Neuron-like tubule extension of giant polymer vesicles

Abstract

Giant polymer vesicles consisting of amphiphilic diblock copolymers are helpful as artificial biomembrane models based on many similarities in their size, structure, morphological transformation, membrane permeability, etc. This paper describes the creation of neuron-like tubule extension employing the polymer vesicles. The polymerization-induced self-assembly was performed in the presence of micron-sized spherical vesicles consisting of poly(methacrylic acid)-block-poly(methyl methacrylate-random-methacrylic acid), PMAA-b-P(MMA-r-MAA), through the photo nitroxide-mediated controlled/living radical polymerization (photo-NMP) using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator. The photo-NMP of methyl methacrylate (MMA) and methacrylic acid (MAA) was carried out in an aqueous methanol solution (CH3OH/H2O = 3/1 v/v) using poly(methacrylic acid) (PMAA) end-capped with MTEMPO and the spherical vesicles of PMAA141-b-P(MMA0.831-r-MAA0.169)368 with an 11.7-mm diameter. The vesicles projected many processes on their surface during the early stage of the polymerization. As the polymerization progressed, only one or two of the processes extended to thick tubules, accompanied by the slow growth of thin tubules. Further progress of the polymerization elongated the thick tubules and caused branching of the tubules. The tubules had a vesicular structure because cup-like vesicles joined in line were formed during the initial stage of the extension. The polymerization livingness supported the tubule extension based on a linear increase in the molecular weight of the component copolymer and a negligible change in the molecular weight distribution versus the monomer conversion. The spherical vesicles were similar to the neurons in the tubule extension for the initial projection, followed by the elongation and branching. This similarity implies that the neurite extension in the neurons is related to the inherent property of the bilayer membrane.