Microchimica Acta

, 186:788 | Cite as

Cysteamine-capped gold-copper nanoclusters for fluorometric determination and imaging of chromium(VI) and dopamine

  • Muthaiah Shellaiah
  • Turibius Simon
  • Natesan Thirumalaivasan
  • Kien Wen SunEmail author
  • Fu-Hsiang Ko
  • Shu-Pao Wu
Original Paper


Highly emissive cysteamine-capped gold-copper bimetallic nanoclusters (CA-AuCu NCs) with a quantum yield of 18% were synthesized via one-pot anti-galvanic reduction. The CA-AuCu NCs were characterized by HR-TEM, XPS, FTIR, MALDI-TOF mass spectrometry, DLS, and zeta potential analyses. The NCs are shown to be viable fluorescent probes for Cr(VI) ions and dopamine (DA) via quenching of the blue fluorescence, typically measured at excitation/emission wavelengths of 350/436 nm. During DA recognition, a dark brown color appears, which is distinguishable from that of Cr(VI) detection. The aggregation induced quenching due to electron transfer was demonstrated by photoluminescence, HR-TEM, FTIR, DLS, and zeta potential interrogations. In buffer of pH 7, response is linear in the 0.2 ~ 100 μM for Cr(VI) and from 0.4 ~ 250 μM for DA. The respective detection limits are 80 and 135 nM. The method was applied to the determination of both Cr(VI) and DA in (spiked) tap, lake and sea water, and in human urine samples. The low toxicity of CA-AuCu NCs was validated by the MTT assay, and their responses to Cr(VI) ions and DA was also proven by Raw 264.7 cell imaging.

Graphical abstract

Cysteamine capped Au-Cu nanoclusters (CA-AuCu NCs) were synthesized via one-pot anti-galvanic reduction and utilized in sensing of Cr(VI) ions and dopamine (DA) with demonstrated real/urine and cell imaging applications.


Au-cu alloy Neurotransmitter Cr(VI) detection Colorimetric sensor Particle aggregation Static quenching Nanomolar detection Cell imaging Spiked urine investigation Real analysis 



The authors are grateful to the Ministry of Science and Technology of Taiwan for financially supporting this research under the contract MOST 107-2811-M-009-015 and MOST 105-2112-M-009-005-MY3.

Compliance with ethical standards

Conflicts of interest

Diluted spiked urine samples used in this study are remnants of our earlier reports and not clinical/collected from any volunteer. The cell lines were provided by the Food Industry Research and Development Institute (Taiwan). The author(s) declare that they have no competing interests.

Supplementary material

604_2019_3974_MOESM1_ESM.pdf (3.8 mb)
ESM 1 (PDF 3865 kb)


