Skip to main content
Log in

11-Mercaptoundecanoic acid capped gold nanoclusters with unusual aggregation-enhanced emission for selective fluorometric hydrogen sulfide determination

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

Abstract

In present study, we discovered unusual solvent-mediated aggregation-enhanced emission (AEE) character of 11-mercaptoundecanoic acid capped gold nanoclusters (MUA-Au NCs). When aggregated in aqueous media, the MUA-Au NCs showed strong emission, which was weakened by adding ethanol. Interestingly, the suppressed emission was selectively enhanced in the presence of hydrogen sulfide (H2S) because H2S was absorbed onto Au NCs through the strong sulfur-gold bonding affinity. The hydrolyzed H2S, namely, HS, made the Au NCs negatively charged, which aggregated again due to decreased solubility. The H2S-mediated fluorescence enhancement can be further amplified by introducing a hydrophilic thiolate (glutathione, GSH) onto the surface of Au NCs (GSH/MUA-Au NCs), which enabled sensitive determination of H2S. Under the optimized condition, a detection limit of 35 nM was achieved. The determination was not interfered by other anions such as F, Cl, Br, I, OAc, N3, NO3, HCO3, SCN, SO32−, and SO42−. This excellent sensing performance allowed practical application of the GSH/MUA-Au NC-based sensing platform to accurate determination of H2S in human serum samples.

Unusual aggregation-enhanced emission character of 11-mercaptoundecanoic acid capped gold nanoclusters is discovered and has been applied for fluorometric hydrogen sulfide detection.

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

Access this article

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

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Jin R, Zeng C, Zhou M, Chen Y (2016) Atomically precise colloidal metal nanoclusters and nanoparticles: fundamentals and opportunities. Chem Rev 116:10346–10413

    Article  CAS  Google Scholar 

  2. Tao Y, Li M, Ren J, Qu X (2015) Metal nanoclusters: novel probes for diagnostic and therapeutic applications. Chem Soc Rev 44:8636–8663

    Article  CAS  Google Scholar 

  3. Zhao J, Jin R (2018) Heterogeneous catalysis by gold and gold-based bimetal nanoclusters. Nano Today 18:86–102

    Article  CAS  Google Scholar 

  4. Chen L-Y, Wang C-W, Yuan Z, Chang H-T (2015) Fluorescent gold nanoclusters: recent advances in sensing and imaging. Anal Chem 87:216–229

    Article  CAS  Google Scholar 

  5. Kurashige W, Niihori Y, Sharma S, Negishi Y (2016) Precise synthesis, functionalization and application of thiolate-protected gold clusters. Coord Chem Rev 320-321:238–250

    Article  CAS  Google Scholar 

  6. Xie J, Zheng Y, Ying JY (2010) Highly selective and ultrasensitive detection of Hg2+ based on fluorescence quenching of Au nanoclusters by Hg2+–Au+ interactions. Chem Commun 46(6):961–963

    Article  CAS  Google Scholar 

  7. Yuan Z, Peng M, He Y, Yeung ES (2011) Functionalized fluorescent gold nanodots: synthesis and application for Pb2+ sensing. Chem Commun 47:11981–11983

    Article  CAS  Google Scholar 

  8. Gao Y, Liu M, Yue X, Du J (2019) Ratiometric fluorometric determination of mercury(II) by exploiting its quenching effect on glutathione-stabilized and tetraphenylporphyrin modified gold nanoclusters. Microchim Acta 186:307

    Article  Google Scholar 

  9. Yin YB, Coonrod CL, Heck KN, Lejarza F, Wong MS (2019) Microencapsulated photoluminescent gold for ppb-level chromium(VI) sensing. ACS Appl Mater Interfaces 11:17491–17500

    Article  CAS  Google Scholar 

  10. Vasimalai N, Fernández-Argüelles MT, Espiña B (2018) Detection of sulfide using mercapto tetrazine-protected fluorescent gold nanodots: preparation of paper-based testing kit for on-site monitoring. ACS Appl Mater Interfaces 10:1634–1645

    Article  CAS  Google Scholar 

  11. Wang L, Chen G, Zeng G, Liang J, Dong H, Yan M, Li Z, Guo Z, Tao W, Peng L (2015) Fluorescent sensing of sulfide ions based on papain-directed gold nanoclusters. New J Chem 39:9306–9312

