Since air pollution is one of the most serious environmental problems, the study of the effects of particulate matter (PM) on physiological processes remains to be an important challenge for scientific communities. The presented studies form part of the project 'Air Pollution versus Autoimmunity: Role of multiphase aqueous Inorganic Chemistry'. In these studies we examined the effect of Standard Reference Material 1648a, supplied by the US National Institute of Standards and Technology (NIST), and its inorganic constituents on the formation of nitrosylcobalamin (CblNO) in the reaction between nitrocobalamin (CblNO 2 ) and ascorbic acid in a weakly acidic medium. We monitored the reaction in the presence of urban NIST PM (SRM 1648a), plasma treated NIST PM (LAP) and a number of metal oxide nanoparticles, including redox active metal oxides. The obtained results clearly demonstrated that the presence of these different nanoparticles affected the rate of formation of CblNO but did not affect the nature of the final product. Special attention was given to systematic studies on the role of inorganic nanoparticles as a part of the selected PM in the reaction between CblNO 2 and ascorbic acid.

Despite detailed studies on nitroxylcobalamin (CblNO) formation, the possible intracellular generation of CblNO via reduction of nitrocobalamin (CblNO2) remains questionable. To study this further, spectroscopic studies on the reaction of CblNO2 with the intracellular antioxidant ascorbic acid (HAsc−) were performed in aqueous solution at pH < 5.0. It was found that nitroxylcobalamin is the final product of this interaction, which is not just a simple reaction but a rather complex chemical process. We clearly show that an excess of nitrite suppresses the formation of CblNO, from which it follows that ascorbic acid cannot reduce coordinated nitrite. We propose that under the influence of ascorbic acid, nitrocobalamin is reduced to Cbl(II) and nitric oxide (·NO), which can subsequently react rapidly to form CblNO. It was further shown that this system requires anaerobic conditions as a result of the rapid oxidation of both Cbl(II) and CblNO.Graphical Abstract Electronic supplementary materialThe online version of this article (10.1007/s00775-018-1540-1) contains supplementary material, which is available to authorized users.

The interaction with nitric oxide (NO) is an important aspect of the biological activity of vitamin B12 (Cbl). Whereas the formation of nitroxylcobalamin (CblNO) via the binding of NO to reduced CblCo(II) has been studied in detail before, the possible intracellular formation of CblNO via reduction of nitrocobalamin (CblNO2) is still questionable. To study this further, spectroscopic and kinetic studies on the reaction of CblNO2 with the intracellular antioxidant ascorbic acid (Asc) were performed in aqueous solution at the physiological pH of 7.2. It was found that the redox pathway of this reaction requires anaerobic conditions as a result of the rapid re-oxidation of reduced CblCo(II). In the studied system, both CblOH2 and CblNO2 are reduced to CblCo(II) by ascorbate at pH 7.2, the CblOH2 complex being two orders of magnitude more reactive than CblNO2. Clear evidence for redox cycling between CblOH2/CblNO2 and CblCo(II) under aerobic conditions was observed as an induction period during which all oxygen was used prior to the formation of CblCo(II) in the presence of an excess of ascorbate. No evidence for the intermediate formation of CblNO or NO radicals during the reduction of CblNO2 could be found. Nitrocob(III)alamin can be reduced by ascorbic acid under physiological conditions. The products of the reaction are cob(II)alamin and nitrite ion. This reaction is ca. 200 times slower than the one involving aquacob(III)alamin.

This review describes a personal journey over the past two decades highlighting experimental and computational mechanistic studies in inorganic chemistry performed with numerous PhD students, post-docs, visiting scientists and colleagues from abroad.

Air pollution remains a serious problem in Krakow, Poland. According to the European Environmental Agency, annual mean levels of both PM2.5 and PM10 recorded in Krakow are much higher than EU limit values. Thus, the influence of particulate matter (PM) on the function of living organisms, as well as different physiological processes, is an urgent subject to be studied. The reported research forms part of the multi-disciplinary project ‘Air Pollution versus Autoimmunity: Role of multiphase aqueous Inorganic Chemistry,’ which aims to demonstrate the PM effect on the immune system. The present studies focused on the role of dust collected in Krakow on the redox cycling of vitamin B12a in the presence of ascorbic acid. Dust samples collected during the winter 2019/2020 and summer 2020 months in the city center of Krakow were characterized using various analytical techniques. The influence of Krakow dusts on the kinetics of the reaction between nitrocobalamin and ascorbic acid was confirmed and discussed in terms of the composition of the samples. Possible reasons for the reported findings are provided.