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Cited by 202biodegradable polymer synthesis and propertiesPolymer crystallization and propertiesCarbon dioxide utilization in catalysis

Chemical synthesis of perfectly isotactic and high melting bacterial poly(3-hydroxybutyrate) from bio-sourced racemic cyclic diolide

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Tang, Xiaoyan, Chen, Eugene Y.-X.·2018·Nature Communications
DOI 10.1038/s41467-018-04734-3PMC PMC5995816
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Abstract

Bacterial poly(3-hydroxybutyrate) (P3HB) is a perfectly isotactic, crystalline material possessing properties suitable for substituting petroleum plastics, but high costs and low volumes of its production are impractical for commodity applications. The chemical synthesis of P3HB via ring-opening polymerization (ROP) of racemic β-butyrolactone has attracted intensive efforts since the 1960s, but not yet produced P3HB with high isotacticity and molecular weight. Here, we report a route utilizing racemic cyclic diolide (rac-DL) derived from bio-sourced succinate. With stereoselective racemic catalysts, the ROP of rac-DL under ambient conditions produces rapidly P3HB with perfect isotacticity ([mm] > 99%), high melting temperature (Tm = 171 °C), and high molecular weight (Mn = 1.54 × 10 5 g mol−1, Đ = 1.01). With enantiomeric catalysts, kinetic resolution polymerizations of rac-DL automatically stops at 50% conversion and yields enantiopure (R,R)-DL and (S,S)-DL with >99% e.e. and the corresponding poly[(S)-3HB] and poly[(R)-3HB] with high Tm = 175 °C.

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  • Bacterial isotactic (R)-P3HB exhibits a high melting temperature (Tm) of 170-180°C and a glass-transition temperature (Tg) ≈0°C.

    “bacterial isotactic ( R )-poly(3-hydroxybutyrate) (( R )-P3HB, the most representative member of the PHA family, exhibits a high melting temperature ( T m) of 170-180 ◦ C and a glass-transition temperature ( T g ) ≈ 0 ◦ C)”

    From Functional and Network PHAs via Stereoselective Polymerization and Tailored Post‐Transformation (2026) · cites this paper as [12]

    The Introduction (page unavailable) identifies bacterial poly[(R)-3-hydroxybutyrate] as perfectly isotactic and describes P3HB as the most prominent PHA. The Results, Thermal properties (page unavailable), report melting temperatures of 170–171 °C for chemically synthesized, perfectly isotactic P3HB, but do not establish the stated 170–180 °C range specifically for bacterial P3HB. Our copy mentions Tg measurement in Methods, Polymer characterizations (page unavailable), but does not give a Tg of approximately 0 °C. (LLM, conf=0.82)

    Experimental — accuracy not yet measured

  • High crystallinity, mechanical brittleness, and poor melt processability of (R)-P3HB largely limit its practical utility.

    “but its high crystallinity, mechanical brittleness, and poor melt processability largely limit practical utility [9-12].”

    From Functional and Network PHAs via Stereoselective Polymerization and Tailored Post‐Transformation (2026) · cites this paper as [12]

    The Introduction (page unavailable) describes bacterial (R)-P3HB as crystalline and says production costs and limited volumes restrict its applications. The Results, under Thermal properties (page unavailable), describe highly crystalline P3HB, but do not identify brittleness or poor melt processability as limits on practical utility; they report a melt-processing window for a synthesized sample. (LLM, conf=0.84)

    Experimental — accuracy not yet measured

  • Stereocomplexation in PHAs is rare; for example, (R)- and (S)-P3HB do not form a sc.

    “Worth noting here is that stereocomplexation in PHAs is rare; for example, ( R )-and ( S )-P3HB do not form a sc [12].”

    From Functional and Network PHAs via Stereoselective Polymerization and Tailored Post‐Transformation (2026) · cites this paper as [12]

    In Results > Kinetic resolution and mechanistic considerations (page unavailable), the paper reports that a 1:1 mixture of enantiomeric P3HB polymers had a lower melting temperature than either pure polymer, indicating no stereocomplexation between those chains. It does not establish the broader claim that stereocomplexation is rare across PHAs. (LLM, conf=0.86)

    Experimental — accuracy not yet measured

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References 72 · Cited by 202

Research works printed but not linked: 64

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Authors
Tang, X., & Chen, E. Y.-X.
Affiliations
Colorado State University (US)
Corresponding author
Chen, Eugene Y.-X.
ORCID
Venue
Nature Communications
Publisher
Springer Science and Business Media LLC
Published
2018-06-11
Volume
9
Issue
1
Pages
2345-2345
ISSN
2041-1723 (ISSN-L)
DOI
10.1038/s41467-018-04734-3
PMC
PMC5995816
OpenAlex
W2806274231
Cited by
202
References
72
Citations by year
2026: 20 · 2025: 31 · 2024: 40 · 2023: 30 · 2022: 27 · 2021: 18 · 2020: 18 · 2019: 13 · 2018: 5
FWCI
4.37
Type
journal article
Language
en
Open access
Licence
Locations
  • Nature Communications (publishedVersion, cc-by)
  • Europe PMC (PubMed Central) (publishedVersion, other-oa)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
Funders
NSF | Directorate for Mathematical & Physical Sciences | Division of Chemistry (1664915)
Topics
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
  • Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
  • Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
Keywords
polyhydroxybutyrate, isotactic polymers, chemical synthesis, ring-opening polymerization, succinic acid, high molecular weight, biodegradable plastics, bio-based monomers
MeSH terms
Polyhydroxybutyrates, Biocompatible Materials, Calorimetry, Differential Scanning, Catalysis, Hot Temperature, Hydroxybutyrates, Molecular Weight, Magnetic Resonance Spectroscopy, Polyesters, Stereoisomerism, Dimerization, 3-Hydroxybutyric Acid, Polymerization

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