A rime ice-inspired bismuth-based flexible sensor for zinc ion detection in human perspiration


A nature-inspired special structure of bismuth is newly presented as Zn ion sensing layer for high-performance electrochemical heavy metal detection sensor applications. The rime ice-like bismuth (RIBi) has been synthesized using an easy ex situ electrodeposition method on the surface of a flexible graphene-based electrode. The flexible graphene-based electrode was fabricated via simple laser-writing and substrate-transfer techniques. The Zn ion sensing performance of the proposed heavy metal sensor was evaluated by square wave anodic stripping voltammetry after investigating the effects of several parameters, such as preconcentration potential, preconcentration time, and pH of acetate buffer. The proposed RIBi-based heavy metal sensor demonstrated a good linear relationship between concentration and current in the range 100–1600 ppb Zn ions with an acceptable sensitivity of 106 nA/ppb·cm2. The result met the requirements in terms of common human perspiration levels (the average Zn ion concentration in perspiration is 800 ppb). In addition, the heavy metal sensor response to Zn ions was successfully performed in human perspiration samples as well, and the results were consistent with those measured by atomic absorption spectroscopy. Besides, the fabricated Zn ion sensor exhibited excellent selectivity, repeatability, and flexibility. Finally, a PANI-LIG-based pH sensor (measurement range: pH 4–7) was also integrated with the Zn ion sensor to form a single chip hybrid sensor. These results may provide a great possibility for the use of the proposed flexible sensor to realize wearable perspiration-based healthcare systems.

Graphical abstract

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5


  1. 1.

    Kumari P, Mathew L, Syal P (2017) Increasing trend of wearables and multimodal interface for human activity monitoring: a review. Biosens Bioelectron 90:298–307. https://doi.org/10.1016/j.bios.2016.12.001

    CAS  Article  PubMed  Google Scholar 

  2. 2.

    Kassala P, Steinberg MD, Steinberg IM (2018) Wireless chemical sensors and biosensors: a review. Sensor Actuat B: Chem 266:228–245. https://doi.org/10.1016/j.snb.2018.03.074

    CAS  Article  Google Scholar 

  3. 3.

    Kim J, Campbell AS, Wang J (2018) Wearable non-invasive epidermal glucose sensors: a review. Talanta 177:163–170. https://doi.org/10.1016/j.talanta.2017.08.077

    CAS  Article  Google Scholar 

  4. 4.

    Bujes-Garrido J, Izquierdo-Bote D, Heras A, Colina A, Arcos-Martínez MJ (2018) Determination of halides using Ag nanoparticles-modified disposable electrodes. A first approach to a wearable sensor for quantification of chloride ions. Anal Chim Acta 1012:42–48. https://doi.org/10.1016/j.aca.2018.01.063

    CAS  Article  PubMed  Google Scholar 

  5. 5.

    Dhanabalan SC, Dhanabalan B, Chen X, Ponral JS, Zhang H (2019) Hybrid carbon nanostructured fibers: steppingstone for intelligent textile-based electronics. Nanoscale 11:3046–3101. https://doi.org/10.1039/C8NR07554A

    CAS  Article  PubMed  Google Scholar 

  6. 6.

    Kim J, Campbell AS, Esteban-Fernández de Ávila B (2019) Wearable biosensors for healthcare monitoring. Nat Biotechnol 37:386–406

    Google Scholar 

  7. 7.

    Li L, Shi P, Hua L, An J, Gong Y, Chen R, Yu C, Hua W, Xiu F, Zhou J, Gao G, Jin Z, Sun G, Huang W (2018) Design of a wearable and shape-memory fibriform sensor for the detection of multimodal deformation. Nanoscale 10:118–123. https://doi.org/10.1039/C7NR06219B

    CAS  Article  Google Scholar 

  8. 8.

