We
report the oriented immobilization of [NiFeSe] hydrogenases
on both covalently and noncovalently modified carbon nanotubes (CNTs)
electrodes. A specific interaction of the [NiFeSe] hydrogenase from Desulfomicrobium baculatum with hydrophobic organic molecules
was probed by electrochemistry, quartz crystal microbalance with dissipation
monitoring (QCM-D), and theoretical calculations. Taking advantage
of these hydrophobic interactions, the enzyme was efficiently wired
on anthraquinone and adamantane-modified CNTs. Because of rational
immobilization onto functionalized CNTs, the O2-tolerant
[NiFeSe]-hydrogenase is able to efficiently operate in a H2/air gas-diffusion enzymatic fuel cell.
The design and characterization of new ruthenium(II) complexes aimed at targeting G‐quadruplex DNA is reported. Importantly, these complexes are based on oxidizing 1,4,5,8‐tetraazaphenanthrene (TAP) ancillary ligands known to favour photo‐induced electron transfer (PET) with DNA. The photochemistry of complexes 1–4 has been studied by classical methods, which revealed two of them to be capable of photo‐abstracting an electron from guanine. From studies of the interactions with DNA through luminescence, circular dichroism, bio‐layer interferometry, and surface plasmon resonance experiments, we have demonstrated the selectivity of these complexes for telomeric G‐quadruplex DNA over duplex DNA. Preliminary biological studies of these complexes have been performed: two of them showed remarkable photo‐cytotoxicity towards telomerase‐negative U2OS osteosarcoma cells, whereas very low mortality was observed in the dark at the same photo‐drug concentration.
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