Expanding the Horizon of Bio‐Inspired Catalyst Design with Tactical Incorporation of Drug Molecules

Abstract

The development of potent H 2 production catalysts is a key aspect in our journey toward the establishment of a sustainable carbon-neutral power infrastructure. Hydrogenase enzymes provide the blueprint for designing efficient catalysts by the rational combination of central metal core and protein scaffold-based outer coordination sphere (OCS). Traditionally, a biomimetic catalyst is crafted by including natural amino acids as OCS features around a synthetic metal motif to functionally imitate the metalloenzyme activity. Here, we have pursued an unconventional approach and implanted two distinct drug molecules (isoniazid and nicotine hydrazide) at the axial position of a cobalt core to create a new genre of synthetic catalysts. The resultant cobalt complexes are active for both electrocatalytic and photocatalytic H 2 production in near-neutral water, where they significantly enhance the catalytic performance of the unfunctionalized parent cobalt complex. The drug molecules showcased a dual effect as they influence the catalytic HER by improving the surrounding proton relay along and exerting subtle electronic effects. The isoniazid-ligated catalyst C1 outperformed the nicotine hydrazide-bound complex C2, as it produced H 2 from water (pH 6.0) at a rate of 3960 s À 1 while exhibiting Faradaic efficiency of about 90 %. This strategy opens up newer avenues of bio-inspired catalyst design beyond amino acidbased OCS features.

Post-synthetic modulation of UiO-66-NH2 with a cobaloxime catalyst for efficient hydrogen production

“…14 Such inclusion of the OCS feature has been replicated by native proteins, engineered peptides, amino acids, neurotransmitters, and even drug molecules, where the identical cobaloxime core was deployed as a screening template. 15–20 However, a cobaloxime outlined by a MOF-based OCS has been rarely explored for both photo- and electrocatalytic HER activity. 10…”

Plastic Chip Electrode: An Emerging Multipurpose Electrode Platform

“…The bulk electrolysis experiment with this catalyst has again been performed on PCE. [88] The anchoring of this catalyst was also found robust on PCE.…”

“…The resultant catalyst is active for both electrocatalytic and photocatalytic HER in near‐neutral water. The bulk electrolysis experiment with this catalyst has again been performed on PCE [88] . The anchoring of this catalyst was also found robust on PCE.…”

Dissociative Photoionization of Dimethylpyridines and Trimethylpyridine at 266 nm: Dynamics of Methyl Radical Release

“…Understanding the photodissociation dynamics of aromatic molecules is crucial in the exploration of photophysical properties of complex biomolecules, wherein methylated aromatic compounds are fundamental building blocks for complex biomolecules. − Among various aromatic molecules, the heterocyclic analogs are important due to their hierarchy in natural selection in the composition of complex biomolecular systems and the heterocyclic analogs of methylated aromatic compounds in particular, such as nucleobase uracil. Changes in the electronic structure and symmetry of the electronic states depending on the type and position of heteroatom substitution within an aromatic ring are known to influence the photophysical properties of these molecules. − In the case of benzene, the absorption of a single photon within the 190–270 nm range gives rise to various radiative and nonradiative decay processes, such as isomerization, photodissociation involving H atom elimination, and ring opening. ,, On the other hand, the photodissociation dynamics of N-substituted heterocyclic analogs of benzene, viz ., pyridine and pyrimidine, exhibit a reduction in the threshold for ring-opening reactions as the number of nitrogen atoms in the ring increases .…”