Skip to main content
Log in

Influence of age on the free-radical scavenging ability of CeO2 and Au/CeO2 nanoparticles

  • Original Paper
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Cerium oxide (CeO2) nanoparticles have been demonstrated as a potential free-radical scavenger. In the present work, gold (Au) nanoparticles were impregnated by deposition precipitation method on the surface of the combustion synthesized 13-nm CeO2 nanoparticles in order to enhance the free-radical scavenging properties of Au-supported CeO2 nanoparticles (Au/CeO2). Raman spectroscopic calculation for CeO2 and Au/CeO2 showed an oxygen vacancy concentration of 1.22 × 1021 and 0.80 × 1021 cm−3, respectively. The dose- and time-dependent free-radical quenching efficacy of CeO2 and Au/CeO2 nanoparticles was evaluated against hydroxyl, superoxide and nitric oxide using in vitro method. CeO2 and Au/CeO2 nanoparticles exhibited efficient scavenging of hydroxyl and superoxide radicals, but the activity was found to be low against nitric oxide radicals. Both the nanoparticles exhibited a concentration-dependent free-radical scavenging in the range of 0.01–0.0001 μM and showed a saturation behaviour above 0.1 μM. Nanoparticle solution aged for 1, 7, 14 and 28 days displayed a lower superoxide and hydroxyl radicals scavenging activity compared to freshly prepared nanoparticle solution while nitric oxide exhibited the opposite behaviour. In comparison, Au/CeO2 showed better radical scavenging activity at lower concentrations than that of CeO2. The observed radical scavenging property can be attributed to the agglomeration as well as changes in surface oxygen vacancy concentration which are important in designing therapeutic agent for oxidative stress complications.

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.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Babu S, Velez A, Wozniak K, Szydlowska J, Seal S (2007) Electron paramagnetic study on radical scavenging properties of ceria nanoparticles. Chem Phys Lett 442:405–408

    Article  Google Scholar 

  2. Karakoti AS, Singh S, Kumar A, Malinska M, Kuchibhatla SVNT, Wozniak K, Self WT, Seal S (2009) PEGylated nanoceria as radical scavenger with tunable redox chemistry. J Am Chem Soc 131:14144–14145

    Article  Google Scholar 

  3. Karakoti AS, Singh S, Dowding JM, Seal S, Self WT (2010) Redox-active radical scavenging nanomaterials. Chem Soc Rev 39:4422–4432

    Article  Google Scholar 

  4. Wason MS, Colon J, Das S, Seal S, Turkson J, Zhao J, Baker CH (2013) Sensitization of pancreatic cancer cells to radiation by cerium oxide nanoparticle-induced ROS production. Nanomedicine: nanotechnol. Biol Med 9:558–569

    Google Scholar 

  5. Babu S, Schulte A, Seal S (2008) Defects and symmetry influence on visible emission of Eu doped nanoceria. Appl Phys Lett 92(123112):1–3

    Google Scholar 

  6. Wu L, Wiesmann HJ, Moodenbaugh AR, Klie RF, Zhu Y, Welch DO, Suenaga M (2004) Oxidation state and lattice expansion of CeO2-x nanoparticles as a function of particle size. Phys Rev B 69(125415):1–9

    Google Scholar 

  7. Xue Y, Luan Q, Yang D, Zhou K (2011) Direct evidence for hydroxyl radical scavenging activity of cerium oxide nanoparticles. J Phys Chem C 115:4433–4438

    Article  Google Scholar 

  8. Dowding JM, Dosani T, Kumar A, Seal S, Self WT (2012) Cerium oxide nanoparticles scavenge nitric oxide radical (NO). Chem Commun 48:4896–4898

    Article  Google Scholar 

  9. Pelletier DA, Suresh AK, Holton GA, McKeown CK, Wang W, Gu B, Mortensen NP, Allison DP, Joy DC, Allison MR, Brown SD, Phelps TJ, Doktycz MJ (2010) Effects of engineered cerium oxide nanoparticles on bacterial growth and viability. Appl Environ Microbiol 76:7981–7989

    Article  Google Scholar 

  10. Lorda MS, Jung MS, Teoh WY, Gunawan C, Vassie JA, Amal R, Whitelock JM (2012) Cellular uptake and reactive oxygen species modulation of cerium oxide nanoparticles in human monocyte cell line U937. Biomaterials 33:7915–7924

