Microsystem Technologies

, Volume 25, Issue 1, pp 11–17 | Cite as

Shrink-induced ultrasensitive mercury sensor with graphene and gold nanoparticles self-assembly

  • Zonghao Wu
  • Gaoshan Jing
  • Tianhong CuiEmail author
Technical Paper


Here we report an ultrasensitive trace mercury(II) micro sensor based on heat-shrinkable polymer (polyolefins, PO). The layer-by-layer self-assembly (LBL SA) method was employed to modify mixed gold nanoparticle (Au NPs) and graphene solution on a micro gold electrode with PO substrate. The unique wrinkle structure of the electrode surface and superior properties of modification film enhanced the performance of LBL SA graphene–Au NPs shrink sensor greatly in determination of Hg(II) using anodic stripping voltammetry (ASV): compared with a shrink gold electrode without surface modification, the sensitivity was improved for about 3.7 times from 0.197 to 0.721 μA/ppb; compared with a same-sized sensor without surface modification nor shrink, the sensitivity was improved for over 50 times. This sensor’s detection limit of Hg(II) was achieved as 0.931 ppb with a sensitivity of 0.721 μA/ppb. This simple but highly sensitive sensor can be widely used in applications of on-line environmental monitoring of Hg(II).



The authors greatly appreciate help from Dr. Xiangyang Wei for the fabrication of micro gold electrode.


