Supramolecular polymer bottlebrushes

Gruschwitz, Franka V.; Klein, Tobias; Catrouillet, Sylvain; Brendel, Johannes C.

doi:10.1039/d0cc01202e

Cited by 41 publications

(42 citation statements)

References 424 publications

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“…We selected bisurea stickers that drive the formation of supramolecular polymer bottlebrushes through directional assembly of the sticker by hydrogen bonds. 11,12,13 The assembly of the polymers in long 1D nanostructures, where the polymer chains are densely packed, might actually alter their solubility properties. 14 If successful, this strategy could allow converting well-known hydrophilic homopolymers into thermosensitive polymers with a CP near body temperature, without copolymerization with hydrophobic monomers.…”

Section: Introductionmentioning

confidence: 99%

Unexpected thermo-responsiveness of bisurea-functionalized hydrophilic polymers in water

Mellot

Jestin

Bouteiller

et al. 2021

Journal of Colloid and Interface Science

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Hypothesis: Thermoresponsive polymers are important materials for various applications. However, the number of polymers that exhibit this property in the temperature range of interest remains limited. The development of novel rational design strategies through the understanding of the thermal transition's origin is therefore of utmost importance. Experiments: Bisurea-functionalized water-soluble polymers were synthesized by RAFT polymerization. After direct dissolution in water, the supramolecular assemblies were analyzed by cryoTEM and SANS. Their temperature-dependent water-solubility was characterized by various techniques, namely DLS, SANS, DSC, IR, to understand the origin of the temperature sensitivity. Findings: The supramolecular assemblies exhibit an unexpected temperature-dependent solubility. For instance, a cloud point of only 39 °C was measured for poly(N,Ndimethylacrylamide) assemblies. This property is not restricted to one specific polymer but is rather a general feature of bisurea-functionalized polymers that form supramacromolecular bottlebrushes in water. The results highlight the existence of two distinct transitions; the first one is a visually perceptible cloud point due to the aggregation of individual micelles, presumably driven by the hydrophobic effect. The second transition is related to the dissociation of intermolecular bisurea hydrogen bonds. Finally, we show that it is possible to widely tune the cloud point temperature through the formation of co-assemblies.

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Section: Introductionmentioning

confidence: 99%

Unexpected thermo-responsiveness of bisurea-functionalized hydrophilic polymers in water

Mellot

Jestin

Bouteiller

et al. 2021

Journal of Colloid and Interface Science

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“…[ 1 ] Recently, more attention has been paid to introducing motifs capable of forming directional, supramolecular interaction forces such as π–π interactions or hydrogen bonds (H‐bonds) that can allow to direct the polymer assembly into elongated structures, such as cylinders, that would otherwise not be accessible. [ 2–7 ] In particular, the so‐called supramolecular polymer bottlebrushes (SPBs) have gained increasing interest due to their potential applications in areas such as nanomedicine, [ 8 ] rheology [ 9 ] , electronics, and photonics. [ 10,11 ]…”

Section: Methodsmentioning

confidence: 99%

Overcoming the Necessity of a Lateral Aggregation in the Formation of Supramolecular Polymer Bottlebrushes in Water

Klein

Ulrich

Gruschwitz

et al. 2020

Macromol. Rapid Commun.

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The assembly of supramolecular polymer bottlebrushes in aqueous systems is, in most cases, associated with a lateral aggregation of the supramolecular building blocks in addition to their axial stacking. Here, it is demonstrated that this limitation can be overcome by attaching three polymer chains to a central supramolecular unit that possesses a sufficiently high number of hydrogen bonding units to compensate for the increased steric strain. Therefore, a 1,3,5‐benzenetrisurea‐polyethylene oxide conjugate is modified with different peptide units located next to the urea groups which should facilitate self‐assembly in water. For a single amino acid per arm, spherical micelles are obtained for all three tested amino acids (alanine, leucine, and phenylalanine) featuring different hydrophobicities. Only a slight increase in size and solution stability of spherical micelles is observed with increasing hydrophobicity of amino acid unit. In contrast, introducing two amino acid units per arm and thus increasing the number of hydrogen bonds per unimer molecule results in the formation of cylindrical structures, that is, supramolecular polymer bottlebrushes, despite a suppressed lateral aggregation. Consequently, it can be concluded that the number of hydrogen bonds has a more profound impact on the resulting solution morphology than the hydrophobicity of the amino acid unit.

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“…Therefore, it is not surprising that in the emerging literature of protein–polymer conjugates, there is hardly any example that actually reveals to what extent the enzymatic degradation of proteins could be prevented by polymer conjugation. In the recent past we have reported 21 supramolecular structure-directing unit (SSDU) regulated entropy driven assembly of hydrophilic polymers by directional molecular interaction in which the self-assembly and morphology of the brush like supramolecular polymer 22 could be regulated by specific molecular interactions instead of the packing parameter. We envisaged this could be equally effective for programmable assembly of SSDU-attached biomacromolecules such as proteins 23 with the potential to address some of the pitfalls of protein–polymer conjugates as discussed before.…”

Section: Introductionmentioning

confidence: 99%

Redox responsive activity regulation in exceptionally stable supramolecular assembly and co-assembly of a protein

2021

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Supramolecular polymer bottlebrushes

Abstract: The assembly of polymer building blocks into supramolecular bottlebrushes by non-covalent forces represents an exciting new field of research. This review provides an overview on suitable motifs and requirements for the formation of such structures.

Cited by 41 publications

References 424 publications

Unexpected thermo-responsiveness of bisurea-functionalized hydrophilic polymers in water

Unexpected thermo-responsiveness of bisurea-functionalized hydrophilic polymers in water

Overcoming the Necessity of a Lateral Aggregation in the Formation of Supramolecular Polymer Bottlebrushes in Water

Redox responsive activity regulation in exceptionally stable supramolecular assembly and co-assembly of a protein

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