    Article  CAS  Google Scholar 

  12. Germain ME, Knapp MJ (2009) Optical explosives detection: from color changes to fluorescence turn-on. Chem Soc Rev 38:2543–2555

    Article  CAS  Google Scholar 

  13. Mei J, Leung NLC, Kwok RTK, Lam JWY, Tang BZ (2015) Aggregation-induced emission: together we shine, united we soar! Chem Rev 115:11718–11940

    Article  CAS  Google Scholar 

  14. Luo J, Xie Z, Lam JWY, Cheng L, Chen H, Qiu C, Kwok HS, Zhan X, Liu Y, Zhu D, Tang BZ (2001) Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole. Chem Commun 1740–1741

  15. Luo Z, Yuan X, Yu Y, Zhang Q, Leong DT, Lee JY, Xie J (2012) From aggregation-induced emission of Au(I)–thiolate complexes to ultrabright Au(0)@Au(I)–thiolate core–shell nanoclusters. J Am Chem Soc 134:16662–16670

    Article  CAS  Google Scholar 

  16. Santiago-Gonzalez B, Monguzzi A, Azpiroz JM, Prato M, Erratico S, Campione M, Lorenzi R, Pedrini J, Santambrogio C, Torrente Y, De Angelis F, Meinardi F, Brovelli S (2016) Permanent excimer superstructures by supramolecular networking of metal quantum clusters. Science 353:571–575

    Article  CAS  Google Scholar 

  17. Wu Z, Du Y, Liu J, Yao Q, Chen T, Cao Y, Zhang H, Xie J (2019) Aurophilic interactions in the self-assembly of gold nanoclusters into nanoribbons with enhanced luminescence. Angew Chem Int Ed 58:8139–8144

    Article  CAS  Google Scholar 

  18. Wang J, Lin X, Su L, Yin J, Shu T, Zhang X (2019) Chemical etching of pH-sensitive aggregation-induced emission-active gold nanoclusters for ultra-sensitive detection of cysteine. Nanoscale 11:294–300

    Article  CAS  Google Scholar 

  19. Yahia-Ammar A, Sierra D, Mérola F, Hildebrandt N, Le Guével X (2016) Self-assembled gold nanoclusters for bright fluorescence imaging and enhanced drug delivery. ACS Nano 10:2591–2599

    Article  CAS  Google Scholar 

  20. You J-G, Tseng W-L (2019) Peptide-induced aggregation of glutathione-capped gold nanoclusters: a new strategy for designing aggregation-induced enhanced emission probes. Anal Chim Acta 1078:101–111

    Article  CAS  Google Scholar 

  21. You J-G, Lu C-Y, Krishna Kumar AS, Tseng W-L (2018) Cerium(III)-directed assembly of glutathione-capped gold nanoclusters for sensing and imaging of alkaline phosphatase-mediated hydrolysis of adenosine triphosphate. Nanoscale 10:17691–17698

    Article  CAS  Google Scholar 

  22. Shan J, Wei L, Daqiao H, Xuejuan Z, Xi K, Wenjun D, Shuang C, Shiqiang W, Shuxin W, Manzhou Z (2018) Aggregation-induced emission (AIE) in Ag−Au bimetallic nanocluster. Chem Eur J 24:3712–3715

    Article  Google Scholar 

  23. Pyo K, Thanthirige VD, Kwak K, Pandurangan P, Ramakrishna G, Lee D (2015) Ultrabright luminescence from gold nanoclusters: rigidifying the Au(I)–thiolate shell. J Am Chem Soc 137:8244–8250

    Article  CAS  Google Scholar 

  24. Yuan Z, Du Y, Tseng Y-T, Peng M, Cai N, He Y, Chang H-T, Yeung ES (2015) Fluorescent gold nanodots based sensor array for proteins discrimination. Anal Chem 87:4253–4259

    Article  CAS  Google Scholar 

  25. Huang C-C, Yang Z, Lee K-H, Chang H-T (2007) Synthesis of highly fluorescent gold nanoparticles for sensing mercury(II). Angew Chem Int Ed 46:6824–6828

    Article  CAS  Google Scholar 

  26. Guo Y, Tong X, Ji L, Wang Z, Wang H, Hu J, Pei R (2015) Visual detection of Ca2+ based on aggregation-induced emission of Au(I)-Cys complexes with superb selectivity. Chem Commun 51:596–598

