Properties of Electrospun Nanofibers of Multi-Block Copolymers of [Poly-ε-caprolactone-b-poly(tetrahydrofuran-co-ε-caprolactone)]m Synthesized by Janus Polymerization

Shah, Muhammad Ijaz; Yang, Zhenghao; Li, Yao; Jiang, Liming; Ling, Jun

doi:10.3390/polym9110559

Cited by 17 publications

(15 citation statements)

References 28 publications

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“…Only statistical copolymers had been used in all experiments and it is hard to predict any behaviour and compare it with block copolymers. Some studies for block copolymers can be found for example in [34]. However, we did not find any studies for electrospinning of statistical copolymers.…”

Section: Electrospinning Processcontrasting

confidence: 58%

Comparison and characterization of different polyester nano/micro fibres for use in tissue engineering applications

Mikeš

Horakova

Saman

et al. 2019

Journal of Industrial Textiles

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The study focuses on a comparison of the electrospinning of various polylactide and polycaprolactone (PLCL) copolymers and poly-L-lactide (PLLA) and polycaprolactone (PCL) homopolymers. The chemical characterisation, electrospinnability, fibrous morphology, degradation rate and interactions with fibroblasts were assessed with respect to copolymers and homopolymers with both lower (around 50,000) and higher (around 95,000) molecular weights. The research investigated commercially available as well as synthesised copolymers. The results revealed that the electrospinnability of polymeric solutions depends on both the molecular weight and the PLA/PCL ratio in the final copolymer. It was determined that PLCL copolymers with a higher content of PCL (≥20%) were not spinnable via the electrospinning process. With the exception of PCL, the resulting fibrous materials were found to be homogeneous and with fibre diameters of slightly more than 1 µm with respect to both the tested molecular weights. The degradation rate was tested under simulation conditions via the utilisation of the lipase and Proteinase K enzymes. The degree of degradation was found to depend on the molecular weight, the crystallinity of the polymer and the specificity of the enzyme applied. While lipase was responsible for the degradation of the PCL polymer, it exerted a minor impact on the PLLA and the copolymers. Proteinase K degraded all the tested polymers with a higher specificity towards PLLA and the PLCL copolymers. All the tested polymers were affected by the surface erosion degradation process via fibrous morphology changes and mass loss with no accompanying shift in the molar mass. The electrospun PLLA materials supported both fibroblast adhesion and proliferation. All the tested materials were determined to be cytocompatible with 3T3 mouse fibroblasts.

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Section: Electrospinning Processcontrasting

confidence: 58%

Comparison and characterization of different polyester nano/micro fibres for use in tissue engineering applications

Mikeš

Horakova

Saman

et al. 2019

Journal of Industrial Textiles

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“…It has also been reported to be a convenient way to synthesize polymers with various topologies. Diblock poly(THF‐ co ‐CL)‐ b ‐PCL, multiblock [(THF‐ co ‐CL)‐ b ‐PCL] m , branched PTHF, branched poly(THF‐ co ‐CL), and 3‐miktoarm star terpolymers [PEG‐ star ‐PCL‐ star ‐P(CL‐ co ‐THF)] have been successfully synthesized through Janus polymerization simply by using appropriate initiators. Janus polymerization provides researchers with a robust tool to construct topologically well‐defined polymers for a better understanding of structure‐property relationships.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Polypeptoid‐Polycaprolactone‐Polytetrahydrofuran Heterograft Molecular Polymer Brushes via a Combination of Janus Polymerization and ROMP

Schacher

Ling

2019

Macromol. Rapid Commun.

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Janus polymerization is a novel and efficient way to synthesize diblock and multiblock copolymers in one step by using Lu(OTf)3 and propylene epoxide as a catalytic system. By modifying the epoxide initiator, which is located at the block junction with various functional groups, the possibility for future topological design is provided. Herein, 2‐bicyclo[2.2.1]hept‐5‐en‐2‐yl oxirane (NB‐EO) is used as an alternative for propylene epoxide to synthesize a poly(THF‐co‐CL)‐b‐PCL diblock copolymer featuring a norbornene group at this position. This also results in multiblock [poly(THF‐co‐CL)‐b‐PCL]m copolymers carrying multiple norbornene moieties through Janus polymerization. Subsequent ring‐opening metathesis copolymerization (ROMP) of the resulting poly(THF‐co‐CL)‐b‐PCL macromonomers with norbornenyl‐terminated polysarcosine (PSar‐NB) allows the facile preparation of heterograft molecular polymer brushes (MPBs). The MPBs feature three heterografts of PCL, P(CL‐co‐THF) and PSar, potentially equipping these structures with biocompatibility, biodegradability, semi‐crystallinity, and amphiphilicity. A phase separation is observed after annealing in both TEM and AFM analysis. Due to their amphiphilic nature, the MPBs also undergo self‐assembly into micelles in aqueous solution. Such materials combining polypeptoids, polyesters, and polyethers segments are expected to attract wide attention in drug delivery applications.

