Tuning the Size of Cylindrical Micelles from Poly(<scp>l</scp>-lactide)-<i>b</i>-poly(acrylic acid) Diblock Copolymers Based on Crystallization-Driven Self-Assembly

Sun, Liang; Petzetakis, Nikos; Pitto-Barry, Anaïs; Schiller, Tara L.; Kirby, Nigel; Keddie, Daniel J.; Boyd, Ben J.; O’Reilly, Rachel K.; Dove, Andrew P.

doi:10.1021/ma401634s

Cited by 113 publications

(127 citation statements)

References 55 publications

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“…[361][362][363][364][365][366][367][368][369][370][371] Purely organic cylindrical micelles and triblock comicelles with narrow length distributions were reported by Manners, Schmalz and coworkers via CDSA using the triblock unimers PS-b-PE-b-PS and PS-b-PE-b-PMMA [where PS 5 polystyrene, PE 5 polyethylene, and PMMA 5 poly(methyl methacrylate)], driven by the crystallization of the PE block. 372 CDSA of amphiphilic diblock copolymers into cylindrical micelles of controlled length using the crystallisable core-forming blocks poly(e-caprolactone) 373 and homochiral poly(lactide) [374][375][376][377][378] were reported in water/organic solvent mixtures. The O'Reilly and Dove laboratories showed that the semicrystalline nature of the poly(L-lactide) or poly(D-lactide) was essential in obtained anisotropic micelles, since amorphous poly(DL-lactide)-based diblock copolymer unimers only produced spherical micelles in H 2 O. Well-defined cylindrical micelles (L n % 90-230 nm, -D % 1.04-1.11) were obtained for example using poly(acrylic acid) 265 -b-poly(L-lactide) 32 , by heating the dissolved amphiphilic unimers to 65 8C for 1 hour, followed by rapid cooling, suggesting that an assembly temperature above the T g of poly(lactide) facilitates crystallization of the core block during the assembly process.…”

Section: Living Supramolecular Polymerizationmentioning

confidence: 99%

“…374 The authors further demonstrated that the length of the poly(L-lactide) block controls the length of the cylindrical micelles whereas the length of the poly(acrylic acid) block governs the width. 376 Winnik and Manners and coworkers have shown that by crosslinking the corona of PI 1424 -b-PFS 63 based selfassembled cylindrical micelles ( -D 5 1.05) that are blocked on one side, seed micelles were produced that could grow unidirectionally. 379 CDSA of block copolymers could thereby be used in order to prepare non-centrosymmetric cylindrical (Fig.…”

Section: Living Supramolecular Polymerizationmentioning

confidence: 99%

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Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

122

102

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The self-assembly into supramolecular polymers is a process driven by reversible non-covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli-responsive properties: (1) endcapping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of selfassembly kinetics of synthetic supramolecular systems. V C 2016

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Section: Living Supramolecular Polymerizationmentioning

confidence: 99%

Section: Living Supramolecular Polymerizationmentioning

confidence: 99%

Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

122

102

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“…3,4 The first examples of rodlike core-crystalline micelles were reported almost 20 years ago for poly(ferrocenyldimethylsilane) (PFS) diblock copolymers. [5][6][7] Since that time, particularly after poly(3-heptylselenophene), 32 poly(L-lactide) [33][34][35] and poly(ferrocenyldimethylgermane)9 as the core-forming block. Compared to block copolymers that form 2D platelet crystals, we have a much poorer understanding of how the semicrystalline polymer chains pack in the core of 1D…”

Section: Introductionmentioning

confidence: 99%

Lateral Growth of 1D Core-Crystalline Micelles upon Annealing in Solution

et al. 2016

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The emergence of one-dimensional (1D) micelles obtained from the crystallization driven self-assembly (CDSA) in solution of crystalline-coil block copolymers has opened the door to the fabrication of a variety of sophisticated structures. While the development of these fascinating nanomaterials is blossoming, there is very little fundamental work dedicated to understanding the morphological evolution of these 1D micelles in solution. Here, using a combination of transmission electron microscopy, electron tomography, and static and dynamic light scattering, we studied the effect of annealing on a colloidal suspension of 1D micelle fragments formed by the self-assembly of a crystalline-coil poly(ferrocenyldimethylsilane)-block-poly(isoprene) (PFS-b-PI) block copolymer in decane, a solvent selective for PI. We are particularly interested in studying the evolution of the rectangular cross-section of the crystalline core of these micelle fragments. By electron tomography, we observed that the shorter dimension of the cross-section became even thinner upon annealing at elevated temperatures, while the longer dimension increased. In parallel, we observed an increase in packing density of the crystalline block as the fragments were annealed at temperatures above 60 °C. From these results, we concluded that annealing the micelle fragments induces a thinning of the crystalline core coupled with a lateral growth.

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“…In our previous studies, we have shown that PLLA-containing block copolymers can be fabricated using a combination of reversible addition-fragmentation chain transfer (RAFT) and ring-opening polymerisation (ROP), where we have been able to achieve tuneable cylindrical micelles with a range of coronal blocks by CDSA. [27][28][29] Further work was carried out to enrich the functionality of the PLLA-based cylinders 30,31 and successfully realize stereocomplexation-triggered morphological transitions, 32 indicating the promising future of these cylindrical particles in the biomedical realm. Similar to conventional phase separation-driven assembly, it can be expected that triblock copolymers will lead to an alternate morphology when undergoing CDSA as a consequence of the extra coil phase.…”

mentioning

confidence: 99%

Understanding the CDSA of poly(lactide) containing triblock copolymers

et al. 2017

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Crystallisation-driven self-assembly (CDSA) has become an extremely valuable technique in the preparation of well-defined nanostructures using diblock copolymers. The use of triblock copolymers is considerably less well-known on account of more complex syntheses and assembly methods despite the functional advantages provided by a third block. Herein, we show the simple preparation of well-defined tuneable 1D and 2D structures based on poly(lactide) triblock copolymers of different block ratios synthesised by ring-opening polymerisation (ROP) and reversible addition-fragmentation chain transfer (RAFT) polymerisation, where a phase diagram based on a novel unimer solubility approach is proposed. Using a series of poly(L-lactide)-b-poly(N,N-dimethylacrylamide) (PLLA-b-PDMA) diblock copolymers and PDMA-b-PLLA-b-PDMA triblock copolymers with different core/corona ratios, single solvent CDSA processes revealed that comparatively hydrophilic polymers were liable to achieve 2D platelets, while the less hydrophilic counterparts yield 'transition state' wide cylinders and pure 1D cylinders. The length of crystalline core block is also shown to play an important role in fixed corona/core ratio systems, where a longer core block is prone to form cylindrical structures due to a lack of overall solubility, whereas a shorter block forms platelets. Importantly, this approach reveals contrary results to conventional theories, which state that longer solvophilic blocks relative to the core-forming block should favour more curved core/corona interfaces. Our morphological transitions are shown in both di-and tri-block copolymer systems, showing the generalisation of these assembly methods towards promising methodologies for the rational design of PLLA-based nanocarriers in the biomedical realm.

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Tuning the Size of Cylindrical Micelles from Poly(l-lactide)-b-poly(acrylic acid) Diblock Copolymers Based on Crystallization-Driven Self-Assembly

Cited by 113 publications

References 55 publications

Controlling supramolecular polymerization through multicomponent self‐assembly

Controlling supramolecular polymerization through multicomponent self‐assembly

Lateral Growth of 1D Core-Crystalline Micelles upon Annealing in Solution

Understanding the CDSA of poly(lactide) containing triblock copolymers

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