  1. 1.
    Zhang H-Y, Wang Y, Xiao S, Wang H, Wang J-H, Feng L (2017) Rapid detection of Cr(VI) ions based on cobalt(II)-doped carbon dots. Biosens Bioelectron 87:46–52CrossRefGoogle Scholar
  2. 2.
    Song J, Zhou H, Gao R, Zhang Y, Zhang H, Zhang Y, Wang G, Wong PK, Zhao H (2018) Selective determination of Cr(VI) by Glutaraldehyde cross-linked chitosan polymer Fluorophores. ACS Sens 3:792–798CrossRefGoogle Scholar
  3. 3.
    Rasheed PA, Lee J-S (2017) Recent advances in optical detection of dopamine using nanomaterials. Microchim Acta 184:1239–1266CrossRefGoogle Scholar
  4. 4.
    Zhang X, Liu W, Li X, Zhang Z, Shan D, Xia H, Zhang S, Lu X (2018) Ultrahigh selective colorimetric quantification of chromium(VI) ions based on gold amalgam catalyst Oxidoreductase-like activity in water. Anal Chem 90:14309–14315CrossRefGoogle Scholar
  5. 5.
    Gualandi I, Tonelli D, Mariani F, Scavetta E, Marzocchi M, Fraboni B (2016) Selective detection of dopamine with an all PEDOT:PSS organic electrochemical transistor. Sci Rep 6:35419CrossRefGoogle Scholar
  6. 6.
    Patriarchi T, Cho JR, Merten K, Howe MW, Marley A, Xiong W-H, Folk RW, Broussard GJ, Liang R, Jang MJ, Zhong H, Dombeck D, Zastrow MV, Nimmerjahn A, Gradinaru V, Williams JT, Tian L (2018) Ultrafast neuronal imaging of dopamine dynamics with designed genetically encoded sensors. Science 360:eaat4422CrossRefGoogle Scholar
  7. 7.
    Gómez V, Callao MP (2006) Chromium determination and speciation since 2000. TrAC Trends Anal Chem 25:1006–1015CrossRefGoogle Scholar
  8. 8.
    Unceta N, Séby F, Malherbe J, Donard OFX (2010) Chromium speciation in solid matrices and regulation: a review. Analy Bioana Chem 397:1097–1111CrossRefGoogle Scholar
  9. 9.
    Perry M, Li Q, Kennedy RT (2009) Review of recent advances in analytical techniques for the determination of neurotransmitters. Anal Chim Acta 653:1–22CrossRefGoogle Scholar
  10. 10.
    van Staden JF, van Staden RIS (2012) Flow-injection analysis systems with different detection devices and other related techniques for the in vitro and in vivo determination of dopamine as neurotransmitter. A review. Talanta 102:34–43CrossRefGoogle Scholar
  11. 11.
    Wu D, Sedgwick AC, Gunnlaugsson T, Akkaya EU, Yoon J, James TD (2017) Fluorescent chemosensors: the past, present and future. Chem Soc Rev 46:7105–7123CrossRefGoogle Scholar
  12. 12.
    Ma Y, Chen Y, Liu J, Han Y, Ma S, Chen X (2018) Ratiometric fluorescent detection of chromium(VI) in real samples based on dual emissive carbon dots. Talanta 185:249–257CrossRefGoogle Scholar
  13. 13.
    Jiang Y, Wang B, Meng F, Cheng Y, Zhu C (2015) Microwave-assisted preparation of N-doped carbon dots as a biosensor for electrochemical dopamine detection. J Colloid Interface Sci 452:199–202CrossRefGoogle Scholar
  14. 14.
    Xu W, Yu L, Xu H, Zhang S, Xu W, Lin Y, Zhu X (2019) Water-dispersed silicon quantum dots for on-off-on fluorometric determination of chromium(VI) and ascorbic acid. Microchim Acta 186:673CrossRefGoogle Scholar
  15. 15.
    Liu S, Shi F, Zhao X, Chen L, Su X (2013) 3-Aminophenyl boronic acid-functionalized CuInS2 quantum dots as a near-infrared fluorescence probe for the determination of dopamine. Biosens Bioelectron 47:379–384CrossRefGoogle Scholar
  16. 16.
    Zhang JR, Zeng AL, Luo HQ, Li NB (2016) Fluorescent silver nanoclusters for ultrasensitive determination of chromium(VI) in aqueous solution. J Hazard Mater 304:66–72CrossRefGoogle Scholar
  17. 17.
    Qu F, Liu Y, Kong R, You J (2017) A versatile DNA detection scheme based on the quenching of fluorescent silver nanoclusters by MoS2 nanosheets: application to aptamer-based determination of hepatitis B virus and of dopamine. Microchim Acta 184:4417–4424CrossRefGoogle Scholar
  18. 18.
    Mutuyimana FP, Liu J, Nsanzamahoro S, Na M, Chen H, Chen X (2019) Yellow-emissive carbon dots as a fluorescent probe for chromium(VI). Microchim Acta 186:163CrossRefGoogle Scholar
