Branched Supramolecular Copolymers: Inducing Branching in Bisurea-Based Monomers Using Multi-Sulfonate Molecules

Columbus, Ishay; Eren, Noga; Elitsur, Renana; Shenhar, Roy

doi:10.1021/acs.macromol.1c01837

Cited by 6 publications

(4 citation statements)

References 74 publications

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“…Colloidal structures in CPCs with a wide range of Ψ 6 can be obtained in one step by tuning the supramolecular crosslinking kinetics at the crystal growth stage, where E is the dominating factor. ,− Here, three assembly conditions with different crystal growth durations of 2.6, 20, and 85 h (Figure a,b) were used to prepare CPCs by tuning E , where E was controlled by regulating the air flow rate and the RH in the environment. Ordering of the CPC structure was estimated via reflection peak intensity and normalized FWHM, indicating that a slow crosslinking rate was favorable for ordered structures (Figure c).…”

Section: Resultsmentioning

confidence: 99%

Structure-Tunable Construction of Colloidal Photonic Composites via Kinetically Controlled Supramolecular Crosslinking

Lyu

et al. 2022

Macromolecules

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Colloidal photonic composites (CPCs) combine a unique array of colloidal particles (CPs) with a polymer matrix and exhibit intriguing optical and mechanical properties strongly depending on their structures. One-step construction of CPCs with tunable structures is crucial for enriching their properties and matching application requirements, which is highly desirable yet challenging. Here, we present a general strategy for CPC construction with tunable structures from short-range to long-range order by one-step kinetically controlling the supramolecular crosslinking between CPs and supramolecular oligomers. Importantly, the assembly process is monitored in situ and the key factors for structural regulation, i.e., the critical volume fraction of CPs and the structural transition from crystal growth to lattice compression, are disclosed, which play critical roles in obtaining CPCs with a wide range of controllable structures. The as-obtained CPCs exhibit structural colors with different angle dependencies, versatile mechanical strengths, and appealing mechanochromic and self-healing capabilities. This work provides insights into the one-step construction of structure-tunable photonic materials, opening up exciting avenues for novel solution-processable photonics.

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Section: Resultsmentioning

confidence: 99%

Structure-Tunable Construction of Colloidal Photonic Composites via Kinetically Controlled Supramolecular Crosslinking

Lyu

et al. 2022

Macromolecules

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“…The smallest ring consists of three reacted functional groups. The molecules bearing more than one reacted functional groups in a network serve as branch points [55]. In Figure 1b, networks consisting of telechelic polymers (n >> 1) carrying gelators at their both ends ( f = 2) are shown.…”

Section: Self-associationmentioning

confidence: 99%

“…The elementary unit of a cross-link is a sandwich complex with multiplicty index (2, 1). A network is made up of ladder cross-links and branch molecules[55] bearing more than one reacted functional groups. (b) Ternary phase diagram for the ladder model of low-mass (n = 6) trifunctional ( f = 3) molecules showing reentrant sol-gel-sol transition (red lines).…”

mentioning

confidence: 99%

Thermoreversible Gelation with Supramolecularly Polymerized Cross-Link Junctions

Tanaka

2023

Gels

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Structure and reversibility of cross-link junctions play pivotal roles in determining the nature of thermoreversible gelation and dynamic mechanical properties of the produced polymer networks. We attempt to theoretically explore new types of sol–gel transitions with mechanical sharpness by allowing cross-links to grow without upper bound. We consider thermoreversible gelation of the primary molecules R{Af} carrying the number f of low molecular weight functional groups (gelators) A. Gelators A are assumed to form supramolecular assemblies. Some examples are: telechelic polymers (f=2) carrying π–π stacking benzene derivatives at their both ends, and trifunctional star molecules (f=3) bearing multiple hydrogen-bonding gelators. The sol–gel transition of the primary molecules becomes sharper with the cooperativity parameter of the stepwise linear growth of the cross-links. There is a polymerization transition (crossover without singularity) of the junctions in the postgel region after the gel point is passed. If the gelator A tends to form supramolecular rings competitively with linear chains, there is another phase transition in the deep postgel region where the average molecular weight of the rings becomes infinite (Bose–Einstein condensation of rings). As a typical example of binary cross-links where gelators A and B form mixed junctions, we specifically consider metal-coordinated binding of ligands A by metal ions B. Two types of multi-nuclear supramolecular complexes are studied: (i) linear stacking (ladder) of the sandwich A2B units, and (ii) linear train of egg-box A4B units. To find the strategy towards experimental realization of supramolecular cross-links, the average molecular weight, the gel fraction, the average length of the cross-link junctions are numerically calculated for all of these models as functions of the functionality f, the concentration of the solute molecules, and the temperature. Potential candidates for the realization of these new types of thermoreversible gelation are discussed.

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“…Supramolecular chemistry was established and presented by Charles Pedersen, Jean-Marie Lehn, and Donald Cram after their Nobel Prize in Chemistry in 1987s [1][2][3][4][5]. Noncovalent interaction in chemistry was produced to explain the supramolecular chemistry that involved the arrangement of molecules via intermolecular force or non-covalent interactions [6][7][8][9][10][11]. This relatively new part of chemistry deals with self-assembly or molecular assembly that results from the association of two or more chemical species held together by intermolecular interactions [12][13][14][15].…”

Section: Introductionmentioning

confidence: 99%

Non-Covalent Interaction on the Self-Healing of Mechanical Properties in Supramolecular Polymers

Buaksuntear

Limarun

Suethao

et al. 2022

IJMS

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Supramolecular polymers are widely utilized and applied in self–assembly or self–healing materials, which can be repaired when damaged. Normally, the healing process is classified into two types, including extrinsic and intrinsic self–healable materials. Therefore, the aim of this work is to review the intrinsic self–healing strategy based on supramolecular interaction or non-covalent interaction and molecular recognition to obtain the improvement of mechanical properties. In this review, we introduce the main background of non-covalent interaction, which consists of the metal–ligand coordination, hydrogen bonding, π–π interaction, electrostatic interaction, dipole–dipole interaction, and host–guest interactions, respectively. From the perspective of mechanical properties, these interactions act as transient crosslinking points to both prevent and repair the broken polymer chains. For material utilization in terms of self–healing products, this knowledge can be applied and developed to increase the lifetime of the products, causing rapid healing and reducing accidents and maintenance costs. Therefore, the self–healing materials using supramolecular polymers or non-covalent interaction provides a novel strategy to enhance the mechanical properties of materials causing the extended cycling lifetime of products before replacement with a new one.

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Branched Supramolecular Copolymers: Inducing Branching in Bisurea-Based Monomers Using Multi-Sulfonate Molecules

Cited by 6 publications

References 74 publications

Structure-Tunable Construction of Colloidal Photonic Composites via Kinetically Controlled Supramolecular Crosslinking

Structure-Tunable Construction of Colloidal Photonic Composites via Kinetically Controlled Supramolecular Crosslinking

Thermoreversible Gelation with Supramolecularly Polymerized Cross-Link Junctions

Non-Covalent Interaction on the Self-Healing of Mechanical Properties in Supramolecular Polymers

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