Elsevier

Biosensors and Bioelectronics

Volume 85, 15 November 2016, Pages 142-150
Biosensors and Bioelectronics

Ultrasensitive photoelectrochemical aptasensing of miR-155 using efficient and stable CH3NH3PbI3 quantum dots sensitized ZnO nanosheets as light harvester

https://doi.org/10.1016/j.bios.2016.04.099Get rights and content

Highlights

  • CH3NH3PbI3 quantum dots sensitized ZnO nanosheets acted as versatile labels toward PEC sensing.

  • CH3NH3PbI3 quantum dots were first used for the biosensing, especially for the aptasensing.

  • Mechanism for PEC property enhancement was systematically investigated.

Abstract

An ultrasensitive photoelectrochemical (PEC) aptasensor based on a novel signal amplification strategy was developed for the quantitative determination of microRNA (miR)-155. CH3NH3PbI3 quantum dots (QDs) functionalized ZnO nanosheets (NSs) were employed as the light harvester. Owing to the synergetic effect between CH3NH3PbI3 QDs and ZnO NSs, ZnO@CH3NH3PbI3 can provide an obviously increasing PEC signal by forming the heterojunction. Due to the larger steric hindrance, the sensitive decrease of the PEC signal can be achieved by the specific recognition between the primers and ssDNA of miR-155. In this sense, this developed aptasensor can achieve a high sensitivity (especially in the presence of the low concentrations of miR-155) and a wide detection range (0.01 fmol/L to 20,000 pmol/L). Under the optimal conditions, the proposed aptasensor offered an ultrasensitive and specific determination of miR-155 down to 0.005 fmol/L. This aptassay method would open up a new promising platform at ultralow levels for early diagnose of different miRNA.

Introduction

MicroRNAs (miRNAs) are a class of naturally occurring, small, noncoding RNAs of ∼22 nucleotides those control gene expression (Bartel, 2004). miR-155 is encoded by a noncoding gene known as bic (Tam, 2001) and is highly inducible in macrophages in response to TLR ligands (O’Connell et al., 2007, Ruggiero et al., 2009). As miR-155 targets SOCS1 in activated macrophages (Androulidaki et al., 2009), leading to blockade of the negative feedback loop, the induction of miR-155 during macrophage activation serves to maximize and prolong the inflammatory process. However, miR-155 does not express at protein level but only at DNA level, so it is very important to detect miR-155 for the early warning. But no work has been done to date. In this work, we proposed a novel PEC aptasensing strategy for the detection of miR-155.

For ZnO, 2D ZnO NSs with a layered structure have been regarded as a key material for the future technology, such as to form various kinds of nanomaterials and nano-optoelectronic devices (Huang et al., 2001, Kim et al., 2014, Timpel et al., 2014, Wang et al., 2014b) owing to its excellent properties (Tusche et al., 2007, Wang, 2009, Weirum et al., 2010). However, the light absorption of ZnO is limited to a small spectral region because of its wide band gap. Expanding its light harvesting in the near-infrared region is one of the strategies which could further broaden the application of ZnO. Some measures have been adopted to decrease its band gap. Among the measures, QDs show good sensitization effect to sensitize ZnO, such as the ordinary QDs—CdS (Chen et al., 2011, Singh et al., 2012, Tak et al., 2009), CdSe (Emin et al., 2013, Kim et al., 2012, Leschkies et al., 2007, Li et al., 2013, Raichlin et al., 2011) and CdTe (Cheng et al., 2014a, Cheng et al., 2014b, Li et al., 2014, Liang et al., 2014, Liu et al., 2013a, Pang et al., 2015a, Vinayaka et al., 2009, Wu and Yan, 2010). Recently, some novel QDs are utilized to improve the light absorbency of ZnO, such as nitrogen-doped carbon quantum dots (NCQDs) (Muthulingam et al., 2015, Pang et al., 2016), carbon quantum dots (CQDs) (Pan et al., 2015, Vuong et al., 2015, Zhang et al., 2013), PbS QDs (Jean et al., 2013, Kawawaki et al., 2015, Park et al., 2014), PbSe QDs (Hoye et al., 2014), graphene QDs (Guo et al., 2013, Moon et al., 2016), CuO QDs (Liu et al., 2013c), Zn2SnO4 QDs (Li et al., 2012). Because QDs are 1 D nanostructure, the sensitization provides a direct rather than zigzag pathway to facilitate the electron transfer (Bai et al., 2012, Leschkies et al., 2007, Tak et al., 2009). However, CH3NH3PbI3 QDs have not been used to dope with ZnO at present. In this work, the novel CH3NH3PbI3 QDs are utilized to enhance the light-harvesting efficiency of ZnO.

