Polymeric Nanofibers Prepared from Self-Organized Supramolecules

Abstract

Nijland, H.; Polushkin, E.; Brinke, G. ten; Mäki-Ontto, R.; Ikkala, O.; M"ki-Ontto, R.; Maki-Ontto, RA facile concept to prepare nano-objects based on self-organizing polymeric supramolecules (also called supramolecular block copolymers) is demonstrated using one particular shape, i.e., nanorods or nanofibers. Cylindrical aggregates consisting of a polystyrene (PS) core and a thin corona of poly(4-vinylpyridine) (P4VP) chains are prepared from P4VP-(pentadecylphenol)-block-PS comb-coil supramolecules. Diblock copolymers P4VP-block-PS are stoichiometrically (with respect to the number of pyridine groups) hydrogen-bonded with pentadecylphenol (PDP) amphiphiles to yield P4VP(PDP)-block-PS comb-coil supramolecules. By the selection of appropriate relative block lengths for P4VP(PDP) and PS, a micro-phaseseparated cylindrical morphology of PS cylinders inside a P4VP(PDP) matrix is obtained. Subsequent removal of the amphiphiles, accounting for ca. 75% of the matrix material, results in cylinders with a core of PS and a corona of easily adjustable thickness of P4VP. The advantages of the present concept compared to the existing procedures are discussed.

Intermediate Segregation Type Chain Length Dependence of the Long Period of Lamellar Microdomain Structures of Supramolecular Comb−Coil Diblocks

“…19 The opposite case of "crew-cut" cylindrical aggregates consisting of a PS core and a thin corona of short P4VP chains has also been realized. 20 In a slightly more complicated example, P4VP is first protonated with a strong acid such as methanesulfonic acid (MSA) to which subsequently PDP is hydrogen bonded, leading to P4VP(MSA)(PDP)-b-PS. The presence of MSA increases the ODT of the short length scale structure to 100°C.…”

Hollow Inorganic Nanospheres and Nanotubes with Tunable Wall Thicknesses by Atomic Layer Deposition on Self‐Assembled Polymeric Templates

“…Block copolymers consist of well-defined mutually repulsive polymeric blocks that are covalently connected, thus leading to competitive interactions and self-assembled nanostructured materials. [23,24] Complementary physical interactions, which are dealt with in supramolecular chemistry, [25] can be applied to bind further structural moieties within block copolymers to achieve additional hierarchy levels, [26] prepare discrete nanoscale objects, [24,27] or direct the self-assembly of inorganic materials. [28][29][30][31][32] In particular, hydrogen-bonded polymer-surfactant complexes of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and alkyl phenols, such as pentadecyl phenol (PDP) and dodecyl phenol (DDP), lead to discrete PS-b-P4VP nanorods with a PS core and P4VP corona.…”

Transport and Electro‐Optical Properties in Polymeric Self‐Assembled Systems

“…Notably, the electrically conducting channels can be discontinuous at the domain boundaries. More generally, aligned and monodomain structures in block copolymers have been pursued using several concepts, for example using thin films where the surface energies play a major role, electric fields, magnetic fields, flow alignment and graphoepitaxy [86,[103][104][105][106][107][108][109][110][111][112][113][114][115][116][117][118][119][120][121][122]. Therefore, in many of the applications requiring enhanced electrical transport, a generic goal in relation to self-assembly is to prepare monodomain structures having e.g.…”

“…nonpolar carbosilane block and rigid helical polyisocyanide blocks form complexes with silver ions and lead to nanowires [365]. Distinct nanowires can be achieved by using polystyrene-b-poly(4-vinylpyridine) where pentadecylphenol is hydrogen bonded to the pyridines, which leads to hierarchical self-assembly [366]: Polystyrene cylinders within poly(4-vinylpyridine)-pentadecylphenol can be obtained and, after aligning and removing the pentadecylphenol, distinct polystyrene wires with a poly(4-vinylpyridine) corona are obtained [86,109,367], which can be metallized with CdSe, Pd, Ag and Au [368,369]. The self-assembled domains of symmetrical polystyrene-b-poly(4-vinylpyridine) diblock copolymers have been used as templates to prepare Ag layers by electroless deposition and anisotropic conductivity was achieved along the lamellae [370].…”