Synthetic and bioinspired metalloporphyrins are a class of redox-active catalysts able to emulate several enzymes such as cytochromes P450, ligninolytic peroxidases, and peroxygenases. Their ability to perform oxidation and degradation of recalcitrant compounds, including aliphatic hydrocarbons, phenolic and non-phenolic aromatic compounds, sulfides, and nitroso-compounds, has been deeply investigated. Such a broad substrate specificity has suggested their use also in the bleaching of textile plant wastewaters. In fact, industrial dyes belong to very different chemical classes, being their effective and inexpensive oxidation an important challenge from both economic and environmental perspective. Accordingly, we review here the most widespread synthetic metalloporphyrins, and the most promising formulations for large-scale applications. In particular, we focus on the most convenient approaches for immobilization to conceive economical affordable processes. Then, the molecular routes of catalysis and the reported substrate specificity on the treatment of the most diffused textile dyes are encompassed, including the use of redox mediators and the comparison with the most common biological and enzymatic alternative, in order to depict an updated picture of a very promising field for large-scale applications.

Metalloporphyrins (MPs) are known to catalyze in vitro a broad range of cytochrome P₄₅₀-mediated reactions occurring in vivo. Most of the biomimetic research using MPs in oxidative catalysis has been directed towards the oxidation of organic compounds presenting significant reactivity features in one functional group. Much less effort has been made to imitate the oxidation of more complex molecules, with a range of functionalities, such as drugs or other xenobiotics. By varying the structure of the porphyrin, the metal ion, the oxidant, and the reaction conditions, it is possible to modulate the regioselectivity of the oxidation reactions. Recently, and along with studies on the synthesis and reactivity of porphyrins, chlorins, and phthalocyanines, our group was able to develop an interesting line of research in the field of biomimetic oxidation of organic compounds using environmentally benign hydrogen peroxide as oxidant and Mn(III) or Fe(III) porphyrin complexes as catalysts. The more up to date results obtained in such work are reviewed here.

Elderberry (Sambucus nigra L.) juice concentrate is highly rich in polyphenols, particularly anthocyanins and flavonols, which have been associated with a wide range of health-promoting properties. Phenolic compounds, in particular anthocyanins, are unstable and may change during storage, which might influence the product color quality and its potential health effects. The aim of this study was to evaluate the changes in the polyphenols profile of elderberry juice concentrate produced at an industrial scale during seven months of storage at 5 °C and at room temperature. The total phenolic content, the total monomeric anthocyanins, the percent polymeric color, and the ABTS^•+ scavenging activity were monitored over time. In addition, the profile and content of the main individual phenolic compounds were also assessed by HPLC-DAD. The results show that cyanidin-3-O-sambubioside, cyanidin-3-O-glucoside, cyanidin-3-O-sambubioside-5-O-glucoside, cyanidin-3,5-O-diglucoside, chlorogenic acid, rutin, and quercetin-3-O-glucoside were the main phenolic compounds identified. Storage at room temperature resulted in a strong reduction in total monomeric anthocyanin content accompanied by an increase in percent polymeric color values. Cyanidin-3-O-sambubioside and cyanidin-3-O-glucoside degraded faster than cyanidin-3,5-O-diglucoside and cyanidin-3-O-sambubioside-5-O-glucoside. Concentration of chlorogenic acid also decreased over storage, whereas rutin and quercetin-3-O-glucoside were quite stable. Storage at 5 °C caused a lower impact on the contents of anthocyanins and chlorogenic acid and the percent polymeric color was not affected. The total phenolic content and the in vitro antioxidant activity remained quite similar over the time, for both temperatures, suggesting that elderberry concentrates still preserve their health benefits of antioxidant capacity after seven months of storage.

The synthesis, characterisation and homogeneous catalytic oxidation results of two manganese(III) porphyrins of the so-called second-generation of metalloporphyrin catalysts, containing one or four 3,5-dichloropyridyl substituents at the meso positions are reported for the first time. The catalytic efficiency of these novel manganese(III) porphyrins was evaluated in the oxidation of cyclooctene and styrene using aqueous hydrogen peroxide as the oxidant, under homogeneous conditions. High conversions were obtained in the presence of both catalysts, obtaining the corresponding epoxide as the major product. The asymmetric metalloporphyrin, chloro[5,10,15-tris(2,6-dichlorophenyl)-20-(3,5-dichloropyridin-4-yl)porphyrinate]manganese(III), CAT-4, evidences a similar activity to that obtained with the well-known and highly efficient second-generation metalloporphyrin catalyst, chloro[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinate]manganese(III), CAT-2. CAT-4 was covalently attached onto Merrifield resin and 3-bromopropylsilica supports. The solid materials obtained were characterized by several techniques including diffuse reflectance, UV—VIS spectrophotometry, SEM and XPS. The catalytic results for the oxidation of cyclooctene and styrene using the immobilized catalysts are also presented. The Merrifield-supported catalyst showed to be very efficient, leading to five catalytic cycles in the oxidation of cyclooctene, using tert-butyl hydroperoxide as the oxidant.