We report the generation and characterization of an intermediate in a mutant form of the toluene/o-xylene monooxygenase hydroxylase component from Pseudomonas stutzeri OX1. The reaction of chemically reduced I100W variant in the presence of the coupling protein, ToMOD, with dioxygen was monitored by stopped-flow UV/visible spectroscopy. Rapid-freeze quench (RFQ) samples were also generated for ...

Iron-catalyzed isomerization of alkenes is reported using an iron(II) ?-diketiminate pre-catalyst. The reaction proceeds with a catalytic amount hydride source, such as pinacol borane (HBpin) or ammonia (H3N?BH3). Reactivity both allyl arenes and aliphatic has been studied. mechanism was investigated by variety means, including deuteration studies, Density Functional Theory (DFT) Electron Param...

Thanks to the use of a sustainable FeIII-based deep eutectic solvent (DES) as promoter/reaction medium, alkynes were hydrated under bench-type reaction conditions (45 °C, air, absence co-catalysts or co-solvents). This Fe-DES could be recycled for up eight consecutives runs in any VOC (E factor = 10). Furthermore, is able promote efficient formal oxidation internal into 1,2-diketones, with syst...

Pseudomonas aeruginosa is a ubiquitous environmental bacterium and versatile opportunistic pathogen. Like most other organisms, P. aeruginosa requires iron for survival, yet iron rapidly reacts with oxygen and water to form stable ferric (FeIII) oxides and hydroxides, limiting its availability to living organisms. During infection, iron is also sequestered by the host innate immune system, furt...

Polyphenolic structures are the putative cause of a variety of seed functions including bird/insect resistance and antioxidant activity. Structure-reactivity relationships are necessary to understand the influence of polyphenolic chromophore structures on the tannin content and free radical quenching ability determined by the traditional calorimetric methods. This study investigated the relatio...

Novel vitamin E chelate siderophore derivatives and their VV FeIII complexes have been synthesised the chemical biological properties evaluated. In particular, α- δ-tocopherol with bis-methyldroxylamino triazine (α-tocTHMA) (δ-tocDPA) as well complexes, [V2VO3(α-tocTHMA)2] [V2IVO3(δ-tocTHMA)2], characterised by infrared (IR), nuclear magnetic resonance (NMR), electron paramagnetic (EPR) ultra v...

We demonstrate the first application of L-edge X-ray absorption spectroscopy (XAS) to the electronic characterization of biological photolysis products. The experimental L-edge XAS spectra of deoxymyoglobin (deoxy Mb), oxymyoglobin (MbO2), carbonmonoxymyoglobin (MbCO), and the low-temperature photoproducts (Mb*CO and Mb*O2) are presented and compared to simulated spectra using a ligand field mu...