Formation of Unstable and very Reactive Chemical Species Catalyzed by Metalloenzymes: A Mechanistic Overview

Nature has tailored a wide range of metalloenzymes that play a vast array of functions in all living organisms and from which their survival and evolution depends on. These enzymes catalyze some of the most important biological processes in nature, such as photosynthesis, respiration, water oxidation, molecular oxygen reduction, and nitrogen fixation. They are also among the most proficient catalysts in terms of their activity, selectivity, and ability to operate at mild conditions of temperature, pH, and pressure. In the absence of these enzymes, these reactions would proceed very slowly, if at all, suggesting that these enzymes made the way for the emergence of life as we know today. In this review, the structure and catalytic mechanism of a selection of diverse metalloenzymes that are involved in the production of highly reactive and unstable species, such as hydroxide anions, hydrides, radical species, and superoxide molecules are analyzed. The formation of such reaction intermediates is very difficult to occur under biological conditions and only a rationalized selection of a particular metal ion, coordinated to a very specific group of ligands, and immersed in specific proteins allows these reactions to proceed. Interestingly, different metal coordination spheres can be used to produce the same reactive and unstable species, although through a different chemistry. A selection of hand-picked examples of different metalloenzymes illustrating this diversity is provided and the participation of different metal ions in similar reactions (but involving different mechanism) is discussed.

Rapid revegetation by sowing seed mixtures of shrub and herbaceous species

Fast revegetation by means of sowing seed mixtures of shrub and herbaceous species is a measure to prevent bare soils from wind and water erosion. A field experiment was used to test the effect of species selection and the ratio of shrub to herbaceous species on vegetation formation and shrub growth. Results showed that herbaceous species hastened cover formation and maintained a high coverage for a longer period. However, the growth of shrubs was hindered. In the North China Plain or where the soil and climate are similar, the ratio of shrub to herbaceous seeds is proposed to be 6 : 4–7 : 3 (weight ratio). Among the herbaceous species tested, Festuca arundinacea Schreb. grows relatively slow, so it should be mixed with other fast-growing species in the practice of rapid revegetation, and a seeding density lower than 6 g m−2 is proposed when applied; Orychophragmus violaceus O. E. Schulz. wilts when the seeds are ripe, leading to a significant decrease of coverage, so other species with different phenology should be involved when it is applied; Viola philippica Car. is a good ground cover plant which grows fast and maintains a stable coverage from July to October, and a seeding density of 1.5 g m−2 is proposed for rapid revegetation. Herbaceous species have different traits. Three different types of herbs were found in our experiment: slow-growing stable species (F. arundinacea), fast-growing unstable species (O. violaceus) and fast-growing stable species (V. philippica). Shrubs, slow-growing stable species and fast-growing unstable species should not be used alone because they cannot cover the ground fast or they cannot maintain a long period of good coverage. A small seeding rate of fast-growing stable species should be used to ensure a fair coverage against erosion. Because natural environmental conditions are heterogeneous and stochastic, more species should be added to enhance the stability of plant community.

Synthesis of the most anti-aromatic 16π porphyrin: an octaethylporphyrin zinc(II) complex with no meso-substituents

The most anti-aromatic 16π porphyrin, an octaethylporphyrin (OEP) zinc(II) complex with no substituents at the meso-positions was generated as a highly unstable species from the reaction of the corresponding 18π porphyrin using strong oxidants such as AgSbF 6/ I 2 or SbF 5. The porphyrin showed a significant blue-shift unique to 16π porphyrins in its UV-vis spectrum. 1 H NMR measurements revealed an evident high-field shift of the meso-protons of the porphyrin ring, thereby establishing that the novel 16π porphyrin has the strongest anti-aromaticity reported so far.