Emergence, evidence, and effect of junction clustering in supramolecular polymer materials

Jangizehi, Amir; Ahmadi, Mostafa; Seiffert, Sebastian

doi:10.1039/d0ma00795a

Cited by 28 publications

(57 citation statements)

References 203 publications

(385 reference statements)

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“…Such a clustering of the supramolecular stickers is generally known to enforce networks if it contributes to a higher coordination number, stabilizes weak supramolecular bonds, or develops intrachain connections to elastically active interchain junctions. 24 In view of these insights and the DLS measurements performed on the precursor polymer solutions, a likely explanation for the enhancement of the here-in investigated PU gels is therefore a comparable sticker aggregation. Based on the calculated mass fraction of the aggregates (≈10 wt %), we suspect the PU networks to be a mixture of binary sticker assemblies with randomly distributed clusters with higher functionalities.…”

Section: ■ Results and Discussionmentioning

confidence: 88%

“…Here, cryo-transmission electron microscopy revealed that the Upy–Upy interactions are shielded from the aqueous surrounding in segregated pockets comprising Upy aggregates. Such a clustering of the supramolecular stickers is generally known to enforce networks if it contributes to a higher coordination number, stabilizes weak supramolecular bonds, or develops intrachain connections to elastically active interchain junctions . In view of these insights and the DLS measurements performed on the precursor polymer solutions, a likely explanation for the enhancement of the here-in investigated PU gels is therefore a comparable sticker aggregation.…”

Section: Resultsmentioning

confidence: 97%

“…Accordingly, the network relaxation times in supramolecular gels comprising sticker clusters are commonly prolonged. 24 Furthermore, the formation of multivalent supernodes with high degrees of network connectivity has been applied to explain counterintuitive network enforcements reported in some studies. In an illustrative example, Weck et al studied reversible networks cross-linked by hydrogen-bond arrays with differing valency and observed that it is rather the sticker tendency to assemble into clusters than their intrinsic association constant which determines the network elasticity.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The binding situation inside these clusters resembles that of a multivalent sticker with a large energy barrier for the dissociation of a single sticker. Accordingly, the network relaxation times in supramolecular gels comprising sticker clusters are commonly prolonged . Furthermore, the formation of multivalent supernodes with high degrees of network connectivity has been applied to explain counterintuitive network enforcements reported in some studies.…”

Section: Introductionmentioning

confidence: 99%

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Sticker Multivalency in Metallo-supramolecular Polymer Networks

2021

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Multivalency is a key concept in the supramolecular science; it allows an additive or even synergetic enhancement of association constants without the need to replace the basic binding motif. To understand the effects of multivalent binding on the mechanical and dynamic properties of metallo-supramolecular polymer gels, we investigate the concentration-and association strength-dependent linear viscoelasticity of two model systems in the semidilute regime, which are based on either telechelic starpoly(ethylene glycol)s (pEGs) or linear multiblock polyurethanes (PUs) with isolated, monotopic, or adjacent, ditopic terpyridine stickers. In the homogeneous star-pEG gels, the ditopic stickers increase the network strength at identical cross-linker concentrations through the formation of higher functional cross-linking junctions, whereas the mechanical enforcement of the partially clustered PU gels is less-pronounced. The ditopic stickers slow down the dynamics of both gel types to a similar extent by increasing the number of sticker-opening attempts required for network relaxation.

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Section: ■ Results and Discussionmentioning

confidence: 88%

Section: Resultsmentioning

confidence: 97%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Sticker Multivalency in Metallo-supramolecular Polymer Networks

2021

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“…Here phase transformation between the perforated nanovesicle and nanovesicle was achieved through changes in the system temperature. Supramolecular nanoaggregates that are driven by hydrogen bonding interactions have also attracted much attention 40–44 . The hydrogen bonding force is influenced by temperature, pH and solvent polarity; therefore, stimuli‐responsive supramolecular nanostructures can be prepared by employing molecules with hydrogen bonds, with potential applications in various materials, such as memory and self‐healing materials 45–49 …”

Section: Introductionmentioning

confidence: 99%

Construction of nanoaggregates from amphiphilic supramolecules containing barbiturate and Hamilton wedge units

Lü

Deng

Zhong

et al. 2021

Polymer International

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The study of supramolecular morphology is gaining significant attention. This may be attributed to the fact that nanostructures of aggregates have been found to significantly influence the photoelectronic properties of supramolecular materials. In this study, the self‐assembling behaviour of rod–coil molecules with barbiturate (Ba) or Hamilton wedge (Hw) units and the supramolecule Ba‐Hw was investigated. In chloroform solution, molecule Hw consisted of an oligo‐ethylene chain with degree of polymerization of 17 as well as biphenyl, phenyl and Hw units. Ba molecules incorporated octyloxy, biphenyl, phenyl and Ba groups that self‐organized into nanofibres with different diameters. Supramolecular amphiphile Hw‐Ba self‐aggregated into different sizes of nanosheet‐like aggregates. In a dimethylsulfoxide/H2O (1:19 v/v) mixed polar solvent, molecules Hw and Ba aggregated into twist‐shaped and nanosheet aggregates, while the supramolecular Hw‐Ba aggregated into larger‐size microtubes. Experimental results obtained for these molecular assemblies suggest that combining Ba and Hw units by employing hydrogen bonds is an effective strategy for forming amphiphilic supramolecules. Compared with the individual rod–coil molecules Ba and Hw, supramolecule Hw‐Ba has stronger π–π intermolecular forces due to the presence of more planar Hw‐Ba building blocks, which form various supramolecular assemblies with less curvature than the rigid and flexible surfaces of the original molecules. © 2021 Society of Industrial Chemistry.

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Effect of Junction Aggregation on the Dynamics of Supramolecular Polymers and Networks

Ahmadi

Jangizehi

Saalwächter

et al. 2022

Macro Chemistry & Physics

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Transient structures based on associative polymers can deliver complex functions; as such, they hold promise for advanced applications as in drug delivery, tissue engineering, and electronics. The network structure and timescale of its rearrangement are key factors that define their range of utility. However, the inevitable phase separation of polar pairwise associations from nonpolar polymer chains frequently causes junction aggregation, whose stability and functionality significantly affect the network structure and dynamics, and as such, redefine its utility. Engineering the extent of association is a necessity for controlling properties of supramolecular materials, yet the current knowledge of the effect of design parameters on specificities of aggregates and their consequent effects on material properties is limited. To address this gap, the importance of aggregation is highlighted, the available theories and models of the dynamics of associative polymers in the presence of aggregates are reviewed, and the existing experimental records to draw a general guideline for interpreting the effect of aggregates on polymer dynamics are classified. Moreover, pitfalls and considerations like the applicability of time-temperature superposition, and the interplay of kinetics and thermodynamics of aggregation that may undermine the authenticity of the reported data are reviewed.

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Emergence, evidence, and effect of junction clustering in supramolecular polymer materials

Abstract: In this review, the origin of clusters in supramolecular polymer materials, their characterization, their effects on the dynamic and mechanical properties, and their potentials for designing functional materials are overviewed.

Cited by 28 publications

References 203 publications

Sticker Multivalency in Metallo-supramolecular Polymer Networks

Sticker Multivalency in Metallo-supramolecular Polymer Networks

Construction of nanoaggregates from amphiphilic supramolecules containing barbiturate and Hamilton wedge units

Effect of Junction Aggregation on the Dynamics of Supramolecular Polymers and Networks

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