    Yapici MK, Alkhidir Y, Samad YA, Liao K (2015) Graphene-clad textile electrodes for electrocardiogram monitoring. Sensor Actuat B: Chem 211:1469–1474. https://doi.org/10.1016/j.snb.2015.07.111

    CAS  Article  Google Scholar 

  9. 9.

    Jayathilaka WADM, Qi K, Qin Y, Chinnappan A, Serrano-García W, Baskar C, Wang H, He J, Cui S, Thomas SW, Ramakrishna S (2018) Significance of nanomaterials in wearables: a review on wearable actuators and sensors. Adv Mater 31:1805921. https://doi.org/10.1002/adma.201805921

    CAS  Article  Google Scholar 

  10. 10.

    Wang Z, Gui M, Asif M, Yu Y, Dong S, Wang H, Wang W, Wang F, Xiao F, Liu H (2018) A facile modular approach to the 2D oriented assembly MOF electrode for non-enzymatic sweat biosensors. Nanoscale 10:6629–6638. https://doi.org/10.1039/C8NR00798E

    CAS  Article  PubMed  Google Scholar 

  11. 11.

    Martin A, Kim JY, Kurniawan JF, Sempionatto JR, Moreto JR, Tang GD, Campbell AS, Shin A, Lee MY, Liu XF, Wang J (2017) Epidermal microfluidic electrochemical detection system: enhanced sweat sampling and metabolite detection. ACS Sens 2017(2):1860–1868. https://doi.org/10.1021/acssensors.7b00729

    CAS  Article  Google Scholar 

  12. 12.

    Jang J, Han JI (2017) High performance cylindrical capacitor as a relative humidity sensor for wearable computing devices. J Electrochem Soc 164:136–141

    Article  Google Scholar 

  13. 13.

    Martínez-Perinan E, Sánchez-Tiradoet E, González-Cortésal A et al (2018) Amperometric determination of endoglin in human serum using disposable immunosensors constructed with poly(pyrrolepropionic) acid-modified electrodes. Electrochim Acta 292:887–894. https://doi.org/10.1016/j.electacta.2018.10.015

    CAS  Article  Google Scholar 

  14. 14.

    Staden RS, Balahura L, Oprisanu-Vulpe A, Gugoasa LA, Staden JF, Ungureanu E, Socaci C, Porav A (2017) Nanostructured materials detect dopamine in biological fluids. J Electrochem Soc 164:561–566

    Article  Google Scholar 

  15. 15.

    Fang Y, Yang X, Chen T, Xu G, Liu M, Liu J, Xu Y (2018) Two-dimensional titanium carbide (MXene)-based solid-state electrochemiluminescent sensor for label-free single-nucleotide mismatch discrimination in human urine. Sensor Actuat B: Chem 263:400–407. https://doi.org/10.1016/j.snb.2018.02.102

    CAS  Article  Google Scholar 

  16. 16.

    Roy S, David-Pur M, Hanein Y (2017) Carbon nanotube-based ion selective sensors for wearable applications. ACS Appl Mater Inter 9:35169–35177. https://doi.org/10.1021/acsami.7b07346

    CAS  Article  Google Scholar 

  17. 17.

    Imani S, Bandodkar AJ, Vinu Mohan AM, Kumar R, Yu S, Wang J, Mercier PP (2016) A wearable chemical-electrophysiological hybrid biosensing system for real-time health and fitness monitoring. Nat Commun 7:11650. https://doi.org/10.1038/ncomms11650

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  18. 18.

    Gao W, Emaminejad S, Nyein HYY, Challa S, Chen K, Peck A, Fahad HM, Ota H, Shiraki H, Kiriya D, Lien DH, Brooks GA, Davis RW, Javey A (2016) Fully integrated wearable sensor arrays for multiplexed in situ perspiration analysis. Nature 529:509–514. https://doi.org/10.1038/nature16521

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  19. 19.

