Advertisement

Microchimica Acta

, 185:294 | Cite as

Polyethyleneimine capped bimetallic Au/Pt nanoclusters are a viable fluorescent probe for specific recognition of chlortetracycline among other tetracycline antibiotics

  • Na Xu
  • Lei Meng
  • Hong-Wei Li
  • Da-Yong Lu
  • Yuqing Wu
Original Paper

Abstract

A highly selective method has been developed for the fluorometric determination of chlortetracycline (CTC) among other tetracycline antibiotics (TCs). It is making use of fluorescent Au/Pt nanoclusters (NCs) capped with polyethyleneimine (Au/PtNCs@PEI). The nanoprobe, with a green emission peaking at 512 nm, was synthesized by an environmentally friendly hydrothermal method. The capped NCs have a large Stokes shift (∼150 nm), are insensitive to extreme pH values and high ionic strength, and are excellently photostable under UV irradiation. In the presence of CTC, the fluorescence of the capped NCs is quenched due to aggregation. The effect is also found for tetracycline, oxytetracycline and doxycycline. This shows that sensitive but non-selective detection of such TCs is possible. However, CTC is specifically complexed by Al(III) ions, and this generates a strong fluorescence peaking at 520 nm even though the fluorescence of the capped NCs is fully quenched. Obviously, the effects are caused by CTC only, and this enables CTC to be specifically recognized by an “on-off-on” strategy. Fluorescence increases linearly in the 0.5 to 10 μM CTC concentration range, and the limit of detection is 0.35 μM. The method was successfully applied to the determination of CTC in (spiked) milk, and the recoveries suggest that this fluorescent probe is an effective tool for detecting CTC in foodstuff.

Graphical abstract

Schematic illustration and photographic images of the luminescence quenching response of Au/Pt nanoclusters (Au/PtNCs) toward chlortetracycline (CTC) (from on to off), and then the recovery upon Al3+ addition (from off to on).

Keywords

Alloy metallic nanoclusters Core-shall structure Hydrothermal method Aluminium ion On-off-on strategy 

Notes

Acknowledgments

The financial support from the projects of NSFC (Nos. 21373101, 21003061 and 91027027) and the State Key Laboratory of Supramolecular Structure and Materials, Jilin University are appreciated greatly.

Compliance with ethical standards

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

Supplementary material

604_2018_2828_MOESM1_ESM.docx (12.6 mb)
ESM 1 (DOCX 12905 kb)

