Fabrication, light emission, and magnetism of silica nanoparticles hybridized with AIE luminogens and inorganic nanostructures

Much research efforts have been devoted in developing new synthetic approaches for fluorescent silica nanoparticles (FSNPs) due to their potential high-technological applications. However, light emissions from most of the FSNPs prepared so far have been rather weak. This is due to the emission quenching caused by the aggregation of fluorophores in the solid state. We have observed a novel phenomenon of aggregation-induced emission (AIE): a series of propeller-shaped molecules such as tetraphenylethene (TPE) and silole are induced to emit efficiently by aggregate formation. Thus, they are ideal fluorophors for the construction of FSNPs and my thesis work focuses on the synthesis of silica nanoparticles containing these luminogens and magnetic nanostructures. Highly emissive FSNPs with core-shell structures are fabricated by surfactant-free sol-gel reactions of tetraphenylethene- (TPE) and silole-functionalized siloxanes followed by the reactions with tetraethoxysilane. The FSNPs are uniformly sized, surface-charged and colloidally stable. The diameters of the FSNPs are tunable in the range of 45–295 nm by changing the reaction conditions. Whereas their TPE and silole precursors are non-emissive, the FSNPs emit strong visible lights, thanks to the novel aggregation-induced emission characteristics of the TPE and silole aggregates in the hybrid nanoparticles. The FSNPs pose no toxicity to living cells and can be utilized to selectively image cytoplasm of HeLa cells. Applying the same tool in the presence of citrate-coated magnetite nanoparticles, uniform magnetic fluorescent silica nanoparticles (MFSNPs) with smooth surfaces are fabricated. These particles exhibit appreciable surface charges and hence good colloidal stability. They are superparamagnetic, exhibiting no hysteresis at room temperature. UV irradiation of a suspension of MFSNPs in ethanol gives strong blue and green emissions. The MFSNPs can selectively stain the cytoplasmic regions of the living cells. Sol-gel reaction in the presence of (3-aminopropyl)triethoxysilane has generated MFSNP-NH2 with numerous amino functionalities decorated on the surfaces, enabling them to immobilize bovine serum albumin efficiently. FSNPs with strong light emissions are facilely fabricated by thio-click chemistry, Cu(I)-catalyzed 1,3-dipolar cycloaddition, and sol-gel reaction. The FSNPs are characterized by SEM, TEM, IR, PL, and zeta potential analyses. They are uniformly sized with smooth surfaces. Upon photoexcitation, the FSNPs emit strong visible lights with fluorescence quantum yields up to 25.5%. Sugar-functionalized fluorescent silica nanoparticles are facilely fabricated by click reaction of azide-modified FSNPs with sugar- containing phenylacetylene catalyzed by Cu(PPh3)3Br in THF. The nanoparticles are uniformly sized and emit efficient light upon photoexcitation. They can function as fluorescent visualizers for intracellular imaging and can target specific cancer cells. Folic acid-functionalized fluorescent silica nanoparticles are facilely fabricated by surface functionalization of FSNPs with folic acid. The nanoparticles are spherical in shape. They possess high zeta potentials and hence exhibit excellent colloidal stability. UV irradiation of suspensions of the nanoparticles in ethanol gives strong blue and green emissions at 465 and 490 nm with absolute fluorescence quantum yields up to 47%. Carboxylic acid and thiol-functionalized fluorescent silica nanoparticles (FSNP-COOH and FSNP-SH) with uniform particle sizes, narrow size distributions, and smooth surface morphologies are fabricated. The nanoparticles possess high surface charges and exhibit strong light emissions upon photoexcitation. They can adsorb lysozyme strongly on their surfaces and for 5 mg of FSNP-COOH and FSNP-SH, they can take 209 and 86 μg of lysozyme. Thus, they are potential carriers for protein and fluorescent probes or biosensors for an array of biological applications