4.8 Article

Highly Ordered Polypeptide with UCST Phase Separation Behavior

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 141, 期 3, 页码 1261-1268

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AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b10168

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资金

  1. Ministry of Education, Culture, Sports, Science and Technology
  2. Center of Innovation (COI) Program, Japan Science and Technology Agency (JST)
  3. KAKENHI from Japan Society for the Promotion of Science [16K01389, 15H01807]
  4. Grants-in-Aid for Scientific Research [16K01389] Funding Source: KAKEN

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Manipulating phase separation structures of thermoresponsive polymers will enhance the usefulness of structure-controllable materials in fields such as drug delivery and tissue engineering. However, behaviors of upper critical solution temperature (UCST) have been less investigated so far, despite the importance of UCST. Here, we examined two citrulline-based polypeptides, poly(D-ornithine-co-D-citrulline) (PDOC) and poly(DL-ornithine-co-DL-citrulline) (PDLOC), to investigate how stereoregularity of the polypeptides influences UCST behavior, in addition to poly(L-ornithine-co-L-citrulline) (FLOC) previously studied. showed phase separation temperatures (T(p)s) higher than that of racemic PDLOC. Moreover, PDLOC underwent liquid to coacervate phase separation at T-p, whereas PLOC and PDOC underwent liquid to solid-like aggregation transitions. From a structural point of view, circular dichroism and small-angle X-ray scattering measurements revealed that homochiral PLOC and PDOC polypeptides formed alpha-helical structures and assembled into a regular hexagonal lattice upon phase separation. Interactions between the pendent ureido groups of homochiral POCs appear to play pivotal roles in helical folding and assembly into the hexagonal structure. In addition, T-p change in response to biodegradation was confirmed for both PLOC and PDLOC. The biodegradability was considerably influenced by phase-separated structures. These findings of UCST-type POCs in this study would provide important insights into structure-controllable and thermoresponsive biomaterials. Homochiral PLOC and 50 PDOC

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