Author’s Accepted Manuscript A sensitive photoelectrochemical biosensor for AFP detection based on ZnO inverse opal electrodes with signal amplification of CdS-QDs Ru Xu, Yandong Jiang, Lei Xia, Tianxiang Zhang, Lin Xu, Shuang Zhang, Dali Liu, Hongwei Song www.elsevier.com/locate/bios
PII: DOI: Reference:
S0956-5663(15)30204-9 http://dx.doi.org/10.1016/j.bios.2015.06.037 BIOS7773
To appear in: Biosensors and Bioelectronic Received date: 18 March 2015 Revised date: 15 June 2015 Accepted date: 17 June 2015 Cite this article as: Ru Xu, Yandong Jiang, Lei Xia, Tianxiang Zhang, Lin Xu, Shuang Zhang, Dali Liu and Hongwei Song, A sensitive photoelectrochemical biosensor for AFP detection based on ZnO inverse opal electrodes with signal amplification of CdS-QDs, Biosensors and Bioelectronic, http://dx.doi.org/10.1016/j.bios.2015.06.037 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
A sensitive photoelectrochemical biosensor for AFP detection based on ZnO inverse opal electrodes with signal amplification of CdS-QDs Ru Xu†, Yandong Jiang†, Lei Xia†, Tianxiang Zhang†, Lin Xu†, Shuang Zhang†, Dali Liu*†, Hongwei Song*†‡
†State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, 2699 Qianjin Street, Changchun, 130012, P. R. China. ‡The State Key Laboratory of Bioelectronics, Southeast University, 210096 P. R. China.
Corresponding to: Prof.
Dali Liu
E-Mail: [emailprotected]
Tel: 86-431-85168241
Prof.
Hongwei Song
E-Mail: [emailprotected]
Tel: 86-431-81736614
Abstract In this work, ZnO inverse opals structure (IOs) based photoelectrochemical (PEC) electrode was fabricated for alpha-fetoprotein (AFP) detection. Then, the uniform CdS quantum dots (QDs) were hydrothermally synthesized, which allowed the binding of AFP and glucose oxidase (GOD) on CdS QDs, forming the AFP-CdS-GOD composite. The competitive immunosensor of AFP and the AFP-CdS-GOD composite with anti-AFP antibodies (Ab) immobilized on FTO (fluorine-doped tin oxide) /ZnO IOs electrode was successfully applied to the detection of AFP. GOD could catalyze glucose to produce hydrogen peroxide (H2O2) acting as an electron donor to scavenge photogenerated holes in the valence band of CdS QDs, reducing the recombination of electrons and holes of CdS QDs. Also the effective energy level matching between the conduction bands of CdS QDs and ZnO widened the range of light absorption, allowing for electron injection from excited CdS QDs to ZnO upon visible light irradiation, which enhanced the photocurrent. The results show that the immunosensor of AFP possesses a large linear detection range of 0.1 - 500 ng/ml with a detection limit of 0.01 ng/ml. It also exhibits excellent anti-interference property and acceptable stability. This work provides a promising method for achieving excellent photoelectrochemical biosensor detection of other proteins.
Keywords: ZnO inverse opals structure, CdS QDs, AFP detection, photoelectrochemical biosensor
1. Introduction AFP, a major plasma protein, mainly generates from the liver, yolk sac and fetal human gastrointestinal tract (Tomasi, 1977). High concentrations of AFP found in adult serum is very possible a symptom of malignant tumor, which can be taken as a specific diagnosis of primary liver cancer clinical indicators. Thus sensitive and accurate early detection and diagnosis is of crucial importance (Srinivas et al., 2001). So far, many techniques have been developed for the detection of AFP, such as enzyme-linked immunoassay (ELISA) (Liew et al., 2007), electrochemical luminescence (ECL) (Qian et al., 2010; Yang et al., 2009), electrochemical method (Dai et al., 2011; Tang et al., 2010; Zhang et al., 2011), mass spectrometry (Stevens et al., 2008), quartz crystal microbalance (QCM) (Chou et al., 2002) and surface plasmon resonance (SPR) (Teramura and Iwata, 2007) immunity determination. Although good sensitivity has been achieved, these protocols were labor-intensive, time-consuming and not suitable for rapid analysis. So it is still very necessary to develop a novel, highly sensitive and alternative detection method of AFP. As a widely attracted for the interest of method, PEC measurements have successfully detected numerous materials, such as glucose, ascorbic acid, cysteine, AFP and carcinoembryonic antigen (Li et al., 2013; Li et al., 2012; Xia et al., 2014; Zhao et al., 2012; Wen and Ju, 2015). In addition, PEC biosensors are detection methods based on photocatalytic
oxidation
or
reduction
biological
molecules,
which
make
photogenerated electrons transferred between the semiconductor electrode and the substances to be detected under light to enhance the PEC response (Wang et al., 2009).
Combining the advantages of both fluorescence sensing and electrochemical sensing, the complete separation of excitation source (light) and detection signal (current) could greatly reduce the undesired background signal (Liang et al., 2006). Photosensitive material, as the principal part of PEC sensing, is critical to the performance of the sensor. Although PEC biosensor has been widely used to detect biological molecules, few photosensitive materials can be available for it (Kang et al., 2010).
As is known, ZnO is an n-type wide-band-gap semiconductor material with a bandwidth of about 3.37 eV, which makes it a good candidate for photoelectronic applications (Arya et al., 2012). Many ZnO nanostructures, including nanorods (Hu et al., 2010), nanotubes (Dai et al., 2009), nanowires (Wan et al., 2004), nanosheets (Tsai et al., 2014), nanoclusters(Zhao et al., 2007), hollow nanospheres (Fang et al., 2011)
and nanoflowers (Zhang et al., 2014a) have been applied in biosensor. IO structure is a kind of three-dimensional photonic crystal (3D-PC). The slow light effect in 3D-PC could increase the effective optical path length and increase the photovoltaic response on photovoltaic cells and the photochemical process (Sakoda, 1999; Baba, 2008; Chen et al., 2006, 2007, 2008). Additionally, the uniform porous structures of inverse opals photonic crystal(IOPCs) possess a large surface area which is helpful of electron transfer and biomolecule immobilization, and shorten the distance of electron diffusion between the FTO substrate and the immobilized subatance, thereby facilitating the capability of electron transfer (Xia et al., 2014).
ZnO has been widely applied in photocatalysis, because of its chemical stability, non-toxicity, biocompatibility and powerful electronic communications (Zhang et al., 2004; Zhu et al., 2007). However, the wide-band-gap of ZnO allows it to absorb only the ultraviolet light (
