Nitrogen-Doped Durian Shell Derived Carbon Dots for Inner Filter Effect Mediated Sensing of Tetracycline and Fluorescent Ink

  • Supuli Jayaweera
  • Ke Yin
  • Wun Jern NgEmail author


Photoluminescent carbon dots have gained increasing attention in recent years due to their unique optical properties. Herein, a facile one-pot hydrothermal process is used to develop nitrogen-doped carbon dots (NCDs) with durian shell waste as the precursor and Tris base as the doping agent. The synthesized NCDs showed a quantum yield of 12.93% with a blue fluorescence under UV-light irradiation and maximum emission at 414 nm at an excitation wavelength of 340 nm. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy showed the presence of nitrogen and oxygen functional groups on the NCD surface. The particles were quasi-spherical with an average particle diameter of 6.5 nm. The synthesized NCDs were resistant to photobleaching and stable under a wide range of pH but were negatively affected by increasing temperature. NCDs showed high selectivity to Tetracycline as the fluorescence of NCDs was quenched significantly by Tetracycline as a result of the inner filter effect. Based on sensitivity experiments, a linear relationship (R2 = 0.989) was developed over a concentration range of 0–30 μM with a detection limit of 75 nM (S/N = 3). The linear model was validated with two water samples (lake water and tap water) with relative recoveries of 98.6–108.5% and an RSD of <3.5%.


Carbon dots Durian shell waste Nitrogen doping Fluorescent ink Tetracycline detection 



The authors would like to thank Interdisciplinary Graduate school of Nanyang Technological University and Nanyang Environment & Water Research Institute for the financial support extended to this study. We would like to acknowledge the Facility for Analysis, Characterization, Testing and Simulation, Nanyang Technological University, Singapore, for use of their transmission electron microscopy facilities.

