Selective immunoclean-up followed by liquid chromatography for the monitoring of a biomarker of exposure to polycyclic aromatic hydrocarbons in urine at the ng l-1 level

A selective clean-up procedure using an immunosorbent (IS) was developed for the trace-level determination, in water and urine samples, of 3-benzo(a)pyrene-glucuronide (3-BP-G), a biomarker of exposure to carcinogenic polycyclic aromatic hydrocarbons (PAHs). First, three sorbents used for the immobilization of antibodies were evaluated for their ability to limit the risk of non-specific interactions and to provide a high bonding density. The best sorbent, i.e. sepharose, was used for the immobilization of two different monoclonal antibodies. The most specific antibody for 3-BP-G was applied to the selective extraction from urine providing a clean extract, an easy and reliable quantification by comparison with a classical SPE process. The sensitivity of the fluorescence associated with the selectivity of the IS provides a limit of detection up to 1.2 ng l(-1) in urine for 3-BP-G.     

Augmenting the Performance of Hydrogenase for Aerobic Photocatalytic Hydrogen Evolution via Solvent Tuning

This work showcases the performance of [NiFeSe] hydrogenase from Desulfomicrobium baculatum for solar-driven hydrogen generation in a variety of organic-based deep eutectic solvents. Despite its well-known sensitivity towards air and organic solvents, the hydrogenase shows remarkable performance under an aerobic atmosphere in these solvents when paired with a TiO₂ photocatalyst. Tuning the water content further increases hydrogen evolution activity to a TOF of 60±3 s⁻¹ and quantum yield to 2.3±0.4 % under aerobic conditions, compared to a TOF of 4 s⁻¹ in a purely aqueous solvent. Contrary to common belief, this work therefore demonstrates that placing natural hydrogenases into non-natural environments can enhance their intrinsic activity beyond their natural performance, paving the way for full water splitting using hydrogenases.