ISSN 1070-4272, Russian Journal of Applied Chemistry, 2016, Vol. 89, No. 8, pp. 1347−1353. © Pleiades Publishing, Ltd., 2016.
Block copolymers can self-assemble into a variety of
ordered structures such as spheres, cylinders, gyroids,
lamellae, and vesicles. Such well deﬁ ned self-assembled
nanostructures may serve as templates for fabrication of
functional micro/nano devices, microelectronics, and
vehicles for drug delivery, and gene therapy etc. It has
been widely studied to develop convenient control and
fabrication of well-deﬁ ned nanostructures through self-
assembly of block copolymers.
Block copolymers with well-designed architectures
have been widely reported to form new type of self-assem-
bly nanostructures with variable functions. However, com-
plicated polymer synthesis and separation often occurred.
Alternatively, supramolecular self-assembly has been dem-
onstrated as efﬁ cient, simple and feasible way to construct
complicated and stimuli-response polymer self-assembly
systems [1, 2]. Some compounds with multiple functional
groups, molecules, ions, polyelectrolytes, and polymers
with multiple functional groups can assemble with other
small molecules or polymers through speciﬁ c non-covalent
interactions to form supramolecular structures.
By combining the supramolecular interactions with
block copolymers, novel self-assembling may occur to
create new self-assembled structures with functionalities.
For example, we have systematically investigated
the helical supramolecular structures formed by the
complexation of sodium dodecyl sulfate (SDS) and
cylindrical brush polymers with poly(L-lysine) side
chains (PLL) by electrostatic interactions in aqueous
solution. The alkyl chain length of the surfactant plays
a key role on the formation of helical structures . On
the other hand, supramolecular thin ﬁ lms with ordered
structures have been reported based on hydrogen bonding
of polystyrene-b-poly(4-vinyl pyridine) (PS-b-P4VP)
and pentadecylphenol (PDP) [4, 5]. Supramolecular
complexes with mesogenic structures were obtained by
the complexation of PS-b-P4VP and a mesogenic small
molecule, cholesteryl hemisuccinate (CholHS) .
Wooley and Pochan et al. reported thermodynamically
stable toroidal micelles , single and double helical
cylindrical micelles , multicompartment cylindrical
micelles  through the complexation of the PAA
containing block copolymers with organic multi-amines.
The hyperbranched multi-arm copolymer poly(3-ethyl-
3-oxetanemethanol)-star-poly(ethylene glycol) (HBPO-
The text was submitted by the authors in English.
Supramolecular Self-Assembly of Block
Copolymer Based on Rigid Surfactant
Yang Cong*, Qi Zhou, Lei Wang, Yuan Xu, and Jiaojiao Fang
School of Material & Chemical Engineering, Ningbo University of Technology,
89 Cuibai Road, Haishu District, Ningbo, Zhejiang Province, 315016, China
Received June 25, 2016
Abstract—The supramolecular self-assembling of pyridine-containing amphiphilic block copolymers (PS-b-
P4VP and PS-PI-P2VP) and 4-biphenylcarboxylic acid (BPCA) in selective solvents has been systematically
studied. BPCA molecules are able to complex with the vinylpyridine (VP) moieties through hydrogen bonding,
which leads to a transformation of spherical block copolymer micelles into structured nanoﬁ bers in solutions.
The effects of molar ratio of BPCA to the VP repeat units, solvent selectivity, and copolymer composition on the
supramolecular complex nanoﬁ ber formation have been systematically investigated by atomic force microscopy
(AFM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The formation
mechanism of supramolecular self-assembly nanoﬁ bers was discussed.