scholarly journals Ring-opening polymerization-induced crystallization-driven self-assembly of poly-L-lactide-block-polyethylene glycol block copolymers (ROPI-CDSA)

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Paul J. Hurst ◽  
Alexander M. Rakowski ◽  
Joseph P. Patterson

Abstract The self-assembly of block copolymers into 1D, 2D and 3D nano- and microstructures is of great interest for a wide range of applications. A key challenge in this field is obtaining independent control over molecular structure and hierarchical structure in all dimensions using scalable one-pot chemistry. Here we report on the ring opening polymerization-induced crystallization-driven self-assembly (ROPI-CDSA) of poly-L-lactide-block-polyethylene glycol block copolymers into 1D, 2D and 3D nanostructures. A key feature of ROPI-CDSA is that the polymerization time is much shorter than the self-assembly relaxation time, resulting in a non-equilibrium self-assembly process. The self-assembly mechanism is analyzed by cryo-transmission electron microscopy, wide-angle x-ray scattering, Fourier transform infrared spectroscopy, and turbidity studies. The analysis revealed that the self-assembly mechanism is dependent on both the polymer molecular structure and concentration. Knowledge of the self-assembly mechanism enabled the kinetic trapping of multiple hierarchical structures from a single block copolymer.

Polymers ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 1357
Author(s):  
Michel Nguyen ◽  
Khalid Ferji ◽  
Sébastien Lecommandoux ◽  
Colin Bonduelle

Nucleobase-containing polymers are an emerging class of building blocks for the self-assembly of nanoobjects with promising applications in nanomedicine and biology. Here we present a macromolecular engineering approach to design nucleobase-containing polypeptide polymers incorporating thymine that further self-assemble in nanomaterials. Diblock and triblock copolypeptide polymers were prepared using sequential ring-opening polymerization of γ-Benzyl-l-glutamate N-carboxyanhydride (BLG-NCA) and γ-Propargyl-l-glutamate N-carboxyanhydride (PLG-NCA), followed by an efficient copper(I)-catalyzed azide alkyne cycloaddition (CuAAc) functionalization with thymidine monophosphate. Resulting amphiphilic copolymers were able to spontaneously form nanoobjects in aqueous solutions avoiding a pre-solubilization step with an organic solvent. Upon self-assembly, light scattering measurements and transmission electron microscopy (TEM) revealed the impact of the architecture (diblock versus triblock) on the morphology of the resulted nanoassemblies. Interestingly, the nucleobase-containing nanoobjects displayed free thymine units in the shell that were found available for further DNA-binding.


2019 ◽  
Vol 10 (42) ◽  
pp. 9782-9787 ◽  
Author(s):  
Ye Sha ◽  
Md Anisur Rahman ◽  
Tianyu Zhu ◽  
Yujin Cha ◽  
C. Wayne McAlister ◽  
...  

Two most prevailing self-assembly methods, PISA and CDSA, are combined in one metallo-block copolymer system via one-pot synchronous ROMP, yielding crystalline nanostructures in a mild, fast, scalable and controlled manner.


RSC Advances ◽  
2016 ◽  
Vol 6 (56) ◽  
pp. 50543-50552 ◽  
Author(s):  
Weiwei Zhang ◽  
Delong Zhang ◽  
Xiaoshan Fan ◽  
Guangyue Bai ◽  
Yuqin Jiang ◽  
...  

Novel dumbbell-shaped amphiphilic copolymers based on P188 and PLA were synthesized by click chemistry and ring opening polymerization. The self-assembly behavior of the stereocomplexes and the DOX release profile from the aggregates were studied.


2011 ◽  
Vol 284-286 ◽  
pp. 1877-1885
Author(s):  
Ke Xin Kang ◽  
Min Ying Liu ◽  
Qing Xiang Zhao ◽  
Peng Fu ◽  
Xiao Bing Wang

A series of amphiphilic block copolymers mPEO-b-PCL with different PCL molecular weight were successfully prepared by combination of anionic ring-opening polymerization with coordination-insertion ring-opening polymerization. Firstly, the linear mPEO was prepared by anionic ring-opening copolymerization of EO with 2-(2-methoxyethoxy) ethoxide potassium as the small molecule initiators, then the mPEO as the macroinitiator was used to initiate the ring-opening polymerization of CL, in the absence of Sn(Oct)2 as the catalyst, and amphiphilic block copolymers mPEO-b-PCL were obtained. By changing the ratio of monomer and macroinitiator, prepared a series of different molecular weight mPEO-b-PCL. The structure of intermediates and final products were characterized by 1H NMR and GPC. The critical micelle concentration (cmc) of the final copolymer was measured. In addition, the sizes and morphologies of the obtained micelles at different PCL chains were studied with Laser nano-particle size analyzer and transmission electron microscopy (TEM).


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