Tuning of the Supramolecular Helicity of Peptide-Based Gel Nanofibers

Misra, Souvik; Singh, Pijush; Singh, Ajeet Kumar; Roy, Lisa; Kuila, Soumen; Dey, Sukantha; Mahapatra, Ajit Kumar; Nanda, Jayanta

doi:10.1021/acs.jpcb.2c06897

Cited by 4 publications

(16 citation statements)

References 107 publications

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“…An in-depth theoretical analysis was carried out using the ω b97xD/6-311+G** level of theory. A similar computational methodology was reported in our previous work to account for the reason behind helical inversion with increasing alkyl spacers in naphthalimides . Thus, this methodology was applied in this study to further evaluate the contribution of chirality for helical inversion in a chromophore with fixed chain length.…”

Section: Resultsmentioning

confidence: 94%

“…The nanoscale morphology of the NMI derivative (NLV) in the present work matches our previous results. 63 In our previous study, the length of the achiral amino acid was varied keeping the chirality of α-amino acid fixed. In the present work, the chirality of the amino acid was changed keeping the chain length fixed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…A similar computational methodology was reported in our previous work to account for the reason behind helical inversion with increasing alkyl spacers in naphthalimides. 63 Thus, this methodology was applied in this study to further evaluate the contribution of chirality for helical inversion in a chromophore with fixed chain length. Non-covalently bound π-stacked dimers at rotations of the interplanar axes along the C1−N1−C2−N2 dihedral angle were investigated with a step size of 10°(Figure 7).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…64 Systematic design of molecules utilizing the non-covalent interactions the same luminogen can be converted to a highly fluorescent system in the aggregated state (AIE) from aggregation-caused quenching (ACQ) system. 57,63,64 Previously, 63 we reported the self-assembling behavior of several dipeptides composed of an achiral amino acid and an αamino acid. Spectroscopic and microscopic analyses showed the formation of a helical morphology at their nanoscale in each case.…”

Section: ■ Introductionmentioning

confidence: 99%

“…This is due to strong hydrogen bonding interactions present in dipeptide fragments and this guides the slippage (J-type) of the unsubstituted NMI units rather than face-to-face stacking (H-type) interactions . Systematic design of molecules utilizing the non-covalent interactions the same luminogen can be converted to a highly fluorescent system in the aggregated state (AIE) from aggregation-caused quenching (ACQ) system. ,, …”

Section: Introductionmentioning

confidence: 99%

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Probing Molecular Chirality on the Self-Assembly and Gelation of Naphthalimide-Conjugated Dipeptides

et al. 2023

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In this work, 1,8-naphthalimide (NMI)-conjugated three hybrid dipeptides constituted of a β-amino acid and an α-amino acid have been designed, synthesized, and purified. Here, in the design, the chirality of the α-amino acid was varied to study the effect of molecular chirality on the supramolecular assembly. Self-assembly and gelation of three NMI conjugates were studied in mixed solvent systems [water and dimethyl sulphoxide (DMSO)]. Interestingly, chiral NMI derivatives [NMI-βAla- l Val-OMe (NLV) and NMI-βAla- d Val-OMe (NDV)] formed self-supported gels, while the achiral NMI derivative [NMI-βAla-Aib-OMe, (NAA)] failed to form any kind of gel at 1 mM concentration and in a mixed solvent (70% water in DMSO medium). Self-assembly processes were thoroughly investigated using UV–vis spectroscopy, nuclear magnetic resonance (NMR), fluorescence, and circular dichroism (CD) spectroscopy. A J-type molecular assembly was observed in the mixed solvent system. The CD study indicated the formation of chiral assembled structures for NLV and NDV, which were mirror images of one another, and the self-assembled state by NAA was CD-silent. The nanoscale morphology of the three derivatives was studied using scanning electron microscopy (SEM). In the case of NLV and NDV, left- and right-handed fibrilar morphologies were observed, respectively. In contrast, a flake-like morphology was noticed for NAA. The DFT study indicated that the chirality of the α-amino acid influenced the orientation of π–π stacking interactions of naphthalimide units in the self-assembled structure that in turn regulated the helicity. This is a unique work where molecular chirality controls the nanoscale assembly as well as the macroscopic self-assembled state.

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Section: Resultsmentioning

confidence: 94%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Probing Molecular Chirality on the Self-Assembly and Gelation of Naphthalimide-Conjugated Dipeptides

et al. 2023

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Supramolecular J‐ and H‐Aggregation of Naphthalimide‐Conjugated Dipeptide in Mixed‐Solvent Systems and its Application in Cell Imaging

Kuila,

Reddy,

Dasgupta

et al. 2024

Chemistry An Asian Journal

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In this work, a core substituted NMI‐conjugated dipeptide (4MNLV) was extensively studied in mixed solvent systems to explore the polarity effect on the self‐assembly pattern and their photophysical property. 4MNLV adopted a J‐ or H‐ type aggregation pattern depending upon the polarity index of the solvent system chosen. The self‐assembly process was achieved through the anti‐solvent effect. UV‐vis study suggested that if the stock solution of 4MNLV was diluted with a relatively more polar solvent (compared to the stock solvent), then the system acquired J‐ type of aggregation pattern by showing a red‐shift in their absorption maxima (λmax). Conversely, when the stock was diluted by a relatively less polar solvent, H‐type of aggregation was observed where blue shift of λmax was noticed. The emission spectra and the lifetime of the self‐assembled materials were also influenced by the chosen solvent system. The chirotopic behaviour of these self‐assembled materials was studied through CD spectroscopy. Morphological study indicated the formation of helical nanofibrillar structures. The bright green fluorescence of these highly biocompatible naphthalimide‐peptide conjugate was used for cell imaging application, indicating its futuristic scope.

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Tips and Tricks in the Modeling of Supramolecular Peptide Assemblies

Piskorz,

Perez-Chirinos,

Qiao

et al. 2024

ACS Omega

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Supramolecular peptide assemblies (SPAs) hold promise as materials for nanotechnology and biomedicine. Although their investigation often entails adapting experimental techniques from their protein counterparts, SPAs are fundamentally distinct from proteins, posing unique challenges for their study. Computational methods have emerged as indispensable tools for gaining deeper insights into SPA structures at the molecular level, surpassing the limitations of experimental techniques, and as screening tools to reduce the experimental search space. However, computational studies have grappled with issues stemming from the absence of standardized procedures and relevant crystal structures. Fundamental disparities between SPAs and protein simulations, such as the absence of experimentally validated initial structures and the importance of the simulation size, number of molecules, and concentration, have compounded these challenges. Understanding the roles of various parameters and the capabilities of different models and simulation setups remains an ongoing endeavor. In this review, we aim to provide readers with guidance on the parameters to consider when conducting SPA simulations, elucidating their potential impact on outcomes and validity.

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Tuning of the Supramolecular Helicity of Peptide-Based Gel Nanofibers

Cited by 4 publications

References 107 publications

Probing Molecular Chirality on the Self-Assembly and Gelation of Naphthalimide-Conjugated Dipeptides

Probing Molecular Chirality on the Self-Assembly and Gelation of Naphthalimide-Conjugated Dipeptides

Supramolecular J‐ and H‐Aggregation of Naphthalimide‐Conjugated Dipeptide in Mixed‐Solvent Systems and its Application in Cell Imaging

Tips and Tricks in the Modeling of Supramolecular Peptide Assemblies

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