Advertisement

Synthesis of highly fluorescent silica nanoparticles in a reverse microemulsion through double-layered doping of organic fluorophores

  • Hyojong Yoo
  • Joonsung Pak
Research Paper

Abstract

Water-soluble, highly fluorescent double-layered silica nanoparticles (FL-DLSN) have been successfully synthesized through a reverse (water-in-oil) microemulsion method. The microemulsion was prepared by mixing a surfactant (Brij35), co-surfactant, organic solvent, water, and fluorescein as an organic fluorophore. The sizes of the silica nanoparticles were successfully controlled in the reverse microemulsion using Brij35 by changing the water-to-Brij35 ratio and by adding HCl. Initially, tetraethylorthosilicate was hydrolyzed by adding NH4OH as a catalyst and then polymerized to generate core fluorescent silica nanoparticles with fluorescein. 3-(Aminopropyl)triethoxysilane (APTS) was sequentially added into the reaction mixture, and reacted on the surface of pre-generated core silica nanoparticles to form the second layer in the form of a shell. The second silica layer that was derived from the condensation of APTS effectively protected the fluorescein dye within the silica matrix. This is a novel and simple synthetic approach to generate highly fluorescent, monodispersed silica nanoparticles by doping organic molecules into a silica matrix.

Graphical Abstract

Keywords

Organic dye-doped Fluorescent silica nanoparticles Reverse microemulsion Fluorescein Brij35 

Notes

Acknowledgments

This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2011-0008968), by Bio-industry Technology Development Program, Ministry for Food, Agriculture, Forestry and Fisheries, Republic of Korea (112029-1), and by Business for Cooperative R&D between Industry, Academy, and Research Institute funded Korea Small and Medium Business Administration in 2011 (Grant No. 00046613).

Supplementary material

11051_2013_1609_MOESM1_ESM.pdf (513 kb)
Supplementary material 1 (PDF 513 kb)

