Study on selective oxidations of gold nanorod and mesoporous silica-coated gold nanorod

  • Zihua WuEmail author
  • Yuling Liang
  • Qing Guo
  • Keqiu Zhang
  • Shifang Liang
  • Liyun Yang
  • Qi Xiao
  • Dan WangEmail author
Chemical routes to materials


The structural control-based manipulation of the anisotropic surface plasmon resonance (SPR) property of gold nanorod (AuNR) is significant and has wide application value in many fields. In this work, the quantitative studies of the ends-selective oxidations of AuNR and silica-coated AuNR using chloroauric acid as a oxidant were carried out. Results show that when the selective oxidation extent of AuNR was denoted by the aspect ratio changing rate, a linear relationship was displayed between this rate and the added amount of the oxidant, which suggested the Au(III)-induced selective oxidation of the nanoscaled Au(0) also proceeded stoichiometrically. In addition, different structural evolutions of silica coating layer that were determined to be caused by the different stabilities of the silica structure and described as the shape-adaptive change and the rigid state were found upon proceeding of oxidation. The study also showed that the structural change of the silica coating layer only had little influences on the mesopore size and its distribution state. These results should be valuable in better understanding the surface chemistry of AuNR and benefit the SPR variation-based and the silica coating-involved applications of AuNR.



This work was financially supported by the National Natural Science Foundation of China (21573078) and BAGUI Scholar Program of Guangxi Province of China.

Author contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2019_3429_MOESM1_ESM.pdf (327 kb)
The Supplementary material is available free of charge on the Springer Publications website at DOI: Data from characterization analysis, UV–Vis–NIR characterization, FT-IR characterization (PDF) (PDF 327 kb)


  1. 1.
    Chen H, Shao L, Li Q, Wang J (2013) Gold nanorods and their plasmonic properties. Chem Soc Rev 42(7):2679–2724CrossRefGoogle Scholar
  2. 2.
    Mayer KM, Hafner JH (2011) Localized surface plasmon resonance sensors. Chem Rev 111(6):3828–3857. CrossRefGoogle Scholar
  3. 3.
    Jayabal S, Pandikumar A, Lim HN, Ramaraj R, Sun T, Huang NM (2015) A gold nanorod-based localized surface plasmon resonance platform for the detection of environmentally toxic metal ions. Analyst 140(8):2540–2555. CrossRefGoogle Scholar
  4. 4.
    Ni W, Kou X, Yang Z, Wang J (2008) Tailoring longitudinal surface plasmon wavelengths, scattering and absorption cross sections of gold nanorods. ACS Nano 2(4):677–686. CrossRefGoogle Scholar
  5. 5.
    González-Rubio G, Díaz-Núñez P, Rivera A, Prada A, Tardajos G, González-Izquierdo J, Bañares L, Llombart P, Macdowell LG, Alcolea Palafox M, Liz-Marzán LM, Peña-Rodríguez O, Guerrero-Martínez A (2017) Femtosecond laser reshaping yields gold nanorods with ultranarrow surface plasmon resonances. Science 358(6363):640CrossRefGoogle Scholar
  6. 6.
    Zhang Q, Han L, Jing H, Blom DA, Lin Y, Xin HL, Wang H (2016) Facet control of gold nanorods. ACS Nano 10(2):2960–2974. CrossRefGoogle Scholar
  7. 7.
    Scarabelli L, Sanchez-Iglesias A, Perez-Juste J, Liz-Marzan LM (2015) A “tips and tricks” practical guide to the synthesis of gold nanorods. J Phys Chem Lett 6(21):4270–4279. CrossRefGoogle Scholar
  8. 8.
    Walsh MJ, Tong W, Katz-Boon H, Mulvaney P, Etheridge J, Funston AM (2017) A mechanism for symmetry breaking and shape control in single-crystal gold nanorods. Acc Chem Res 50(12):2925–2935. CrossRefGoogle Scholar
  9. 9.