    Promphet N, Rattanawaleedirojn P, Siralertmukul K, Soatthiyanon N, Potiyaraj P, Thanawattano C, Hinestroza JP, Rodthongkum N (2019) Non-invasive textile based colorimetric sensor for the simultaneous detection of sweat pH and lactate. Talanta 192:424–430. https://doi.org/10.1016/j.talanta.2018.09.086

    CAS  Article  PubMed  Google Scholar 

  20. 20.

    Lee H, Choi TK, Lee YB, Cho H, Ghaffari R, Wang L, Choi HJ, Chung TD, Lu N, Hyeon T, Choi SH, Kim D (2016) A graphene-based electrochemical device with thermoresponsive microneedles for diabetes monitoring and therapy. Nat Nanotechnol 11:566–572

    Article  Google Scholar 

  21. 21.

    Xu H, Lu YF, Xiang JX, Zhang MK, Zhao YJ, Xie ZY, Gu ZZ (2018) A multifunctional wearable sensor based on a graphene/inverse opal cellulose film for simultaneous, in situ monitoring of human motion and sweat. Nanoscale 10:2090–2098. https://doi.org/10.1039/C7NR07225B

    CAS  Article  PubMed  Google Scholar 

  22. 22.

    Kim J, Jeerapan I, Imani S, Cho TN, Bandodkar A, Cinti S, Mercier PP, Wang J (2016) Noninvasive alcohol monitoring using a wearable tattoo-based iontophoretic-biosensing system. ACS Sens. 1:1011–1019. https://doi.org/10.1021/acssensors.6b00356

    CAS  Article  Google Scholar 

  23. 23.

    Munje RD, Muthukumar S, Prasad S (2017) Lancet-free and label-free diagnostics of glucose in sweat using zinc oxide based flexible bioelectronics. Sensor Actuat B: Chem 238:482–490. https://doi.org/10.1016/j.snb.2016.07.088

    CAS  Article  Google Scholar 

  24. 24.

    Harvey CJ, LeBouf RF, Stefaniak AB (2010) Formulation and stability of a novel artificial human sweat under conditions of storage and use. Toxicol in Vitro 24:1790–1796. https://doi.org/10.1016/j.tiv.2010.06.016

    CAS  Article  PubMed  Google Scholar 

  25. 25.

    Bandodkar AJ, Jia W, Wang J (2015) Tattoo-based wearable electrochemical devices: a review. Electroanalysis 27:562–572. https://doi.org/10.1002/elan.201400537

    CAS  Article  Google Scholar 

  26. 26.

    Fraga CG (2005) Relevance, essentiality and toxicity of trace elements in human health. Mol Asp Med 26:235–244. https://doi.org/10.1016/j.mam.2005.07.013

    CAS  Article  Google Scholar 

  27. 27.

    Heyland DK, Jones N, Cvijanovich NZ, Wong H (2008) Zinc supplementation in critically ill patients: a key pharmaconutrient? JPEN-Parenter Enter 32:509–519. https://doi.org/10.1177/0148607108322402

    CAS  Article  Google Scholar 

  28. 28.

    Gao W, Nyein HYY, Shahpar Z, Fahad HM, Chen K, Emaminejad S, Gao YJ, Tai LC, Ota H, Wu E, Bullock J, Zeng Y, Lien DH, Javey A (2016) Wearable microsensor array for multiplexed heavy metal monitoring of body fluids. ACS Sens. 1:866–874. https://doi.org/10.1021/acssensors.6b00287

    CAS  Article  Google Scholar 

  29. 29.

    Dias AA, Chagas CLS, Silva-Neto HDA, Lobo-Junior EO, Sgobbi LF, de Araujo WR, Paixao TRLC, Coltro WKT (2019) Environmentally friendly manufacturing of flexible graphite electrodes for a wearable device monitoring zinc in sweat. ACS Appl Mater Interfaces 11:39484–39492. https://doi.org/10.1021/acsami.9b12797

    CAS  Article  PubMed  Google Scholar 

  30. 30.