    Article  Google Scholar 

  11. Kuchibhatla SVNT, Karakoti AS, Baer DR, Samudrala S, Engelhard MH, Amonette JE, Thevuthasan S, Seal S (2012) Influence of aging and environment on nanoparticle chemistry: implication to confinement effects in nanoceria. J Phys Chem C 116:14108–14114

    Article  Google Scholar 

  12. Arunkumar P, Meena M, Babu KS (2012) A review on cerium oxide-based electrolytes for ITSOFC. Nanomater Energy 1:288–305

    Article  Google Scholar 

  13. Osawa T, Nakai Y, Mouri A, Lee IYS (2013) Studies of the preparation method of ceria-promoted nickel catalyst for carbon dioxide reforming of methane. Appl Catal A 474:100–106

    Article  Google Scholar 

  14. Perez JM, Asati A, Nath S, Kaittanis C (2008) Synthesis of biocompatible dextran-coated nanoceria with pH-dependent antioxidant properties. Small 4:552–556

    Article  Google Scholar 

  15. Lee SS, Song W, Cho M, Puppala HL, Nguyen P, Zhu H, Segatori L, Colvin VL (2013) Antioxidant properties of cerium oxide nanocrystals as a function of nanocrystal diameter and surface coatings. ACS Nano 7:9693–9703

    Article  Google Scholar 

  16. Lal S, Clare SE, Halas NJ (2008) Nanoshell-enabled photothermal cancer therapy: impending clinical impact. Acc Chem Res 41:1842–1851

    Article  Google Scholar 

  17. Anker JN, Hall WP, Lyandres O, Shah NC, Zhao J, Duyne RPV (2008) Biosensing with plasmonic nanosensors. Nat Mater 7:442–453

    Article  Google Scholar 

  18. Fan C, Zhang L, Wang S, Wang D, Lu L, Xu A (2012) Novel CeO2 yolk-shell structures loaded with tiny Au nanoparticles for superior catalytic reduction of p-nitrophenol. Nanoscale 4:6835–6840

    Article  Google Scholar 

  19. Zhang J, Chen G, Chaker M, Rosei F, Ma D (2013) Gold nanoparticle decorated ceria nanotubes with significantly high catalytic activity for the reduction of nitrophenol and mechanism study. Appl Catal B 132:107–115

    Article  Google Scholar 

  20. Ramamurthy CH, Padma M, Samadanam IDM, Mareeswaran R, Suyavaran A, Sureshkumar M, Premkumar K, Thirunavukkarasu C (2013) The extra cellular synthesis of gold and silver nanoparticles and their free radical scavenging and antibacterial properties. Colloids Surf B 102:808–815

    Article  Google Scholar 

  21. Vincent A, Inerbaev TM, Babu S, Karakoti AS, Self WT, Masunov AE, Seal S (2010) Tuning hydrated nanoceria surfaces: experimental/theoretical investigations of ion exchange and implications in organic and inorganic interactions. Langmuir 26:7188–7198

    Article  Google Scholar 

  22. Menchón C, Martín R, Apostolova N, Victor VM, Alvaro M, Herance JR, García H (2012) Gold nanoparticles supported on nanoparticulate ceria as a powerful agent against intracellular oxidative stress. Small 8:1895–1903

    Article  Google Scholar 

  23. Halliwell B, Gutteridge JMC, Aruoma OI (1987) The deoxyribose method: a Simple, “test-tube” assay for determination of rate constants for reactions of hydroxyl radicals. Anal Biochem 165:215–219

    Article  Google Scholar 

  24. Nishikimi M, Rao NA, Yagi K (1972) The occurrence of superoxide anion in the reaction of reduced phenazine methosulfate and molecular oxygen. Biochem Biophys Res Commun 46:849–854

    Article  Google Scholar 

  25. Sousa C, Valentão P, Ferreres F, Seabra RM, Andrade PB (2008) Tronchuda cabbage (Brassica oleracea L. var. costata DC): scavenger of reactive nitrogen species. J Agric Food Chem 56:4205–4211

    Article  Google Scholar 

  26. Aboukaïs A, Aouad S, El-Ayadi H, Skaf M, Labaki M, Cousin R, Abi-Aad E (2012) Physicochemical characterization of Au/CeO2 solid. Part 1: the deposition-precipitation preparation method. Mat Chem Phys 137:34–41

    Article  Google Scholar 

  27. Gu L, Meng G (2007) Powder synthesis and characterization of nanocrystalline CeO2 via the combustion processes. Mater Res Bull 42:1323–1331

