Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers

Coe, Zachary; Weems, Andrew C.; Dove, Andrew P.; O’Reilly, Rachel K.

doi:10.3791/59772

Cited by 4 publications

(5 citation statements)

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Section: Bcp Solution Self‐assemblymentioning

confidence: 99%

“…Another group that has extensively studied CDSA as a method for producing cylindrical micelles originating from BCPs containing mainly biocompatible and biodegradable crystallizable blocks like poly(ε-caprolactone) (PCL) and poly(L-lactide) or poly(D-lactide) (PLLA or PDLA), is that of Dove, O'Reilly and their co-workers. [31][32][33][34][35] Among other interesting findings, they reported that while homochiral PLLA-PAA and PDLA-PAA BCPs independently form cylinders with crystalline cores in THF/H 2 O at 65 C, upon heating a 1:1 mixture of both BCPs in solution or a mixture of the respective cylinders under the same conditions, small stereocomplex spherical micelles are formed by a unimer-exchange process. 31 Apart from these characteristic examples, several more crystallizable polymers have been utilized for the formation of cylindrical/"fiber-like" micelles with crystalline cores and a detailed account can be found in the recent review of MacFarlane et al, 24 while an equally interesting review on the preparation of anisotropic nanoparticles, including cylindrical micelles, and their applications has been published lately by Pearce et al 36…”

Section: Cylindrical Micellesmentioning

confidence: 99%

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Block copolymer solution self‐assembly: Recent advances, emerging trends, and applications

Karayianni

Pispas

2021

Journal of Polymer Science

130

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The self‐assembly process of block copolymers (BCPs) in solution has been at the focus of extended scientific research over the past several decades owing to the astonishing morphological diversity and attainable complexity of the resulting nanoassemblies, including spheres, cylinders, lamellae, vesicles, and many other complex, bicontinuous or even hierarchical structures. The ever‐increasing sophistication in the development of synthetic chemistry methods and techniques has led to a myriad of available macromolecules with varying chemical compositions, architectures, features, and properties. This assortment of characteristics has led in turn to a plethora of intriguing self‐organized polymeric nanostructures, with countless possible applications in several nanotechnological fields relevant to physics, chemistry, material science, nanomedicine, and biomaterials. The present review aims to illuminate the importance and fascinating potential of BCPs solution self‐assembly by highlighting recent advances and emerging trends in the field, as well as significant application‐oriented progress, through characteristic contemporary examples.

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Section: Bcp Solution Self‐assemblymentioning

confidence: 99%

Section: Cylindrical Micellesmentioning

confidence: 99%

Block copolymer solution self‐assembly: Recent advances, emerging trends, and applications

Karayianni

Pispas

2021

Journal of Polymer Science

130

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“…Next to BCPs with a PFS block, a variety of other crystallizable polymer blocks were employed in CDSA, e.g. polyethylene (PE) [ 68 , 92 , 93 , 94 ], poly(ethylene oxide) [ 95 ], polyesters (poly( ε -caprolactone) (PCL) or poly( L -lactide) (PLLA)) [ 86 , 96 , 97 , 98 , 99 , 100 , 101 ], polycarbonate [ 102 ], poly(2- iso -propyl-2-oxazoline) (P i PrOx) [ 103 , 104 ], liquid crystalline polymers [ 71 , 105 ], poly(vinylidene fluoride) [ 106 ], polypeptoids [ 107 , 108 ], and various conjugated polymers (e.g., poly(3-hexyl thiophene) (P3HT) and OPV) [ 75 , 109 , 110 , 111 , 112 , 113 ].…”

Section: Crystallization-driven Self-assembly (Cdsa)mentioning

confidence: 99%

Patchy Micelles with a Crystalline Core: Self-Assembly Concepts, Properties, and Applications

et al. 2021

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Crystallization-driven self-assembly (CDSA) of block copolymers bearing one crystallizable block has emerged to be a powerful and highly relevant method for the production of one- and two-dimensional micellar assemblies with controlled length, shape, and corona chemistries. This gives access to a multitude of potential applications, from hierarchical self-assembly to complex superstructures, catalysis, sensing, nanomedicine, nanoelectronics, and surface functionalization. Related to these applications, patchy crystalline-core micelles, with their unique, nanometer-sized, alternating corona segmentation, are highly interesting, as this feature provides striking advantages concerning interfacial activity, functionalization, and confinement effects. Hence, this review aims to provide an overview of the current state of the art with respect to self-assembly concepts, properties, and applications of patchy micelles with crystalline cores formed by CDSA. We have also included a more general discussion on the CDSA process and highlight block-type co-micelles as a special type of patchy micelle, due to similarities of the corona structure if the size of the blocks is well below 100 nm.

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“…However, other driving forces such as electrostatic interaction (“coacervation”) or crystallization may also be involved. The latter is being exploited to create novel nanostructures in crystallization-driven self-assembly (CDSA). − Crystallization, or at least packing into semiordered structures, is also important in more complex systems such as in the cell membrane…”

Section: Introductionmentioning

confidence: 99%

Spherical Micelles with Nonspherical Cores: Effect of Chain Packing on the Micellar Shape

et al. 2020

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Self-assembly of amphiphilic polymers into micelles is an archetypical example of a “self-confined” system due to the formation of micellar cores with dimensions of a few nanometers. In this work, we investigate the chain packing and resulting shape of C n -PEOx micelles with semicrystalline cores using small/wide-angle X-ray scattering (SAXS/WAXS), contrast-variation small-angle neutron scattering (SANS), and nuclear magnetic resonance spectroscopy (NMR). Interestingly, the n-alkyl chains adopt a rotator-like conformation and pack into prolate ellipses (axial ratio ϵ ≈ 0.5) in the “crystalline” region and abruptly arrange into a more spheroidal shape (ϵ ≈ 0.7) above the melting point. We attribute the distorted spherical shape above the melting point to thermal fluctuations and intrinsic rigidity of the n-alkyl blocks. We also find evidence for a thin dehydrated PEO layer (≤1 nm) close to the micellar core. The results provide substantial insight into the interplay between crystallinity and molecular packing in confinement and the resulting overall micellar shape.

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Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers

Cited by 4 publications

References 0 publications

Block copolymer solution self‐assembly: Recent advances, emerging trends, and applications

Block copolymer solution self‐assembly: Recent advances, emerging trends, and applications

Patchy Micelles with a Crystalline Core: Self-Assembly Concepts, Properties, and Applications

Spherical Micelles with Nonspherical Cores: Effect of Chain Packing on the Micellar Shape

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