  19. 19.
    Cui M, Wang C, Yang D, Song Q (2017) Fluorescent iridium nanoclusters for selective determination of chromium(VI). Microchim Acta 185:8CrossRefGoogle Scholar
  20. 20.
    Liu X, Zhang W, Huang L, Hu N, Liu W, Liu Y, Li S, Yang C, Suo Y, Wang J (2018) Fluorometric determination of dopamine by using molybdenum disulfide quantum dots. Microchim Acta 185:234CrossRefGoogle Scholar
  21. 21.
    Shellaiah M, Sun KW (2017) Luminescent metal Nanoclusters for potential Chemosensor applications. Chemosensors 5:36CrossRefGoogle Scholar
  22. 22.
    Kang H, Kim B-G, Na HB, Hwang S (2015) Anti-galvanic reduction of silver ion on gold and its role in anisotropic growth of gold Nanomaterials. J Phys Chem C 119:25974–25982CrossRefGoogle Scholar
  23. 23.
    Sun J, Wu H, Jin Y (2014) Synthesis of thiolated Ag/au bimetallic nanoclusters exhibiting an anti-galvanic reduction mechanism and composition-dependent fluorescence. Nanoscale 6:5449–5457CrossRefGoogle Scholar
  24. 24.
    Bao Z, Zhang K, Jian J, Hu Z, Yuan K, Shao H, Peng K, Jiang Z, Zapien JA, Yan Y, Zhang C, Zhou H (2018) Strongly fluorescent cysteamine-coated copper nanoclusters as a fluorescent probe for determination of picric acid. Microchim Acta 185:507CrossRefGoogle Scholar
  25. 25.
    Shellaiah M, Simon T, Venkatesan P, Sun KW, Ko F-H, Wu S-P (2017) Nanodiamonds conjugated to gold nanoparticles for colorimetric detection of clenbuterol and chromium(III) in urine. Microchim Acta 185:74CrossRefGoogle Scholar
  26. 26.
    Zhang X, Zhao H, Xue Y, Wu Z, Zhang Y, He Y, Li X, Yuan Z (2012) Colorimetric sensing of clenbuterol using gold nanoparticles in the presence of melamine. Biosens Bioelectron 34:112–117CrossRefGoogle Scholar
  27. 27.
    Pakiari AH, Jamshidi Z (2010) Nature and strength of M−S bonds (M = au, Ag, and cu) in binary alloy gold clusters. J Phys Chem A 114:9212–9221CrossRefGoogle Scholar
  28. 28.
    Wilcoxon JP, Abrams BL (2006) Synthesis, structure and properties of metal nanoclusters. Chem Soc Rev 35:1162–1194CrossRefGoogle Scholar
  29. 29.
    Liu M, Zhou W, Wang T, Wang D, Liu L, Ye J (2016) High performance au–cu alloy for enhanced visible-light water splitting driven by coinage metals. Chem Commun 52:4694–4697CrossRefGoogle Scholar
  30. 30.
    Yang X, Feng Y, Zhu S, Luo Y, Zhuo Y, Dou Y (2014) One-step synthesis and applications of fluorescent cu nanoclusters stabilized by l-cysteine in aqueous solution. Anal Chim Acta 847:49–54CrossRefGoogle Scholar
  31. 31.
    Goswami N, Giri A, Bootharaju MS, Xavier PL, Pradeep T, Pal SK (2011) Copper quantum clusters in protein matrix: potential sensor of Pb2+ ion. Anal Chem 83:9676–9680CrossRefGoogle Scholar
  32. 32.
    Das NK, Ghosh S, Priya A, Datta S, Mukherjee S (2015) Luminescent copper Nanoclusters as a specific cell-imaging probe and a selective metal ion sensor. J Phys Chem C 119:24657–24664CrossRefGoogle Scholar
  33. 33.
    Noh M, Kim T, Lee H, Kim C-K, Joo S-W, Lee K (2010) Fluorescence quenching caused by aggregation of water-soluble CdSe quantum dots. Colloids Surf A Physicochem Eng Asp 359:39–44CrossRefGoogle Scholar
  34. 34.
    Govindaraju S, Ankireddy SR, Viswanath B, Kim J, Yun K (2017) Fluorescent gold Nanoclusters for selective detection of dopamine in cerebrospinal fluid. Sci Rep 7:40298CrossRefGoogle Scholar
  35. 35.
    Song X-R, Goswami N, Yang H-H, Xie J (2016) Functionalization of metal nanoclusters for biomedical applications. Analyst 141:3126–3140CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Muthaiah Shellaiah
    • 1
  • Turibius Simon
    • 2
  • Natesan Thirumalaivasan
    • 1
  • Kien Wen Sun
    • 1
    Email author
  • Fu-Hsiang Ko
    • 2
  • Shu-Pao Wu
    • 1
  1. 1.Department of Applied ChemistryNational Chiao Tung UniversityHsinchuTaiwan
  2. 2.Department of Materials Science and EngineeringNational Chiao Tung UniversityHsinchuTaiwan

Personalised recommendations