title: Two-Component Fluorescent-Semiconducting Hydrogel from Naphthalene Diimide-Appended Peptide with Long-Chain Amines: Variation in Thermal and Mechanical Strengths of Gels.
abstract: Two-component fluorescent hydrogels have been discovered, containing the mixtures of naphthalene diimide (NDI)-conjugated peptide-functionalized bola-amphiphile and primary amines with long alkyl chains at physiological pH 7.46. The aggregation-induced enhanced emission associated with an NDI-appended peptide in aqueous medium is rare, as water is known to be a good quencher of fluorescence. In this study, an NDI-containing gelator peptide forms a highly fluorescent aggregate in aqueous medium. Absorption and emission spectroscopic techniques reveal the formation of J-aggregates among the chromophoric moieties in their aggregated state in aqueous medium. However, this NDI-containing peptide does not form any gel in aqueous medium. In the presence of the primary amines with long alkyl chains in the buffer solution, it forms two-component fluorescent hydrogels exhibiting bright yellow fluorescence under a UV lamp (365 nm). Probably, the acid-amine interaction between the amines and the bola-amphiphile triggers the gel formation, as evident from Fourier transform infrared data, indicating the presence of a carboxylate group (-COO-) and an ammonium species (NH3+) in the coassembled two-component gel system. Low- and wide-angle powder X-ray diffraction and small-angle X-ray scattering further support the fact that the coassembled state in the gel form is produced by the supramolecular interaction between the NDI-based bola-amphiphile and the long-chain amines. Field-emission scanning electron microscopy and high-resolution transmission electron microscopy images reveal that the π-conjugated coassembled hydrogels exhibit nanofibrillar network morphologies. Interestingly, the coassembled hydrogels exhibit an enhanced fluorescence emission, excited-state lifetime, and quantum yield when compared with those of the NDI-containing amphiphile alone in its self-assembled state in aqueous medium. Moreover, the thermal stability and mechanical strength of these gels have been successfully tuned by varying the alkyl chain length of the corresponding amine. Moreover, these NDI-peptide-conjugated soft materials exhibit semiconducting behavior in their respective coassembled states. This holds future promise to use these peptide-appended NDI-based coassembled soft materials for applications in optoelectronic and other devices.
authors.affiliation: Department of Biological Chemistry, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700032, India.
authors.forename: Nibedita
authors.initials: N
authors.lastname: Nandi
authors.affiliation: Department of Biological Chemistry, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700032, India.
authors.forename: Shibaji
authors.initials: S
authors.lastname: Basak
authors.affiliation: Department of Chemistry, University of Reading , Whitenights, Reading RG6 6AD, U.K.
authors.forename: Steven
authors.initials: S
authors.lastname: Kirkham
authors.affiliation: Department of Chemistry, University of Reading , Whitenights, Reading RG6 6AD, U.K.
authors.forename: Ian W
authors.initials: IW
authors.lastname: Hamley
authors.affiliation: Department of Biological Chemistry, Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700032, India.
authors.forename: Arindam
authors.initials: A
authors.lastname: Banerjee