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A voltammetric hybridization assay for microRNA-21 using carboxylated graphene oxide decorated with gold-platinum bimetallic nanoparticles

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Abstract

An electrochemical hybridization assay is described for the determination of microRNA-21. Fluorine tin oxide (FTO) sheets were coated with carboxylated graphene oxide followed by deposition of gold-platinum bimetallic nanoparticles by using chronoamperometry at a potential of −0.2 V for 350 s. The capture probe was immobilized on the surface of the modified FTO sheets by biotin-avidin interaction. On exposure to microRNA-21, hybridization occurs, and that can be detected at a relatively low working potential of 0.25 V by using ferri/ferro-cyanide as an electrochemical probe. The various modifications of the FTO sheets were characterized by means of FE-SEM, FT-IR, contact angle studies and electrochemical techniques. The effects of pH value, EDC-NHS activation time, concentration of capture probe and incubation time were optimized. The sensor has a wide linear response that extends from 1 fM to 1 μM of microRNA-21, and the detection limit is 1 fM. The sensor is stable for about 15 days (by retaining 90% of its initial activity) and can be reused for about 3 times (85% of initial activity) after regeneration with 50 mM NaOH solution. The sensor was applied to the analysis of spiked human serum and gave recoveries between 90 and 111%.

Carboxylated graphene oxide (CGO) coated on a fluorine tin oxide (FTO) electrode was decorated with Au-Pt bimetallic nanoparticles (Au-PtBNPs). The Au-PtBNPs/CGO/FTO electrode surface was used for immobilizing streptavidin and biotinylated capture probe which can electrochemically detect microRNA-21 based on its sequence complementarity.

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References

  1. Chun L, Kim SE, Cho M, Choe WS, Nam J, Lee DW, Lee Y (2013) Electrochemical detection of HER2 using single stranded DNA aptamer modified gold nanoparticles electrode. Sensors Actuators B Chem 186:446–450

    Article  CAS  Google Scholar 

  2. Gupta P, Bharti A, Kaur N, Singh S, Prabhakar N (2018) An electrochemical aptasensor based on gold nanoparticles and graphene oxide doped poly(3,4-ethylenedioxythiophene) nanocomposite for detection of MUC1. J Electroanal Chem 813:102–108

    Article  CAS  Google Scholar 

  3. Chang CC, Chiu NF, Lin DS, Chu-Su Y, Liang YH, Lin CW (2010) High-sensitivity detection of carbohydrate antigen 15-3 using a gold/zinc oxide thin film surface Plasmon resonance-based biosensor. Anal Chem 82:1207–1212

    Article  CAS  Google Scholar 

  4. Mattick JS, Makunin IV (2006) Non-coding RNA. Hum Mol Genet 15:R17–R29

    Article  CAS  Google Scholar 

  5. Leng QX, Lin YL, Jiang FR, Lee CJ, Zhan M, Fang HB, Wang Y, Jiang F (2017) A plasma miRNA signature for lung cancer early detection. Oncotarget 8:111902–111911

    PubMed  PubMed Central  Google Scholar 

  6. Lanza G, Ferracin M, Gafa R, Veronese A, Spizzo R, Pichiorri F, Liu CG, Calin GA, Croce CM, Negrini M (2007) mRNA/microRNA gene expression profile in microsatellite unstable colorectal cancer. Mol Cancer 6:54

    Article  Google Scholar 

  7. Xin FX, Li M, Balch C, Thomson M, Fan MY, Liu Y, Hammond SM, Kim S, Nephew KP (2009) Computational analysis of microRNA profiles and their target genes suggests significant involvement in breast cancer antiestrogen resistance. Bioinformatics 25:430–434

    Article  CAS  Google Scholar 

  8. McGuire A, Brown JAL, Kerin MJ (2015) Metastatic breast cancer: the potential of miRNA for diagnosis and treatment monitoring. Cancer Metastasis Rev 34:145–155

    Article  CAS  Google Scholar 

  9. Lowery AJ, Miller N, McNeill RE, Kerin MJ (2008) MicroRNAs as prognostic indicators and therapeutic targets: potential effect on breast cancer management. Clin Cancer Res 14:360–365

    Article  CAS  Google Scholar 

  10. Chan M, Liaw CS, Ji SM, Tan HH, Wong CY, Thike AA, Tan PH, Ho GH, Lee ASG (2013) Identification of circulating microRNA signatures for breast cancer detection. Clin Cancer Res 19:4477–4487