    Walsh MJ, Barrow SJ, Tong W, Funston AM, Etheridge J (2015) Symmetry breaking and silver in gold nanorod growth. ACS Nano 9(1):715–724. CrossRefGoogle Scholar
  10. 10.
    Katz-Boon H, Walsh M, Dwyer C, Mulvaney P, Funston AM, Etheridge J (2015) Stability of crystal facets in gold nanorods. Nano Lett 15(3):1635–1641. CrossRefGoogle Scholar
  11. 11.
    Chang H-H, Murphy CJ (2018) Mini gold nanorods with tunable plasmonic peaks beyond 1000 nm. Chem Mater 30(4):1427–1435. CrossRefGoogle Scholar
  12. 12.
    Ye X, Zheng C, Chen J, Gao Y, Murray CB (2013) Using binary surfactant mixtures to simultaneously improve the dimensional tunability and monodispersity in the seeded growth of gold nanorods. Nano Lett 13(2):765–771. CrossRefGoogle Scholar
  13. 13.
    Burrows ND, Harvey S, Idesis FA, Murphy CJ (2017) Understanding the seed-mediated growth of gold nanorods through a fractional factorial design of experiments. Langmuir 33(8):1891–1907. CrossRefGoogle Scholar
  14. 14.
    Vigderman L, Zubarev ER (2013) High-yield synthesis of gold nanorods with longitudinal SPR peak greater than 1200 nm using hydroquinone as a reducing agent. Chem Mater 25(8):1450–1457. CrossRefGoogle Scholar
  15. 15.
    Kozek KA, Kozek KM, Wu WC, Mishra SR, Tracy JB (2013) Large-scale synthesis of gold nanorods through continuous secondary growth. Chem Mater 25(22):4537–4544. CrossRefGoogle Scholar
  16. 16.
    Zhou R, Shi M, Chen X, Wang M, Chen H (2009) Atomically monodispersed and fluorescent sub-nanometer gold clusters created by biomolecule-assisted etching of nanometer-sized gold particles and rods. Chemistry 15(19):4944–4951. CrossRefGoogle Scholar
  17. 17.
    Rodriguez FJ, Perez JJ, Mulvaney P, Liz-Marzan LM (2005) Spatially-directed oxidation of gold nanoparticles by Au(III)-CTAB complexes. J Phys Chem B 109(30):14257–14261. CrossRefGoogle Scholar
  18. 18.
    Tsung C, Kou X, Shi Q, Zhang J, Yeung MH, Wang J, Stucky GD (2006) Selective shortening of single-crystalline gold nanorods by mild oxidation. J Am Chem Soc 128(16):5352–5353CrossRefGoogle Scholar
  19. 19.
    Wang T-T, Chai F, Wang C-G, Li L, Liu H-Y, Zhang L-Y, Su Z-M, Liao Y (2011) Fluorescent hollow/rattle-type mesoporous Au@SiO2 nanocapsules for drug delivery and fluorescence imaging of cancer cells. J Colloid Interface Sci 358(1):109–115. CrossRefGoogle Scholar
  20. 20.
    Zou R, Guo X, Yang J, Li D, Peng F, Zhang L, Wang H, Yu H (2009) Selective etching of gold nanorods by ferric chloride at room temperature. CrystEngComm 11(12):2797. CrossRefGoogle Scholar
  21. 21.
    Zhang Z, Chen Z, Chen L (2015) Ultrasensitive visual sensing of molybdate based on enzymatic-like etching of gold nanorods. Langmuir 31(33):9253–9259. CrossRefGoogle Scholar
  22. 22.
    Zhang Z, Chen Z, Pan D, Chen L (2015) Fenton-like reaction-mediated etching of gold nanorods for visual detection of Co(2+). Langmuir 31(1):643–650. CrossRefGoogle Scholar
  23. 23.
