Search Results (3)

The exchange coupling, represented by the J parameter, is of tremendous importance in understanding the reactivity and magnetic behavior of open-shell molecular systems. In the past, it was the subject of theoretical investigations, but these studies are mostly limited to the interaction between metallic centers. The exchange coupling between paramagnetic metal ions and radical ligands has hitherto received scant attention in theoretical studies, and thus the understanding of the factors governing this interaction is lacking. In this paper, we use DFT, CASSCF, CASSCF/NEVPT2, and DDCI3 methods to provide insight into exchange interaction in semiquinonato copper(II) complexes. Our primary objective is to identify structural features that affect this magnetic interaction. We demonstrate that the magnetic character of Cu(II)-semiquinone complexes are mainly determined by the relative position of the semiquinone ligand to the Cu(II) ion. The results can support the experimental interpretation of magnetic data for similar systems and can be used for the in-silico design of magnetic complexes with radical ligands. Full article

Environmentally persistent free radicals (EPFRs) are a kind of hazardous substance that exist stably in the atmosphere for a long time. EPFRs combined with fine particulate matter (PM_2.5) can enter the human respiratory tract through respiration, causing oxidative stress and DNA damage, and they are also closely related to lung cancer. In this study, the inhalation risk for EPFRs in PM_2.5 and factors influencing this risk were assessed using the equivalent number of cigarette tar EPFRs. The daily inhalation exposure for EPFRs in PM_2.5 was estimated to be equivalent to 0.66–8.40 cigarette tar EPFRs per day. The concentration level and species characteristics were investigated using electron paramagnetic resonance spectroscopy. The concentration of EPFRs in the study ranged from 1.353–4.653 × 10¹³ spins/g, and the types of EPFRs were mainly oxygen- or carbon-centered semiquinone-type radicals. Our study showed that there is a strong correlation between the concentrations of EPFRs and conventional pollutants, except for sulfur dioxide. The major factors influencing EPFR concentration in the atmosphere were temperature and wind speed; the higher the temperature and wind speed, the lower the concentration of EPFRs. The findings of this study provide an important basis for further research on the formation mechanism and health effects of EPFRs. Full article

The main aim of this study was to investigate metabolic responses of fruits, leaves, and shoots of pistachio trees (Pistacia vera L. cv. Kirmizi) during their development. Electron paramagnetic resonance spectroscopy revealed significant increase in generation of semiquinone radicals in fruits and leaves of pistachio, while the flower cluster thinning application was conducted in relation to the control; especially at the second term of the plant material collection. Moreover, flower abscission caused an increase in the level of phytohormones such as indole-3-acetic acid and abscisic acid in fruits at the first term of fruits sampling. In turn, high-performance liquid chromatography analysis revealed differences both in the profile as well as the contents of soluble sugars detected in pistachio organs. The highest total sugar content was found in fruits of pistachio where the flower cluster thinning application was made early. Total sugar levels were higher also in leaves and shoots of the above-mentioned pistachio plants in relation to the control until the third sampling time. The importance of high levels of fructose in the fruits following the flower abscission was observed. Additionally, analyses of mineral elements in organs showed that copper and phosphorus contents in fruits were higher after the flower abscission in relation to the control. To conclude, our findings signal on contribution of semiquinone radicals, paramagnetic manganese ions, phytohormones, nutrients, and sugars in pistachio organs development on the background of the flower cluster thinning which was applied before fructification. Full article