Dimensional and shape properties of a single linear polycatenane: Effect of catenation topology

Lei, Huanqing; Zhang, Jianguo; Wang, Liming

doi:10.1016/j.polymer.2020.123160

Cited by 17 publications

(9 citation statements)

References 83 publications

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“…Linear catenanes, or poly[ n ]catenanes, are the simplest systems where the emergent properties of mechanical bonding can be addressed and contrasted with those of conventionally bonded linear polymers. ,, Starting from the seminal study of ref, where linear catenanes of up to 27 macrocycles were successfully synthesized, several efforts have been spent in this direction. We now know how catenanes respond to mechanical stretching, , how their relaxation dynamics in isolation or in solution varies at different scales, − and how metric scaling is defined by the interplay of the size and number of linked rings. − …”

Section: Introductionmentioning

confidence: 99%

Effect of Ring Rigidity on the Statics and Dynamics of Linear Catenanes

Chiarantoni

Micheletti

2022

Macromolecules

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We used molecular dynamics simulations to investigate the statics and dynamics of poly[n]catenanes for different bending rigidities of the constituent rings. We show that stiffer rings yield catenanes with more extended and, at the same time, more flexible backbones. The softening of the backbone reflects the decreasing steric interactions of catenated rings as their shape becomes more oblate due to increased rigidity. The internal dynamics of catenanes is affected too. Going from flexible to rigid rings causes a several-fold slowing of different processes, from segmental rotations and size fluctuations to Rouse modes. Finally, by considering the statics and dynamics of crowded solutions of catenanes, we isolate another emergent property controlled by the rigidity of the rings. Specifically, we show that catenanes with rigid rings hinder each other’s motion more than those with flexible rings. Thus, in equally crowded solutions, the diffusion coefficient is smaller for catenanes with stiffer rings.

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Section: Introductionmentioning

confidence: 99%

Effect of Ring Rigidity on the Statics and Dynamics of Linear Catenanes

Chiarantoni

Micheletti

2022

Macromolecules

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“…Although catenated DNA has been investigated by experiments − for a long time, the investigation is inspired by advances in chemical synthesis in recent decades in which theoretical analysis and computer simulations on polycatenanes, − as a typical TIM in the science of polymer material, have been comprehensively conducted. The simulation results on the static and dynamic properties of polycatenanes show that there are different contributions from the rings and the backbone, , and the decomposition of the contributions is crucial for the study of the TIMs.…”

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confidence: 99%

Double Asymptotic Structures of Topologically Interlocked Molecules

Yao

Wang

et al. 2021

ACS Macro Lett.

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The mean square size of topologically interlocked molecules (TIMs) is presented as a linear combination of contributions from the backbone and subcomponents. Using scaling analyses and extensive molecular dynamics simulations of polycatenanes as a typical example of TIMs, we show that the effective exponent ν(m) for the size dependence of the backbone on the monomer number of subcomponent m is asymptotic to a value ν (∼0.588 in good solvents) with a correction of m –0.47, which is the same as for the covalently linked polymer. However, the effective exponent for the size dependence of subcomponents on m is asymptotic to the same value ν but with a new correction of m –1.0. The different corrections to the scaling on the backbone and subcomponent structure induce a surprising double asymptotic behavior for the architecture of the TIMs. The scaling model that takes into account the double asymptotic behavior is in good quantitative agreement with the simulation result that the effective exponent for the size dependence of TIMs on m increases with the subcomponent number n. The full scaling functional form of the size dependence on m and n for polycatenanes in a good solvent is well described by a simple sum of two limiting behaviors with different corrections.

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“…This is most apparent in poly[ n ]catenanes (Fig. 18e), 134 in which a clear separation between ring-like and chain-like dynamics is observed, leading to multiple sub-diffusive regimes in the monomer mean-squared displacement, even in the absence of reptation behavior. 135 However, this clean separation fails to account for the unusual rheological behaviour of these systems: the viscosity decreases with increasing ring size and molecular weight, in strong contrast to the behaviour of typical polymer melts (Fig.…”

Section: Polycatenane Properties: a Physical Point Of Viewmentioning

confidence: 97%