    Article  Google Scholar 

  28. Taguchi M, Takami S, Adschiri T, Nakane T, Sato K, Naka T (2011) Supercritical hydrothermal synthesis of hydrophilic polymer-modified water-dispersible CeO2 nanoparticles. Cryst Eng Comm 13:2841–2848

    Article  Google Scholar 

  29. Kominami H, Tanaka A, Hashimoto K (2011) Gold nanoparticles supported on cerium (IV) oxide powder for mineralization of organic acids in aqueous suspensions under irradiation of visible light of λ = 530 nm. Appl Catal A 397:121–126

    Article  Google Scholar 

  30. Wei Y, Liu J, Zhao Z, Duan A, Jiang G (2012) The catalysts of three-dimensionally ordered macroporous Ce1−xZrxO2-supported gold nanoparticles for soot combustion: the metal-support interaction. J Catal 287:13–29

    Article  Google Scholar 

  31. Kumar A, Babu S, Karakoti AS, Schulte A, Seal S (2009) Luminescence properties of europium-doped cerium oxide nanoparticles: role of vacancy and oxidation states. Langmuir 25:10998–11007

    Article  Google Scholar 

  32. Spanier JE, Robinson RD, Zheng F, Chan SW, Herman IP (2001) Size-dependent properties of CeO2-y nanoparticles as studied by Raman scattering. Phys Rev B 64:245407–245415

    Article  Google Scholar 

  33. Keramidast VG, White WB (1973) Raman spectra of oxides with the fluorite structure. J Chem Phys 59:1561–1562

    Article  Google Scholar 

  34. Mandal S, Bando KK, Santra C, Maity S, James OO, Mehtad D, Chowdhury B (2013) Sm-CeO2 supported gold nanoparticle catalyst for benzyl alcohol oxidation using molecular O2. Appl Catal A 452:94–104

    Article  Google Scholar 

  35. Patil S, Seal S, Guo Y, Schulte A, Norwood J (2006) Role of trivalent La and Nd dopants in lattice distortion and oxygen vacancy generation in cerium oxide nanoparticles. Appl Phys Lett 88:243110–243113

    Article  Google Scholar 

  36. Parayanthal P, Pollak FH (1984) Raman scattering in alloy semiconductors: “spatial correlation” model. Phys Rev Lett 52:1822–1825

    Article  Google Scholar 

  37. Trogadas P, Parrondo J, Ramani V (2012) CeO2 surface oxygen vacancy concentration governs in situ free radical scavenging efficacy in polymer electrolytes. ACS Appl Mater Interfaces 4:5098–5102

    Article  Google Scholar 

  38. Nolan M (2012) Charge transfer and formation of reduced Ce3+ upon adsorption of metal atoms at the ceria (110) surface. J Chem Phys 136:134703–134711

    Article  Google Scholar 

  39. Korsvik C, Patil S, Seal S, Self WT (2007) Superoxide dismutase mimetic properties exhibited by vacancy engineered ceria nanoparticles. Chem Commun 14:1056–1058

    Article  Google Scholar 

  40. Aboukaïs A, Aouad S, El-Ayadi H, Skaf M, Labaki M, Cousin R, Abi-Aad E (2012) Physicochemical characterization of Au/CeO2 solid. Part 1: the deposition–precipitation preparation method. Mater Chem Phys 137:34–41

    Article  Google Scholar 

  41. Chen B, Shi C, Crocker M, Wang Y, Zhu A (2013) Catalytic removal of formaldehyde at room temperature over supported gold catalysts. Appl Catal B Environ 132:245–255

    Article  Google Scholar 

Download references

Acknowledgements

Authors gratefully acknowledge the funding support from Start Up Grant (PU/PC/Start-up Grant/2011-12/312) provided by Pondicherry University, India as well as Indian Council of Medical Research (ICMR Ref: 52/13/2007) and Department of Science and Technology (NO.SR/FT/LS-63/2011), New Delhi, India. The authors wish to thank Central Instrumentation Facility (CIF), Pondicherry University for the characterization.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to K. Suresh Babu.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Anandkumar, M., Ramamurthy, C.H., Thirunavukkarasu, C. et al. Influence of age on the free-radical scavenging ability of CeO2 and Au/CeO2 nanoparticles. J Mater Sci 50, 2522–2531 (2015). https://doi.org/10.1007/s10853-014-8811-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-014-8811-1

Keywords

Navigation