Size-Controlled Microwave-Assisted Synthesis of Water-Dispersible Cd(Se,S) Quantum Dots for Potential Biological Applications
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abstract
Nanomedicine is fostering significant advances in the development of platforms for early detection and treatment of diseases. Nanoparticles (NPs) like quantum dots (QDs) exhibit size-dependent optical properties for light-driven technologies, which might become important in bio-imaging, sensing and photo-dynamic therapy (PDT) applications. The present research addresses the synthesis of water-stable Cd-based QDs via a Microwave-Assisted synthesis approach using cadmium sulfate salt, and thioglycolic acid as Cd- and S-precursors, respectively. Selenide ions were available by reductive leaching of metallic Selenium in Sodium bisulfite solution. The size control and the tunability of the optical properties were achieved by a suitable control of the reaction temperature (in the 140°C- 190°C range) and reaction time (10 minutes-40 minutes). X-ray diffraction analyses suggested the development of a CdSe,S face cubic centered structure; the broadening of the diffraction peaks indicated the presence of very small nanocrystals in the samples. The average crystallite size was estimated at 5.50 nm ± 1.17nm and 3.72 nm ± 0.04 nm, for nanoparticles synthesized at 180°C after 40 minutes or 10 minutes of reaction, respectively. HRTEM images confirmed the crystalline nature and the small size of the synthesized nanocrystals. In turn, the exciton was red-shifted from 461nm to 549 nm when the reaction temperature was prolonged from 140°C to 190 °C, suggesting the crystal growth. The corresponding band gap values were approximately 2.2 eV, confirming the quantum confinement effect (bulk value 1.74eV). This red shift was also evidenced in PL measurements where the main emission peak was shifted from 507 nm to 564 nm when the samples were excited at 420 nm. A narrow size-tunable emission also was supported by the full width at half maximum (∼ 45 nm) for the synthesized nanocrystals. The reactive oxygen species generation capability of as-synthesized QDs was also investigated. The correlation between the particle size and the generation of (ROS) by the degradation of methylene blue was evident with a reduction of MB concentration from 10μM to 7.5μM and 6.7μM after 15 minutes of UV irradiation for reaction time of 10 min. and 40 min. respectively. No additional degradation was noticed after 60 minutes of irradiation.
