroxide modified electrode. Sensors Actuators B 135:245–249Google Scholar
  62. 62.
    Mahmoud R, Mojtaba S, Seied MP (2012) Amprometric detection of glycine, L-serine, and L-alanine using glassy carbon electrode modified by NiO nanoparticles. J Appl Electrochem 42:1005–1011Google Scholar
  63. 63.
    Zheng L, Song J-F (2009) Nicken(II)-baicalein complex modified multiwall carbon nanotube paste electrode and its electrocatalytic oxidation toward glycine. Anal Biochem 391:56–63PubMedGoogle Scholar
  64. 64.
    Zhen-HS, Xiao QZ et al (2012) Electrochemical sensor based on nitrogen doped graphene: simultaneous determination of ascorbic acid, dopamine and uric acid. Biosens Bioelectron 34:125Z–131Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Analytical ChemistryUniversity of MadrasChennaiIndia

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