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.
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Bagwe RP, Yang C, Hilliard LR, Tan W (2004) Optimization of dye-doped silica nanoparticles prepared using a reverse microemulsion method. Langmuir 20(19):8336–8342
Bagwe RP, Hilliard LR, Tan W (2006) Surface modification of silica nanoparticles to reduce aggregation and nonspecific binding. Langmuir 22(9):4357–4362
Brinker CJ, Scherer GW (1990) Sol–gel science: the physics and chemistry of sol–gel processing. Academic, Boston
Chang CL, Fogler HS (1997) Controlled formation of silica particles from tetraethyl orthosilicate in nonionic water-in-oil microemulsions. Langmuir 13(13):3295–3307
Durgun G, Ocakoglu K, Ozcelik S (2011) Systematic tuning the hydrodynamic diameter of uniformed fluorescent silica nanoparticles. J Phys Chem C 115(33):16322–16332
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):1714–1720
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):1519–1526
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):1408–1415
Jang MH, Kim JK, Tak H, Yoo H (2011) Controllable synthesis of multi-layered gold spirangles. J Mater Chem 21:17606–17608
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):4088–4092
Lakowicz JR (2006) Principles of fluorescence spectroscopy, 3rd edn. Springer, USA
Lei J, Wang L, Zhang J (2011) Superbright multifluorescent core-shell mesoporous nanospheres as trackable transport carrier for drug. ACS Nano 5(5):3447–3455
Nyffenegger R, Quellet C, Ricka J (1993) Synthesis of fluorescent, monodisperse, colloidal silica particles. J Colloid Interface Sci 159(1):150–157
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):113–117
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)
Pant D, Levinger NE (2000) Polar solvation dynamics in nonionic reverse micelles and model polymer solutions. Langmuir 16(26):10123–10130
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):4988–4993
Santra S, Wang K, Tapec R, Tan W (2001b) Development of novel dye-doped silica nanoparticles for biomarker application. J Biomed Opt 6(2):160–166
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):2165–2169
Slowing II, Trewyn BG, Giri S, Lin VSY (2007) Mesoporous silica nanoparticles for drug delivery and biosensing applications. Adv Funct Mater 17(8):1225–1236
Stöber W, Fink A, Bohn E (1968) Controlled growth of monodisperse silica spheres in the micron size range. J Colloid Interface Sci 26(1):62–69
Tapec R, Zhao XJ, Tan W (2002) Development of organic dye-doped silica nanoparticles for bioanalysis and biosensors. J Nanosci Nanotechnol 2(3–4):405–409
Van Blaaderen A, Vrij A (1992) Synthesis and characterization of colloidal dispersions of fluorescent, monodisperse silica spheres. Langmuir 8(12):2921–2931
Verhaegh NAM, Blaaderen A (1994) Dispersions of rhodamine-labeled silica spheres: synthesis, characterization, and fluorescence confocal scanning laser microscopy. Langmuir 10(5):1427–1438
Wang L, Zhao W, O’Donoghu MB, Tan W (2007a) Fluorescent nanoparticles for multiplexed bacteria monitoring. Bioconjug Chem 18(2):297–301
Wang L, Lofton C, Popp M, Tan W (2007b) Using luminescent nanoparticles as staining probes for affymetrix genechips. Bioconjug Chem 18(3):610–613
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):518–524
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):117–120
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):13664–13665
Yoo H, Sharma J, Kim JK, Shreve AP, Martinez JS (2011) Tailored microcrystal growth: a facile solution-phase synthesis of gold rings. Adv Mater 23:4431–4434
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):10153–10158
Zhao X, Tapec-Dytioco R, Tan W (2003) Ultrasensitive DNA detection using highly fluorescent bioconjugated nanoparticles. J Am Chem Soc 125(38):11474–11475
Zhao X, Bagwe RP, Tan W (2004) Development of organic-dye-doped silica nanoparticles in a reverse microemulsion. Adv Mater 16(2):173–176
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).
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Yoo, H., Pak, J. Synthesis of highly fluorescent silica nanoparticles in a reverse microemulsion through double-layered doping of organic fluorophores. J Nanopart Res 15, 1609 (2013). https://doi.org/10.1007/s11051-013-1609-2
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DOI: https://doi.org/10.1007/s11051-013-1609-2