    Córdova A, Navas FJ (1998) Effect of training on zinc metabolism: changes in serum and sweat zinc concentrations in sportsmen. Ann Nutr Metab 42:274–282. https://doi.org/10.1159/000012744

    Article  PubMed  Google Scholar 

  31. 31.

    Maalouf NM, Cameron MA, Moe OW, Sakhaee K (2010) Metabolic basis for low urine pH in type 2 diabetes. Clin J Am Soc Nephrol 5:1277–1281. https://doi.org/10.2215/CJN.08331109

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  32. 32.

    Salmain M, Vessieres A, Jaouen G, Butler IS (1991) Fourier transform infrared spectroscopic method for the quantitative trace analysis of transition-metal carbonyl-labeled bioligands. Anal Chem 63:2323–2329. https://doi.org/10.1021/ac00020a023

    CAS  Article  PubMed  Google Scholar 

  33. 33.

    Salazara P, Rico V, González-Elipe AR (2017) Non-enzymatic hydrogen peroxide detection at NiO nanoporous thin film- electrodes prepared by physical vapor deposition at oblique angles. Electrochim Acta 235:534–542

    Article  Google Scholar 

  34. 34.

    Jothimuthu P, Wilson RA, Herren J, Pei X, Kang W, Daniels R, Wong H, Beyette F, Heineman WR, Papautsky I (2013) Zinc detection in serum by anodic stripping voltammetry on microfabricated bismuth electrodes. Electroanalysis 25:401–407. https://doi.org/10.1002/elan.201200530

    CAS  Article  Google Scholar 

  35. 35.

    Jiang Y, Cui S, Xia T, Sun T, Tan H, Yu F, Su Y, Wu S, Wang D, Zhu N (2020) Real-time monitoring of heavy metals in healthcare via twistable and washable smartsensors. Anal Chem 92:14536–14541. https://doi.org/10.1021/acs.analchem.0c02723

    CAS  Article  PubMed  Google Scholar 

  36. 36.

    Kim J, Araujo WRD, Same IA, Bandodkar AJ, Jia W, Brunetti B, Paixão TRLC, Wang J (2015) Wearable temporary tattoo sensor for real-time trace metal monitoring in human sweat. Electrochem Commun 51:41–45. https://doi.org/10.1016/j.elecom.2014.11.024

    CAS  Article  Google Scholar 

  37. 37.

    Xuan X, Park JY (2018) A miniaturized and flexible cadmium and lead ion detection sensor based on micro-patterned reduced graphene oxide/carbon nanotube/bismuth composite electrodes. Sensor Actuat B-Chem 255:1220–1227. https://doi.org/10.1016/j.snb.2017.08.046

    CAS  Article  Google Scholar 

  38. 38.

    Lu Z, Dai W, Lin X, Liu B, Zhang J, Ye J (2018) Facile one-step fabrication of a novel 3D honeycomb-like bismuth nanoparticles decorated N-doped carbon nanosheet frameworks: ultrasensitive electrochemical sensing of heavy metal ions. Electrochim Acta 266:94–102. https://doi.org/10.1016/j.electacta.2018.01.188

    CAS  Article  Google Scholar 

  39. 39.

    Bansod B, Kumar T, Thakur R, Rana S, Singh I (2017) A review on various electrochemical techniques for heavy metal ions detection with different sensing platforms. Biosens Bioelectron 94:443–455. https://doi.org/10.1016/j.bios.2017.03.031

    CAS  Article  PubMed  Google Scholar 

  40. 40.

    Rico MAG, Olivares-Marín M, Gil EP (2009) Modification of carbon screen-printed electrodes by adsorption of chemically synthesized Bi nanoparticles for the voltammetric stripping detection of Zn(II), Cd(II) and Pb(II). Talanta 80:631–635. https://doi.org/10.1016/j.talanta.2009.07.039

    CAS  Article  PubMed  Google Scholar 

  41. 41.