References

  1. 1.
    Fritsche TR, Strabala PA, Sader HS, Dowzicky MJ, Jones RN (2005) Activity of tigecycline tested against a global collection of Enterobacteriaceae, including tetracycline-resistant isolates. Diagn Microbiol Infec Dis 52:209CrossRefGoogle Scholar
  2. 2.
    Rodriguez JA, Espinosa J, Aguilar-Arteaga K, Ibarra IS, Miranda JM (2010) Determination of tetracyclines in milk samples by magnetic solid phase extraction flow injection analysis. Microchim Acta 171:407CrossRefGoogle Scholar
  3. 3.
    Feng Y, Zhong D, Miao H, Yang X (2015) Carbon dots derived from rose flowers for tetracycline sensing. Talanta 140:128CrossRefPubMedGoogle Scholar
  4. 4.
    Wang P, Wu TH, Zhang Y (2016) Novel silver nanoparticle-enhanced fluorometric determination of trace tetracyclines in aqueous solutions. Talanta 146:175CrossRefPubMedGoogle Scholar
  5. 5.
    Yang Y, Niu H, Zhang H (2016) Direct and highly selective drug Optosensing in real, undiluted biological samples with quantum-dot-labeled hydrophilic molecularly imprinted polymer microparticles. ACS Appl Mater Interfaces 8:15741CrossRefPubMedGoogle Scholar
  6. 6.
    Liu B, Zhang B, Chen G, Tang D (2014) Biotin-avidin-conjugated metal sulfide nanoclusters for simultaneous electrochemical immunoassay of tetracycline and chloramphenicol. Microchim Acta 181:257CrossRefGoogle Scholar
  7. 7.
    Zhan X, Hu G, Wagberg T, Zhan S, Xu H, Zhou P (2016) Electrochemical aptasensor for tetracycline using a screen-printed carbon electrode modified with an alginate film containing reduced graphene oxide and magnetite (Fe3O4) nanoparticles. Microchim Acta 183:723CrossRefGoogle Scholar
  8. 8.
    Qu F, Sun Z, Liu D, Zhao X, You J (2016) Direct and indirect fluorescent detection of tetracyclines using dually emitting carbon dots. Microchim Acta 183:2547CrossRefGoogle Scholar
  9. 9.
    Yang K, Wang S, Wang Y, Miao H, Yang X (2017) Dual-channel probe of carbon dots cooperating with gold nanoclusters employed for assaying multiple targets. Biosens Bioelectron 91:566CrossRefPubMedGoogle Scholar
  10. 10.
    Xu N, Yuan Y, Yin JH, Wang X, Meng L (2017) One-pot hydrothermal synthesis of luminescent silicon-based nanoparticles for highly specific detection of oxytetracycline via ratiometric fluorescent strategy. RSC Adv (76):48429Google Scholar
  11. 11.
    Xie J, Zheng Y, Ying JY (2009) Protein-directed synthesis of highly fluorescent gold nanoclusters. J Am Chem Soc 131:888CrossRefPubMedGoogle Scholar
  12. 12.
    Xu N, Li HW, Yue Y, Wu Y (2016) Synthesis of bovine serum albumin-protected high fluorescence Pt16-nanoclusters and their application to detect sulfide ions in solutions. Nanotechnology 27:425602CrossRefPubMedGoogle Scholar
  13. 13.
    Xu N, Li HW, Wu Y (2017) Hydrothermal synthesis of polyethylenimine-protected high luminescent Pt-nanoclusters and their application to the detection of nitroimidazoles. Anal Chim Acta 958:51CrossRefPubMedGoogle Scholar
  14. 14.
    Dou X, Yuan X, Yu Y, Luo Z, Yao Q, Leong DT, Xie J (2014) Lighting up thiolated Au@Ag nanoclusters via aggregation-induced emission. Nano 6:157Google Scholar
  15. 15.
    Ataee-Esfahani H, Wang L, Nemoto Y, Yamauchi Y (2010) Synthesis of bimetallic Au@Pt nanoparticles with Au Core and nanostructured Pt Shell toward highly active Electrocatalysts. Chem Mater 22:6310CrossRefGoogle Scholar
  16. 16.
    Zheng C, Zheng AX, Liu B, Zhang XL, He Y, Li J, Yang HH, Chen G (2014) One-pot synthesized DNA-templated ag/Pt bimetallic nanoclusters as peroxidase mimics for colorimetric detection of thrombin. Chem Commun 50:13103CrossRefGoogle Scholar
  17. 17.