    Article  CAS  Google Scholar 

  27. Lu X, Wang T, Shu T, Qu X, Zhang X, Liang F, Su L (2016) Combination of chemical etching of gold nanoclusters with aggregation-induced emission for preparation of new phosphors for the development of UV-driven phosphor-converted white light-emitting diodes. J Mater Chem C 4:11482–11487

    Article  CAS  Google Scholar 

  28. Yuan Z, Peng M, Shi L, Du Y, Cai N, He Y, Chang H-T, Yeung ES (2013) Disassembly mediated fluorescence recovery of gold nanodots for selective sulfide sensing. Nanoscale 5:4683–4686

    Article  CAS  Google Scholar 

  29. Kozawa D, Kumar R, Carvalho A, Kumar Amara K, Zhao W, Wang S, Toh M, Ribeiro RM, Castro Neto AH, Matsuda K, Eda G (2014) Photocarrier relaxation pathway in two-dimensional semiconducting transition metal dichalcogenides. Nat Commun 5:4543

    Article  CAS  Google Scholar 

  30. Yuan Z, Lu F, Peng M, Wang C-W, Tseng Y-T, Du Y, Cai N, Lien C-W, Chang H-T, He Y, Yeung ES (2015) Selective colorimetric detection of hydrogen sulfide based on primary amine-active ester cross-linking of gold nanoparticles. Anal Chem 87:7267–7273

    Article  CAS  Google Scholar 

  31. Jin M, Huang L, Tang Y, Wang G, Ma Z, Yuan Z, Lu C (2019) Rapid sulfite screening using nitrobenzofurazan anchored asymmetric naphthorhodamine via electrostatic attraction mediated reaction kinetics. Sensors Actuators B Chem 297:126748

    Article  CAS  Google Scholar 

  32. Bitziou E, Joseph MB, Read TL, Palmer N, Mollart T, Newton ME, Macpherson JV (2014) In situ optimization of pH for parts-per-billion electrochemical detection of dissolved hydrogen sulfide using boron doped diamond flow electrodes. Anal Chem 86:10834–10840

    Article  CAS  Google Scholar 

  33. Wen Z, Song S, Hu T, Wang C, Qu F, Wang P, Yang M (2019) A dual emission nanocomposite prepared from copper nanoclusters and carbon dots as a ratiometric fluorescent probe for sulfide and gaseous H2S. Microchim Acta 186:258

    Article  Google Scholar 

  34. Liu J, Bao H, Ma D-L, Leung C-H (2019) Silver nanoclusters functionalized with Ce(III) ions are a viable “turn-on-off” fluorescent probe for sulfide. Microchim Acta 186:16

    Article  Google Scholar 

  35. Zhang X, Zhou W, Yuan Z, Lu C (2015) Colorimetric detection of biological hydrogen sulfide using fluorosurfactant functionalized gold nanorods. Analyst 140:7443–7450

    Article  CAS  Google Scholar 

  36. Chang H-Y, Chang H-T, Hung Y-L, Hsiung T-M, Lin Y-W, Huang C-C (2013) Ligand effect on the luminescence of gold nanodots and its application for detection of total mercury ions in biological samples. RSC Adv 3:4588–4597

    Article  CAS  Google Scholar 

  37. Chen L, Huang P, Tan H, Wang L (2017) A terbium(III)-based coordination polymer for time-resolved determination of hydrogen sulfide in human serum via displacement of copper(II). Anal Methods 9:1004–1010

    Article  CAS  Google Scholar 

Download references

Funding

This work was supported by the National Natural Science Foundation of China (21605003, 21521005, and 21575010), the Fundamental Research Funds for the Central Universities (buctrc201619), the Open Research Fund Program of Beijing Key Lab of Plant Resource Research and Development, Beijing Technology and Business University (PRRD-2018-YB3).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Ying Tang or Zhiqin Yuan.

Ethics declarations

Conflict of interest

The authors declare no competing financial interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOCX 614 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lu, F., Yang, H., Tang, Y. et al. 11-Mercaptoundecanoic acid capped gold nanoclusters with unusual aggregation-enhanced emission for selective fluorometric hydrogen sulfide determination. Microchim Acta 187, 200 (2020). https://doi.org/10.1007/s00604-020-4159-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-020-4159-1

Keywords

Navigation