EPR spectroscopy investigation of oxygen radical production by methylene blue and indocyanine green in aqueous solutions under laser irradiation in the context of antibacterial photodynamic therapy

Introduction: Antibacterial photodynamic therapy is a promising treatment modality in the anti-infective therapy of numerous oral diseases. It involves photo activation of a reactive substance (dye), thus releasing reactive oxygen species (ROS-radicals) which are highly destructive to the bacterial cell. However, thorough investigation of radical production properties of different dyes is not common in literature. Aim: The aim of this study was to investigate and evaluate oxygen radical-producing potential of two commonly used photoactive dyes in the context of antibacterial photodynamic therapy. Materials and methods: The radical-producing properties of two commonly used dyes for photodynamic therapy in oral medicine, methylene blue and indocyanine green, irradiated under laser irradiation are investigated using electron paramagnetic resonance (EPR) spectroscopy. The detection of reactive oxygen species is performed with “spin-trapping” technique. Results: The selected photoactive dyes showed promising yields of reactive oxygen species (ROS) in aqueous solutions. The comparative analysis of the results deemed methylene blue as the more productive photoactive agent. Conclusions: By employing the spin-trapping technique, this study indicates EPR-spectroscopy as a promising method of relative quantification of reactive oxygen species released by the photodynamic reaction in aqueous solutions.

Electrospun Nanosystems Based on PHBV and ZnO for Ecological Food Packaging

The electrospun nanosystems containing poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and 1 wt% Fe doped ZnO nanoparticles (NPs) (with the content of dopant in the range of 0–1 wt% Fe) deposited onto polylactic acid (PLA) film were prepared for food packaging application. They were investigated by scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), antimicrobial analysis, and X-ray photoelectron spectrometry (XPS) techniques. Migration studies conducted in acetic acid 3% (wt/wt) and ethanol 10% (v/v) food simulants as well as by the use of treated ashes with 3% HNO3 solution reveal that the migration of Zn and Fe falls into the specific limits imposed by the legislation in force. Results indicated that the PLA/PHBV/ZnO:Fex electrospun nanosystems exhibit excellent antibacterial activity against the Pseudomonas aeruginosa (ATCC-27853) due to the generation of a larger amount of perhydroxyl (˙OOH) radicals as assessed using electron paramagnetic resonance (EPR) spectroscopy coupled with a spin trapping method.

Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase

Short-lived highly reactive atmospheric species, such as organic peroxy radicals (RO2) and stabilized Criegee intermediates (SCIs), play an important role in controlling the oxidative removal and transformation of many natural and anthropogenic trace gases in the atmosphere. Direct speciated measurements of these components are extremely helpful for understanding their atmospheric fate and impact. We describe the development of an online method for measurements of SCIs and RO2 in laboratory experiments using chemical derivatization and spin trapping techniques combined with H3O+ and NH4+ chemical ionization mass spectrometry (CIMS). Using chemical derivatization agents with low proton affinity, such as electron-poor carbonyls, we scavenge all SCIs produced from a wide range of alkenes without depleting CIMS reagent ions. Comparison between our measurements and results from numeric modeling, using a modified version of the Master Chemical Mechanism, shows that the method can be used for the quantification of SCIs in laboratory experiments with a detection limit of 1.4×107 molecule cm−3 for an integration time of 30 s with the instrumentation used in this study. We show that spin traps are highly reactive towards atmospheric radicals and form stable adducts with them by studying the gas-phase kinetics of the reaction of spin traps with the hydroxyl radical (OH). We also demonstrate that spin trap adducts with SCIs and RO2 can be simultaneously probed and quantified under laboratory conditions with a detection limit of 1.6×108 molecule cm−3 for an integration time of 30 s for RO2 species with the instrumentation used in this study. Spin trapping prevents radical secondary reactions and cycling, ensuring that measurements are not biased by chemical interferences, and it can be implemented for detecting RO2 species in laboratory studies and potentially in the ambient atmosphere.