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“…Ling and co-workers [41,100] developed a concept of "Janus polymerization," which combines the incompatible cationic and anionic polymerization mechanisms coexisting in a single growing polymer chain. [101] By employing this "Janus polymerization," a novel Janus macromonomer poly(tetrahydrofuran-cocaprolactone)-b-polycaprolactone (p(THF-co-CL)-b-PCL) with NB functionality was synthesized in one step. [102] Subsequently, Janus-like mixed bottlebrush polymers were obtained by the copolymerization of the resulting Janus macromonomers with norbornenyl-terminated polysarcosine via grafting-through approach ( Figure 5).…”

Section: Grafting-through Approachmentioning

confidence: 99%

Design, Synthesis, and Self‐Assembly of Janus Bottlebrush Polymers

Chen

Zhu

et al. 2020

Macromol. Rapid Commun.

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in solution, [28-30] and at the interfaces [31,32] features the unique microstructures and varied applications (Figure 1C). Janus bottlebrush polymers are a class of special molecular brushes, which have two incompatible side chains on the same repeating unit of the backbone. [33] "Janus" is the god in ancient Roman religion and myth with two faces looking to the past and the future. [34] In scientific community, the phrases containing Janus, such as "Janus nanoparticles," [35-38] "Janus beads," [39,40] and "Janus polymerization," [41-43] indicate something consisting of counterparts. [44-46] The design of Janus bottlebrush polymers was inspired by Janus particles. [35,47-49] The characteristic of Janus bottlebrush polymers is that the repeating unit of the backbone possesses two immiscible side chains. [50-52] Core-shell bottlebrush polymers with block copolymers as the side chains are usually not Janus-type unless the block side chains are unsymmetrical. [6] An emerging Janus core-shell bottlebrush polymer has been developed by transferring the side chains from homo polymers to two different block copolymers. [53] Design, synthesis, and self-assembly of Janus bottlebrush polymers have arouse much interest in polymer chemistry and material science. [54,55] In general, Janus bottlebrush polymers could be prepared via backbone-first [50] (grafting-to and graftingfrom) or side-chain-first [56] (grafting-through) strategy. Most of Janus bottlebrush polymers were reported via grafting-through approach. Macromonomers are first designed and subsequently polymerizations occur to form the backbone. [23] Backbonefirst route also allows for the synthesis of Janus bottlebrush polymers by using combined grafting-to and grafting-from approach. [57] The special unsymmetrical architectures enable Janus bottlebrush polymers to achieve ideal phase separation in bulk, [58,59] in solution, [52] and at the interface. [32] The preorganized interface can promote self-assembly process and avoid the distorted phase separation. [32,33] The self-assembly of Janus bottlebrush polymers achieves small domain size and tunable bulk property, [58,59] which is challenging for the traditional linear or bottlebrush polymers. [60,61] Therefore, Janus bottlebrush polymers have great potential applications in nanolithography, [58] photonic crystals, [62] biomedicine, [53] surfactants, [63] etc. The big families of bottlebrush polymers have been nicely reviewed by Grubbs and co-workers, [64] Müllner and coworkers, [65-67] Rzayev and co-workers, [7] Verduzco and coworkers, [6] and Matyjaszewski and co-workers [2]. As a young but significant class, Janus bottlebrush polymers have achieved remarkable advances in recent years. Therefore, this review attempts to focus on Janus bottlebrush polymers, covering Janus bottlebrush polymers are a class of special molecular brushes, which have two immiscible side chains on the repeating unit of the backbone. The characteristic architectures of Janus bottlebrush polymers enable unique selfassembly properties and br...

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Properties of Electrospun Nanofibers of Multi-Block Copolymers of [Poly-ε-caprolactone-b-poly(tetrahydrofuran-co-ε-caprolactone)]m Synthesized by Janus Polymerization

Cited by 17 publications

References 28 publications

Comparison and characterization of different polyester nano/micro fibres for use in tissue engineering applications

Comparison and characterization of different polyester nano/micro fibres for use in tissue engineering applications

Synthesis of Polypeptoid‐Polycaprolactone‐Polytetrahydrofuran Heterograft Molecular Polymer Brushes via a Combination of Janus Polymerization and ROMP

Design, Synthesis, and Self‐Assembly of Janus Bottlebrush Polymers

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