    Cinti S, De Lellis B, Moscone D, Arduini F (2017) Sustainable monitoring of Zn(II) in biological fluids using office paper. Sensors Actuators B 253:1199–1206. https://doi.org/10.1016/j.snb.2017.07.161

    CAS  Article  Google Scholar 

  42. 42.

    Pei X, Kang W, Yue W, Bange A, Heineman WR, Papautsky I (2014) Improving reproducibility of lab-on-a-chip sensor with bismuth working electrode for determining Zn in serum by anodic stripping voltammetry. J Electrochem Soc 161:3160–3166

    Article  Google Scholar 

  43. 43.

    Wang J (2005) Stripping analysis at bismuth electrodes: a review. Electroanalysis 17:15–16. https://doi.org/10.1002/elan.200403270

    CAS  Article  Google Scholar 

  44. 44.

    Xuan X, Kim JY, Hui X, Das PS, Yoon HS, Park JY (2018) A highly stretchable and conductive 3D porous graphene metal nanocomposite based electrochemical-physiological hybrid biosensor. Biosens Bioelectron 120:160–167. https://doi.org/10.1016/j.bios.2018.07.071

    CAS  Article  PubMed  Google Scholar 

  45. 45.

    Yoon HS, Nah J, Kim H, Ko S, Sharifuzzaman M, Barman SC, Xuan X, Kim J, Park JY (2020) A chemically modified laser-induced porous graphene based flexible and ultrasensitive electrochemical biosensor for sweat glucose detection. Sensors Actuators B 311:127866. https://doi.org/10.1016/j.snb.2020.127866

    CAS  Article  Google Scholar 

  46. 46.

    Yang Y, Song Y, Bo X, Min J, Pak OS, Zhu L, Wang M, Tu J, Kogan A, Zhang H, Hsiai TK, Li Z, Gao W (2020) A laser-engraved wearable sensor for sensitive detection of uric acid and tyrosine in sweat. Nat Biotech 38:217–224. https://doi.org/10.1038/s41587-019-0321-x

    CAS  Article  Google Scholar 

  47. 47.

    Tehrani F, Beltrán-Gastélum M, Sheth K, Karajic A, Yin L, Kumar R, Soto F, Kim J, Wang J, Barton S, Michelle M, Wang J (2019) Laser-induced graphene composites for printed, stretchable, and wearable electronics. Adv Mater Technol 4:1900162. https://doi.org/10.1002/admt.201900162

    CAS  Article  Google Scholar 

  48. 48.

    Prabhakaran A, Nayak P (2020) Surface engineering of laser-scribed graphene sensor enables non-enzymatic glucose detection in human body fluids. ACS Appl Nano Mater 3:391–398. https://doi.org/10.1021/acsanm.9b02025

    CAS  Article  Google Scholar 

  49. 49.

    Bauer M, Wunderlich L, Weinzierl F, Lei Y, Duerkop A, Alshareef HN, Baeumner AJ (2020) Electrochemical multi-analyte point-of-care perspiration sensors using on-chip three-dimensional graphene electrodes. Anal Bioanal Chem 742:763–777. https://doi.org/10.1007/s00216-020-02939-4

    CAS  Article  Google Scholar 

  50. 50.

    Lin J, Peng Z, Liu Y, Ruiz-Zepeda F, Ye R, Samuel ELG, Yacaman MJ, Yakobson BI, Tour JM (2014) Laser-induced porous graphene films from commercial polymers. Nat Commun 5:5714. https://doi.org/10.1038/ncomms6714

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  51. 51.

    Ren M, Zhang J, Tour JM (2018) Laser-induced graphene synthesis of Co3O4 in graphene for oxygen electrocatalysis and metal-air batteries. Carbon 139:880–887. https://doi.org/10.1016/j.carbon.2018.07.051

    CAS  Article  Google Scholar 

  52. 52.

