Self-Assembly of Porphyrin Dipeptide Conjugates toward Hydrogen Production

Abstract

In this work, the diphenylalanine dipeptide was covalently attached to a tripyridyl porphyrin macrocycle and conveyed self-assembling properties to the resulting hybrid. This hybrid was metallated with non-noble metals, Zn and Sn, and investigated toward photocatalytic hydrogen evolution. The Sn derivative, SnPy3P-FF, was able to produce hydrogen photocatalytically in the presence of a known cobaloxime catalyst and TEOA as a sacrificial electron donor. When the self-assembling nanostructures of SnPy3P-FF were employed in the photocatalytic system, enhanced hydrogen production was observed. Fluorescence and transient absorption experiments were performed in order to shed light on the electron transfer processes that take place during the photocatalysis.

Porphyrins and phthalocyanines as biomimetic tools for photocatalytic H2production and CO2reduction

“…In another work of Nikoloudakis et al 88 we covalently connected the diphenylalanine dipeptide with tris(pyridyl)porphyrin in order to transfer self-assembling properties to the resulting hybrid. The pyridyl substitution was chosen since it led to superior photocatalytic activity in previous reports from the same group.…”

Dipeptide self-assembly into water-channels and gel biomaterial

“…2,3 Potential fields of applications are numerous and very diverse, and they range from medicine, 4–7 to bioelectronics, 8–10 and energy. 11,12…”

“…2,3 Potential fields of applications are numerous and very diverse, and they range from medicine, [4][5][6][7] to bioelectronics, [8][9][10] and energy. 11,12 However, it is well-known that prediction of supramolecular behaviour of dipeptides is very challenging, owing to their richness in available conformations, and diversity in their functional groups, so that even subtle structural differences are amplified through cooperative self-assembly, into dramatically different outcomes. [13][14][15] The most widely used strategy in their design is based on the use of polyaromatic N-caps, which can easily stack and drive self-aggregation.…”

Single-atom substitution enables supramolecular diversity from dipeptide building blocks

“…Short peptides are attractive, low-cost building blocks for self-assembled materials that do not persist in the environment and can be formed in benign solvents, such as aqueous solutions. 1 Thanks to the great chemical diversity of natural and non-canonical amino acids, 2 it is possible to tune the physico-chemical properties of the final product, and this is an attractive feature for different applications spanning from innovative solutions in medicine 3–6 to energy 7,8 and bioelectronics. 9–11 To enable translation into the market, it is key to design systems with low-cost and easy scale-up.…”