    Article  CAS  Google Scholar 

  11. Lusi EA, Passamano M, Guarascio P, Scarpa A, Schiavo L (2012) Innovative electrochemical approach for an early detection of microRNAs. Anal Chem 81:2819–2822

    Article  Google Scholar 

  12. Kilic T, Topkaya SN, Ariksoysal DO, Ozsoz M, Ballar P, Erac Y, Gozen O (2012) Electrochemical based detection of microRNA, mir21 in breast cancer cells. Biosens Bioelectron 38:195–201

    Article  CAS  Google Scholar 

  13. Liu LZ, Song C, Zhang Z, Yang J, Zhou LL, Zhang X, Xie GM (2015) Ultrasensitive electrochemical detection of microRNA-21 combining layered nanostructure of oxidized single-walled carbon nanotubes and nanodiamonds by hybridization chain reaction. Biosens Bioelectron 70:351–357

    Article  CAS  Google Scholar 

  14. Zhai Q, He Y, Li XL, Guo J, Li SQ, Yi G (2015) A simple and ultrasensitive electrochemical biosensor for detection of microRNA based on hybridization chain reaction amplification. J Electroanal Chem 758:20–25

    Article  CAS  Google Scholar 

  15. Miao XM, Wang WH, Kang TS, Liu JB, Shiu KK, Leung CH, Ma DL (2016) Ultrasensitive electrochemical detection of miRNA-21 by using an iridium(III) complex as catalyst. Biosens Bioelectron 86:454–458

    Article  CAS  Google Scholar 

  16. Azzouzi S, Mak WC, Kor K, Turner APF, Ben Ali M, Beni V (2017) An integrated dual functional recognition/amplification bio-label for the one-step impedimetric detection of micro-RNA-21. Biosens Bioelectron 92:154–161

    Article  CAS  Google Scholar 

  17. Mandli J, Mohammadi H, Amine A (2017) Electrochemical DNA sandwich biosensor based on enzyme amplified microRNA-21 detection and gold nanoparticles. Bioelectrochemistry 116:17–23

    Article  CAS  Google Scholar 

  18. Su S, Cao WF, Liu W, Lu ZW, Zhu D, Chao J, Weng LX, Wang LH, Fan CH, Wang LH (2017) Dual-mode electrochemical analysis of microRNA-21 using gold nanoparticle-decorated MoS2 nanosheet. Biosens Bioelectron 94:552–559

    Article  CAS  Google Scholar 

  19. Rafiee-Pour HA, Behpour M, Keshavarz M (2016) A novel label-free electrochemical miRNA biosensor using methylene blue as redox indicator: application to breast cancer biomarker miRNA-21. Biosens Bioelectron 77:202–207

    Article  CAS  Google Scholar 

  20. Tian L, Qian K, Qi J, Liu QY, Yao C, Song W, Wang YH (2018) Gold nanoparticles superlattices assembly for electrochemical biosensor detection of microRNA-21. Biosens Bioelectron 99:564–570

    Article  CAS  Google Scholar 

  21. Kangkamano T, Numnuam A, Limbut W, Kanatharana P, Vilaivan T, Thavarungkul P (2018) Pyrrolidinyl PNA polypyrrole/silver nanofoam electrode as a novel label free electrochemical miRNA-21 biosensor. Biosens Bioelectron 102:217–225

    Article  CAS  Google Scholar 

  22. Zhang KY, Zhang N, Zhang L, Wang HY, Shi HW, Liu Q (2018) Label-free impedimetric sensing platform for microRNA-21 based on ZrO2-reduced graphene oxide nanohybrids coupled with catalytic hairpin assembly amplification. RSC Adv 8:16146–16151

    Article  CAS  Google Scholar 

  23. Tian L, Qi JX, Ma XY, Wang XJ, Yao C, Song W, Wang YH (2018) A facile DNA strand displacement reaction sensing strategy of electrochemical biosensor based on N-carboxymethyl chitosan/molybdenum carbide nanocomposite for microRNA-21 detection. Biosens Bioelectron 122:43–50

    Article  CAS  Google Scholar 

  24. Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) The chemistry of graphene oxide. Chem Soc Rev 39:228–240

    Article  CAS  Google Scholar 

  25. Li Z, An ZZ, Guo YY, Zhang KN, Chen XL, Zhang DX, Xue ZH, Zhou XB, Lu XQ (2016) Au-Pt bimetallic nanoparticles supported on functionalized nitrogen-doped graphene for sensitive detection of nitrite. Talanta 161:713–720

