Peroxide-Mediated Oxygenation of Organic Compounds by Fungal Peroxygenases

Unspecific peroxygenases (UPOs), whose sequences can be found in the genomes of thousands of filamentous fungi, many yeasts and certain fungus-like protists, are fascinating biocatalysts that transfer peroxide-borne oxygen (from H2O2 or R-OOH) with high efficiency to a wide range of organic substrates, including less or unactivated carbons and heteroatoms. A twice-proline-flanked cysteine (PCP motif) typically ligates the heme that forms the heart of the active site of UPOs and enables various types of relevant oxygenation reactions (hydroxylation, epoxidation, subsequent dealkylations, deacylation, or aromatization) together with less specific one-electron oxidations (e.g., phenoxy radical formation). In consequence, the substrate portfolio of a UPO enzyme always combines prototypical monooxygenase and peroxidase activities. Here, we briefly review nearly 20 years of peroxygenase research, considering basic mechanistic, molecular, phylogenetic, and biotechnological aspects.

Hydrogen peroxide measurements: its wet deposition in Higashi-Hiroshima city, concentration in Kurose River and role towards hydroxyl radical formation

No Abstract.

Wavelength, dose, skin type and skin model related radical formation in skin

The exposure to sun radiation is indispensable to our health; however, a long-term and high exposure could lead to cell damage, erythema, premature skin aging, and promotion of skin tumors. An underlying pathomechanism is the formation of free radicals which may induce oxidative stress at elevated concentrations. Different skin models, such as porcine-, murine-, human- ex vivo skin, reconstructed human skin (RHS) and human skin in vivo, were investigated during and after irradiation using X- and L-band EPR spectroscopy within different spectral regions (UVC to NIR). The amount of radical formation was quantified with the spin probe PCA and the radical types were measured ex vivo with the spin trap DMPO. The radiation dose influences the types of radicals formed in the skin. While reactive oxygen species (ROS) are always pronounced at low doses, there is an increase in lipid oxygen species (LOS) at high doses. Furthermore, the radical types arise independent from the irradiation wavelength, whereas the general amount of radical formation differs with the irradiation wavelength. Heat pre-stressed porcine skin already starts with higher LOS values. Thus, the radical type ratio might be an indicator of stress and the reversal of ROS/LOS constitutes the point where positive stress turns into negative stress.Compared to light skin types, darker types produce less radicals in the ultraviolet, similar amounts in the visible and higher ones in the infrared spectral region, rendering skin type-specific sun protection a necessity.

Defluorination and adsorption of tetrafluoroethylene (TFE) on TiO2(110) and Cr2O3(0001)

Here, we show that metal oxide surfaces catalyze the formation of intermediate defluorinated tetrafluoroethylene (TFE) radicals, resulting in enhanced binding on the corresponding metal oxide surfaces. We attribute the preferential adsorption and radical formation of TFE on Cr2O3(0001) relative to TiO2(110) to the low oxygen coordination of Cr surface atoms. This hints at a possible dependence of the TFE binding strength to the surface stoichiometry of metal-oxide surfaces.

THE RADICAL FORMATION DURING THE HYDROQUINONE AUTOOXIDATION IN THE STRONG ALKALINE MEDIUM

При окислении гидрохинона в сильнощелочных средах основной вклад в процесс окисления вносит реакция прямого взаимодействия бианиона гидрохинона с кислородом. В результате исследования ингибированного аскорбиновой кислотой окисления гидрохинона в сильнощелочной среде хемилюминесцентным и спектрофотометрическим методами установлена константа скорости этой реакции, равная 241 ± 44 (М·с). The direct interaction between the dianion of hydroquinone and oxygen has made the major contribution in the process of hydroquinone oxidation in the strong alkaline media. As a result of the investigation of hydroquinone oxidation inhibited by ascorbic acid with chemiluminescence and spectrophotometric methods the rate constant of this reaction has been determined to be equal to 241 ± 44 (М·s).

Methane/Ammonia Radical Formation during High Temperature Reactions in Swirl Burners

Recent studies have demonstrated that ammonia is an emerging energy vector for the distribution of hydrogen from stranded sources. However, there are still many unknown parameters that need to be understood before ammonia can be a substantial substitute in fuelling current power generation systems. Therefore, current attempts have mainly utilised ammonia as a substitute for natural gas (mainly composed of methane) to mitigate the carbon footprint of the latter. Co-firing of ammonia/methane is likely to occur in the transition of replacing carbonaceous fuels with zero-carbo options. Hence, a better understanding of the combustion performance, flame features, and radical formation of ammonia/methane blends is required to address the challenges that these fuel combinations will bring. This study involves an experimental approach in combination with numerical modelling to elucidate the changes in radical formation across ammonia/methane flames at various concentrations. Radicals such as OH*, CH*, NH*, and NH2* are characterised via chemiluminescence whilst OH, CH, NH, and NH2 are described via RANS κ-ω SST complex chemistry modelling. The results show a clear progression of radicals across flames, with higher ammonia fraction blends showing flames with more retreated shape distribution of CH* and NH* radicals in combination with more spread distribution of OH*. Simultaneously, equivalence ratio is a key parameter in defining the flame features, especially for production of NH2*. Since NH2* distribution is dependent on the equivalence ratio, CFD modelling was conducted at a constant equivalence ratio to enable the comparison between different blends. The results denote the good qualitative resemblance between models and chemiluminescence experiments, whilst it was recognised that for ammonia/methane blends the combined use of OH, CH, and NH2 radicals is essential for defining the heat release rate of these flames.