  1. Abollino O, Giacomino A, Malandrino M, Piscionieri G, Mentasti E (2010) Determination of mercury by anodic stripping voltammetry with a gold nanoparticle-modified glassy carbon electrode. Electroanalysis 20:75–83CrossRefGoogle Scholar
  2. And MAN, Kounaves SP (1999) Microfabricated array of iridium microdisks as a substrate for direct determination of Cu2+ or Hg2+ using square-wave anodic stripping voltammetry. Anal Chem 71:3567–3573CrossRefGoogle Scholar
  3. Bader M, Dietz MC, Ihrig A, Triebig G (1999) Biomonitoring of manganese in blood, urine and axillary hair following low-dose exposure during the manufacture of dry cell batteries. Int Arch Occup Environ Health 72:521CrossRefGoogle Scholar
  4. Daniel MC, Astruc D (2004) Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem Rev 104:293CrossRefGoogle Scholar
  5. Davis F, Higson SP (2013) Arrays of microelectrodes: technologies for environmental investigations. Environ Sci Process Impacts 15:1477–1489CrossRefGoogle Scholar
  6. Dominik M et al (2016) Titanium oxide thin films obtained with physical and chemical vapour deposition methods for optical biosensing purposes. Biosens Bioelectron 93:102CrossRefGoogle Scholar
  7. Fang Y, Guo S, Zhu C, Zhai Y, Wang E (2010) Self-assembly of cationic polyelectrolyte-functionalized graphene nanosheets and gold nanoparticles: a two-dimensional heterostructure for hydrogen peroxide. Sens Langmuir ACS J Surf Colloids 26:11277CrossRefGoogle Scholar
  8. Ghaemi F, Yunus R, Salleh MAM, Hong NL, Rashid SA (2015) Bulk production of high-purity carbon nanosphere by combination of chemical vapor deposition methods. Fuller Sci Technol 23:669–675Google Scholar
  9. Gómez-Ariza JL, Lorenzo F, García-Barrera T (2005) Comparative study of atomic fluorescence spectroscopy and inductively coupled plasma mass spectrometry for mercury and arsenic multispeciation. Anal Bioanal Chem 382:485–492CrossRefGoogle Scholar
  10. Harada M (1995) Minamata disease: methylmercury poisoning in Japan caused by environmental pollution. Crit Rev Toxicol 25:1–24CrossRefGoogle Scholar
  11. Harrington CF, Merson SA, Silva TMD (2004) Method to reduce the memory effect of mercury in the analysis of fish tissue using inductively coupled plasma mass spectrometry. Anal Chim Acta 505:247–254CrossRefGoogle Scholar
  12. Hauke A et al (2017) Superwetting and aptamer functionalized shrink-induced high surface area electrochemical sensors. Biosens Bioelectron 94:438CrossRefGoogle Scholar
  13. Hillmyer MA, Lipic PM, Hajduk DA (2015) Self-Assembly and polymerization of epoxy resin-amphiphilic block copolymer nanocomposites. J Am Chem Soc 119:76–77Google Scholar
  14. Kokkinos C, Economou A, Raptis I, Speliotis T (2009) Novel disposable microfabricated antimony-film electrodes for adsorptive stripping analysis of trace Ni(II). Electrochem Commun 11:250–253CrossRefGoogle Scholar
  15. Kokkinos C, Economou A, Raptis I, Speliotis T (2011) Disposable microfabricated bismuth microelectrode arrays for trace metal analysis by stripping voltammetry. Proc Eng 25:880–883CrossRefGoogle Scholar
  16. Li D, Müller MB, Gilje S, Kaner RB, Wallace GG (2008) Processable aqueous dispersions of graphene nanosheets. Nat Nanotechnol 3:101CrossRefGoogle Scholar
  17. Mergler D, Anderson HA, Chan LHM, Mahaffey KR, Murray M, Sakamoto M, Stern AH (2007) Methylmercury exposure and health effects in humans: a worldwide concern. Ambio 36:3CrossRefGoogle Scholar
  18. Murdock RC, Shen L, Griffin DK, Kelley-Loughnane N, Papautsky I, Hagen JA (2013) Optimization of a paper-based ELISA for a human performance biomarker. Anal Chem 85:11634CrossRefGoogle Scholar
  19. Niu P, Fernández-Sánchez C, Gich M, Navarro-Hernández C, Fanjul-Bolado P, Roig A (2016) Screen-printed electrodes made of a bismuth nanoparticle porous carbon nanocomposite applied to the determination of heavy metal ions. Microchim Acta 183:617–623CrossRefGoogle Scholar
  20. Sarajlić M, Đurić ZG, Jović VB, Petrović SP, Đorđević DS (2013) An adsorption-based mercury sensor with continuous readout. Microsyst Technol 19:749–755CrossRefGoogle Scholar
  21. Shin SH, Hong HG (2010) Anodic stripping voltammetric detection of arsenic(III) at platinum–iron(III) nanoparticle modified carbon nanotube on glassy carbon electrode. Bull Korean Chem Soc 31:3077–3083CrossRefGoogle Scholar
  22. Townsend AT, Miller KA, Mclean S, Aldous S (1998) The determination of copper, zinc, cadmium and lead in urine by high resolution ICP-MS. J Anal At Spectrom 13:1213–1219CrossRefGoogle Scholar
  23. Wang S, Wang X, Jiang SP (2011) Self-assembly of mixed Pt and Au nanoparticles on PDDA-functionalized graphene as effective electrocatalysts for formic acid oxidation of fuel cells. Phys Chem Chem Phys PCCP 13:6883CrossRefGoogle Scholar
  24. Wu Z, Jing G, Cui T (2017) An ultrasensitive mercury sensor based on self-assembled graphene and gold nanoparticles on shrink polymer. In: International conference on solid-state sensors, actuators and microsystems, pp 234–237Google Scholar
  25. Xu H, Zeng L, Xing S, Shi G, Xian Y, Jin L (2008) Microwave-radiated synthesis of gold nanoparticles/carbon nanotubes composites and its application to voltammetric detection of trace mercury(II). Electrochem Commun 10:1839–1843CrossRefGoogle Scholar
  26. Zahir F, Rizwi SJ, Haq SK, Khan RH (2005) Low dose mercury toxicity human health. Environ Toxicol Pharmacol 20:351–360CrossRefGoogle Scholar
  27. Zhang B, Zhang M, Song K, Li Q, Cui T (2013) Shrink induced nanostructures for energy conversion efficiency enhancement in photovoltaic devices. Appl Phys Lett 103:133–135Google Scholar
  28. Zhang W, Zhang H, Williams SE, Zhou A (2015) Microfabricated three-electrode on-chip PDMS device with a vibration motor for stripping voltammetric detection of heavy metal ions. Talanta 132:321CrossRefGoogle Scholar
  29. Zhuang P, Mcbride MB, Xia H, Li N, Li Z (2009) Health risk from heavy metals via consumption of food crops in the vicinity of Dabaoshan mine. South China Sci Total Environ 407:1551–1561CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Precision InstrumentTsinghua UniversityBeijingChina
  2. 2.Department of Mechanical EngineeringUniversity of MinnesotaMinneapolisUSA

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