TY - JOUR
T1 - Extending the Scope of "living" Crystallization-Driven Self-Assembly
T2 - Well-Defined 1D Micelles and Block Comicelles from Crystallizable Polycarbonate Block Copolymers
AU - Finnegan, John R.
AU - He, Xiaoming
AU - Street, Steven T.G.
AU - Garcia-Hernandez, J. Diego
AU - Hayward, Dominic W.
AU - Harniman, Robert L.
AU - Richardson, Robert M.
AU - Whittell, George R.
AU - Manners, Ian
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/12/12
Y1 - 2018/12/12
N2 - Fiber-like block copolymer (BCP) micelles offer considerable potential for a variety of applications; however, uniform samples of controlled length and with spatially tailored chemistry have not been accessible. Recently, a seeded growth method, termed "living" crystallization-driven self-assembly (CDSA), has been developed to allow the formation of 1D micelles and block comicelles of precisely controlled dimensions from BCPs with a crystallizable segment. An expansion of the range of core-forming blocks that participate in living CDSA is necessary for this technique to be compatible with a broad range of applications. Few examples currently exist of well-defined, water-dispersible BCP micelles prepared using this approach, especially from biocompatible and biodegradable polymers. Herein, we demonstrate that BCPs containing a crystallizable polycarbonate, poly(spiro[fluorene-9,5′-[1,3]-dioxan]-2′-one) (PFTMC), can readily undergo living CDSA processes. PFTMC-b-poly(ethylene glycol) (PEG) BCPs with PFTMC:PEG block ratios of 1:11 and 1:25 were shown to undergo living CDSA to form near monodisperse fiber-like micelles of precisely controlled lengths of up to ∼1.6 μm. Detailed structural characterization of these micelles by TEM, AFM, SAXS, and WAXS revealed that they comprise a crystalline, chain-folded PFTMC core with a rectangular cross-section that is surrounded by a solvent swollen PEG corona. PFTMC-b-PEG fiber-like micelles were shown to be dispersible in water to give colloidally stable solutions. This allowed an assessment of the toxicity of these structures toward WI-38 and HeLa cells. From these experiments, we observed no discernible cytotoxicity from a sample of 119 nm fiber-like micelles to either healthy (WI-38) or cancerous (HeLa) cell types. The living CDSA process was extended to PFTMC-b-poly(2-vinylpyridine) (P2VP), and addition of this BCP to PFTMC-b-PEG seed micelles led to the formation of well-defined segmented fibers with spatially localized coronal chemistries.
AB - Fiber-like block copolymer (BCP) micelles offer considerable potential for a variety of applications; however, uniform samples of controlled length and with spatially tailored chemistry have not been accessible. Recently, a seeded growth method, termed "living" crystallization-driven self-assembly (CDSA), has been developed to allow the formation of 1D micelles and block comicelles of precisely controlled dimensions from BCPs with a crystallizable segment. An expansion of the range of core-forming blocks that participate in living CDSA is necessary for this technique to be compatible with a broad range of applications. Few examples currently exist of well-defined, water-dispersible BCP micelles prepared using this approach, especially from biocompatible and biodegradable polymers. Herein, we demonstrate that BCPs containing a crystallizable polycarbonate, poly(spiro[fluorene-9,5′-[1,3]-dioxan]-2′-one) (PFTMC), can readily undergo living CDSA processes. PFTMC-b-poly(ethylene glycol) (PEG) BCPs with PFTMC:PEG block ratios of 1:11 and 1:25 were shown to undergo living CDSA to form near monodisperse fiber-like micelles of precisely controlled lengths of up to ∼1.6 μm. Detailed structural characterization of these micelles by TEM, AFM, SAXS, and WAXS revealed that they comprise a crystalline, chain-folded PFTMC core with a rectangular cross-section that is surrounded by a solvent swollen PEG corona. PFTMC-b-PEG fiber-like micelles were shown to be dispersible in water to give colloidally stable solutions. This allowed an assessment of the toxicity of these structures toward WI-38 and HeLa cells. From these experiments, we observed no discernible cytotoxicity from a sample of 119 nm fiber-like micelles to either healthy (WI-38) or cancerous (HeLa) cell types. The living CDSA process was extended to PFTMC-b-poly(2-vinylpyridine) (P2VP), and addition of this BCP to PFTMC-b-PEG seed micelles led to the formation of well-defined segmented fibers with spatially localized coronal chemistries.
UR - http://www.scopus.com/inward/record.url?scp=85058151067&partnerID=8YFLogxK
U2 - 10.1021/jacs.8b09861
DO - 10.1021/jacs.8b09861
M3 - Article
C2 - 30392357
AN - SCOPUS:85058151067
SN - 0002-7863
VL - 140
SP - 17127
EP - 17140
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -
