Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers

Satoshi Katsuhara; Yasuko Takagi; Naoki Sunagawa; Kiyohiko Igarashi; Takuya Yamamoto; Kenji Tajima; Takuya Isono; Toshifumi Satoh

doi:10.1021/acssuschemeng.1c02180

Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers

Satoshi Katsuhara
, Yasuko Takagi
, Naoki Sunagawa
, Kiyohiko Igarashi
, Takuya Yamamoto
, Kenji Tajima^*
, Takuya Isono
, Toshifumi Satoh

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

12 Citations (Scopus)

Abstract

Herein, we compared the microphase-separation behavior and mechanical properties of cellulose- and amylose-based block copolymers (BCPs). Various cellooligosaccharide triacetate-b-poly(δ-decanolactone)-b-cellooligosaccharide triacetates (AcCel _n-b-PDL-b-AcCel _ns), which are cellulose-based ABA-type BCPs, with PDL molecular weights of approximately 5, 10, and 20 kg mol ^-1and PDL volume fractions of 0.65, 0.77, and 0.87, were synthesized from α,ω-diazido-end-functionalized PDLs and propargyl-end-functionalized cellooligosaccharide triacetates via click chemistry. We adopted the cellodextrin-phosphorylase-mediated oligomerization of α-glucose-1-phosphase in the presence of a propargyl-end-functionalized cellobiose primer to synthesize the functional cellooligosaccharide segment. The maltooligosaccharide triacetate-b-poly(δ-decanolactone)-b-maltooligosaccharide triacetate (AcMal _n-b-PDL-b-AcMal _ns) amylose counterparts were also synthesized in a similar manner. Small-angle X-ray scattering experiments and atomic force microscopy revealed that AcCel _n-b-PDL-b-AcCel _ns are more likely to microphase-separate into ordered nanostructures compared to AcMal _n-b-PDL-b-AcMal _ns, despite their comparable chemical compositions and molecular weights. Furthermore, AcCel _n-b-PDL-b-AcCel _ns exhibited significantly superior mechanical performance compared to their amylose counterparts under tensile testing, with Young’s modulus and stress at break of AcCel _n-b-PDL _10k-b-AcCel _nbeing 2.3 and 1.8 times higher, respectively, than those of AcMal _n-b-PDL _10k-b-AcMal _n. The enhanced microphase-separation and mechanical properties of AcCel _n-b-PDL-b-AcCel _ns were found to be attributable to the stiffness and crystalline nature of the AcCel _nsegments. These results demonstrate the advantages of using cellulose derivatives to synthesize novel biofunctional materials.

Original language	English
Pages (from-to)	9779-9788
Number of pages	10
Journal	ACS Sustainable Chemistry and Engineering
Volume	9
Issue number	29
DOIs	https://doi.org/10.1021/acssuschemeng.1c02180
Publication status	Published - 26 Jul 2021
MoE publication type	A1 Journal article-refereed

Funding

This work was financially supported by a JSPS Grant-in-Aid for Scientific Research (B) (No. 19H02549, K.T.; No. 20H02792, I.T.; No. 19H02769, T.S.), the Frontier Chemistry Center (Hokkaido University, T.I.), the Photoexcitonix Project (Hokkaido University, T.S.), the Creative Research Institute (Hokkaido University, T.S.), the Iketani Science and Technology Foundation (T.I.), the Asahi Glass Foundation (T.I.), and Toyota Riken (T.I.).