Compliance with Ethical Standards

Conflicts of Interest



  1. 1.
    Rooj B, Dutta A, Islam S, Mandal U (2018) Green synthesized carbon quantum dots from Polianthes tuberose L. petals for copper (II) and iron (II) detection. J Fluoresc 28(5):1261–1267Google Scholar
  2. 2.
    Shen J, Shang S, Chen X, Wang D, Cai Y (2017) Highly fluorescent N, S-co-doped carbon dots and their potential applications as antioxidants and sensitive probes for Cr (VI) detection. Sensors Actuators B Chem 248:92–100CrossRefGoogle Scholar
  3. 3.
    Liu X-J, Guo M-L, Yin X-Y, Huang J (2013) A simple route to prepare carbonaceous nanospheres from bagasse. Mater Lett 106:30–32CrossRefGoogle Scholar
  4. 4.
    Gedda G, Lee C-Y, Lin Y-C, Wu H-f (2016) Green synthesis of carbon dots from prawn shells for highly selective and sensitive detection of copper ions. Sensors Actuators B Chem 224:396–403CrossRefGoogle Scholar
  5. 5.
    Shi J, Ni G, Tu J, Jin X, Peng J (2017) Green synthesis of fluorescent carbon dots for sensitive detection of Fe 2+ and hydrogen peroxide. J Nanopart Res 19(6):209CrossRefGoogle Scholar
  6. 6.
    Chang MMF, Ginjom IR, Ngu-Schwemlein M, Ng SM (2016) Synthesis of yellow fluorescent carbon dots and their application to the determination of chromium (III) with selectivity improved by pH tuning. Microchim Acta 183(6):1899–1907CrossRefGoogle Scholar
  7. 7.
    Shi Y, Pan Y, Zhang H, Zhang Z, Li M-J, Yi C, Yang M (2014) A dual-mode nanosensor based on carbon quantum dots and gold nanoparticles for discriminative detection of glutathione in human plasma. Biosens Bioelectron 56:39–45CrossRefGoogle Scholar
  8. 8.
    Dai H, Shi Y, Wang Y, Sun Y, Hu J, Ni P, Li Z (2014) A carbon dot based biosensor for melamine detection by fluorescence resonance energy transfer. Sensors Actuators B Chem 202:201–208CrossRefGoogle Scholar
  9. 9.
    Bharathi D, Siddlingeshwar B, Krishna RH, Singh V, Kottam N, Divakar DD, Alkheraif AA (2018) Green and cost effective synthesis of fluorescent carbon quantum dots for dopamine detection. J Fluoresc 28(2):573–579CrossRefGoogle Scholar
  10. 10.
    Hua J, Jiao Y, Wang M, Yang Y (2018) Determination of norfloxacin or ciprofloxacin by carbon dots fluorescence enhancement using magnetic nanoparticles as adsorbent. Microchim Acta 185(2):137CrossRefGoogle Scholar
  11. 11.
    Niu J, Gao H (2014) Synthesis and drug detection performance of nitrogen-doped carbon dots. J Lumin 149:159–162CrossRefGoogle Scholar
  12. 12.
    Gullberg E, Cao S, Berg OG, Ilbäck C, Sandegren L, Hughes D, Andersson DI (2011) Selection of resistant bacteria at very low antibiotic concentrations. PLoS Pathog 7(7):e1002158CrossRefGoogle Scholar
  13. 13.
    de Marco BA, Natori JSH, Fanelli S, Tótoli EG, Salgado HRN (2017) Characteristics, properties and analytical methods of amoxicillin: a review with green approach. Crit Rev Anal Chem 47(3):267–277CrossRefGoogle Scholar
  14. 14.
    Foo K, Hameed B (2011) Transformation of durian biomass into a highly valuable end commodity: trends and opportunities. Biomass Bioenergy 35(7):2470–2478CrossRefGoogle Scholar
  15. 15.
    Foo K, Hameed B (2012) Textural porosity, surface chemistry and adsorptive properties of durian shell derived activated carbon prepared by microwave assisted NaOH activation. Chem Eng J 187:53–62CrossRefGoogle Scholar
  16. 16.
    Tan Y, Abdullah A, Hameed B (2017) Fast pyrolysis of durian (Durio zibethinus L) shell in a drop-type fixed bed reactor: pyrolysis behavior and product analyses. Bioresour Technol 243:85–92CrossRefGoogle Scholar
  17. 17.
    Jayaweera S, Yin K, Hu X, Ng WJ (2018) Facile preparation of fluorescent carbon dots for label-free detection of Fe3+. J Photochem Photobiol A Chem 370:156–163Google Scholar
  18. 18.
