Bioinspired polymer functionalized with a diiron carbonyl model complex and its assembly onto the surface of a gold electrode via “click” chemistry

Abstract

A complex pendant with two ethynyl groups, [Fe2(μ‐SCH2CCH)2(CO)6] (2), as a model of the diiron subunit of [FeFe]‐hydrogenase was polymerized and the {Fe2(CO)6} core was successfully incorporated into the polymer matrix. The polymer was characterized by a variety of spectroscopic techniques, TGA, FTIR, SEM, TEM, and NMR. The resultant polymer was immobilized via “click” chemistry using its terminal CCH bond onto the surface of a gold electrode, which was premodified with azidothiol by self‐assembled monolayer (SAM). The assembled electrode showed electrochemical responses. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2410–2417, 2010

Diiron Complexes with Pendant Phenol Group(s) as Mimics of the Diiron Subunit of [FeFe]‐Hydrogenase: Synthesis, Characterisation, and Electrochemical Investigation

“…Therefore, the organic moieties of the two thiolates can take three possible conformations, syn, synЈ, and anti, as observed widely in their analogues. [26][27][28][29] In the first conformation, both phenyl rings point away from the diiron centre. The opposite conformation is the synЈ form, but it is thermodynamically unfavoured and hardly observed.…”

Artificial [FeFe]‐Hydrogenase: On Resin Modification of an Amino Acid to Anchor a Hexacarbonyldiiron Cluster in a Peptide Framework

“…In these investigations, a number of synthetic strategies have been developed for coupling relevant diiron models to electrode surfaces, redox cofactors, or photoactive centers. [21][22][23][24][25] In parallel, strategies for investigating the impact of second coordination sphere interactions and burial of the active site in superstructures isolated from bulk solvent are starting to emerge. [22,[26][27][28][29][30][31][32] On the other hand, relatively little attention has been paid to developing strategies for attachment of diiron models to amino acids [28,[33][34][35] or peptidic scaffolds [36,37] -this, despite the fact that evidence continues to build indicating that the enzyme tertiary structure plays a crucial role in tuning the properties of the active site to achieve near diffusion-limited, bidirectional catalysis.…”

Introducing polyethyleneimine (PEI) into the electrospun fibrous membranes containing diiron mimics of [FeFe]-hydrogenase: Membrane electrodes and their electrocatalysis on proton reduction in aqueous media

“…Consequently, the membrane electrode assembled from the EFM is operational in aqueous solution. Compared to the assembled electrodes we reported previously [44,47], the assembled electrode showed also improved durability due to the protection offered by the matrix. The disadvantage of complex 1 is that its interactions with the matrix are not sufficient due to its hydrophobicity.…”

“…To this end, we have tried a number of strategies to develop polymeric materials functionalised with diiron mimics, (ⅰ) directly polymerising diiron model complexes containing an alkynyl group [44,45]; (ⅱ) using "click chemistry" reaction between an alkynyl and an organic azide [46]; (ⅲ) chemically immobilising diiron mimics onto commercially available polymers such as PVC (polyvinyl chloride) and PEI (polyenthylenimine) [36,47]; (ⅳ) incorporating a diiron mimic into fibrous membranes via electrospinning technique [48].…”