Keywords

amylose
block copolymers
cellulose
self-assembly
sustainable elastomers

Access to Document

10.1021/acssuschemeng.1c02180

Cite this

@article{6273614abcbd42abbc6d2d6562ff0df6,

title = "Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers",

abstract = "Herein, we compared the microphase-separation behavior and mechanical properties of cellulose- and amylose-based block copolymers (BCPs). Various cellooligosaccharide triacetate-b-poly(δ-decanolactone)-b-cellooligosaccharide triacetates (AcCel n-b-PDL-b-AcCel ns), which are cellulose-based ABA-type BCPs, with PDL molecular weights of approximately 5, 10, and 20 kg mol -1and PDL volume fractions of 0.65, 0.77, and 0.87, were synthesized from α,ω-diazido-end-functionalized PDLs and propargyl-end-functionalized cellooligosaccharide triacetates via click chemistry. We adopted the cellodextrin-phosphorylase-mediated oligomerization of α-glucose-1-phosphase in the presence of a propargyl-end-functionalized cellobiose primer to synthesize the functional cellooligosaccharide segment. The maltooligosaccharide triacetate-b-poly(δ-decanolactone)-b-maltooligosaccharide triacetate (AcMal n-b-PDL-b-AcMal ns) amylose counterparts were also synthesized in a similar manner. Small-angle X-ray scattering experiments and atomic force microscopy revealed that AcCel n-b-PDL-b-AcCel ns are more likely to microphase-separate into ordered nanostructures compared to AcMal n-b-PDL-b-AcMal ns, despite their comparable chemical compositions and molecular weights. Furthermore, AcCel n-b-PDL-b-AcCel ns exhibited significantly superior mechanical performance compared to their amylose counterparts under tensile testing, with Young{\textquoteright}s modulus and stress at break of AcCel n-b-PDL 10k-b-AcCel nbeing 2.3 and 1.8 times higher, respectively, than those of AcMal n-b-PDL 10k-b-AcMal n. The enhanced microphase-separation and mechanical properties of AcCel n-b-PDL-b-AcCel ns were found to be attributable to the stiffness and crystalline nature of the AcCel nsegments. These results demonstrate the advantages of using cellulose derivatives to synthesize novel biofunctional materials. ",

keywords = "amylose, block copolymers, cellulose, self-assembly, sustainable elastomers",

author = "Satoshi Katsuhara and Yasuko Takagi and Naoki Sunagawa and Kiyohiko Igarashi and Takuya Yamamoto and Kenji Tajima and Takuya Isono and Toshifumi Satoh",

note = "Funding Information: This work was financially supported by a JSPS Grant-in-Aid for Scientific Research (B) (No. 19H02549, K.T.; No. 20H02792, I.T.; No. 19H02769, T.S.), the Frontier Chemistry Center (Hokkaido University, T.I.), the Photoexcitonix Project (Hokkaido University, T.S.), the Creative Research Institute (Hokkaido University, T.S.), the Iketani Science and Technology Foundation (T.I.), the Asahi Glass Foundation (T.I.), and Toyota Riken (T.I.). Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = jul,

day = "26",

doi = "10.1021/acssuschemeng.1c02180",

language = "English",

volume = "9",

pages = "9779--9788",

journal = "ACS Sustainable Chemistry and Engineering",

issn = "2168-0485",

publisher = "American Chemical Society ACS",

number = "29",

}

Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers. / Katsuhara, Satoshi; Takagi, Yasuko; Sunagawa, Naoki et al.
In: ACS Sustainable Chemistry and Engineering, Vol. 9, No. 29, 26.07.2021, p. 9779-9788.

Research output: Contribution to journal › Article › Scientific › peer-review

TY - JOUR

T1 - Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers

T2 - Comparisons with Amylose-Based Triblock Copolymers

AU - Katsuhara, Satoshi

AU - Takagi, Yasuko

AU - Sunagawa, Naoki

AU - Igarashi, Kiyohiko

AU - Yamamoto, Takuya

AU - Tajima, Kenji

AU - Isono, Takuya

AU - Satoh, Toshifumi

N1 - Funding Information: This work was financially supported by a JSPS Grant-in-Aid for Scientific Research (B) (No. 19H02549, K.T.; No. 20H02792, I.T.; No. 19H02769, T.S.), the Frontier Chemistry Center (Hokkaido University, T.I.), the Photoexcitonix Project (Hokkaido University, T.S.), the Creative Research Institute (Hokkaido University, T.S.), the Iketani Science and Technology Foundation (T.I.), the Asahi Glass Foundation (T.I.), and Toyota Riken (T.I.). Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/7/26