    Article  CAS  Google Scholar 

  26. Ghani M, Masoum S, Ghoreishi SM (2018) Three-dimensional Pd/Pt bimetallic nanodendrites on a highly porous copper foam fiber for headspace solid-phase microextraction of BTEX prior to their quantification by GC-FID. Microchim Acta 185:527

    Article  Google Scholar 

  27. Jain U, Gupta S, Chauhan N (2017) Construction of an amperometric glycated hemoglobin biosensor based on au–Pt bimetallic nanoparticles and poly (indole-5-carboxylic acid) modified au electrode. Int J Biol Macromol 105:549–555

    Article  CAS  Google Scholar 

  28. Lee CY, Van Le Q, Kim C, Kim SY (2015) Use of silane-functionalized graphene oxide in organic photovoltaic cells and organic light-emitting diodes. Phys Chem Chem Phys 17:9369–9374

    Article  CAS  Google Scholar 

  29. Peng SG, Liu CY, Fan XJ (2015) Surface modification of graphene oxide by carboxyl-group: preparation, characterization, and application for proteins immobilization. Integr Ferroelectr 163:42–53

    Article  CAS  Google Scholar 

  30. Yang T, Zhou N, Li QH, Guan Q, Zhang W, Jiao K (2012) Highly sensitive electrochemical impedance sensing of PEP gene based on integrated au-Pt alloy nanoparticles and polytyramine. Colloids Surf B: Biointerfaces 97:150–154

    Article  CAS  Google Scholar 

  31. Thakur H, Kaur N, Sabherwal P, Sareen D, Prabhakar N (2017) Aptamer based voltammetric biosensor for the detection of mycobacterium tuberculosis antigen MPT64. Microchim Acta 184:1915–1922

    Article  CAS  Google Scholar 

  32. Cui M, Wang Y, Wang HP, Wu YM, Luo XL (2017) A label-free electrochemical DNA biosensor for breast cancer marker BRCA1 based on self-assembled antifouling peptide monolayer. Sensors Actuators B Chem 244:742–749

    Article  CAS  Google Scholar 

  33. Wen W, Huang JY, Bao T, Zhou J, Xia HX, Zhang XH, Wang SF, Zhao YD (2016) Increased electrocatalyzed performance through hairpin oligonucleotide aptamer-functionalized gold nanorods labels and graphene-streptavidin nanomatrix: highly selective and sensitive electrochemical biosensor of carcinoembryonic antigen. Biosens Bioelectron 83:142–148

    Article  CAS  Google Scholar 

  34. Yu S, Liu J, Zhu W, Hu ZT, Lim TT, Yan X (2015) Facile room-temperature synthesis of carboxylated graphene oxide-copper sulfide nanocomposite with high photodegradation and disinfection activities under solar light irradiation. Sci Rep 5:16369

    Article  CAS  Google Scholar 

  35. Lapin NA, Chabal YJ (2009) Chabal, infrared characterization of biotinylated silicon oxide surfaces, surface stability, and specific attachment of streptavidin. J Phys Chem B 113:8776–8783

    Article  CAS  Google Scholar 

  36. Banyay M, Sarkar M, Graslund A (2003) A library of IR bands of nucleic acids in solution. Biophys Chem 104:477–488

    Article  CAS  Google Scholar 

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Acknowledgements

This work was financially supported by Department of Science and Technology [DST-Purse II], Special Assistance Programme (UGC-SAP) [F.4-7/2015/DRS-III (SAP-II)] and DST-SERB sponsored project [EEQ/2017/000239]. Council of Scientific & Industrial Research (CSIR) is highly acknowledged for the award of SRF [09/135(0729)/2016-EMR-I]. Authors also acknowledge Central Instrument Laboratory (CIL) facility of Panjab University, Chandigarh for FE-SEM studies. We are thankful to Dr. Shweta Rana (Department of Chemistry, Panjab University, Chandigarh) and Dr. Suman Singh (Central Scientific Instruments Organisation (CSIR-CSIO), Chandigarh) for their support in performing FT-IR and Contact angle studies, respectively.

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  1. Department of Biochemistry, Panjab University, Chandigarh, 160014, India

    Anu Bharti, Navneet Agnihotri & Nirmal Prabhakar

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  1. Anu Bharti
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  3. Nirmal Prabhakar
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Correspondence to Nirmal Prabhakar.

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Bharti, A., Agnihotri, N. & Prabhakar, N. A voltammetric hybridization assay for microRNA-21 using carboxylated graphene oxide decorated with gold-platinum bimetallic nanoparticles. Microchim Acta 186, 185 (2019). https://doi.org/10.1007/s00604-019-3302-3

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