Mechanistic Study of the Titanocene(III)‐Catalyzed Radical Arylation of Epoxides

An atom‐economical and catalytic arylation of epoxide‐derived radicals is described. The key step of the catalytic system is a sequential electron and proton transfer for the rearomatization of the radical σ‐complex and catalyst regeneration. Kinetic, computational, spectroscopic, and cyclovoltammetric investigations highlight the key issues of the reaction mechanism and catalyst stabilization by collidine hydrochloride. Studies employing radicophiles rule out the participation of cations as reactive intermediates.     

Synergistic Effects of Co and Fe on the Oxygen Evolution Reaction Activity of LaCoxFe1−xO3

In a combined experimental and theoretical study we assess the role of Co incorporation on the OER activity of LaCo_xFe_1−xO₃. Phase pure perovskites were synthesized up to in 0.025/0.050 steps. HAADF STEM and EDX analysis points towards FeO₂-terminated (001)-facets in LaFeO₃, in accordance with the stability diagram obtained from density functional theory calculations with a Hubbard U term (DFT+U). Linear sweep voltammetry conducted in a rotating disk electrode setup shows a reduction of the OER overpotential and a nonmonotonic trend with x, with double layer capacitance measurements indicating an intrinsic nature of activity. This is supported by DFT+U results that show reduced overpotentials for both Fe and Co reaction sites with the latter reaching values of 0.32–0.40 V, ∼0.3 V lower than for Fe. This correlates with a stronger reduction of the binding energy difference of the *O and *OH intermediates towards an optimum value of 1.6 eV for , the OH deprotonation being the potential limiting step in most cases. Significant variations of the magnetic moments of both surface and subsurface Co and Fe during OER demonstrate that the beneficial effect is a result of a concerted action involving many surrounding ions, which extends the concept of the active site.     

Intracellular Assembly of Interacting Enzymes Yields Highly-Active Nanoparticles for Flow Biocatalysis

All-enzyme hydrogel (AEH) particles with a hydrodynamic diameter of up to 120 nm were produced intracellularly with an Escherichia coli-based in vivo system. The inCell-AEH nanoparticles were generated from polycistronic vectors enabling simultaneous expression of two interacting enzymes, the Lactobacillus brevis alcohol dehydrogenase (ADH) and the Bacillus subtilis glucose-1-dehydrogenase (GDH), fused with a SpyCatcher or SpyTag, respectively. Formation of inCell-AEH was analyzed by dynamic light scattering and atomic force microscopy. Using the stereoselective two-step reduction of a prochiral diketone substrate, we show that the inCell-AEH approach can be advantageously used in whole-cell flow biocatalysis, by which flow reactors could be operated for >4 days under constant substrate perfusion. More importantly, the inCell-AEH concept enables the recovery of efficient catalyst materials for stable flow bioreactors in a simple and economical one-step procedure from crude bacterial lysates. We believe that our method will contribute to further optimization of sustainable biocatalytic processes.     

Liquid chromatograpic-mass spectrometric analysis of phenolics and free radical scavenging activity of rosemary extract from different raw material

The antioxidant activity of rosemary (Rosmarinus officinalis) extract from different raw materials has been studied. Extracts were prepared from wild or drip-irrigated plants, as well as from the by-product resulting from the distillation of the aromatic essential oil. The radical scavenging activity of rosemary extracts was compared with that of antioxidants widely used in food, such as BHT and delta-tocopherol, using an optimization of the method based on the reduction of the radical 2,2-diphenyl-1-picrylhydrazyl (DPPH). The results pointed the excellent antioxidant activity of the crude fresh rosemary extracts, which was almost identical to that of pure delta-tocopherol, and higher than that of BHT; extracts prepared from distilled rosemary showed the lowest activity, although they are also of interest due to the low cost of the raw material. High performance liquid chromatography (HPLC) combined with diode array (DAD) and electrospray (ESI)-ion trap-MS detection was used to separate and identify the compounds present in the rosemary extracts. Rosmarinic acid, carnosic acid and seven of their terpene-type metabolites, and seven flavones were identified. The drying and/or distillation treatments used with the plant material strongly affected the content of the two compounds of higher antioxidant activity: rosmarinic acid and carnosic acid.