Improved size-tunable synthesis and SERS properties of Au nanostars

  • Boris KhlebtsovEmail author
  • Elizaveta Panfilova
  • Vitaly Khanadeev
  • Nikolai Khlebtsov
Research Paper


Multibranched Au nanoparticles with sharp tips (commonly called nanostars, NSTs) have attracted significant attention as bright scattering labels, photothermal transducers, nanocarriers, and surface-enhanced Raman scattering (SERS) tags. However, for surfactant-free synthesized NSTs, the existing data on the size tuning and the relation between the size of NSTs and their SERS efficiency still remain limited. Here, we address these questions by synthesizing and comparing SERS for surfactant-free NSTs of different sizes and plasmon resonance (PR) wavelengths. The NSTs were fabricated by seeded growth through a two-step surfactant-free approach in which quasispherical seeds were overgrown via reduction of added Au by ascorbic acid in the presence of Ag ions. By varying the seed size from 3 to 35 nm, we tuned the final NST size from 45 to 150 nm while retaining the star-like morphology with sharp tips and ensuring PR tunability from 630 to 900 nm. The NST size and PR limits can be expanded from 40 to 200 nm and from 600 to 930 nm, respectively, by simultaneous variation in the seed size and concentration. The SERS efficiency of the fabricated NSTs was examined by Raman measurements of 1,4-aminothiophenol (ATP) adsorbed on the surface of colloidal NST particles. Although the homogenous analytical enhancement factor (AEF) did not depend essentially on the NST size and varied from 4 × 106 to 107, the enhancing properties of single-particle NST tags were strongly size-dependent. Specifically, the AEF for 150-nm NST35-ATP complexes was 30 and 100 times greater than that for 70-nm NST15-ATP and 45-nm NST3-ATP complexes, respectively. These properties make the NST–ATP complex a prospective platform for SERS imaging.


Au nanostars Surfactant-free synthesis Plasmon resonance Extinction spectra SERS 



The work by BN and NK was supported by grant No. 14-13-01167 from the Russian Scientific Foundation. The work on NST synthesis by EP and VK was supported by grants from the Russian Foundation for Basic Research (no. 13-02-12413), the Government of the Russian Federation (no. 14.Z50.31.0004), and a scholarship from the President of the Russian Federation CП-3575.2013.4. We thank D.N. Tychinin (IBPPM RAS) for his help in preparation of the manuscript.

Supplementary material

11051_2014_2623_MOESM1_ESM.pdf (40 kb)
Supplementary material 1 (PDF 40 kb)


