Hierarchical excluded volume screening in solutions of bottlebrush polymers

Paturej, Jarosław; Kreer, T.

doi:10.1039/c7sm01968h

Cited by 37 publications

(56 citation statements)

References 92 publications

(162 reference statements)

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“…Recent simulations have also shown that there are significant in the concentration-dependent changes in the size of the bottlebrush polymers in solution. 87 Recent experiments by Bates et al 88 have also indicated that the conformation of the bottlebrush backbones is more 'coiled' than initially anticipated, which is consistent with our findings.…”

Section: Backbone Conformation Characterizationsupporting

confidence: 93%

A comparative study of thermodynamic, conformational, and structural properties of bottlebrush with star and ring polymer melts

Chremos

Douglas

2018

The Journal of Chemical Physics

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Thermodynamic, conformational, and structural properties of bottlebrush polymer melts are investigated with molecular dynamics simulations and compared to linear, regular star, and unknotted ring polymer melts to gauge the influence of molecular topology on polymer melt properties. We focus on the variation of the backbone chain length, the grafting density along the backbone, and the length of the side chains at different temperatures above the melt glass transition temperature. Based on these comparisons, we find that the segmental density, isothermal compressibility, and isobaric thermal expansion of bottlebrush melts are quantitatively similar to unknotted ring polymer melts and star polymer melts having a moderate number ( f = 5 to 6) of arms. These similarities extend to the mass scaling of the chain radius of gyration. Our results together indicate that the configurational properties of bottlebrush polymers in their melt state are more similar to randomly branched polymers than linear polymer chains. We also find that the average shape of bottlebrush polymers having short backbone chains with respect to the side chain length is also rather similar to the unknotted ring and moderately branched star polymers in their melt state. As a general trend, the molecular shape of bottlebrush polymers becomes more spherically symmetric when the length of the side chains has a commensurate length as the backbone chain. Finally, we calculate the partial static structure factor of the backbone segments and we find the emergence of a peak at the length scales that characterizes the average distance between the backbone chains. This peak is absent when we calculate the full static structure factor. We characterize the scaling of this peak with parameters characterizing the bottlebrush molecular architecture to aid in the experimental characterization of these molecules by neutron scattering.

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Section: Backbone Conformation Characterizationsupporting

confidence: 93%

A comparative study of thermodynamic, conformational, and structural properties of bottlebrush with star and ring polymer melts

Chremos

Douglas

2018

The Journal of Chemical Physics

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“…Both values are with very good agreement to the theoretical prediction given by Eq. (7). Note that the values of ρ calculated in the course of our simulations are much closer to the analytical theory results as compared to existing numerical data 35 .…”

Section: Integration Over the Wave Vector Q 1 Givessupporting

confidence: 85%

“…in expression(28), for f r = 0 , both at f c = 1 and f c = 2 we restore the universal size ratio of a linear polymer (5), whereas f c > 2 and f r = 0 gives the expression for a star polymer(7). For f c = 0 and f r = 1 we reproduce the known analytical expression of a single ring from Eq.…”

mentioning

confidence: 65%

“…Polymer macromolecules of complex branched structure attract considerable attention both from academical 1 , 2 and applied 3 , 4 perspective, being encountered as building blocks of materials like synthetic and biological gels 5 , thermoplastics 6 , melts and elastomers 7 , 8 . High functionality of polymers provides novel properties with applications in diverse fields like drug delivery 9 , tissue engineering 10 , super-soft materials 11 , and antibacterial surfaces 12 etc.…”

Section: Introductionmentioning

confidence: 99%

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Universal size ratios of Gaussian polymers with complex architecture: radius of gyration vs hydrodynamic radius

Haydukivska

Blavatska

Paturej

2020

Sci Rep

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We study the impact of arm architecture of polymers with a single branch point on their structure in solvents. Many physical properties of polymer liquids strongly dependent on the size and shape measures of individual macromolecules, which in turn are determined by their topology. Here, we use combination of analytical theory, based on path integration method, and molecular dynamics simulations to study structural properties of complex Gaussian polymers containing f c linear branches and f r closed loops grafted to the central core. We determine size measures such as the gyration radius R g and the hydrodynamic radii R H , and obtain the estimates for the size ratio R g /R H with its dependence on the functionality f = f c + f r of grafted polymers. In particular, we obtain the quantitative estimate of the degree of compactification of these polymers with increasing number of closed loops f r as compared to linear or star-shape molecules of the same total molecular weight. numerical simulations corroborate theoretical prediction that R g /R H decreases towards unity with increasing f. These findings provide qualitative description of polymers with complex architecture in θ solvents.

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“…The validity of theoretically derived ratios ρ chain and ρ ring was confirmed in several simulation studies [15,17,18]. Polymer macromolecules of complex branched structure attract considerable attention both from academical [19,20] and applied [21,22] perspective, being encountered as building blocks of materials like synthetic and biological gels [23], thermoplastics [24], melts and elastomers [25,26]. High functionality of polymers provides novel properties with applications in diverse fields like drug delivery [27], tissue engineering [28], super-soft materials [29], and antibacterial surfaces [30] etc.…”

Section: Introductionmentioning

confidence: 65%

Universal size ratios of Gaussian polymers with complex architecture: Radius of gyration vs hydrodynamic radius

Haydukivska,

Blavatska,

Paturej

2020

Preprint

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We study universal structural properties of Gaussian complex polymer architectures, containing f c linear branches and f r closed loops grafted to the central core. Attention is paid to calculation of the gyration radius R 2 g and the hydrodynamic radii RH . We use combination of analytical theory, based on path integration method, and molecular dynamics simulations. We obtain the estimates for the size ratio R 2 g /RH and its dependence on functionality f = f c + f r of grafted polymers.

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Hierarchical excluded volume screening in solutions of bottlebrush polymers

Cited by 37 publications

References 92 publications

A comparative study of thermodynamic, conformational, and structural properties of bottlebrush with star and ring polymer melts

A comparative study of thermodynamic, conformational, and structural properties of bottlebrush with star and ring polymer melts

Universal size ratios of Gaussian polymers with complex architecture: radius of gyration vs hydrodynamic radius

Universal size ratios of Gaussian polymers with complex architecture: Radius of gyration vs hydrodynamic radius

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