Self-assembling Characteristics of Amphiphilic Star Block Copolymers with a Polyelectrolyte Shell

1 Results Amphiphilic block copolymers are capable of forming supramolecular assemblies resembling those observed in nature,such as spherical micelles,worm micelles,and vesicles.Changing the solvent composition,ionic strength or pH of the polymer solution may induce the self-assembly of block copolymers or trigger the transition between the geometries of noncovalent assemblies.In the current work,we have synthesised starlike amphiphilic block copolymers having hydrophobic poly(methyl methacrylate),PMMA,...

Synthesis of Self-assembled Star/Linear Block Copolymer Blends via Aqueous RAFT Dispersion Polymerization

Reversible addition-fragmentation chain transfer(RAFT)-mediated polymerization-induced self-assembly(PISA)of star block copolymer and linear block copolymer using a binary mixture of a star-like macro-RAFT agent and a linear macro-RAFT agent is reported.With this formulation,star block copolymer and diblock copolymer were formed simultaneously to generate colloidally stable star/linear block copolymer assemblies.Size exclusion chromatography(SEC)analysis confirmed the presence of two types of polymers in the final samples.The molar ratio of the star-like macro-RAFT agent and the linear macro-RAFT agent has a significant impact on the morphology of polymer assemblies.It was found that increasing the amount of star-like macro-RAFT agent facilitated the formation of higher-order morphologies.Additionally,effects of other reaction parameters including the length/number of the arm of the star-like macro-RAFT agent,degree of polymer(DP),monomer concentration on the morphology of star/linear block copolymer assemblies were also investigated.We expect that this work will offer new possibilities for the scalable preparation of polymer assemblies with unique structures and functions.

Resorcinarene-centered Amphiphilic Star-block Copolymers: Synthesis, Micellization and Controlled Drug Release

Eight-arm star-shaped poly（■-caprolactone）-block-poly（ethylene glycol）s（SPCL-b-PEG） have been prepared by a combination of controlled ring-opening polymerization（CROP） and coupling reaction. First, eight-arm star-shaped poly（■-caprolactone）s（SPCL） with a resorcinarene core were synthesized using octamethyl tetraundecylresorcinarene octaacetate as octa-initiator and yttrium tris（2,6-di-tert-butyl-4-methylphenolate） [Y（DBMP）3] as catalyst. Then the coupling reaction was carried out between SPCLs and carboxyl-terminated methoxy poly（ethylene glycol）s（mP EG-COOH） in the presence of N,N′-dicyclohexylcarbodiimide（DCC） and 4-dimethylaminopyridine（DMAP）, resulting in eight-arm star-shaped SPCL-b-PEGs with controlled molecular weight and well-defined architecture. Furthermore, these amphiphilic eight-arm SPCL-b-PEGs could self-assemble into micelles with low critical micellar concentrations（CMC）, which was characterized by fluorescent spectroscopy. Moreover, indomethacin loaded micelles with high drug loading content and high encapsulation efficiency can be prepared, which is probably due to the highly branched architecture. The morphologies of micelles were characterized by transmission electron microscopy（TEM）, which exhibited diverse nanostructures as the drug loading contents varied. In vitro drug release of indomethacin from SPCL-b-PEG micelles was carried out in PBS, from which a sustained release behavior was observed. SPCL-b-PEG micelles did not show significant cytotoxicity at copolymer concentrations up to 1000 mg/L, making them very promising for drug delivery.

Amphiphilic Seven-arm Star Triblock Copolymers with Diverse Morphologies in Aqueous Solution Induced by Crystallization and pH

Well-defined amphiphilic seven-arm star triblock copolymers containing hydrophobic crystalline poly（e-caprolactoneXPCL） blocks, hydrophobic non-crystalline poly（tert-butyl acrylate）（PtBA） blocks and hydrophilic poly（ethylene glycol）（PEG） blocks were precisely synthesized by a combination of ring-opening polymerization（ROP）, atom transfer radical polymerization（ATRP） and ＂click＂ reaction. Such star copolymers could self-assemble into ＂core-shell-corona＂ micelles and ＂multi-layer＂ vesicles depending on the fraction of each block. Meanwhile, the selective hydrolysis of middle PtBA blocks into the poly（acrylic acidXPAA） blocks allowed the star block copolymers to further change their morphologies of aqueous aggregates m response to pH values.

Synthesis and Self-assembly of a Triarm Star-shaped Rod-Rod Block Copolymer

We designed and synthesized a triarm star-shaped rod-rod block copolymer（BCP）,（poly{2,5-bis[（4-methoxyphenyl）-oxycarbonyl]styrene}-block-poly（γ-benzyl-L-glutamate））3,（PMPCS-b-PBLG）3. The triarm core with three PMPCS-N3 segments was prepared by copper-mediated atom transfer radical polymerization of 2,5-bis[（4-methoxyphenyl）-oxycarbonyl]styrene initiated by a trifunctional initiator and a subsequent azide reaction. And the PBLG block with alkyne functionality was synthesized through ring-opening polymerization of γ-benzyl-L-glutamate N-carboxyanhydride initiated by propargylamine. Finally, Huisgen＇s 1,3-dipolar cycloaddition was employed to combine the triarm（PMPCS-N3）3 and PBLG segments. The chemical structure of the BCP was confirmed by 1H-NMR spectroscopy, Fourier-transform infrared spectroscopy, and gel permeation chromatographic analysis. Results from differential scanning calorimetry, polarized light microscopy, one-dimensional and two-dimensional wide-angle X-ray diffraction, and transmission electron microscopy techniques demonstrate that the triarm star-shaped rod-rod BCP self-assembles into a hexagon-in-lamella morphology, with the PMPCS block in the columnar nematic phase and the PBLG block in the hexagonal columnar arrangement packed in bilayers due to the rigid nature of the two blocks and the covalent connections in the star-shaped BCP.