References

  1. Bagwe RP, Yang C, Hilliard LR, Tan W (2004) Optimization of dye-doped silica nanoparticles prepared using a reverse microemulsion method. Langmuir 20(19):8336–8342CrossRefGoogle Scholar
  2. Bagwe RP, Hilliard LR, Tan W (2006) Surface modification of silica nanoparticles to reduce aggregation and nonspecific binding. Langmuir 22(9):4357–4362CrossRefGoogle Scholar
  3. Brinker CJ, Scherer GW (1990) Sol–gel science: the physics and chemistry of sol–gel processing. Academic, BostonGoogle Scholar
  4. Chang CL, Fogler HS (1997) Controlled formation of silica particles from tetraethyl orthosilicate in nonionic water-in-oil microemulsions. Langmuir 13(13):3295–3307CrossRefGoogle Scholar
  5. Durgun G, Ocakoglu K, Ozcelik S (2011) Systematic tuning the hydrodynamic diameter of uniformed fluorescent silica nanoparticles. J Phys Chem C 115(33):16322–16332CrossRefGoogle Scholar
  6. Hartlen KD, Athanasopoulos APT, Kitaev V (2008) Facile preparation of highly monodisperse small silica spheres (15 to >200 nm) suitable for colloidal templating and formation of ordered arrays. Langmuir 24(5):1714–1720CrossRefGoogle Scholar
  7. He X, Chen J, Wang K, Qin D, Tan W (2007) Preparation of luminescent Cy5 doped core-shell SFNPs and its application as a near-infrared fluorescent marker. Talanta 72(4):1519–1526CrossRefGoogle Scholar
  8. Imhof A, Megens M, Engelberts JJ, De Lang DTN, Sprik R, Vos WL (1999) Spectroscopy of fluorescein (FITC) dyed colloidal silica spheres. J Phys Chem B 103(9):1408–1415CrossRefGoogle Scholar
  9. Jang MH, Kim JK, Tak H, Yoo H (2011) Controllable synthesis of multi-layered gold spirangles. J Mater Chem 21:17606–17608CrossRefGoogle Scholar
  10. Jang MH, Kim JK, Yoo H (2012) Nonionic brij surfactant-mediated synthesis of raspberry-like gold nanoparticles with high surface area. J Nanosci Nanotechnol 12(5):4088–4092CrossRefGoogle Scholar
  11. Lakowicz JR (2006) Principles of fluorescence spectroscopy, 3rd edn. Springer, USACrossRefGoogle Scholar
  12. Lei J, Wang L, Zhang J (2011) Superbright multifluorescent core-shell mesoporous nanospheres as trackable transport carrier for drug. ACS Nano 5(5):3447–3455CrossRefGoogle Scholar
  13. Nyffenegger R, Quellet C, Ricka J (1993) Synthesis of fluorescent, monodisperse, colloidal silica particles. J Colloid Interface Sci 159(1):150–157CrossRefGoogle Scholar
  14. Ow H, Larson DR, Srivastava M, Baird BA, Webb WW, Wiesner U (2005) Bright and stable core-shell fluorescent silica nanoparticles. Nano Lett 5(1):113–117CrossRefGoogle Scholar
  15. Pak J, Yoo H (2013) Facile synthesis of spherical nanoparticles with a silica shell and multiple Au nanodots as the core. J Mater Chem A. doi: 10.1039/c3ta10613f (ASAP)Google Scholar
  16. Pant D, Levinger NE (2000) Polar solvation dynamics in nonionic reverse micelles and model polymer solutions. Langmuir 16(26):10123–10130CrossRefGoogle Scholar
  17. Santra S, Zhang P, Wang K, Tapec R, Tan W (2001a) Conjugation of biomolecules with luminophore-doped silica nanoparticles for photostable biomarkers. Anal Chem 73(20):4988–4993CrossRefGoogle Scholar
  18. Santra S, Wang K, Tapec R, Tan W (2001b) Development of novel dye-doped silica nanoparticles for biomarker application. J Biomed Opt 6(2):160–166CrossRefGoogle Scholar
  19. Santra S, Bagwe RP, Dutta D, Stanley JT, Walter GA, Tan W, Moudgil BM, Mericle RA (2005) Synthesis and characterization of fluorescent, radio-opaque, and paramagnetic silica nanoparticles for multimodal bioimaging applications. Adv Mater 17(18):2165–2169CrossRefGoogle Scholar
  20. Slowing II, Trewyn BG, Giri S, Lin VSY (2007) Mesoporous silica nanoparticles for drug delivery and biosensing applications. Adv Funct Mater 17(8):1225–1236CrossRefGoogle Scholar
  21. Stöber W, Fink A, Bohn E (1968) Controlled growth of monodisperse silica spheres in the micron size range. J Colloid Interface Sci 26(1):62–69CrossRefGoogle Scholar
  22. Tapec R, Zhao XJ, Tan W (2002) Development of organic dye-doped silica nanoparticles for bioanalysis and biosensors. J Nanosci Nanotechnol 2(3–4):405–409CrossRefGoogle Scholar
  23. Van Blaaderen A, Vrij A (1992) Synthesis and characterization of colloidal dispersions of fluorescent, monodisperse silica spheres. Langmuir 8(12):2921–2931CrossRefGoogle Scholar
  24. Verhaegh NAM, Blaaderen A (1994) Dispersions of rhodamine-labeled silica spheres: synthesis, characterization, and fluorescence confocal scanning laser microscopy. Langmuir 10(5):1427–1438CrossRefGoogle Scholar
  25. Wang L, Zhao W, O’Donoghu MB, Tan W (2007a) Fluorescent nanoparticles for multiplexed bacteria monitoring. Bioconjug Chem 18(2):297–301CrossRefGoogle Scholar
  26. Wang L, Lofton C, Popp M, Tan W (2007b) Using luminescent nanoparticles as staining probes for affymetrix genechips. Bioconjug Chem 18(3):610–613CrossRefGoogle Scholar
  27. Yao G, Wang L, Wu Y, Smith J, Xu J, Zhao W, Lee E, Tan W (2006) Flodots: luminescent nanoparticles. Anal Bioanal Chem 385(3):518–524CrossRefGoogle Scholar
  28. Yin D, Liu B, Zhang L, Xie C, Zhang L (2010) Synthesis of Ru(bpy)3-doped silica nanoparticle and its application in fluorescent immunoassay. Nano Biomed Eng 2(2):117–120CrossRefGoogle Scholar
  29. Yokoi T, Sakamoto Y, Terasaki O, Kubota Y, Okubo T, Tatsumi T (2006) Periodic arrangement of silica nanospheres assisted by amino acids. J Am Chem Soc 128(42):13664–13665CrossRefGoogle Scholar
  30. Yoo H, Sharma J, Kim JK, Shreve AP, Martinez JS (2011) Tailored microcrystal growth: a facile solution-phase synthesis of gold rings. Adv Mater 23:4431–4434CrossRefGoogle Scholar
  31. Zhang R, Wu C, Tong L, Tang B, Xu QH (2009) Multifunctional core–shell nanoparticles as highly efficient imaging and photosensitizing agents. Langmuir 25(17):10153–10158CrossRefGoogle Scholar
  32. Zhao X, Tapec-Dytioco R, Tan W (2003) Ultrasensitive DNA detection using highly fluorescent bioconjugated nanoparticles. J Am Chem Soc 125(38):11474–11475CrossRefGoogle Scholar
  33. Zhao X, Bagwe RP, Tan W (2004) Development of organic-dye-doped silica nanoparticles in a reverse microemulsion. Adv Mater 16(2):173–176CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  1. 1.Department of ChemistryHallym UniversityChuncheon-siRepublic of Korea

Personalised recommendations