Skip to main content
SpringerLink
Log in

Functionalized N-doped graphene quantum dots for electrochemical determination of cholesterol through host-guest inclusion

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

Functionalized nitrogen-doped graphene quantum dots (N-GQD) with mean particle size of 8.5 ± 0.5 nm were covalently linked to β-cyclodextrin (β-CD) to form a β-CD@N-GQD nanoprobe. The probe is shown to enable voltammetric determination of cholesterol via selective host-guest recognition and by using ferrocene (FC) as the redox indicator. FC is first included in β-cyclodextrin. Cholesterol has a higher affinity for β-CD (in comparison to FC). It forms a strong inclusion complex with β-CD and can replace FC from its cavities. The quantity of released FC is proportional to the concentration of cholesterol. The differential pulse voltammetric signal for FC (with a peak at typically 0.22 V vs Ag/AgCl) increases linearly in the 0.5–100 μM cholesterol concentration range, with a limit of detection as low as 80 nM. The assay is found to be highly selective over 15 potentially interfering species. The method was successfully applied to the detection of cholesterol in spiked serum samples which gave recoveries between 96 and 101%. The probe can be stored for at least 28 days after which the activity still is 87%.

This scheme illustrates the detection of cholesterol by differential pulse voltammetry (DPV) technique. The β-cyclodextrin functionalized nitrogen-doped graphene quantum dot (β-CD@N-GQD) probe was developed to enable voltammetric determination of cholesterol using selective host-guest recognition.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme. 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Bindumadhavan K, Chang PY, Doong RA (2017) Silver nanoparticles embedded boron-doped reduced graphene oxide as anode material for high performance lithium ion battery. Electrochim Acta 243:282–290

    Article  CAS  Google Scholar 

  2. Sahu RS, Li DL, Doong RA (2018) Unveiling the hydrodechlorination of trichloroethylene by reduced graphene oxide supported bimetallic Fe/Ni nanoparticles. Chem Eng J 334:30–40

    Article  CAS  Google Scholar 

  3. Alagiri M, Rameshkumar P, Pandikumar A (2017) Gold nanorod-based electrochemical sensing of small biomolecules: a review. Microchim Acta 184:3069–3092

    Article  CAS  Google Scholar 

  4. Zhang B, Huang L, Tang M, Hunter KW, Feng Y, Sun Q, Wang J, Chen G (2018) A nickel nanoparticle/nafion-graphene oxide modified screen-printed electrode for amperometric determination of chemical oxygen demand. Microchim Acta 185:385

    Article  Google Scholar 

  5. Zhu J, Zhang S, Wang L, Jia D, Xu M, Zhao Z, Qiu J, Jia L (2018) Engineering cross-linking by coal-based graphene quantum dots toward tough, flexible, and hydrophobic electrospun carbon nanofiber fabrics. Carbon 129:54–62

    Article  CAS  Google Scholar 

  6. Ganganboina AB, Dutta Chowdhury A, Doong RA (2017) New avenue for appendage of graphene quantum dots on halloysite nanotubes as anode materials for high performance supercapacitors. ACS Sustain Chem Eng 5:4930–4940

    Article  CAS  Google Scholar 

  7. Ganganboina AB, Chowdhury AD, Doong RA (2017) Nano assembly of N-doped graphene quantum dots anchored Fe3O4/halloysite nanotubes for high performance supercapacitor. Electrochim Acta 245:912–923

    Article  CAS  Google Scholar 

  8. Guo J, Zhu H, Sun Y, Tang L, Zhang X (2016) Boosting the lithium storage performance of MoS2 with graphene quantum dots. J Mater Chem A 4:4783–4789

    Article  CAS  Google Scholar 

  9. Rao H, Zhao X, Liu X, Zhong J, Zhang Z, Zou P, Jiang Y, Wang X, Wang Y (2018) A novel molecularly imprinted electrochemical sensor based on graphene quantum dots coated on hollow nickel nanospheres with high sensitivity and selectivity for the rapid determination of bisphenol S. Biosens Bioelectron 100:341–347

    Article  CAS  Google Scholar 

  10. Álvarez-Diduk R, Orozco J, Merkoçi A (2017) Paper strip-embedded graphene quantum dots: a screening device with a smartphone readout. Sci Rep 7:976

    Article  Google Scholar 

  11. Nasir M, Nawaz MH, Latif U, Yaqub M, Hayat A, Rahim A (2017) An overview on enzyme-mimicking nanomaterials for use in electrochemical and optical assays. Microchim Acta 184:323–342

    Article  CAS  Google Scholar 

  12. Dutta CA, Doong RA (2016) Highly sensitive and selective detection of nanomolar ferric ions using dopamine functionalized graphene quantum dots. ACS Appl Mater Interfaces 8:21002–21010

    Article  Google Scholar 

  13. Ganganboina AB, Dutta CA, Doong RA (2018) N-doped graphene quantum dots decorated V2O5 nanosheet for fluorescence turn off-on detection of cysteine. ACS Appl Mater Interfaces 10:614–624

