Silica-and organic polymer insulated superparamagnetic nanoparticles have been studied and applied within a range of biomedical applications.1,2 Surface insulating layers can decrease the cytotoxicity of the internal magnetic particle core during in vivo-and in vitro applications. Besides the quenching effect on toxicity, surface coating layers can work as platforms to impart additional functionality. Especially, silica surface chemistry serves a good hydrophilic function and augments easy modification for tagging biomedicalfunctioning moieties.
3-6Reliable and rapid monitoring of bio-events and environments can provide early information of surroundings. Realtime sensing systems normally monitor changes in optical or electrical signals, allowing us to quickly recognize variations in our environment.7,8 Surface plasmonic resonance (SPR) is a colligative value of oscillation changes at a metal surface, and its oscillation frequency is much dependent on the refractive index of materials adsorbed onto the metal surface. For example, when biomolecules are adsorbed onto the metal surface, it would induce a local refractive index change, and thereby change the SPR extinction and frequency.9 Complementary base conjugated Au nanoparticle assembly has been applied to detect analyte by visual effects. However, there are scanty studies on recyclable Au nanohybrid sensors.
10In this study, we developed a real-time and recyclable optical biosensor using nanohybrids of Au and superparamagnetic nanoparticles. For utilizing SPR effects, Au nanoparticle was conjugated onto silica coated magnetic nanoparticles (see Figure 1). Controlled silica shell thickness caused tunable SPR effects.First, monodisperse silica-coated Fe 2 O 3 nanoparticles, hereafter noted as SiO 2 /Fe 2 O 3 , were prepared. γ-Fe 2 O 3 nanoparticles were coated with thin (~2 nm) or thick (~17 nm) silica shell employing water-in-cyclohexane reverse microemulsion technique. For a thin (2 nm-thick) silica shell, polyoxyethylene(5)nonylphenyl ether (0.56 mmol) was dispersed in cyclohexane (4.2 mL) by sonication. Then 400 μL of Fe 2 O 3 solution (0.8 mg/mL of cyclohexane) was added. The resulting mixture was vortexed, and ammonium hydroxide (29.4%, 35 μL) was added to form a transparent reverse microemulsion. Next, tetraethylorthosilicate (2 μL, TEOS) was added, and the reaction was continued for 12 h at room temperature. In the case of thick silica shell (17 nmthick) preparation, TEOS content and sol-gel aging time were increased to 20 μL and 48 h, respectively. By adding methanol into the reaction solution, SiO 2 /Fe 2 O 3 nanoparticles were precipitated and collected by a magnet. They were functionalized with amine functionalities, which have been known to have strong affinity with transition metal nanoclusters, such as Fe 3 O 4 , and Au.11,12 In this study, 340 mg of SiO 2 /Fe 2 O 3 were functionalized with 0.075 mmol of n-(2-amino ethyl)-3-aminopropyltrimethoxysilane (AAPS, Gelest) by refluxing in toluene for 30 h. Next, Au was introduced as HAuCl 4 to the surfa...