Sub-20 nm Microphase-Separated Structures in Hybrid Block Copolymers Consisting of Polycaprolactone and Maltoheptaose

Isono, Takuya; Otsuka, Issei; Halila, Sami; Kakuchi, Toyoji; Satoh, Toshifumi

doi:10.2494/photopolymer.28.635

Cited by 8 publications

(4 citation statements)

References 35 publications

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“…However, studies on morphology changes related to this process are very limited. 30,46,47 Otsuka et al reported order−order transition in maltoheptaose-b-poly(ε-caprolactone) diblock copolymers, and they attributed the morphology transition to the caramelization-induced volume fraction change in maltoheptaose. 30 In this study, we find that saccharide dehydration can also cause molecular changes.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Ordered Microdomain Structures in Saccharide–Polystyrene–Saccharide Hybrid Conjugates

et al. 2021

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Hybrid conjugates consist of synthetic polymers and naturally occurring saccharides, and are capable of microphase separation at small molecular weights to form ordered domain structures. In this study, we synthesize ABA triblock-like conjugates with polystyrene as the synthetic mid-segment and either trisaccharide maltotriose (MT) or disaccharide maltose (Mal) as the end unit. Hybrid conjugates of varying compositions are prepared by a combination of atom transfer radical polymerization and a click reaction, and their morphologies are examined by small-angle X-ray scattering and transmission electron microscopy. The MT-containing conjugates are found to form well-ordered domain structures with a sub-10 nm periodicity, and morphology transition from cylinders to spheres to disordered spheres is observed with decreasing saccharide weight fraction. The Mal-containing conjugates also show microphase separation. However, the observed domain morphologies lack regular packing due to the close proximity of polymer glass transition temperature and order–disorder transition temperature. The saccharide-containing conjugates are also found to undergo an irreversible morphology change at high temperatures, attributed to saccharide dehydration-induced pentablock-like structure formation.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Ordered Microdomain Structures in Saccharide–Polystyrene–Saccharide Hybrid Conjugates

et al. 2021

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“…In addition, the fact that oligosaccharides can be obtained from various renewable biomass resources renders them attractive raw materials for the preparation of novel BCPs. On the basis of these advantages, we previously reported a number of oligosaccharide-containing BCP systems suitable for nanopatterning applications, including maltoheptaose- b -poly(styrene) ,− and maltoheptaose- b -poly(ε-caprolactone), − to achieve microphase separation with a domain spacing of <20 nm. However, petroleum-based resources were still required for preparation of the hydrophobic polymer segments of these systems.…”

Section: Introductionmentioning

confidence: 99%

Highly Ordered Cylinder Morphologies with 10 nm Scale Periodicity in Biomass-Based Block Copolymers

Isono¹,

Ree²,

Tajima³

et al. 2018

Macromolecules

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Microphase-separated structures of block copolymers (BCPs) have attracted considerable attention for their potential application in the bottom-up fabrication of 10 nm scale nanostructured materials. To realize sustainable development within this field, the creation of novel BCP materials from renewable biomass resources is of fundamental interest. Thus, we herein focused on maltoheptaose-b-poly(δdecanolactone)-b-maltoheptaose (MH-b-PDL-b-MH) as a sustainable alternative for nanostructure-forming BCPs, in which both constitutional blocks can be derived from renewable biomass resources, in the case, δ-decanolactone and amylose. Well-defined MH-b-PDL-b-MHs with varying PDL lengths were synthesized through a combination of controlled/living ring-opening polymerization and the click reaction. The prepared MH-b-PDL-b-MHs successfully self-assembled into highly ordered hexagonal cylindrical structures with a domainspacing of ∼12−14 nm in both the bulk and thin film states. Interestingly, the as-cast thin films of MH-b-PDL-b-MHs (with PDL lengths of 9K and 13K) form horizontal cylinders, with thermal annealing (180 °C, 30 min) resulting in a drastic change in the domain orientation from horizontal to vertical. Thus, the results presented herein demonstrated that the combination of oligosaccharides and biomass-derived hydrophobic polymers appears promising for the sustainable development of nanotechnology and related fields.

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“…Since the MH/PCL BCPs promise to be fully biodegradable and biocompatible, the resulting carbohydrate-decorated nanoparticles should be of interest for applications in the biomedical fields. In addition, we have already established an efficient synthetic route toward well-defined MH/PCL BCPs involving the organocatalytic living ring-opening polymerization and click reaction, with which the precise synthesis of the linear AB-type diblock copolymers (MH- b -PCLs) and AB y -type miktoarm star polymers ( y = 2, MH- b -(PCL) 2 ; y = 3, MH- b -(PCL) 3 , respectively) had already been achieved. − To gain a deeper insight into the relationship between the macromolecular architecture and nanoparticle properties, we have additionally synthesized an A 2 B 2 -type miktoarm star polymer ((MH) 2 - b -(PCL) 2 ) and two A x B-type miktoarm star polymers ( x = 2, (MH) 2 - b -PCL; x = 3, (MH) 3 - b -PCL, respectively). With these well-defined BCPs in hand, the carbohydrate-decorated nanoparticles were prepared by employing the nanoprecipitation method, and the morphology and size of the resulting nanoparticles were characterized by dynamic light scattering and microscopy measurements.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of Maltoheptaose-block-polycaprolactone Copolymers: Carbohydrate-Decorated Nanoparticles with Tunable Morphology and Size in Aqueous Media

Isono¹,

Miyachi²,

Satoh³

et al. 2016

Macromolecules

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This paper describes the systematic investigation into the aqueous self-assembly of a series of block copolymers (BCPs) consisting of maltoheptaose (MH; as the A block) and poly(ε-caprolactone) (PCL; as the B block), i.e., linear AB-type diblock copolymers with varied PCL molecular weights (MH-b-PCL (2.5k,3.3k,5k,10k) ), AB y -type (y = 2, MH-b-, which had been precisely synthesized via the combination of the living ringopening polymerization and click reaction. Under similar conditions, the nanoprecipitation method was employed to self-assemble them in an aqueous medium. Imaging and dynamic light scattering techniques indicated the successful formation of the carbohydrate-decorated nanoparticles via self-assembly. The MH-b-PCLs formed regular core−shell micellar nanoparticles with the hydrodynamic radius (R h ) of 17−43 nm. MH-b-(PCL 5k ) 2 and MH-b-(PCL 3.3k ) 3 , which have an N PCL comparable to MH-b-PCL 10k , were found to form large compound micelles with relatively large radii (R h of 49 and 56 nm, respectively). On the other hand, (MH) 2 -b-(PCL 5k ) 2 , (MH) 2 -b-PCL 10k , and (MH) 3 -b-PCL 10k predominantly formed the regular core−shell micellar nanoparticles (R h = 29−39 nm) with a size smaller than that of MH-b-PCL 10k (R h = 43 nm).

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Sub-20 nm Microphase-Separated Structures in Hybrid Block Copolymers Consisting of Polycaprolactone and Maltoheptaose

Cited by 8 publications

References 35 publications

Ordered Microdomain Structures in Saccharide–Polystyrene–Saccharide Hybrid Conjugates

Ordered Microdomain Structures in Saccharide–Polystyrene–Saccharide Hybrid Conjugates

Highly Ordered Cylinder Morphologies with 10 nm Scale Periodicity in Biomass-Based Block Copolymers

Self-Assembly of Maltoheptaose-block-polycaprolactone Copolymers: Carbohydrate-Decorated Nanoparticles with Tunable Morphology and Size in Aqueous Media

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