Microchimica Acta

, 186:826 | Cite as

Photoelectrochemical aptasensor for lead(II) by exploiting the CdS nanoparticle-assisted photoactivity of TiO2 nanoparticles and by using the quercetin-copper(II) complex as the DNA intercalator

  • Yanyan Niu
  • Guiling Luo
  • Hui Xie
  • Yujiao Zhuang
  • Xianqun Wu
  • Guangjiu Li
  • Wei SunEmail author
Original Paper


A photoelectrochemical (PEC) aptasensor for Pb(II) detection is described. A nanocomposite consisting of CdS (2.5 μm) and TiO2 nanoparticles (10 nm) was used as a photoactive material, and gold nanochains (Au NCs) as the support for immobilization of the Pb(II)-binding aptamer. The quercetin-copper(II) complex was further employed as the intercalator for the improvement of the photoactivity by embedding it into dsDNA. In the presence of Pb(II), a Pb(II)-stabilized G-quadruplex was formed between Pb(II) and DNA S1. This is accompanied by unwinding of the dsDNA and the release of the quercetin-copper(II) complex from the surface of the sensor. This results in a decrease of the photocurrent that drops linearly from 5.0 × 10−12 to 1.0 × 10−8 mol·L−1 Pb(II) concentration range with a detection limit of 1.6 × 10−12 mol·L−1. The method was applied to the determination of Pb(II) in various samples and gave satisfactory results.

Graphical abstract

A photoelectrochemical aptasensor was fabricated for the detection of Pb(II) based on CdS-TiO2 nanocomposite modified indium tin oxide (ITO) electrode. Gold nanochains (AuNCs) were used as anchor to immobilize the aptamers S1 and S2 that form a double helix structure by DNA hybridization. After embedding of quercetin-copper(II) complex as intercalator and electron donor, the concentrations of Pb(II) were determined by the changes of photocurrents.


Aptamer G-quadruplex CdS-TiO2 nanocomposite Quercetin-copper(II) Photoelectrochemistry Lead ion 



This work was supported by National Natural Science Foundation of China (21665007), Hainan Provincial Natural Science Foundation of China (219QN207), and Key Science and Technology Program of Haikou City (2017042).

Supplementary material

604_2019_3951_MOESM1_ESM.doc (234 kb)
ESM 1 (DOC 234 kb)


