Polymer globule with fractal properties caused by intramolecular nanostructuring and spatial constrains

AA Glagoleva and VV Vasilevskaya and AR Khokhlov, SOFT MATTER, 12, 5138-5145 (2016).

DOI: 10.1039/c6sm00747c

By means of computer simulation, we studied macromolecules composed of N dumbbell amphiphilic monomer units with attractive pendant groups. In poor solvents, these macromolecules form spherical globules that are dense in the case of short chains (the gyration radius R-G similar to N-1/3), or hollow inside and obey the R-G similar to N-1/2 law when the macromolecules are sufficiently long. Due to the specific intramolecular nanostructuring, the vesicle-like globules of long amphiphilic macromolecules posses some properties of fractal globules, by which they (i) could demonstrate the same scaling statistics for the entire macromolecule and for short subchains with m monomer units and (ii) possess a specific territorial structure. Within a narrow slit, the globule loses its inner cavity, takes a disk-like shape and scales as N-1/2 for much shorter macromolecules. However, the field of end-to-end distance r(m) similar to m(1/2) dependence for subchains becomes visibly smaller. The results obtained were compared with the homopolymer case.

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