Ring-opening supramolecular polymerization controlled by orthogonal non-covalent interactions

Xiao, Tangxin; Zhong, Weiwei; Qi, Lijie; Gu, Jiande; Feng, Xun; Yin, Yuanyuan; Li, Zhengyi; Sun, Xiaoqiang; Cheng, Ming; Wang, Leyong

doi:10.1039/c9py00312f

Cited by 23 publications

(8 citation statements)

References 80 publications

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“…The results show that the [M] crit values for CM-2, -5, -10, and -20 were, respectively, 0.856, 0.329, 0.125, and 0.063 mM. Ideally, [M] crit is expected to be equal to the asymptotic [M] CM at a higher [M] 0 . , However, in practice, the slope of each [M] SP is less than 1; [M] crit is smaller than each asymptotic [M] CM (1.59, 0.70, 0.23, and 0.085 mM at the highest [M] 0 ).…”

Section: Resultsmentioning

confidence: 95%

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Entropy-Driven Supramolecular Ring-Opening Polymerization of a Cyclic Hemoglobin Monomer for Constructing a Hemoglobin–PEG Alternating Polymer with Structural Regularity

Matsuhira

Sakai

2021

Biomacromolecules

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Our earlier report described that a cyclic hemoglobin (Hb) monomer with two β subunits of a Hb molecule (α 2 β 2 ) bound through a flexible polyethylene glycol (PEG) chain undergoes reversible supramolecular ring-opening polymerization (S-ROP) to produce a supramolecular Hb polymer with a Hb−PEG alternating structure. In this work, we polymerized cyclic Hb monomers with different ring sizes (2, 5, 10, or 20 kDa PEG) to evaluate the thermodynamics of S-ROP equilibrium. Quantification of the produced supramolecular Hb polymers and the remaining cyclic Hb monomers in the equilibrium state revealed a negligibly small enthalpy change in S-ROP (ΔH p ≤ 1 kJ•mol −1 ) and a markedly positive entropy change increasing with the ring size (ΔS p = 26.8−33.2 J•mol −1 •K −1 ). The results suggest an entropy-driven mechanism in S-ROP: a cyclic Hb monomer with the larger ring size prefers to form a supramolecular Hb polymer. The S-ROP used for this study has the potential to construct submicrometer-sized Hb−PEG alternating polymers having structural regularity.

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Section: Resultsmentioning

confidence: 95%

“…Ideally, [M] crit is expected to be equal to the asymptotic [M] CM at a higher [M] 0 . 38,39 However, in practice, the slope of each 8). The result indicates that [M] eq is independent of the temperature in the region of 4−45 °C and indicates that ΔH p are negligibly small (Table 4).…”

Section: Resultsmentioning

confidence: 99%

Entropy-Driven Supramolecular Ring-Opening Polymerization of a Cyclic Hemoglobin Monomer for Constructing a Hemoglobin–PEG Alternating Polymer with Structural Regularity

Matsuhira

Sakai

2021

Biomacromolecules

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“…To realize directional chain growth (i.e., to induce directional intermolecular interactions) in artificial supramolecular polymerization, one terminus of a supramolecular polymer would have to be activated during the entire elongation process. Employing geometrically asymmetric monomers capable of such reactions would be one way to induce directional elongation . A more general strategy would be to generate an asymmetric reaction field in which monomers could distinguish between the two termini of the growing polymer, regardless of the monomers’ chemical properties or the ability to self-assemble.…”

Section: Introductionmentioning

confidence: 99%

Directional Supramolecular Polymerization in a Dynamic Microsolution: A Linearly Moving Polymer’s End Striking Monomers

et al. 2021

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Although directional chain reactions are common in nature’s self-assembly processes and in covalent polymerizations, it has been challenging to perform such processes in artificial one-dimensional self-assembling systems. In this paper, we describe a system, employing perylene bisimide (PBI) derivatives as monomers, for selectively activating one end of a supramolecular polymer during its growth and, thereby, realizing directional supramolecular polymerization. Upon introduction of a solution containing only a single PBI monomer into the microflow channel, nucleation was induced spontaneously. The dependency of the aggregation efficiency on the flow rate suggested that the shear force facilitated collisions among the monomers to overcome the activation energy required for nucleation. Next, by introducing a solution containing both monomer and polymer, we investigated how the shear force influenced the monomer–polymer interactions. In situ fluorescence spectra and linear dichroism revealed that growth of the polymers was accelerated only when they were oriented under the influence of shear stress. Upon linear motion of the oriented polymer, polymer growth at that single end became predominant relative to the nucleation of freely diffusing monomers. When applying this strategy to a two-monomer system, the second (less active) monomer reacted selectively at the forward-facing terminus of the first polymer, leading to the creation of a diblock copolymer through formation of a molecular heterojunction. This strategyfriction-induced activation of a single end of a polymershould be applicable more generally to directional supramolecular block copolymerizations of various functional molecules, allowing molecular heterojunctions to be made at desired positions in a polymer.

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“…[28][29][30][31][32][33][34][35][36] The interesting pillar-shape architectures of pillar[n]arenes endow them with the ability to bind with a variety of guest molecules. 37 As a result, pillar[n]arenes exhibit significant potentials in building various functional materials, 38 such as dynamic organogels or hydrogels, [39][40][41][42][43][44][45] functional supramolecular polymers, [46][47][48][49][50][51][52] transmembrane channels, 53 nonporous adaptive crystals, [54][55][56][57] and other nanomaterials. 58,59 Meanwhile, the development of water-soluble pillar[n]arene (WP[n]) based supra-amphiphiles has also progressed rapidly in recent years due to the simplicity of modification of the pillar[n]arene framework.…”

Section: Introductionmentioning

confidence: 99%

Stimuli-responsive nanocarriers constructed from pillar[n]arene-based supra-amphiphiles

Xiao

Zhong

et al. 2019

Mater. Chem. Front.

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104

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Ring-opening supramolecular polymerization controlled by orthogonal non-covalent interactions

Abstract: The π–π interaction has been successfully utilized to orthogonally regulate the supramolecular polymerization driven by quadruple hydrogen bonding.

Cited by 23 publications

References 80 publications

Entropy-Driven Supramolecular Ring-Opening Polymerization of a Cyclic Hemoglobin Monomer for Constructing a Hemoglobin–PEG Alternating Polymer with Structural Regularity

Entropy-Driven Supramolecular Ring-Opening Polymerization of a Cyclic Hemoglobin Monomer for Constructing a Hemoglobin–PEG Alternating Polymer with Structural Regularity

Directional Supramolecular Polymerization in a Dynamic Microsolution: A Linearly Moving Polymer’s End Striking Monomers

Stimuli-responsive nanocarriers constructed from pillar[n]arene-based supra-amphiphiles

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