  1. 1.
    Zhao W, Xu J, Chen H (2016) Photoelectrochemical aptasensing. Trends Anal Chem 82:307–315CrossRefGoogle Scholar
  2. 2.
    Yang X, Wu L, Ma L, Li X, Wang T, Liao S (2015) Pd nano-particles (NPs) confined in titanate nanotubes (TNTs) for hydrogenation of cinnamaldehyde. Catal Commun 59:184–188CrossRefGoogle Scholar
  3. 3.
    Wang W, Savadogo O, Ma Z (2012) The oxygen reduction reaction on Pt/TiOxNy-based electrocatalyst for PEM fuel cell applications. J Appl Electrochem 42:857–866CrossRefGoogle Scholar
  4. 4.
    Li L, Chen R, Zhu X, Liao Q, Ye D, Zhang B, He X, Jiao L, Feng H, Zhang W (2018) A ternary hybrid CdS/SiO2/TiO2 photoanode with enhanced photoelectrochemical activity. Renew Energy 127:524–530CrossRefGoogle Scholar
  5. 5.
    Zou Z, Xie C, Zhang S, Liu Y, Zhang S, Zeng D (2013) Extraordinarily enhanced gas phase photoelectric response of CdS/TiO2 nanocomposite photoelectrode: CdS as a sensitizer and a hole capturer. J Nanopart Res 15:1734–1744CrossRefGoogle Scholar
  6. 6.
    Qi X, She G, Liu Y, Mu L, Shi W (2012) Electrochemical synthesis of CdS/ZnO nanotube arrays with excellent photoelectrochemical properties. Chem Commun 48:242–244CrossRefGoogle Scholar
  7. 7.
    Chen Y, Huang L, Wu W, Ruan Y, Wu Z, Xue Z, Fu F (2014) Speciation analysis of lead in marine animals by using capillary electrophoresis couple on-line with inductively coupled plasma mass spectrometry. Electrophoresis 35:1346–1352CrossRefGoogle Scholar
  8. 8.
    Tsogas GZ, Giokas DL, Vlessidis AG (2009) Graphite furnace and hydride generation atomic absorption spectrometric determination of cadmium, lead, and tin traces in natural surface waters: study of preconcentration technique performance. J Hazard Mater 163:988–994CrossRefGoogle Scholar
  9. 9.
    Jiang D, Du X, Chen D, Zhou L, Chen W, Li Y, Hao N, Qian J, Liu Q, Wang K (2016) One-pot hydrothermal route to fabricate nitrogen doped graphene/Ag-TiO2: efficient charge separation and high-performance on-off-on switch system based photoelectrochemical biosensing. Biosens Bioelectron 83:149–155CrossRefGoogle Scholar
  10. 10.
    Wang Y, Chen F, Ye X, Wu T, Wu K, Li C (2017) Photoelectrochemical immunosensing of tetrabromobisphenol a based on the enhanced effect of dodecahedral gold nanocrystals/MoS2 nanosheets. Sensors Actuators B 245:205–212CrossRefGoogle Scholar
  11. 11.
    Wang H, Liu P, Jiang W, Li X, Yin H, Ai S (2017) Photoelectrochemical immunosensing platform for M. SssI methyltransferase activity analysis and inhibitor screening based on g-C3N4 and CdS quantum dots. Sensors Actuators B 244:458–465CrossRefGoogle Scholar
  12. 12.
    Duan N, Wu S, Dai S, Miao T, Chen J, Wang Z (2015) Simultaneous detection of pathogenic bacteria using an aptamer based biosensor and dual fluorescenceresonance energy transfer from quantum dots to carbon nanoparticles. Microchim Acta 182:917–923CrossRefGoogle Scholar
  13. 13.
    Taghdisi SM, Danesh NM, Lavaee P, Ramezani M, Abnous K (2015) An aptasensor for selective, sensitive and fast detection of lead (II) based on polyethyleneimine and gold nanoparticles. Environ Toxicol Pharmacol 39:1206–1211CrossRefGoogle Scholar
  14. 14.
    Zhu Y, Zeng G, Zhang Y, Tang L, Chen J, Cheng M, Zhang L, He L, Guo Y, He X, Lai M, He Y (2014) Highly sensitive electrochemical sensor using a MWCNTs/GNPs-modified electrode for lead (II) detection based on Pb2+-induced G-rich DNA conformation. Analyst 139:5014–5020CrossRefGoogle Scholar
  15. 15.
    Xiao S, Chen L, Xiong X, Zhang Q, Feng J, Deng S, Zhou L (2018) A new impedimetric sensor based on anionic intercalator for detection of lead ions with low cost and high sensitivity. J Electroanal Chem 827:175–180CrossRefGoogle Scholar
  16. 16.
    Okoth OK, Yan K, Feng J, Zhang J (2018) Label-free photoelectrochemical aptasensing of diclofenca based on gold nanoparticles and graphene-doped CdS. Sensors Actuators B 256:334–341CrossRefGoogle Scholar
  17. 17.
    Li F, Feng Y, Zhao C, Tang B (2011) Crystal violet as a G-quadruplex-selective probe for sensitive amperometric sensing of lead. Chem Commun 47:11909–11911CrossRefGoogle Scholar
  18. 18.
    Li H, Xue Y, Wang W (2014) Femtomole level photoelectrochemical aptasensing for mercury ions using quercetin-copper (II) complex as the DNA intercalator. Biosens Bioelectron 54:317–322CrossRefGoogle Scholar
  19. 19.
