Expanding the scope of the crystallization-driven self-assembly of polylactide-containing polymers

Pitto-Barry, Anaïs; Kirby, Nigel; Dove, Andrew P.; O’Reilly, Rachel K.

doi:10.1039/c3py01048a

Cited by 68 publications

(71 citation statements)

References 29 publications

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“…1-(3,5-Bis(trifluoromethyl)phenyl)-3-cyclohexyl-thiourea was prepared and purified as reported. 29 2,2′-Azobis(isobutyronitrile) (AIBN) was received from Molekula. After recrystallisation from methanol it was stored at 4°C.…”

Section: Methodsmentioning

confidence: 99%

“…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.…”

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confidence: 99%

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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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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Understanding the CDSA of poly(lactide) containing triblock copolymers

et al. 2017

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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%

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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“…29 In this context, BCPs with crystallizable poly(ferrocenyldimethylsilane) (PFS), 30 polycaprolactone, 31,32 poly(L-lactic acid), 33,34 polyethylene, 35 polyacrylonitrile 36 , polythiophene, 37,38 and polyselenophene 39 core-forming blocks have been reported to form polydisperse cylindrical micelles. By optimizing the self-assembly conditions, researchers have been able to achieve some control over the length of cylindrical micelles formed by a variety of poly(L-lactic acid)- [40][41][42][43][44] and polycaprolactone-based 45 BCPs in aqueous media. In addition, post-self-assembly methods such as fragmentation during extrusion have also been employed to reduce the length of cylindrical micelles.…”

Section: Introductionmentioning

confidence: 99%

Monodisperse Cylindrical Micelles and Block Comicelles of Controlled Length in Aqueous Media

et al. 2016

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Cylindrical block copolymer micelles have shown considerable promise in various fields of biomedical research. However, unlike spherical micelles and vesicles, control over their dimensions in biologically-relevant solvents has posed a key challenge that potentially limits in depth studies and their optimisation for applications. Here, we report the preparation of cylindrical micelles of length in the wide range of 40 nm -1.10 µm in aqueous media with narrow length distributions (length polydispersities < 1.10). In our approach, an amphiphilic linear-brush block copolymer, with high potential for functionalization, was synthesized based on poly(ferrocenyldimethylsilane)-b-poly(allyl glycidyl ether) (PFS-b-PAGE) decorated with triethylene glycol (TEG), abbreviated as PFS-b-(PEO-g-TEG). PFS-b-(PEO-g-TEG) cylindrical micelles of controlled length with low polydispersities were prepared in N,N-dimethylformamide using small seed initiators via living crystallization-driven self-assembly. Successful dispersion of these micelles into aqueous media was achieved by dialysis against deionized water. Furthermore, B-A-B amphiphilic triblock comicelles with PFS-b-poly(2-vinylpyridine) (P2VP) as hydrophobic "B" blocks and hydrophilic PFS-b-(PEO-g-TEG) "A" segments were prepared and their hierarchical self-assembly in aqueous media studied. It was found that superstructures formed depend on the length of the hydrophobic blocks. Quaternization of P2VP was shown to cause the disassembly of the superstructures, resulting in the first examples of water-soluble cylindrical multi-block comicelles. We also demonstrate the ability of the triblock comicelles with quaternized terminal segments to complex DNA and, thus, to potentially function as gene vectors.

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Expanding the scope of the crystallization-driven self-assembly of polylactide-containing polymers

Cited by 68 publications

References 29 publications

Understanding the CDSA of poly(lactide) containing triblock copolymers

Understanding the CDSA of poly(lactide) containing triblock copolymers

Controlling supramolecular polymerization through multicomponent self‐assembly

Monodisperse Cylindrical Micelles and Block Comicelles of Controlled Length in Aqueous Media

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