    Lamberti A, Clerici F, Fontana M, Scaltrito L (2016) A highly stretchable supercapacitor using laser-induced graphene electrodes onto elastomeric substrate. Adv Energy Mater 6:1600050. https://doi.org/10.1002/aenm.201600050

    CAS  Article  Google Scholar 

  53. 53.

    Hassan HK, Atta NF, Galal A (2012) Electropolymerization of aniline over chemically converted graphene-systematic study and effect of dopant. Int J Electrochem Sci 7:11161–11181

    CAS  Google Scholar 

  54. 54.

    Peng Z, Ye R, Mann JA, Zakhidov D, Li Y, Smalley PR, Lin J, Tour JM (2015) Flexible boron-doped laser-induced graphene microsupercapacitors. ACS Nano 9:5868–5875. https://doi.org/10.1021/acsnano.5b00436

    CAS  Article  PubMed  Google Scholar 

  55. 55.

    Hwang GH, Han WK, Park JS, Kang SG (2018) Determination of trace metals by anodic stripping voltammetry using a bismuth-modified carbon nanotube electrode. Talanta 76:301–308

    Article  Google Scholar 

  56. 56.

    Sahoo PK, Panigrahy B, Sahoo S, Satpati AK, Li D, Bahadur D (2013) In situ synthesis and properties of reduced graphene oxide/Bi nanocomposites: as an electroactive material for analysis of heavy metals. Biosens Bioelectron 43:293–296

    CAS  Article  Google Scholar 

  57. 57.

    Injang U, Noyrod P, Siangproh W, Dungchai W, Motomizu S, Chailapakul O (2010) Determination of trace heavy metals in herbs by sequential injection analysis-anodic stripping voltammetry using screen-printed carbon nanotubes electrodes. Anal Chim Acta 668:54–60

    CAS  Article  Google Scholar 

  58. 58.

    Hwang GH, Han WK, Park JS, Kang SG (2008) Determination of trace heavy metals by sequential injection-anodic stripping voltammetry using bismuth film screen-printed printed carbon electrode. Talanta 76:301–308

    CAS  Article  Google Scholar 

Download references


This work was supported by the Bio & Medical Technology Development Program of the NRF grant funded by the Korean Government (MSIT) (NRF-2017M3A9F1031270) and the Technology Innovation Program (20000773, Development of nanomultisensors based on wearable patch for nonhematological monitoring of metabolic syndrome) funded by the Ministry of Trade, Industry & Energy (MI, Korea). The authors are grateful for the technical support and discussion of the Advanced Sensor and Energy Research (ASER) Laboratory group members of Kwangwoon University.

Author information




Xing Xuan and Xue Hui have contributed equally to the work. Xing Xuan designed hybrid sensors. Xue Hui, Hyosang Yoon, and Sanghyuk Yoon helped to fabricate the hybrid electrodes. Xing Xuan and Xue Hui prepared the materials and performed the electrochemical experiments and results analysis, and Sanghyuk Yoon helped to do the data measurements and analysis. Xing Xuan and Hyosang Yoon managed and discussed drawing and plot the figures in the manuscript. Xing Xuan and Xue Hui completed the manuscript. Hyosang Yoon and Sanghyuk Yoon commented on the manuscript. Jae Yeong Park advised all research phases, provided technical guidance, and revised the manuscript. All authors read and approved the final manuscript.

Corresponding author

Correspondence to Jae Yeong Park.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information


(DOCX 1912 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Xuan, X., Hui, X., Yoon, H. et al. A rime ice-inspired bismuth-based flexible sensor for zinc ion detection in human perspiration. Microchim Acta 188, 97 (2021). https://doi.org/10.1007/s00604-021-04752-x

Download citation


  • Rime ice-inspired bismuth
  • Laser-induced graphene electrode
  • Flexible hybrid sensor
  • Zn ion detection
  • Human perspiration