    Srinivasan SS, Wade J, Stefanakos EK (2006) Visible light photocatalysis via CdS/TiO2 nanocomposite materials. J Nanomater 2006:87326. CrossRefGoogle Scholar
  20. 20.
    Lang QQ, Chen YH, Huang TL, Yang LN, Zhong SX, Wu LJ, Chen JR, Bai S (2018) Graphene “bridge” in transferring hot electrons from plasmonic Ag nanocubes to TiO2 nanosheets for enhanced visible light photocatalytic hydrogen evolution. Appl Catal B 220:182–190CrossRefGoogle Scholar
  21. 21.
    Zhang ZM, Jiang YH, Yu QH, Ding YH, Jiang Y, Yin JR, Zhang P (2017) Facile preplaration of exposed {001} facet TiO2 nanobelts coated by monolayer carbon and its high-performance photocatalytic activity. J Mater Sci 52:13586–13595CrossRefGoogle Scholar
  22. 22.
    You DT, Pan B, He YS, Wang XX, Su WY (2017) Enhanced visible light photocatalytic H2 evolution over CeO2 loaded with Pt and CdS. Res Chem Intermed 43:5103–5112CrossRefGoogle Scholar
  23. 23.
    Malashchonak MV, Mazanik AV, Korolik OV, Streltsov EA, Kulak AI (2015) Influence of wide band gap oxide substrates on the photoelectrochemical properties and structural disorder of CdS nanoparticles grown by the successive ionic layer adsorption and reaction (SILAR) method. Beilstein J Nanotech 6:2252–2262CrossRefGoogle Scholar
  24. 24.
    Pang X, Bian H, Wang W, Liu C, Khan MS, Wang Q, Qi J, Wei Q, Du B (2017) A bio-chemical application of N-GQDs and g-C3N4 QDs sensitized TiO2 nanopillars for the quantitative detection of pcDNA3-HBV. Biosens Bioelectron 91:456–464CrossRefGoogle Scholar
  25. 25.
    Xin Y, Zhao Y, Qiu B, Zhang Z (2017) Sputtering gold nanoparticles on nanoporous bismuth vanadate for sensitive and selective photoelectrochemical aptasensing of thrombin. Chem Commun 53:8898–8901CrossRefGoogle Scholar
  26. 26.
    Cai H, Lee TMH, Hsing IM (2006) Label-free protein recognition using an aptamer-based impedance measurement assay. Sensors Actuators B 114:433–437CrossRefGoogle Scholar
  27. 27.
    Lin Z, Li X, Kraatz HB (2011) Impedimetric immobilized DNA-based sensor for simultaneous detection of Pb2+, Ag+ and Hg2+. Anal Chem 83:6896–6901CrossRefGoogle Scholar
  28. 28.
    Zang Y, Lei J, Hao Q, Ju H (2014) “Signal-on” photoelectrochemical sensing strategy based on target-dependent aptamer conformational conversion for selective detection of lead (II) ion. ACS Appl Mater Interfaces 6:15991–15997CrossRefGoogle Scholar
  29. 29.
    Li M, Zhou X, Guo S, Wu N (2013) Detection of lead (II) with a “turn-on” fluorescent biosensor based on energy transfer from CdSe/ZnS quantum dots to graphene oxide. Biosens Bioelectron 43:69–74CrossRefGoogle Scholar
  30. 30.
    Pang S, Liu S, Su X (2015) An ultrasensitive sensing strategy for the detection of lead (II) ions based on the intermolecular G-quadruplex and graphene oxide. Sensors Actuators B 208:415–420CrossRefGoogle Scholar
  31. 31.
    Qian ZS, Shan XY, Chai LJ, Chen JR, Feng H (2015) A fluorescent nanosensor based on graphene quantum dots-aptamer probe and graphene oxide platform for detection of lead (II) ion. Biosens Bioelectron 68:225–231CrossRefGoogle Scholar
  32. 32.
    Wang S, Si S (2013) Aptamer biosensing platform based on carbon nanotube longrange energy transfer for sensitive, selective and multicolor fluorescent heavy metal ion analysis. Anal Methods 5:2947–2953CrossRefGoogle Scholar
  33. 33.
    Zhou B, Yang XY, Wang YS, Yi JC, Zeng Z, Zhang H, Chen YT, Hu XJ, Suo QL (2019) Label-free fluorescent aptasensor of Cd2+ detection based on the conformational switching of aptamer probe and SYBR green I. Microchem J 144:377–382CrossRefGoogle Scholar
  34. 34.
    Lotfi Zadeh Zhad HR, Rodríguez Torres YM, Lai RY (2017) A reagentless and reusable electrochemical aptamer-based sensor for rapid detection of cd(II). J Electroanal Chem 803:89–94CrossRefGoogle Scholar
  35. 35.
    Wu Y, Zhan S, Wang L, Zhou P (2014) Selection of a DNA aptamer for cadmium detection based on cationic polymer mediated aggregation of gold nanoparticles. Analyst 139:1550–1561CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Key Laboratory of Water Pollution Treatment and Resource Reuse of Hainan Province, College of Chemistry and Chemical EngineeringHainan Normal UniversityHaikouPeople’s Republic of China
  2. 2.Key Laboratory of Optic-Electric Sensing and Analytical Chemistry for Life Science of Ministry of Education, College of Chemistry and Molecular EngineeringQingdao University of Science and TechnologyQingdaoPeople’s Republic of China

Personalised recommendations