Spontaneous structural transition and crystal formation in minimal supramolecular polymer model

Fichman, Galit; Guterman, Tom; Damron, Joshua T.; Adler‐Abramovich, Lihi; Schmidt, Judith; Kesselman, Ellina; Shimon, Linda J. W.; Ramamoorthy, Ayyalusamy; Talmon, Yeshayahu; Gazit, Ehud

doi:10.1126/sciadv.1500827

Cited by 67 publications

(77 citation statements)

References 61 publications

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“…[45][46][47][48] Importantly, we found that in addition to functioning as a crosslinker of the network, adding a crosslinker also modulates the size and surface chemistry of the spherical aggregates that act as depots of unreacted building block 4, dictating the self-assembly pathway of the low molecular weight gelator material over the various stages of nucleation, fiber growth, and bundling (Scheme 2). However, this method of modulating the materials properties can prove more complex as not all crosslinkers are equivalent in how they can interact with the scaffold monomers during their self-assembly process.…”

Section: Doi: 101002/adma201603769mentioning

confidence: 96%

Crosslinker‐Induced Effects on the Gelation Pathway of a Low Molecular Weight Hydrogel

et al. 2017

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The use of polymeric crosslinkers is an attractive method to modify the mechanical properties of supramolecular materials, but their effects on the self-assembly of the underlying supramolecular polymer networks are poorly understood. Modulation of the gelation pathway of a reaction-coupled low molecular weight hydrogelator is demonstrated using (bio)polymeric crosslinkers of disparate physicochemical identities, providing a handle for control over materials properties.

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Section: Doi: 101002/adma201603769mentioning

confidence: 96%

Crosslinker‐Induced Effects on the Gelation Pathway of a Low Molecular Weight Hydrogel

et al. 2017

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“…In order to investigate the unusual two‐step gelation (as shown in Figure a) in terms of the underlying supramolecular process, a combination of spectroscopic and microscopic techniques was employed. Time‐dependent TEM images (Figure 2b) exhibited a morphological transformation from spheres to fibers over time suggesting a molecular rearrangement of the hypergelator, as observed for another Fmoc‐protected gelator . Powder X‐ray diffraction (PXRD) performed on lyophilized hydrogels that were frozen at similar time‐points (Figure 2c) showed the emergence of specific, nonsharp peaks over time, indicating the formation of long‐range order in the self‐assembled structures.…”

Section: Characteristics Of the Studied Peptide Analogues The Originmentioning

confidence: 99%

Unusual Two‐Step Assembly of a Minimalistic Dipeptide‐Based Functional Hypergelator

et al. 2020

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Self‐assembled peptide hydrogels represent the realization of peptide nanotechnology into biomedical products. There is a continuous quest to identify the simplest building blocks and optimize their critical gelation concentration (CGC). Herein, a minimalistic, de novo dipeptide, Fmoc‐Lys(Fmoc)‐Asp, as an hydrogelator with the lowest CGC ever reported, almost fourfold lower as compared to that of a large hexadecapeptide previously described, is reported. The dipeptide self‐assembles through an unusual and unprecedented two‐step process as elucidated by solid‐state NMR and molecular dynamics simulation. The hydrogel is cytocompatible and supports 2D/3D cell growth. Conductive composite gels composed of Fmoc‐Lys(Fmoc)‐Asp and a conductive polymer exhibit excellent DNA binding. Fmoc‐Lys(Fmoc)‐Asp exhibits the lowest CGC and highest mechanical properties when compared to a library of dipeptide analogues, thus validating the uniqueness of the molecular design which confers useful properties for various potential applications.

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“…26 FASAAs are the minimal representation of this class of hydrogelators and studies of these compounds have focused on FASAA analogues of coded amino acids, namely Fmoc-phenylalanine (Fmoc-Phe) and Fmoc-tyrosine (Fmoc-Tyr). 32,33 Fmoc-DOPA is especially interesting due to the multifunctional nature of the catecholic moiety, which is capable to act as an antioxidant, radical trapper, metal chelator, oxidizable reducing agent, etc. 13 Later studies reported the pH-dependent gelation of Fmoc-Tyr, where a gradual decrease in pH from alkaline to acidic led to protonation of the carboxylate group and to the subsequent conversion of solubilized Fmoc-Tyr to ordered fibrillar assemblies in a gel matrix.…”

Section: Introductionmentioning

confidence: 99%

Synergetic functional properties of two-component single amino acid-based hydrogels

et al. 2015

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The formation of hydrogels by low molecular weight building blocks results in important supramolecular assemblies for technological applications. N-modified amino acids are especially interesting components for the organization of such structures due to the high efficiency of association, inherent biocompatibility, and structural diversity. The fluorenylmethoxycarbonyl (Fmoc)-modified tyrosine (Fmoc-Tyr) has been extensively studied as a notably simple yet highly efficient hydrogelator. Here we present the ability to use a combination of Fmoc-Tyr and the catechol-containing Fmoc-3,4-dihydroxyphenylalanine (Fmoc-DOPA) to form a functional two-component hydrogel which combines the physical characteristics as observed with Fmoc-Tyr hydrogels together with the functionality of the catechol groups. We demonstrate that a combination of the two building blocks results in the rapid formation of three-dimensional selfsupporting gels. Rheological analysis indicated that the observed hybrid gel has very high storage modulus, in the same order of magnitude as that of the Fmoc-Tyr gel. In addition to the envisioned mechanical properties, the combined gel also displayed a clear silver ion reduction activity. Taken together, we illustrate the ability to utilize two-component gels to achieve synergetic properties, combining rigidity and functionality.behavior, as previously reported. 32 TEM imaging of the weak Fmoc-DOPA gel revealed fibrillar assemblies which appeared linear, unbranched and extending to the length of micrometers (Fig. 2b). The width of the fibers ranged from 5 to 10 nm and lateral bundling was observed. The obtained Fmoc-Tyr hydrogels were semi-transparent and presented similar underlying fibers, albeit wider, with an approximated width of 15 nm, as imaged by TEM (Fig 2b). These observations are in line with previous reports concerning the hydrogelation of Fmoc-Tyr by using the solvent-switch method. 30 Next, we examined the hybrid hydrogels. These gels presented similar macroscopic behavior to those of Fmoc-Tyr and similar fibrillar assemblies of 15 nm in width were imaged by TEM (Fig. 2b).absence of silver nitrate, which were higher than their respective loss moduli by an order of magnitude (Fig. S4). This direct comparison of rheological properties shows that the high mechanical rigidity of the Fmoc-Tyr:Fmoc-DOPA hybrid gels is retained in their redox-active state, further demonstrating the functional synergy of the two gelators.

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Spontaneous structural transition and crystal formation in minimal supramolecular polymer model

Abstract: A comprehensive minimalistic model for spontaneous structural transition that is governed by distinct molecular interactions.

Cited by 67 publications

References 61 publications

Crosslinker‐Induced Effects on the Gelation Pathway of a Low Molecular Weight Hydrogel

Crosslinker‐Induced Effects on the Gelation Pathway of a Low Molecular Weight Hydrogel

Unusual Two‐Step Assembly of a Minimalistic Dipeptide‐Based Functional Hypergelator

Synergetic functional properties of two-component single amino acid-based hydrogels

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