Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers
Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers
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纤维素基三嵌段共聚物的增强自组装和机械性能：与直链淀粉基三嵌段共聚物的比较
DOI：
10.1021/acssuschemeng.1c02180
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Satoh Toshifumi
中科院分区：
文献类型：
--
作者：
Katsuhara Satoshi;Takagi Yasuko;Sunagawa Naoki;Igarashi Kiyohiko;Yamamoto Takuya;Tajima Kenji;Isono Takuya;Satoh Toshifumi
在此，我们比较了纤维素和直链淀粉基嵌段共聚物（BCP）的微相分离行为和机械性能。各种纤维寡糖三乙酸酯-b-聚（δ-癸内酯）-b-纤维寡糖三乙酸酯（AcCeln-b-PDL-b-AcCelns）是基于纤维素的 ABA 型 BCP，其 PDL 分子量约为 5、10 和 20 kg mol–1，PDL 体积分数为 0.65、0.77 和 0.87。通过点击化学生成 α,ω-二叠氮基末端功能化的 PDL 和炔丙基末端功能化的纤维寡糖三乙酸酯。我们采用纤维糊精磷酸化酶介导的α-d-葡萄糖-1-磷酸低聚反应，在存在炔丙基末端功能化纤维二糖引物的情况下，合成功能性纤维寡糖片段。麦芽低聚糖三乙酸酯-b-聚(δ-癸内酯)-b-麦芽低聚糖三乙酸酯(AcMaln-b-PDL-b-AcMalns)直链淀粉对应物也以类似的方式合成。小角 X 射线散射实验和原子力显微镜表明，与 AcMaln-b-PDL-b-AcMalns 相比，AcCeln-b-PDL-b-AcCelns 更有可能微相分离成有序纳米结构，尽管它们的化学成分和分子量相当。此外，在拉伸测试中，与直链淀粉相比，AcCeln-b-PDL-b-AcCelns 表现出明显优越的机械性能，AcCeln-b-PDL10k-b-AcCeln 的杨氏模量和断裂应力分别是 AcMaln-b-PDL10k-b-AcMaln 的 2.3 和 1.8 倍。人们发现 AcCeln-b-PDL-b-AcCelns 增强的微相分离和机械性能归因于 AcCelns 段的刚度和结晶性质。这些结果证明了使用纤维素衍生物合成新型生物功能材料的优势。
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 (AcCeln-b-PDL-b-AcCelns), 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-d-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 (AcMaln-b-PDL-b-AcMalns) amylose counterparts were also synthesized in a similar manner. Small-angle X-ray scattering experiments and atomic force microscopy revealed that AcCeln-b-PDL-b-AcCelns are more likely to microphase-separate into ordered nanostructures compared to AcMaln-b-PDL-b-AcMalns, despite their comparable chemical compositions and molecular weights. Furthermore, AcCeln-b-PDL-b-AcCelns exhibited significantly superior mechanical performance compared to their amylose counterparts under tensile testing, with Young’s modulus and stress at break of AcCeln-b-PDL10k-b-AcCelnbeing 2.3 and 1.8 times higher, respectively, than those of AcMaln-b-PDL10k-b-AcMaln. The enhanced microphase-separation and mechanical properties of AcCeln-b-PDL-b-AcCelns were found to be attributable to the stiffness and crystalline nature of the AcCelnsegments. These results demonstrate the advantages of using cellulose derivatives to synthesize novel biofunctional materials.
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纤维素-b-聚苯乙烯的合成与表征
影响因子：
2.8
作者：
Shunsuke Yagi;Natsuki Kasuya;K. Fukuda
通讯作者：
K. Fukuda
DOI：
--
发表时间：
2020
期刊：
影响因子：
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作者：
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作者：
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影响因子：
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作者：
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通讯作者：
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影响因子：
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作者：
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通讯作者：
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