    Article  CAS  Google Scholar 

  14. Chowdhury AD, Ganganboina AB, Park EY, Doong RA (2018) Impedimetric biosensor for detection of cancer cells employing carbohydrate targeting ability of Concanavalin A. Biosens Bioelectron 122:95–103

    Article  CAS  Google Scholar 

  15. Li D, Nie F, Tang T, Tian K (2018) Determination of ferric ion via its effect on the enhancement of the chemiluminescece of the permanganate-sulfite system by nitrogen-doped graphene quantum dots. Microchim Acta 185:431

    Article  Google Scholar 

  16. Tiwari JN, Vij V, Kemp KC, Kim KS (2015) Engineered carbon-nanomaterial-based electrochemical sensors for biomolecules. ACS Nano 10:46–80

    Article  Google Scholar 

  17. Xu J, Wang Y, Hu S (2017) Nanocomposites of graphene and graphene oxides: synthesis, molecular functionalization and application in electrochemical sensors and biosensors. A review Microchim Acta 184:1–44

    Article  CAS  Google Scholar 

  18. Chowdhury AD, Ganganboina AB, Y-c T, Chiu HC, Doong RA (2018) Multifunctional GQDs-Concanavalin A@Fe3O4 nanocomposites for cancer cells detection and targeted drug delivery. Anal Chim Acta 027:109–120

    Article  Google Scholar 

  19. Widenmaier SB, Snyder NA, Nguyen TB, Arduini A, Lee GY, Arruda AP, Saksi J, Bartelt A, Hotamisligil GS (2017) NRF1 is an ER membrane sensor that is central to cholesterol homeostasis. Cell 171:1094–1109

    Article  CAS  Google Scholar 

  20. Sun Q, Fang S, Fang Y, Qian Z, Feng H (2017) Fluorometric detection of cholesterol based on β-cyclodextrin functionalized carbon quantum dots via competitive host-guest recognition. Talanta 167:513–519

    Article  CAS  Google Scholar 

  21. Yang L, Zhao H, Fan S, Zhao G, Ran X, Li C-P (2015) Electrochemical detection of cholesterol based on competitive host–guest recognition using a β-cyclodextrin/poly (N-acetylaniline)/graphene-modified electrode. RSC Adv 5:64146–64155

    Article  CAS  Google Scholar 

  22. Huang Y, Tan J, Cui L, Zhou Z, Zhang Z, Zheng R et al (2017) Graphene and au NPs co-mediated enzymatic silver deposition for the ultrasensitive electrochemical detection of cholesterol. Biosens Bioelectron 102:560–567

    Article  Google Scholar 

  23. Shi X, Gu W, Li B, Chen N, Zhao K, Xian Y (2014) Enzymatic biosensors based on the use of metal oxide nanoparticles. Microchim Acta 181:1–22

    Article  CAS  Google Scholar 

  24. Zhang L, Wang J, Tian Y (2014) Electrochemical in-vivo sensors using nanomaterials made from carbon species, noble metals, or semiconductors. Microchim Acta 181:1471–1484

    Article  CAS  Google Scholar 

  25. Dong S, Bi Q, Qiao C, Sun Y, Zhang X, Lu X, Zhao L (2017) Electrochemical sensor for discrimination tyrosine enantiomers using graphene quantum dots and β-cyclodextrins composites. Talanta 173:94–100

    Article  CAS  Google Scholar 

  26. Lenik J (2017) Cyclodextrins based electrochemical sensors for biomedical and pharmaceutical analysis. Curr Med Chem 24:2359–2391

    Article  CAS  Google Scholar 

  27. Tang C, Qian Z, Huang Y, Xu J, Ao H, Zhao M, Zhou J, Chen J, Feng H (2016) A fluorometric assay for alkaline phosphatase activity based on β-cyclodextrin-modified carbon quantum dots through host-guest recognition. Biosens Bioelectron 83:274–280

    Article  CAS  Google Scholar 

  28. Taleat Z, Khoshroo A, Mazloum-Ardakani M (2014) Screen-printed electrodes for biosensing: a review (2008–2013). Microchim Acta 181:865–891

    Article  CAS  Google Scholar 

  29. Lin T, Zhong L, Chen H, Li Z, Song Z, Guo L, Fu F (2017) A sensitive colorimetric assay for cholesterol based on the peroxidase-like activity of MoS2 nanosheets. Microchim Acta 184:1233–1237

    Article  CAS  Google Scholar 

  30. Qu D, Zheng M, Li J, Xie Z, Sun Z (2015) Tailoring color emissions from N-doped graphene quantum dots for bioimaging applications. Light Sci Appl 4:364

    Article  Google Scholar 

  31. Li Z, Wang Y, Ni Y, Kokot S (2015) A rapid and label-free dual detection of hg (II) and cysteine with the use of fluorescence switching of graphene quantum dots. Sensors Actuators B Chem 207:490–497

    Article  CAS  Google Scholar 

  32. Tian Z, Zhang X, Li D, Zhou D, Jing PT, Shen DZ, Qu S, Zboril R, Rogach AL (2017) Full-color inorganic carbon dot phosphorus for white-light-emitting diodes. Adv Optical Mater 5:1700416