    Wang S, Meng X, Das A, Li T, Song Y, Cao T, Zhu X, Zhu M, Jin R (2014) A 200-fold quantum yield boost in the photoluminescence of silver-doped AgxAu25−x nanoclusters: the 13 th silver atom matters. Angew Chem Int Ed 53:2376CrossRefGoogle Scholar
  18. 18.
    Lei Z, Pei XL, Jiang ZG, Wang QM (2014) Cluster linker approach: preparation of a luminescent porous framework with NbO topology by linking silver ions with gold(I) clusters. Angew Chem Int Ed 53:12771CrossRefGoogle Scholar
  19. 19.
    Soldan G, Aljuhani MA, Bootharaju MS, AbdulHalim LG, Parida MR, Emwas AH, Mohammed OF, Bakr OM (2016) Gold doping of silver nanoclusters: a 26-fold enhancement in the luminescence quantum yield. Angew Chem Int Ed 128:5843CrossRefGoogle Scholar
  20. 20.
    Yan J, Su H, Yang H, Malola S, Lin S, Häkkinen H, Zheng N (2015) Total structure and electronic structure analysis of doped Thiolated silver MAg24(SR)18 2− (M = Pd, Pt) clusters. J Am Chem Soc 137:11880CrossRefPubMedGoogle Scholar
  21. 21.
    Suntivich J, Xu Z, Carlton CE, Kim J, Han B, Lee SW, Bonnet N, Marzari N, Allard LF, Gasteiger HA, Hamad-Schifferli K, Shao-Horn Y (2013) Surface composition tuning of Au–Pt bimetallic nanoparticles for enhanced carbon monoxide and methanol electro-oxidation. J Am Chem Soc 135:7985CrossRefPubMedGoogle Scholar
  22. 22.
    Zhang H, Toshima N (2013) Synthesis of Au/Pt bimetallic nanoparticles with a Pt-rich shell and their high catalytic activities for aerobic glucose oxidation. J Colloid Interface Sci 394:166CrossRefPubMedGoogle Scholar
  23. 23.
    Guo S, Li J, Dong S, Wang E (2010) Three-dimensional Pt-on-Au bimetallic dendritic nanoparticle: one-step, high-yield synthesis and its bifunctional Plasmonic and catalytic properties. J Phys Chem C 114:15337CrossRefGoogle Scholar
  24. 24.
    Kim Y, Hong JW, Lee YW, Kim M, Kim D, Yun WS, Han SW (2010) Synthesis of AuPt Heteronanostructures with enhanced Electrocatalytic activity toward oxygen reduction. Angew Chem Int Ed 122:10395CrossRefGoogle Scholar
  25. 25.
    Landry AM, Iglesia E (2016) Synthesis of bimetallic AuPt clusters with clean surfaces via sequential displacement-reduction processes. Chem Mater 28:5872CrossRefGoogle Scholar
  26. 26.
    Luo Y, Xu J, Li Y, Gao H, Guo J, Shen F, Sun C (2015) A novel colorimetric aptasensor using cysteamine-stabilized gold nanoparticles as probe for rapid and specific detection of tetracycline in raw milk. Food Control 54:7CrossRefGoogle Scholar
  27. 27.
    Peng X, Song F, Lu E, Wang Y, Zhou W, Fan J, Gao Y (2005) Heptamethine cyanine dyes with a large stokes shift and strong fluorescence: a paradigm for excited-state intramolecular charge transfer. J Am Chem Soc 127:4170CrossRefPubMedGoogle Scholar
  28. 28.
    Zhang H, Wang L, Lu L, Toshima N (2016) Preparation and catalytic activity for aerobic glucose oxidation of crown Jewel structured Pt/Au bimetallic nanoclusters. Sci Rep-UK 6:30752CrossRefGoogle Scholar
  29. 29.
    Guidi LR, Santos FA, Ribeiro ACSR, Fernandes C, Silva LHM, Gloria MBA (2017) A simple, fast and sensitive screening lc-esi-ms/ms method for antibiotics in fish. Talanta 163:85CrossRefPubMedGoogle Scholar
  30. 30.
    Chang WB, Zhao YB, Ci YX, Hu LY (1992) Fluorimetric determination of tetracycline and anhydrotetracycline. Fresenius J Anal Chem 344:128CrossRefGoogle Scholar
  31. 31.
    Hall D (1976) Fluorimetric assay of tetracycline mixtures. J Pharm Pharmacol 28:420CrossRefPubMedGoogle Scholar
  32. 32.
    Brust M, Walker M, Bethell D, Schiffrin DJ, Whyman R (1994) Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system. J Am Chem Soc Chem Commun (7):801Google Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical ChemistryJilin UniversityChangchunChina
  2. 2.College of Materials Science and EngineeringJilin Institute of Chemical TechnologyJilinChina

Personalised recommendations