Organometal halide perovskites (such as CH3NH3PbI3) show a suitable band gap energy for the sunlight absorption (Frost et al., 2014a, Stoumpos et al., 2013, Xing et al., 2013) with a high absorption coefficient (>104 cm−1) (Frost et al., 2014b) and long-range exciton diffusion lengths (>1 µm) (Ma and Wang, 2014, Niu et al., 2015). Moreover, CH3NH3PbI3 can absorb the visible light in the wavelength range of 400–800 nm (Kojima et al., 2009). CH3NH3PbI3 have been introduced as a new kind of light-harvesting material for solar light absorption (Abrusci et al., 2013, Chung et al., 2012, Kagan et al., 1999, Kojima et al., 2009, Lee et al., 2012, Liu et al., 2013b) since the first report in 2009 (Jeon et al., 2015, Kojima et al., 2009). By now, except the application in solar cell, CH3NH3PbI3 has also been applied in controlling humidity environments (Yang et al., 2015), cytosensing (Pang et al., 2016), 1D field-effect phototransistors (Spina et al., 2016), low-intensity light detection (Spina et al., 2015). However, very few reports focus on the preparation and application of CH3NH3PbI3 QDs. Even more no report appears about the application of CH3NH3PbI3 QDs in bio-sensing. Thus, in this work, the preparation of CH3NH3PbI3 QDs was carried out and changed the preparation method of other perovskite (Kim et al., 2014). The prepared novel CH3NH3PbI3 QDs were used as an excellent candidate to improve the visible light absorption of ZnO.

In this work, CH3NH3PbI3 QDs sensitized ZnO NSs were adopted to construct a novel PEC aptasensor for the detection of miR-155 based on photoelectrochemistry via the specific hybridization between the primer probes and ssDNA of miR-155. The strategy of employing in situ narrow-bandgap semiconductors to enhance the photocurrent opens an alternative horizon for PEC sensing.

Section snippets

Reagents and apparatus

Phosphate buffered solution (PB, 0.067 mol/L KH2PO4 and 0.067 mol/L Na2HPO4) was used as the electrolyte for all the PEC experiments. All other chemical reagents were directly used without further purification. The ultrapure water was with a resistivity of 18.25  cm. Pipette tips were put into LDZX-30KBS pressure steam sterilizer (Shanghai Shenan Medical Instrument) and sterilized for 40 min at 121 °C. After cooling to room temperature, they were stored in a 4 °C refrigerator.

Scanning electron

Characterization of ZnO NSs and CH3NH3PbI3 QDs

SEM image of the synthesized ZnO NSs was shown in Fig. 1A. It can be observed that ZnO exhibited typical nano-sheet structure, which was like some beautiful roseleaves. The feature was further confirmed by Fig. 1B. As mentioned in Section 2.2 and the cited literature (Gupta et al., 2013), ZnO NSs and ZnO nanorods (NRs) maybe co-exist in the preparation process, which situation was verified in Fig. 1C. It can be seen under the accident condition that some ZnO NRs were bare and some were covered

Conclusions

This work has developed an ultrasensitive PEC aptasensor based on a novel signal amplification strategy. ZnO@CH3NH3PbI3 heterojunction was employed as the light harvester for the quantitative determination of miR-155. The signal generator of ZnO@CH3NH3PbI3 showed obviously enhanced PEC property. The combination of ZnO NSs and CH3NH3PbI3 QDs depressed h+/e recombination effectively, and improved the charge separation efficiency and charge transfer ability. The high-sensitive detection result

Acknowledgments

This research was supported by National Natural Science Foundation of China (Nos. 21375047, 21377046, 21405059, 21575050, 21505051), the Science and Technology Development Plan of Shandong Province (No. 2014GSF120004, 2015GGH301001), the research was also supported by Shandong Key Laboratory of Fluorine Chemistry and Chemical Engineering Materials, the Special Project for Independent Innovation and Achievements Transformation of Shandong Province (No. 2014ZZCX05101), Shandong Provincial Natural

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