Bending moduli of dendritic polymer brushes in a good solvent

Mikhaylov, I. V.; Borisov, Oleg V.; Darinskii, A. A.; Leermakers, F.A.M.; Birshtein, T.M.

doi:10.1134/s0965545x17050108

Cited by 2 publications

(8 citation statements)

References 12 publications

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“…This trend has been observed by the numerical SCF analysis performed in our previous work on brushes formed by regular dendrons with quenched grafting densities under good solvent conditions. However, the analytical model used in ref was based on a simplifying assumption of independence of ratio between equilibrium values of F int and F elastic of the brush curvature. Although this approximation provides correct values of the exponents in power law dependencies of bending moduli, it leads to incorrect numerical prefactors.…”

Section: Discussionsupporting

confidence: 74%

“…Then, eq provides an expansion (up to the second order) of the brush thicknesses on both sides of the membrane in powers of the reduced curvature ρ = H 1 ( s )/ R as By substituting eq into eq and retaining only terms up to the second order in the reduced curvature ρ = H 1 ( s )/ R ≪ 1, we obtain Subsequently, from eq one obtains the bending moduli Here we remark that eqs and differ by numerical prefactors from similar ones, derived in ref for a particular case of regular dendron brushes. As it was mentioned above, this difference is a result of incorrect calculation of the entropic contribution to the free energy of the bent brush in ref .…”

Section: Self-consistent Field Analytical Theorymentioning

confidence: 80%

“…19 The latter has been previously used by us to study dendronized surfaces; 20,21 it spans extended parameter space and fills the gap between analytical, semianalytical, and scaling approaches and computer simulations. 22−29 This combined analytical and numerical approach was used in our previous work 30 where we specifically focused on bending rigidity of brushes formed by regular dendrons tethered to a surface with quenched grafting density. This limitation is relaxed in the present study: Here we allow tethered macromolecules to reallocate from concave to convex side of the bent membrane, thus reducing the free energy penalty for bending.…”

Section: Introductionmentioning

confidence: 99%

“…This combined analytical and numerical approach was used in our previous work where we specifically focused on bending rigidity of brushes formed by regular dendrons tethered to a surface with quenched grafting density. This limitation is relaxed in the present study: Here we allow tethered macromolecules to reallocate from concave to convex side of the bent membrane, thus reducing the free energy penalty for bending.…”

Section: Introductionmentioning

confidence: 99%

“…This limitation is relaxed in the present study: Here we allow tethered macromolecules to reallocate from concave to convex side of the bent membrane, thus reducing the free energy penalty for bending. Furthermore, in the present work we implement the rigorous SS-SCF analytical approach for calculating conformational entropy of branched (or cyclic) macromolecules in concave and convex brushes, in contrast to a simplifying approximation which was used in ref and led to incorrect numerical values for the bending moduli.…”

Section: Introductionmentioning

confidence: 99%

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Impact of Macromolecular Architecture on Bending Rigidity of Dendronized Surfaces

et al. 2018

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Nanomechanical properties of natural and artificial nanomembranes can be strongly affected by anchored or tethered macromolecules. The intermolecular interactions in polymeric layers give rise to so-called induced bending rigidity which complements the bare rigidity of the membrane. Using analytical mean-field theory, we explore how macromolecular architecture of tethered polymers affects the bending rigidities of the polymer-decorated membranes. The developed theory enables us to consider explicitly various polymer architectures including regular dendrons, Ψ-shaped, star-and comblike macromolecules as well as macrocycles. Numerical self-consistent field computations for selected (regular dendritic) topology complement the analytical theory and support its predictions. We consider both cases of (i) quenched symmetric distribution of tethered molecules on both sides of the membrane and (ii) annealing distribution in which the tethered polymers can relocate from the concave to the convex side of the membrane upon bending. We demonstrate that at a given surface coverage an increase in the degree of branching or cyclization leads to the decrease in the induced bending rigidity. Relocation of the tethered molecules from concave to convex surfaces leads to the additional decrease in polymer contribution to the membrane bending rigidity. In the latter case, a decrease in configurational entropy due to this redistributions substantially contributes to the bending rigidity.

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Section: Discussionsupporting

confidence: 74%

Section: Self-consistent Field Analytical Theorymentioning

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Impact of Macromolecular Architecture on Bending Rigidity of Dendronized Surfaces

et al. 2018

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The effect of dendritic pendants on the folding of amphiphilic copolymers via supramolecular interactions

Huurne

Vantomme

Bersselaar

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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This manuscript is dedicated to Professor Mitsuo Sawamoto's outstanding achievements in polymer chemistry and recognizes his recent retirement from 40 years of exceptional service to Kyoto University.ABSTRACT: The supramolecular folding of amphiphilic heterograft copolymers equipped with dendritic pendants is investigated using a combination of proton nuclear magnetic resonance ( 1 H NMR) spectroscopy, small-angle X-ray scattering, and circular dichroism spectroscopy. Hereto, the linear poly(ethylene glycol) pendants normally used to convey water compatibility are partially substituted with branched analogues. For one set of copolymers, second-generation polyglycerol dendrons are directly attached to the polymer backbone, while for the other a hydrophilic linker is placed in between. The results show that the branching of the hydrophilic pendants affects the local structure of the folded copolymer but does not influence the overall conformation and single-chain character of the folded copolymers in solution. All copolymers fold into 4-5 nm single-chain polymeric nanoparticles with a very compact spherical morphology, independent of the dendritic content of the copolymer. Intriguingly, the incorporation of the dendritic pendants affects the formation of a structured interior even at low incorporation ratios.

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Bending moduli of dendritic polymer brushes in a good solvent

Cited by 2 publications

References 12 publications

Impact of Macromolecular Architecture on Bending Rigidity of Dendronized Surfaces

Impact of Macromolecular Architecture on Bending Rigidity of Dendronized Surfaces

The effect of dendritic pendants on the folding of amphiphilic copolymers via supramolecular interactions

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