    Gorelikov I, Matsuura N (2008) Single-step coating of mesoporous silica on cetyltrimethyl ammonium bromide-capped nanoparticles. Nano Lett 8(1):369–373. CrossRefGoogle Scholar
  24. 24.
    Pastoriza-Santos I, Perez-Juste J, Liz-Marzan LM (2006) Silica-coating and hydrophobation of CTAB-stabilized gold nanorods. Chem Mater 18(10):2465–2467. CrossRefGoogle Scholar
  25. 25.
    Chen Y-S, Frey W, Kim S, Homan K, Kruizinga P, Sokolov K, Emelianov S (2010) Enhanced thermal stability of silica-coated gold nanorods for photoacoustic imaging and image-guided therapy. Opt Express 18(9):8867–8878. CrossRefGoogle Scholar
  26. 26.
    Liu J, Detrembleur C, De Pauw-Gillet MC, Mornet S, Jerome C, Duguet E (2015) Gold nanorods coated with mesoporous silica shell as drug delivery system for remote near infrared light-activated release and potential phototherapy. Small 11(19):2323–2332. CrossRefGoogle Scholar
  27. 27.
    Luo GF, Chen WH, Lei Q, Qiu WX, Liu Y-X, Cheng Y-J, Zhang X-Z (2016) A triple-collaborative strategy for high-performance tumor therapy by multifunctional mesoporous silica-coated gold nanorods. Adv Funct Mater 26(24):4339–4350. CrossRefGoogle Scholar
  28. 28.
    Liu Y, Yang M, Zhang J, Zhi X, Li C, Zhang C, Pan F, Wang K, Yang Y, Martinez de la Fuentea J, Cui D (2016) Human induced pluripotent stem cells for tumor targeted delivery of gold nanorods and enhanced photothermal therapy. ACS Nano 10(2):2375–2385. CrossRefGoogle Scholar
  29. 29.
    Burrows ND, Lin W, Hinman JG, Dennison JM, Vartanian AM, Abadeer NS, Grzincic EM, Jacob LM, Li J, Murphy CJ (2016) Surface chemistry of gold nanorods. Langmuir 32(39):9905–9921. CrossRefGoogle Scholar
  30. 30.
    Chiu SJ, Wang SY, Chou HC, Liu YL, Hu TM (2014) Versatile synthesis of thiol- and amine-bifunctionalized silica nanoparticles based on the ouzo effect. Langmuir 30(26):7676–7686. CrossRefGoogle Scholar
  31. 31.
    Knopp D, Tang D, Niessner R (2009) Review: bioanalytical applications of biomolecule-functionalized nanometer-sized doped silica particles. Anal Chim Acta 647(1):14–30. CrossRefGoogle Scholar
  32. 32.
    Jankiewicz BJ, Jamiola D, Choma J, Jaroniec M (2012) Silica–metal core–shell nanostructures. Adv Colloid Interface 170(1):28–47. CrossRefGoogle Scholar
  33. 33.
    Li H, Tan LL, Jia P, Li Q-L, Sun YL, Zhang J, Ning YQ, Yu J, Yang YW (2014) Near-infrared light-responsive supramolecular nanovalve based on mesoporous silica-coated gold nanorods. Chem Sci 5(7):2804–2808CrossRefGoogle Scholar
  34. 34.
    Wu Z, Zeng Q, Wang H (2016) Structural controls of AuNR@mSiO2: tuning of the SPR, and manipulation of the silica shell thickness and structure. J Mater Chem C 4(13):2614–2620. CrossRefGoogle Scholar
  35. 35.
    Deng T-S, van der Hoeven JES, Yalcin AO, Zandbergen HW, van Huis MA, van Blaaderen A (2015) Oxidative etching and metal overgrowth of gold nanorods within mesoporous silica shells. Chem Mater 27(20):7196–7203. CrossRefGoogle Scholar
  36. 36.
    Kim J-H, Bryan WW, Lee TR (2008) Preparation, characterization, and optical properties of gold, silver, and gold-silver alloy nanoshells having silica cores. Langmuir 24(19):11147–11152. CrossRefGoogle Scholar
  37. 37.