Y1 - 2021/7/26

N2 - Herein, we compared the microphase-separation behavior and mechanical properties of cellulose- and amylose-based block copolymers (BCPs). Various cellooligosaccharide triacetate-b-poly(δ-decanolactone)-b-cellooligosaccharide triacetates (AcCel n-b-PDL-b-AcCel ns), which are cellulose-based ABA-type BCPs, with PDL molecular weights of approximately 5, 10, and 20 kg mol -1and PDL volume fractions of 0.65, 0.77, and 0.87, were synthesized from α,ω-diazido-end-functionalized PDLs and propargyl-end-functionalized cellooligosaccharide triacetates via click chemistry. We adopted the cellodextrin-phosphorylase-mediated oligomerization of α-glucose-1-phosphase in the presence of a propargyl-end-functionalized cellobiose primer to synthesize the functional cellooligosaccharide segment. The maltooligosaccharide triacetate-b-poly(δ-decanolactone)-b-maltooligosaccharide triacetate (AcMal n-b-PDL-b-AcMal ns) amylose counterparts were also synthesized in a similar manner. Small-angle X-ray scattering experiments and atomic force microscopy revealed that AcCel n-b-PDL-b-AcCel ns are more likely to microphase-separate into ordered nanostructures compared to AcMal n-b-PDL-b-AcMal ns, despite their comparable chemical compositions and molecular weights. Furthermore, AcCel n-b-PDL-b-AcCel ns exhibited significantly superior mechanical performance compared to their amylose counterparts under tensile testing, with Young’s modulus and stress at break of AcCel n-b-PDL 10k-b-AcCel nbeing 2.3 and 1.8 times higher, respectively, than those of AcMal n-b-PDL 10k-b-AcMal n. The enhanced microphase-separation and mechanical properties of AcCel n-b-PDL-b-AcCel ns were found to be attributable to the stiffness and crystalline nature of the AcCel nsegments. These results demonstrate the advantages of using cellulose derivatives to synthesize novel biofunctional materials.

AB - Herein, we compared the microphase-separation behavior and mechanical properties of cellulose- and amylose-based block copolymers (BCPs). Various cellooligosaccharide triacetate-b-poly(δ-decanolactone)-b-cellooligosaccharide triacetates (AcCel n-b-PDL-b-AcCel ns), which are cellulose-based ABA-type BCPs, with PDL molecular weights of approximately 5, 10, and 20 kg mol -1and PDL volume fractions of 0.65, 0.77, and 0.87, were synthesized from α,ω-diazido-end-functionalized PDLs and propargyl-end-functionalized cellooligosaccharide triacetates via click chemistry. We adopted the cellodextrin-phosphorylase-mediated oligomerization of α-glucose-1-phosphase in the presence of a propargyl-end-functionalized cellobiose primer to synthesize the functional cellooligosaccharide segment. The maltooligosaccharide triacetate-b-poly(δ-decanolactone)-b-maltooligosaccharide triacetate (AcMal n-b-PDL-b-AcMal ns) amylose counterparts were also synthesized in a similar manner. Small-angle X-ray scattering experiments and atomic force microscopy revealed that AcCel n-b-PDL-b-AcCel ns are more likely to microphase-separate into ordered nanostructures compared to AcMal n-b-PDL-b-AcMal ns, despite their comparable chemical compositions and molecular weights. Furthermore, AcCel n-b-PDL-b-AcCel ns exhibited significantly superior mechanical performance compared to their amylose counterparts under tensile testing, with Young’s modulus and stress at break of AcCel n-b-PDL 10k-b-AcCel nbeing 2.3 and 1.8 times higher, respectively, than those of AcMal n-b-PDL 10k-b-AcMal n. The enhanced microphase-separation and mechanical properties of AcCel n-b-PDL-b-AcCel ns were found to be attributable to the stiffness and crystalline nature of the AcCel nsegments. These results demonstrate the advantages of using cellulose derivatives to synthesize novel biofunctional materials.

KW - amylose

KW - block copolymers

KW - cellulose

KW - self-assembly

KW - sustainable elastomers

UR - https://www.scopus.com/pages/publications/85111192323

U2 - 10.1021/acssuschemeng.1c02180

DO - 10.1021/acssuschemeng.1c02180

M3 - Article

AN - SCOPUS:85111192323

SN - 2168-0485

VL - 9

SP - 9779

EP - 9788

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

IS - 29

ER -

Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this