    Wang T, Zhai Y, Zhu Y, Li C, Zeng G (2018) A review of the hydrothermal carbonization of biomass waste for hydrochar formation: process conditions, fundamentals, and physicochemical properties. Renew Sust Energ Rev 90:223–247CrossRefGoogle Scholar
  19. 19.
    Jelinek R (2017) Carbon-dot synthesis. In: Carbon quantum dots synthesis, properties and applications (pp. 5–27). Springer International Publishing.
  20. 20.
    Sahu S, Behera B, Maiti TK, Mohapatra S (2012) Simple one-step synthesis of highly luminescent carbon dots from orange juice: application as excellent bio-imaging agents. Chem Commun 48(70):8835–8837CrossRefGoogle Scholar
  21. 21.
    Loo AH, Sofer Z, Bouša D, Ulbrich P, Bonanni A, Pumera M (2016) Carboxylic carbon quantum dots as a fluorescent sensing platform for DNA detection. ACS Appl Mater Interfaces 8(3):1951–1957CrossRefGoogle Scholar
  22. 22.
    Wu ZL, Zhang P, Gao MX, Liu CF, Wang W, Leng F, Huang CZ (2013) One-pot hydrothermal synthesis of highly luminescent nitrogen-doped amphoteric carbon dots for bioimaging from Bombyx mori silk–natural proteins. J Mater Chem B 1(22):2868–2873CrossRefGoogle Scholar
  23. 23.
    Jalalian SH, Taghdisi SM, Danesh NM, Bakhtiari H, Lavaee P, Ramezani M, Abnous K (2015) Sensitive and fast detection of tetracycline using an aptasensor. Anal Methods 7(6):2523–2528CrossRefGoogle Scholar
  24. 24.
    Brouwer AM (2011) Standards for photoluminescence quantum yield measurements in solution (IUPAC Technical Report). Pure Appl Chem 83(12):2213–2228CrossRefGoogle Scholar
  25. 25.
    Adedokun O, Roy A, Awodugba AO, Devi PS (2017) Fluorescent carbon nanoparticles from Citrus sinensis as efficient sorbents for pollutant dyes. Luminescence 32(1):62–70CrossRefGoogle Scholar
  26. 26.
    Hsu P-C, Chang H-T (2012) Synthesis of high-quality carbon nanodots from hydrophilic compounds: role of functional groups. Chem Commun 48(33):3984–3986CrossRefGoogle Scholar
  27. 27.
    Edison TNJI, Atchudan R, Shim J-J, Kalimuthu S, Ahn B-C, Lee YR (2016) Turn-off fluorescence sensor for the detection of ferric ion in water using green synthesized N-doped carbon dots and its bio-imaging. J Photochem Photobiol B Biol 158:235–242CrossRefGoogle Scholar
  28. 28.
    Xu H, Xie L, Hakkarainen M (2017) Coffee-ground-derived quantum dots for aqueous processable nanoporous graphene membranes. ACS Sustain Chem Eng 5(6):5360–5367CrossRefGoogle Scholar
  29. 29.
    Mewada A, Pandey S, Shinde S, Mishra N, Oza G, Thakur M, Sharon M, Sharon M (2013) Green synthesis of biocompatible carbon dots using aqueous extract of Trapa bispinosa peel. Mater Sci Eng C 33(5):2914–2917CrossRefGoogle Scholar
  30. 30.
    Ye Q, Yan F, Luo Y, Wang Y, Zhou X, Chen L (2017) Formation of N, S-codoped fluorescent carbon dots from biomass and their application for the selective detection of mercury and iron ion. Spectrochim Acta A Mol Biomol Spectrosc 173:854–862CrossRefGoogle Scholar
  31. 31.
    Zhang H, Kang S, Wang G, Zhang Y, Zhao H (2016) Fluorescence determination of nitrite in water using prawn-shell derived nitrogen-doped carbon nanodots as fluorophores. ACS Sensors 1(7):875–881CrossRefGoogle Scholar
  32. 32.
    Desimoni E, Brunetti B (2015) X-ray photoelectron spectroscopic characterization of chemically modified electrodes used as chemical sensors and biosensors: a review. Chemosensors 3(2):70–117CrossRefGoogle Scholar
  33. 33.
    De B, Karak N (2013) A green and facile approach for the synthesis of water soluble fluorescent carbon dots from banana juice. RSC Adv 3(22):8286–8290CrossRefGoogle Scholar
  34. 34.
    Wang Y, Hu A (2014) Carbon quantum dots: synthesis, properties and applications. J Mater Chem C 2(34):6921–6939CrossRefGoogle Scholar
  35. 35.