    Zhang Z, Zhang P, Guo K, Liang G, Chen H, Liu B, Kong J (2011) Facile synthesis of fluorescent Au@SiO2 nanocomposites for application in cellular imaging. Talanta 85(5):2695–2699. CrossRefGoogle Scholar
  38. 38.
    Link S, Mohamed MB, El-Sayed MA (1999) Simulation of the optical absorption spectra of gold nanorods as a function of their aspect ratio and the effect of the medium dielectric constant. J Phys Chem B 103(16):3073–3077. CrossRefGoogle Scholar
  39. 39.
    Link S, El-Sayed MA (2005) Simulation of the optical absorption spectra of gold nanorods as a function of their aspect ratio and the effect of the medium dielectric constant. J Phys Chem B 109(20):10531–10532. CrossRefGoogle Scholar
  40. 40.
    Zhan Q, Qian J, Li X, He S (2010) A study of mesoporous silica-encapsulated gold nanorods as enhanced light scattering probes for cancer cell imaging. Nanotechnology 21(5):055704–055715. CrossRefGoogle Scholar
  41. 41.
    Wu C, Xu Q-H (2009) Stable and functionable mesoporous silica-coated gold nanorods as sensitive localized surface plasmon resonance (LSPR) nanosensors. Langmuir 25(16):9441–9446. CrossRefGoogle Scholar
  42. 42.
    Orendorff CJ, Murphy CJ (2006) Quantitation of metal content in the silver-assisted growth of gold nanorods. J Phys Chem B 110(9):3990–3994. CrossRefGoogle Scholar
  43. 43.
    Hendel T, Wuithschick M, Kettemann F, Birnbaum A, Rademann K, Polte J (2014) In situ determination of colloidal gold concentrations with UV–Vis spectroscopy: limitations and perspectives. Anal Chem 86(22):11115–11124. CrossRefGoogle Scholar
  44. 44.
    Yildirim A, Bayindir M (2015) A porosity difference based selective dissolution strategy to prepare shape-tailored hollow mesoporous silica nanoparticles. J Mater Chem A 3(7):3839–3846. CrossRefGoogle Scholar
  45. 45.
    Park S-J, Kim Y-J, Park S-J (2008) Size-dependent shape evolution of silica nanoparticles into hollow structures. Langmuir 24(21):12134–12137. CrossRefGoogle Scholar
  46. 46.
    Lin M, Wang Y, Sun X, Wang W, Chen L (2015) “Elastic” property of mesoporous silica shell: for dynamic surface enhanced Raman scattering ability monitoring of growing noble metal nanostructures via a simplified spatially confined growth method. ACS Appl Mater Interfaces 7(14):7516–7525. CrossRefGoogle Scholar
  47. 47.
    Lu J, Chang YX, Zhang NN, Wei Y, Li AJ, Tai J, Xue Y, Wang ZY, Yang Y, Zhao L, Lu ZY, Liu K (2017) Chiral plasmonic nanochains via the self-assembly of gold nanorods and helical glutathione oligomers facilitated by cetyltrimethylammonium bromide micelles. ACS Nano 11(4):3463–3475. CrossRefGoogle Scholar
  48. 48.
    Tan SF, Anand U, Mirsaidov U (2017) Interactions and attachment pathways between functionalized gold nanorods. ACS Nano 11(2):1633–1640. CrossRefGoogle Scholar
  49. 49.
    Tang F, Li L, Chen D (2012) Mesoporous silica nanoparticles: synthesis, biocompatibility and drug delivery. Adv Mater 24(12):1504–1534. CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Chemistry and MaterialsNanning Normal UniversityNanningPeople’s Republic of China
  2. 2.Guangxi Key Laboratory of Natural Polymer Chemistry and PhysicsNanning Normal UniversityNanningPeople’s Republic of China

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