Assembly of peptide–thiophene conjugates: the influence of peptide content and location

<div><p>Biomolecule-directed self-assembly of π-conjugated oligomers has attracted great attention in the past decade. In this contribution, two conjugates composed of quaterthiophene and tetrapeptide (Gly-Val-Gly-Val) were synthesised, namely peptide–thiophene–peptide (PTP) and thiophene–peptide–thiophene (TPT), to investigate the influence of peptide content ratio and its location in the molecular structures on the nanostructures and properties of the assemblies. Both conjugates formed organogels consisting of left-handed twisted nanostructures; however, anti-parallel β-sheets were observed in PTP while parallel β-sheets were obtained for TPT, although in both cases oligothiophenes adopted an H-like stacking mode. Obvious solvent-induced supramolecular chirality inversion from the oligothiophene segment was observed for PTP while such phenomenon was not clear for TPT. PTP and TPT gels also showed different stabilities towards temperature increase, as evidenced by variable-temperature circular dichroism study. From the data, it is suggested that the rational design of the location and ratio of peptide plays a key role in constructing materials with determined properties based on peptide–thiophene conjugates.</p></div

Contribution of the Polarity of Mussel-Inspired Adhesives in the Realization of Strong Underwater Bonding

Although the role of 3,4-dihydroxyphenyl-<i>L</i>-alanine­(DOPA)­in mussel foot proteins (mfps) in the realization of underwater bonding has been widely recognized, the role of the polarity of the polymer was largely overlooked. Here, by systematically comparing the underwater bonding properties of four mussel-inspired adhesives with different amide/lactam contents but similar catechol contents and molecular weights, we came to the conclusion that the polarity of the polymers also contributes to the strong underwater bonding. With the increase in the amide/lactam contents, the polarity of the polymeric adhesive increases, which correlates to the improved underwater bonding strength. A dielectric constant is introduced to evaluate the polarity of the polymer, which may be used as a guidance for the design of mussel-inspired adhesives with even better underwater bonding properties