Stiffness and conformations of molecular bottle-brushes strongly adsorbed on a flat surface

Khokhlov, Alexei R.; Reineker, P.

doi:10.1007/s101890170147

Cited by 37 publications

(52 citation statements)

References 21 publications

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“…In a good solvent, the bottlebrush radius is predicted [79][80][81][82][83] it is important to note that side-chain conformations within the 2D plane are highly anisotropic. 82 In a theta solvent, the bottlebrush radius is predicted to scale with N 2/3 or N 3/4 , depending on the model assumptions, 80,84 while the radius of free linear chains scales with N 1/2 (ideal chain).…”

Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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Bottlebrush polymers are a type of branched or graft polymer with polymeric side-chains attached to a linear backbone, and the unusual architecture of bottlebrushes provides a number of unique and potentially useful properties. These include a high entanglement molecular weight, enabling rapid self-assembly of bottlebrush block copolymers into large domain structures, the self-assembly of bottlebrush block copolymer micelles in a selective solvent even at very low dilutions, and the functionalization of bottlebrush side-chains for recognition, imaging, or drug 2 delivery in aqueous environments. This review article focuses on recent developments in the field of bottlebrush polymers with an emphasis on applications of bottlebrush copolymers.Bottlebrush copolymers contain two (or more) different types of polymeric side-chains. Recent work has explored the diverse properties and functions of bottlebrush polymers and copolymers in solutions, films, and melts, and applications explored include photonic materials, bottlebrush films for lithographic patterning, drug delivery, and tumor detection and imaging. We provide a brief introduction to bottlebrush synthesis and physical properties and then discuss work related to: i) bottlebrush self-assembly in melts and bulk thin films, ii) bottlebrushes for photonics and lithography, iii) bottlebrushes for small molecule encapsulation and delivery in solution, and iv) bottlebrush micelles and assemblies in solution. We briefly discuss three potential areas for future research, including developing a more quantitative model of bottlebrush self-assembly in the bulk, studying the properties of bottlebrushes at interfaces, and investigating the solution assembly of bottlebrush copolymers.

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Section: Synthesis Of Bottlebrush Polymersmentioning

confidence: 99%

Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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“…It is known that the induced persistent length (the bending modulus) of comb-like macromolecules increases with the increase of both the length of the side chains (groups) and their grafting density. [13] We have performed the comparative conformational analysis in a more quantitative manner, as described below. Femtoscan software was used for analysing the SFM images of the adsorbed macromolecules.…”

Section: Resultsmentioning

confidence: 99%

Conformational Behaviour of Comb‐Like Poly(4‐vinylpyridinium) Salts and their Complexes with Surfactants in Solution and on a Flat Surface

Gallyamov

Starodubtsev

Bragina

et al. 2007

Macro Chemistry & Physics

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We synthesised P4VP bromides with octyl and dodecyl pendant groups; the bromide anions in these polymer salts were further substituted with dodecylsulfate or bis(2‐ethylhexylsuccinate) anions. Direct SFM visualisation of the original P4VP chains, of the macromolecular salts and of their complexes, showed that the attachment of the pendant groups and especially the complexation with the surfactants promotes stretching of the macromolecules while adsorbing on mica substrate. On the other hand, viscosimetry showed that in solution (chloroform) the comb‐like chains and their complexes with dodecylsulfate had more compact conformations than those of the original P4VP. The scaling exponents describing the correlation between the contour length and the end‐to‐end distance of the adsorbed macromolecules were found to be ca. 3/4, which is indicative of 2D self‐avoiding walk statistics.magnified image

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“…Here ν is the still unknown parameter. The persistence length of 2D brush with fixed (quenched) dis-tribution of the side chains with respect to the backbone has a cubic dependence on the number of segments in the side chain M , λ ≈ aM 3 [44,45], where a is the linear size of the segment. Within the Flory theory, the elastic free energy of the 2D molecule takes the form…”

Section: Discussionmentioning

confidence: 99%

Individual bottle brush molecules in dense 2D layers restoring high degree of extension after collapse-decollapse cycle: Directly measured scaling exponent

et al. 2009

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We prepared dense films of adsorbed brush-like macromolecules on mica substrate by transfer of compressed Langmuir monolayers from water subphase. The main macromolecular contours in the dense films were clearly resolved by SFM. The films were subjected to successive treatments by ethanol and water vapours. In accordance with previous results for isolated macromolecules, the films underwent collapse and subsequent decollapse morphological transformations in the changing vapour environment. Statistical analysis of the macromolecular dimensions in the films allowed us to measure the values of the scaling exponent nu determining the correlation between mean lateral and linear dimensions of the macromolecules. The analysis showed that the macromolecular conformations in the film as transferred were similar to the previously described conformations of the same macromolecules deposited directly on mica as isolated chains at much lower surface densities. The determined nu was close to the 0.75 value corresponding to the 2D SAW statistics. We assumed that the molecules retained the high degree of extension during the compression step due to suppressed reorganisation of the side chains. Differently from previous observations for isolated macromolecules, the restored conformations in the dense films after collapse-decollapse cycle were more extended with the nu of about 0.73 value. A theoretical explanation of the high degree of re-extension is proposed.

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Stiffness and conformations of molecular bottle-brushes strongly adsorbed on a flat surface

Cited by 37 publications

References 21 publications

Structure, function, self-assembly, and applications of bottlebrush copolymers

Structure, function, self-assembly, and applications of bottlebrush copolymers

Conformational Behaviour of Comb‐Like Poly(4‐vinylpyridinium) Salts and their Complexes with Surfactants in Solution and on a Flat Surface

Individual bottle brush molecules in dense 2D layers restoring high degree of extension after collapse-decollapse cycle: Directly measured scaling exponent

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