Li-li Chen, Fan Zhang, Tao Chen, Ye Chen, Jia-ping Lin. SYNTHESIS AND pH REVERSIBLE AGGREGATING BEHAVIOR OF POLY(AMINO ACID) BASED LINEAR-DENDRON-LIKE POLYAMPHOLYTE. [J]. Acta Polymerica Sinica (2):270-278(2013)
DOI:
Li-li Chen, Fan Zhang, Tao Chen, Ye Chen, Jia-ping Lin. SYNTHESIS AND pH REVERSIBLE AGGREGATING BEHAVIOR OF POLY(AMINO ACID) BASED LINEAR-DENDRON-LIKE POLYAMPHOLYTE. [J]. Acta Polymerica Sinica (2):270-278(2013) DOI: 10.3724/SP.J.1105.2013.12270.
SYNTHESIS AND pH REVERSIBLE AGGREGATING BEHAVIOR OF POLY(AMINO ACID) BASED LINEAR-DENDRON-LIKE POLYAMPHOLYTE
A linear-dendron-like polyampholyte was synthesized via the combination of ring-opening polymerization (ROP)
divergent synthesis procedure and click chemistry.First
azide-terminated poly(-benzyl-L-glutamate) (PBLG-N3) and the second generation PAMAM (D2) with alkyne focal group and four terminal primary amine groups were synthesized by the ROP of -benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) and divergent synthesis procedure
respectively.Subsequently
PBLG-N3 was click conjugated with alkyne focal group of D2 to generate primary amine-terminated linear-dendron-like PBLG-b-D2
which was then used as the microinitiator for the ROP of -benzyloxycarbonyl-L-lysine N-carboxyanhydride (ZLL-NCA) to produce the linear-dendron-like copolymer PBLG-b-D2-(PZLL)4.The targeted linear-dendron-like polyampholyte
PLGA50-b-D2-(PLL9)4
where PLGA is poly(L-glutamic acid) and PLL is poly(L-lysine)
was obtained by the hydrolysis of protecting benzyl and benzyloxycarbonyl groups of PBLG and PZLL
respectively.The molecular structures of the intermediates and the final polyampholyte were characterized by 1H-NMR
Fourier transform-infrared spectroscopy (FTIR) and gel permeation chromatograph (GPC).The physical properties and pH-responsive behavior in aqueous solution were investigated via potentiometric and conductometric titration
1H-NMR
zeta potential measurement
laser light scattering (LLS)
scanning electron microscopy (SEM) and circular dichroism spectroscopy (CD).The results show that PLGA50-b-D2-(PLL9)4 can self-assemble into schizophrenic micelles which can be reversibly produced as a function of pH in pure water
i.e.
it can self-assemble into spherical micelles with PLGA-core at acidic pH and rod-like micelles with PLL-core at alkaline pH
accompanied with the coil-to-helix conformational transition of PLGA and PLL.The linear-dendron-like asymmetrical topological structure is believed to play an impotent role in the morphology formation of self-assembly nanostructures.