    Article  Google Scholar 

  33. Shin Y, Park J, Hyun D, Yang J, Lee J-H, Kim J-H, Lee H (2015) Acid-free and oxone oxidant-assisted solvothermal synthesis of graphene quantum dots using various natural carbon materials as resources. Nanoscale 7:5633–5637

    Article  CAS  Google Scholar 

  34. Luo M, Hua Y, Liang Y, Han J, Liu D, Zhao W, Wang P (2017) Synthesis of novel β-cyclodextrin functionalized S, N codoped carbon dots for selective detesection of testosterone. Biosens Bioelectron 98:195–201

    Article  CAS  Google Scholar 

  35. Lin X, Ni Y, Kokot S (2016) Electrochemical cholesterol sensor based on cholesterol oxidase and MoS2-AuNPs modified glassy carbon electrode. Sensors Actuators B Chem 233:100–106

    Article  CAS  Google Scholar 

  36. Soylemez S, Udum YA, Kesik M, Hızlıateş CG, Ergun Y, Toppare L (2015) Electrochemical and optical properties of a conducting polymer and its use in a novel biosensor for the detection of cholesterol. Sensors Actuators B Chem 212:425–433

    Article  CAS  Google Scholar 

  37. Shrestha BK, Ahmad R, Shrestha S, Park CH, Kim CS (2017) In situ synthesis of cylindrical spongy polypyrrole doped protonated graphitic carbon nitride for cholesterol sensing application. Biosens Bioelectron 94:686–693

    Article  CAS  Google Scholar 

  38. Cao S, Zhang L, Chai Y, Yuan R (2013) An integrated sensing system for detection of cholesterol based on TiO2–graphene–Pt–Pd hybridnanocomposites. Biosens Bioelectron 42:532–538

    Article  CAS  Google Scholar 

  39. Ahmad M, Pan C, Gan L, Nawaz Z, Zhu J (2009) Highly sensitive amperometric cholesterol biosensor based on Pt-incorporated fullerene-like ZnO nanospheres. J Phys Chem C 114:243–250

    Article  Google Scholar 

  40. Agnihotri N, Chowdhury AD, De A (2015) Non-enzymatic electrochemical detection of cholesterol using β-cyclodextrin functionalized graphene. Biosens Bioelectron 63:212–217

    Article  CAS  Google Scholar 

  41. Solanki PR, Kaushik A, Ansari AA, Tiwari A, Malhotra B (2009) Multi-walled carbon nanotubes/sol–gel-derived silica/chitosan nanobiocomposite for total cholesterol sensor. Sensors Actuators B Chem 137:727–735

    Article  CAS  Google Scholar 

  42. Rahman MM, Li X-b, Kim J, Lim BO, Ahammad AS, Lee J-J (2014) A cholesterol biosensor based on a bi-enzyme immobilized on conducting poly (thionine) film. Sensors Actuators B Chem 202:536–542

    Article  CAS  Google Scholar 

  43. Huang Y, Cui L, Xue Y, Zhang S, Zhu N, Liang J, Li G (2017) Ultrasensitive cholesterol biosensor based on enzymatic silver deposition on gold nanoparticles modified screen-printed carbon electrode. Mater Sci Eng C 77:1–8

    Article  Google Scholar 

  44. He Y, Niu X, Shi L, Zhao H, Li X, Zhang W, Pan J, Zhang X, Yan Y, Lan M (2017) Photometric determination of free cholesterol via cholesterol oxidase and carbon nanotube supported Prussian blue as a peroxidase mimic. Microchim Acta 184:2181–2189

    Article  CAS  Google Scholar 

  45. Mondal A, Jana NR (2012) Fluorescent detection of cholesterol using β-cyclodextrin functionalized graphene. Chem Commun 48:7316–7318

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank the Ministry of Science and Technology (MOST), Taiwan for financial support under grant Nos. MOST 105-2113-M-009-023-MY3 and 106-3114-E-009-012. Akhilesh Babu Ganganboina is acknowledged to the MOST, Taiwan for financial support.

Author information

Authors and Affiliations

  1. Department of Biomedical Engineering and Environmental Sciences, National Tsing Hua University, 101, Section 2, Kuang Fu Road, Hsinchu, 30013, Taiwan

    Akhilesh Babu Ganganboina & Ruey-an Doong

  2. Institute of Environmental Engineering, National Chiao Tung University, 1001 University Road, Hsinchu, 30010, Taiwan

    Ruey-an Doong

Authors
  1. Akhilesh Babu Ganganboina
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ruey-an Doong
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ruey-an Doong.

Ethics declarations

The author(s) declare that they have no competing interests.

Electronic supplementary material

ESM 1

(PDF 576 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ganganboina, A.B., Doong, Ra. Functionalized N-doped graphene quantum dots for electrochemical determination of cholesterol through host-guest inclusion. Microchim Acta 185, 526 (2018). https://doi.org/10.1007/s00604-018-3063-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-018-3063-4

Keywords

Search

Navigation