  1. Allgeyer ES, Pongan A, Browne M, Mason MD (2009) Optical signal comparison of single fluorescent molecules and Raman active gold nanostars. Nano Lett 9:3816–3819CrossRefGoogle Scholar
  2. Bakr OM, Wunsch BH, Stellacci F (2006) High-yield synthesis of multi-branched urchinlike gold nanoparticles. Chem Mater 18:3297–3301CrossRefGoogle Scholar
  3. Barbosa S, Agrawal A, Rodrıguez-Lorenzo L, Pastoriza-Santos I, Alvarez-Puebla RA, Kornowski A, Weller H, Liz-Marzán LM (2010) Tuning size and sensing properties in colloidal gold nanostars. Langmuir 26:14943–14950CrossRefGoogle Scholar
  4. Blaber MG, Schatz GC (2011) Extending SERS into the infrared with gold nanosphere dimers. Chem Commun 47:3769–3771CrossRefGoogle Scholar
  5. Burt JL, Elechiguerra JL, Reyes-Gasga J, Montejano-Carrizales JM (2005) Beyond archimedean solids: star polyhedral gold nanocrystals. J Cryst Growth 285:681–691CrossRefGoogle Scholar
  6. Cao YWC, Jin RC, Mirkin CA (2002) Nanoparticles with Raman spectroscopic fingerprints for DNA and RNA detection. Science 297:1536–1540CrossRefGoogle Scholar
  7. Duff DG, Baiker A, Edwards PP (1993) A new hydrosol of gold clusters. 1. Formation and particle size variation. Langmuir 9:2301–2309CrossRefGoogle Scholar
  8. Frens G (1973) Controlled nucleation for regulation of particle-size in monodisperse gold suspensions. Nat Phys Sci 241:20–22CrossRefGoogle Scholar
  9. Greeneltch NG, Blaber MG, Henry A-I, Schatz GC, Van Duyne RP (2013a) Immobilized nanorod assemblies: fabrication and understanding of large area surface-enhanced Raman spectroscopy substrates. Anal Chem 85:2297–2303CrossRefGoogle Scholar
  10. Greeneltch NG, Blaber MG, Schatz GC, Van Duyne RP (2013b) Plasmon-sampled surface-enhanced Raman excitation spectroscopy on silver immobilized nanorod assemblies and optimization for near infrared (λex = 1,064 nm) studies. J Phys Chem C 117:2554–2558CrossRefGoogle Scholar
  11. Guerrero-Martínez A, Barbosa S, Pastoriza-Santos I, Liz-Marzán LM (2011) Nanostars shine bright for you. Curr Opin Colloid Interface Sci 16:118–127CrossRefGoogle Scholar
  12. Hao E, Bailey RC, Scharz GC, Hupp JT, Li S (2004) Synthesis and optical properties of “branched” gold nanocrystals. Nano Lett 4:327–330CrossRefGoogle Scholar
  13. Haynes CL, McFarland AD, Van Duyne RP (2005) Surface-enhanced Raman spectroscopy. Anal Chem 77:338A–346ACrossRefGoogle Scholar
  14. Kang T, Yoo SM, Yoon I, Lee SY, Kim B (2010) Patterned multiplex pathogen DNA detection by Au particle-on-wire SERS sensor. Nano Lett 10:1189–1193CrossRefGoogle Scholar
  15. Khlebtsov NG (2008) Determination of size and concentration of gold nanoparticles from extinction spectra. Anal Chem 80:6620–6625CrossRefGoogle Scholar
  16. Khlebtsov NG, Bogatyrev VA, Dykman LA, Melnikov AG (1996) Spectral extinction of colloidal gold and its biospecific conjugates. J Colloid Interface Sci 180:436–445CrossRefGoogle Scholar
  17. Khoury CG, Vo-Dinh T (2008) Gold nanostars for surface-enhanced Raman scattering: synthesis, characterization and optimization. J Phys Chem C 112:18849–18859CrossRefGoogle Scholar
  18. Kneipp J, Kneipp H, Rice WL, Kneipp K (2005) Optical probes for biological applications based on surface-enhanced Raman scattering from indocyanine green on gold nanoparticles. Anal Chem 77:2381–2385CrossRefGoogle Scholar
  19. Kumar PS, Pastoriza-Santos I, Rodríguez-González B, García de Abajo FJ, Liz-Marzán LM (2008) High-yield synthesis and optical response of gold nanostars. Nanothechnology 19:015606CrossRefGoogle Scholar
  20. Lakowicz JR (2006) Principles of fluorescence spectroscopy, 3rd edn. Springer, New YorkCrossRefGoogle Scholar
  21. Le Ru EC, Blackie E, Meyer M, Etchegoin PG (2007) Surface enhanced Raman scattering enhancement factors: a comprehensive study. J Phys Chem C 111:13794–13803CrossRefGoogle Scholar
  22. Li M, Cushing SK, Zhang J, Lankford J, Aguilar ZP, Ma D, Wu N (2012) Shape-dependent surface-enhanced Raman scattering in gold–Raman-probe–silica sandwiched nanoparticles for biocompatible applications. Nanotechnology 23:115501CrossRefGoogle Scholar
  23. Liu Y, Chang Z, Yuan H, Fales AM, Vo-Dinh T (2013) Quintuple-modality (SERS-MRI-CT-TPL-PTT) plasmonic nanoprobe for theranostics. Nanoscale 5:12126–12131CrossRefGoogle Scholar
  24. Osawa M, Matsuda N, Yoshii K, Uchida I (1994) Charge transfer resonance Raman process in surface-enhanced Raman scattering from p-aminothiophenol adsorbed on silver: Herzberg-Teller contribution. J Phys Chem 98:12702–12707CrossRefGoogle Scholar
