SCIENCE CHINA Chemistry, Volume 60, Issue 5: 642-648(2017) https://doi.org/10.1007/s11426-016-0457-9

Electrochemiluminescence of metal-organic complex nanowires based on graphene-Nafion modified electrode for biosensing application

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  • ReceivedNov 8, 2016
  • AcceptedDec 15, 2016
  • PublishedMar 7, 2017


In this work, we chose tris(2,2′-bipyridyl)ruthenium(II)hexafluorophosphate (Ru(bpy)3(PF6)2), a metal-organic complex material, to prepare nanowires, which were subsequently applied for the construction of electrochemiluminescence (ECL) biosensor by immobilizing them onto a glassy carbon electrode (GCE) with graphene-Nafion composite films. The graphene therein, being a two-dimensional carbon nanomaterial with outstanding electronic properties, can obviously improve the conductivity of the Nafion film, as well as enhance the electrochemical signal and ECL intensity of the Ru(bpy)3(PF6)2 nanowires (RuNWs) at low graphene concentration. The developed biosensor exhibited excellent ECL stability with tripropylamine (TPrA) as co-reactant. The ECL biosensor exhibited high sensitive ECL response in a wide linear range and low detection limit for the detection of proline. It is considered that the oxidation products of proline would be responsible for the ECL enhancement. The large electro-active area of the nanowires and the enhancement effect of the graphene played critical roles in the high detection performance of the ECL biosensor. The results demonstrated herein may provide a useful enlightenment for the design of more sensitive ECL biosensors.

Funded by

Natural Science Foundation of China(21406053,21521062)

Ministry of Science and Technology of China(2012YQ120060)

Natural Science Foundation of Hebei Province(B2016208082)

Science and Technology Research Projects in Hebei Universities(QN2015243,YQ2014015)

Five Platform Open Fund Projects of Hebei University of Science and Technology(2014YY25)


This work was supported by the National Natural Science Foundation of China (21406053, 21521062), the Ministry of Science and Technology of China (2012YQ120060), Natural Science Foundation of Hebei Province (B2016208082), Science and Technology Research Projects in Hebei Universities (QN2015243, YQ2014015), and Five Platform Open Fund Projects of Hebei University of Science and Technology (2014YY25).

Interest statement

The authors declare that they have no conflict of interest.


The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Figure 1

    (a) Low-magnification SEM image of RuNWs; (b) high-magnification SEM image of the nanowire; (c) TEM image of a single nanowire (inset: SAED pattern of the corresponding wire); (d) fluorescence microscopy image of the nanowires excited with the UV band (330–380 nm) of a mercury lamp (color online).

  • Figure 2

    ECL intensities of the (a) RuNWs/GCE and (b) Nafion/RuNWs/GCE in 0.20 M PBS (pH 8.0) solution containing 0.05 mM TPrA under continuous cyclic scans (color online).

  • Figure 3

    The cyclic voltammograms (CVs) of the (a) Nafion/RuNW/GCE and (b) graphene-Nafion/RuNWs/GCE in 0.20 M pH 8.0 PBS containing 0.05 mM TPrA. Scan rate: 100 mV/s. Inset: graphene-Nafion/RuNWs modified the GCE. The radius of (a) is shorter than that of (b). The EIS measurements were performed in the presence of 1 mM K3[Fe(CN)6]/K4[Fe(CN)6] (1:1) mixture as a redox probe in 0.1 M KCl aqueous solution. The frequency range was 0.01–100000 Hz with a signal amplitude of 5 mV. Scan rate: 100 mV/s (color online).

  • Figure 4

    ECL intensities of the graphene-Nafion/RuNWs/GCE as a function of the graphene doping ratio. The graphene concentrtration from left to right: 0, 1%, 2%, 4%, 6%, 8%, 10%, 20%, 50%, 80%. Inset: the ECL-time profile of the RuNWs immobilized by different films (color online).

  • Figure 5

    ECL intensities of the graphene-Nafion/RuNWs/GCE at various scan rates. From left to right: 10, 30, 80, 100, 150, 200, 250, 300, 500, and 1000 mV/s.

  • Figure 6

    ECL emission spectra of RuNWs in 0.2 M PBS (pH 8.0). The TPrA concentrtration from bottom to top: 0.0, 2.5, 5.0, 7.5 μM. Scan rate: 100 mV/s (color online).

  • Figure 7

    ECL stability of the sensor in 0.20 M PBS (pH 8.0) containing 0.05 mM TPrA under optimized condition.

  • Figure 8

    Linear calibration plot for Pro determination. I0 and I are the ECL intensity of the graphene-Nafion/RuNWs/GCE without and with Pro, respectively. Inset: dependence of the ECL intensity of the graphene-Nafion/RuNWs/GCE on the concentration of Pro in 0.20 M PBS (pH 8.0). The concentration of Pro from bottom to top: 0.1, 0.5, 2.0, 4.0, 5.0 and 6.0 mM. Scan rate: 100 mV/s (color online).

  • Figure 9

    Schematic of ECL mechanism of the RuNWs with Proline. PPro is the oxidation product of Proline (color online).

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