ABSTRACT
We have synthesized anthracene and metal@anthracene core-shell nanoparticles to combine radiation (RT) and photodynamic (PDT) therapies. Synthesis of anthracene nanoparticles in the presence of colloidal silver or gold reduced the nanoparticles hydrodynamic radius, caused core-shell nanostructures to grow, and led to plasmon-enhanced fluorescence. Singlet oxygen (1O2) generation was investigated by electron spin resonance (ESR) and fluorescence spectroscopies. In the presence of a porphyrin, anthracene nanoparticles and the core-shell nanoparticles acted as energy mediators and increased 1O2 generation under exposure to light, as evidenced by the ESR results. Fluorescence suppression experiments showed that the core-shell nanoparticles captured 1O2 at rates higher than anthracene nanoparticles, suggesting that overall production of 1O2 (1O2 captured by spin-trap + 1O2 captured by surface anthracene molecules) was higher for the core-shell nanoparticles. Moreover, the Ag@anthracene nanoparticles stood out as a new and more sensitive fluorescent probe for 1O2. During irradiation with X-rays, both anthracene and Ag@anthracene nanoparticles trapped 1O2; subsequently, they afforded sustained release of the trapped 1O2 for up 12 days after irradiation. This could be an interesting strategy to extend the radiation therapy treatment after the irradiation sessions. Furthermore, the presence of the metallic nanoparticle in the core of the core-shell nanostructure increased interaction with X-rays, raising the radiation dose around the nanoparticle. Therefore, metal@anthracene nanostructures may allow combination of cancer treatments by different approaches depending on the adopted nanoparticle configuration.
Subject(s)
Metal Nanoparticles , Nanoparticles , Neoplasms , Photochemotherapy , Anthracenes , Gold , Neoplasms/drug therapy , SilverABSTRACT
The optical properties of core-shell nanoparticles consisting of a ZnO shell grown on Ag and Au nanoparticle cores by a solution method have been investigated. Both the ZnO/Ag and ZnO/Au particles exhibit strongly enhanced near-band-edge UV emission from the ZnO when excited at 325 nm. Furthermore, the UV intensity increases with the metal nanoparticle concentration, with 60-fold and 17-fold enhancements for the ZnO/Ag and ZnO/Au, core-shell nanoparticles respectively. Accompanying the increase in UV emission, there is a corresponding decrease in the broad band defect emission with nanoparticle concentration. Nonetheless, the broad band luminescence increases with laser power. The results are consistent with enhanced exciton emission in the ZnO shells due to coupling with surface plasmon resonance of the metal nanoparticles. Luminescence measurements during and after exposure to X-rays also exhibit enhanced UV luminescence. These observations suggest that metal nanoparticles may be suitable for enhancing optical detection of ionizing radiation.
ABSTRACT
In this work, we aim to experimentally assess increments of dose due to nanoparticle-radiation interactions via electron spin resonance (ESR) dosimetry performed with a biological-equivalent sensitive material.We employed 2-Methyl-Alanine (2MA) in powder form to compose the radiation sensitive medium embedding gold nanoparticles (AuNPs) 5 nm in diameter. Dosimeters manufactured with 0.1% w/w of AuNPs or no nanoparticles were irradiated with clinically utilized 250 kVp orthovoltage or 6 MV linac x-rays in dosimetric conditions. Amplitude peak-to-peak (App) at the central ESR spectral line was used for dosimetry. Dose-response curves were obtained for samples with or without nanoparticles and each energy beam. Dose increments due to nanoparticles were analyzed in terms of absolute dose enhancements (DEs), calculated as App ratios for each dose/beam condition, or relative dose enhancement factors (DEFs) calculated as the slopes of the dose-response curves.Dose enhancements were observed to present an amplified behavior for small doses (between 0.1-0.5 Gy), with this effect being more prominent with the kV beam. For doses between 0.5-5 Gy, dose-independent trends were observed for both beams, stable around (2.1 ± 0.7) and (1.3 ± 0.4) for kV and MV beams, respectively. We found DEFs of (1.62 ± 0.04) or (1.27 ± 0.03) for the same beams. Additionally, we measured no interference between AuNPs and the ESR apparatus, including the excitation microwaves, the magnetic fields and the paramagnetic radicals.2MA was demonstrated to be a feasible paramagnetic radiation-sensitive material for dosimetry in the presence of AuNPs, and ESR dosimetry a powerful experimental method for further verifications of increments in nanoparticle-mediated doses of biological interest. Ultimately, gold nanoparticles can cause significant and detectable dose enhancements in biological-like samples irradiated at both kilo or megavoltage beams.