  25. Palonpon AF, Ando J, Yamakoshi H, Dodo K, Sodeoka M, Kawata S, Fujita K (2013) Raman and SERS microscopy for molecular imaging of live cells. Nat Protoc 8:677–692CrossRefGoogle Scholar
  26. Pelton M, Aizpurua J, Bryant G (2008) Metal-nanoparticle plasmonics. Laser Photonics Rev 2:136–159CrossRefGoogle Scholar
  27. Pham T, Jackson JB, Halas NJ, Lee TR (2002) Preparation and characterization of gold nanoshells coated with self-assembled monolayers. Langmuir 18:4915–4920CrossRefGoogle Scholar
  28. Qian X, Peng XH, Ansari DO, Yin-Goen Q, Chen GZ, Shin DM, Yang L, Young AN, Wang MD, Nie Sh (2008) In vivo tumor targeting and spectroscopic detection with surface-enhanced Raman nanoparticle tags. Nat Biotechnol 26:83–90CrossRefGoogle Scholar
  29. Van De Broek B, Devoogdt N, Dhollander A, Gijs HL, Jans K, Lagae L, Muyldermans S, Maes G, Borghs G (2011a) Specific cell targeting with nanobody conjugated branched gold nanoparticles for photothermal therapy. ACS Nano 5:4319–4328CrossRefGoogle Scholar
  30. Van De Broek B, Grandjean D, Trekker J, Ye J, Verstreken K, Maes G, Borghs G, Nikitenko S, Lagae L, Bartic C, Temst K, Van Bael MJ (2011b) Temperature determination of resonantly excited plasmonic branched gold nanoparticles by X-ray absorption spectroscopy. Small 7:2498–2506Google Scholar
  31. Wabuyele MB, Vo-Dinh T (2005) Detection of human immunodeficiency virus type 1 DNA sequence using plasmonics nanoprobes. Anal Chem 77:7810–7815CrossRefGoogle Scholar
  32. Wang Y, Seebald JL, Szeto DP, Daniel P, Irudayaraj J (2010) Biocompatibility and biodistribution of surface-enhanced Raman scattering nanoprobes in zebrafish embryos: in vivo and multiplex imaging. ACS Nano 4:4039–4053CrossRefGoogle Scholar
  33. We Q, Song H-M, Leonov AP, Hale JA, Oh D, Ong QK, Ritchie K, Wei A (2009) Gyromagnetic imaging: dynamic optical contrast using gold nanostars with magnetic cores. J Am Chem Soc 131:9728–9734CrossRefGoogle Scholar
  34. Wei L, Jin B, Dai S (2012) Polymer microbead-based surface enhanced Raman scattering immunoassays. J Phys Chem C 116:17174–17181CrossRefGoogle Scholar
  35. Xie J, Lee JY, Wang DIC (2007) Seedless, surfactantless, high-yield synthesis of branched gold nanocrystals in HEPES buffer solution. Chem Mater 19:2823–2830CrossRefGoogle Scholar
  36. Xie J, Zhang ZQ, Lee JY, Wang DIC (2008) The synthesis of SERS-active gold nanoflower tags for in vivo applications. ACS Nano 2:2473–2480CrossRefGoogle Scholar
  37. Ye J, Hutchison JA, Uji H, Hofkens J, Lagae L, Maes G, Borghs G, Van Dorpe P (2012) Excitation wavelength dependent surface enhanced Raman scattering of 4-aminothiophenol on gold nanorings. Nanoscale 4:1606–1611CrossRefGoogle Scholar
  38. Yuan H, Ma W, Chen C, Zhao J, Liu J, Zhu H et al (2007) Shape and SPR evolution of thorny gold nanoparticles promoted by silver ions. Chem Mater 19:1592–1600CrossRefGoogle Scholar
  39. Yuan H, Khoury CG, Hwang H, Wilson CM, Grant GA, Vo-Dinh T (2012) Gold nanostars: surfactant-free synthesis, 3D modelling, and two-photon photoluminescence imaging. Nanotechnology 23:075102CrossRefGoogle Scholar
  40. Yuan H, Fales AM, Khoury CG, Liu J, Vo-Dinh T (2013a) Spectral characterization and intracellular detection of Surface-enhanced Raman scattering (SERS)-encoded plasmonic gold nanostars. J Raman Spectrosc 44:234–239CrossRefGoogle Scholar
  41. Yuan H, Liu Y, Fales AM, Li YL, Liu J, Vo-Dinh T (2013b) Quantitative surface-enhanced resonant Raman scattering multiplexing of biocompatible gold nanostars for in vitro and ex vivo detection. Anal Chem 85:208–212CrossRefGoogle Scholar
  42. Zhang Y, Qian J, Wang D, Wang Y, He S (2013) Multifunctional gold nanorods with ultrahigh stability and tunability for in vivo fluorescence imaging, SERS detection, and photodynamic therapy. Angew Chem Int Ed 52:1148–1151CrossRefGoogle Scholar
  43. Zong S, Wang Z, Yang J, Wang C, Xu S, Cui Y (2012) A SERS and fluorescence dual mode cancer cell targeting probe based on silica coated Au@Ag core–shell nanorods. Talanta 97:368–375CrossRefGoogle Scholar
  44. Zou X, Ying E, Dong S (2006) Seed-mediated synthesis of branched gold nanoparticles with the assistance of citrate and their surface-enhanced Raman scattering properties. Nanothecnology 17:4758–4764CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • Boris Khlebtsov
    • 1
    • 2
    Email author
  • Elizaveta Panfilova
    • 1
    • 2
  • Vitaly Khanadeev
    • 1
    • 2
  • Nikolai Khlebtsov
    • 1
    • 2
  1. 1.Institute of Biochemistry and Physiology of Plants and MicroorganismsSaratovRussia
  2. 2.Saratov State UniversitySaratovRussia

Personalised recommendations