    Zhang J-H, Niu A, Li J, Fu J-W, Xu Q, Pei D-S (2016) In vivo characterization of hair and skin derived carbon quantum dots with high quantum yield as long-term bioprobes in zebrafish. Sci Rep 6:37860CrossRefGoogle Scholar
  36. 36.
    Yang R, Guo X, Jia L, Zhang Y, Zhao Z, Lonshakov F (2017) Green preparation of carbon dots with mangosteen pulp for the selective detection of Fe3+ ions and cell imaging. Appl Surf Sci 423:426–432CrossRefGoogle Scholar
  37. 37.
    Li H, He X, Kang Z, Huang H, Liu Y, Liu J, Lian S, Tsang CHA, Yang X, Lee ST (2010) Water-soluble fluorescent carbon quantum dots and photocatalyst design. Angew Chem Int Ed 49(26):4430–4434CrossRefGoogle Scholar
  38. 38.
    Meiling TT, Cywiński PJ, Bald I (2016) White carbon: fluorescent carbon nanoparticles with tunable quantum yield in a reproducible green synthesis. Sci Rep 6:28557CrossRefGoogle Scholar
  39. 39.
    Su Z, Ye H, Xiong Z, Lou Q, Zhang Z, Tang F, Tang J, Dai J, Shan C, Xu S (2018) Understanding and manipulating luminescence in carbon nanodots. Carbon 126:58–64CrossRefGoogle Scholar
  40. 40.
    Baker SN, Baker GA (2010) Luminescent carbon nanodots: emergent nanolights. Angew Chem Int Ed 49(38):6726–6744CrossRefGoogle Scholar
  41. 41.
    Sun D, Ban R, Zhang P-H, Wu G-H, Zhang J-R, Zhu J-J (2013) Hair fiber as a precursor for synthesizing of sulfur-and nitrogen-co-doped carbon dots with tunable luminescence properties. Carbon 64:424–434CrossRefGoogle Scholar
  42. 42.
    Yu P, Wen X, Toh Y-R, Tang J (2012) Temperature-dependent fluorescence in carbon dots. J Phys Chem C 116(48):25552–25557CrossRefGoogle Scholar
  43. 43.
    Liu ML, Chen BB, Yang T, Wang J, Liu XD, Huang CZ (2017) One-pot carbonization synthesis of europium-doped carbon quantum dots for highly selective detection of tetracycline. Methods Appl Fluoresc 5(1):015003CrossRefGoogle Scholar
  44. 44.
    Lin M, Zou HY, Yang T, Liu ZX, Liu H, Huang CZ (2016) An inner filter effect based sensor of tetracycline hydrochloride as developed by loading photoluminescent carbon nanodots in the electrospun nanofibers. Nanoscale 8(5):2999–3007CrossRefGoogle Scholar
  45. 45.
    Hou J, Li H, Wang L, Zhang P, Zhou T, Ding H, Ding L (2016) Rapid microwave-assisted synthesis of molecularly imprinted polymers on carbon quantum dots for fluorescent sensing of tetracycline in milk. Talanta 146:34–40CrossRefGoogle Scholar
  46. 46.
    Yang J, Lin Z-Z, Nur A-Z, Lu Y, Wu M-H, Zeng J, Chen X-M, Huang Z-Y (2018) Detection of trace tetracycline in fish via synchronous fluorescence quenching with carbon quantum dots coated with molecularly imprinted silica. Spectrochim Acta A Mol Biomol Spectrosc 190:450–456CrossRefGoogle Scholar
  47. 47.
    Gao C, Liu Z, Chen J, Yan Z (2013) A novel fluorescent assay for oxytetracycline hydrochloride based on fluorescence quenching of water-soluble CdTe nanocrystals. Luminescence 28(3):378–383CrossRefGoogle Scholar
  48. 48.
    Zhou Z, Lu K, Wei X, Hao T, Xu Y, Lv X, Zhang Y (2016) A mesoporous fluorescent sensor based on ZnO nanorods for the fluorescent detection and selective recognition of tetracycline. RSC Adv 6(75):71061–71069CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Nanyang Environment & Water Research Institute and Interdisciplinary Graduate SchoolNanyang Technological UniversitySingaporeSingapore
  2. 2.Residues & Resource Reclamation Centre, Nanyang Environment & Water Research InstituteNanyang Technological UniversitySingaporeSingapore
  3. 3.Department of Environmental Engineering, School of Biology and the EnvironmentNanjing Forestry UniversityNanjingChina
  4. 4.Environmental Bio-innovations Group (EBiG), School of Civil and Environmental EngineeringNanyang Technological UniversitySingaporeSingapore

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