Sourcing, thermodynamics, and ring-opening (co)polymerization of substituted δ-lactones: a review

McMichael, Peter; Schultze, Xavier; Cramail, Henri; Peruch, Frédéric

doi:10.1039/d3py00657c

Cited by 4 publications

(3 citation statements)

References 132 publications

(257 reference statements)

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“…One of advantages of the block copolymer biosynthesis system over chemical methods, such as ROP, is high molecular weight of the polymers. In many cases, the molecular weight of chemically synthesized polyesters by ROP is limited ≤ 10 4 in order of magnitude (McMichael et al 2023 ; Saar and Lienkamp 2020 ). Furthermore, the strict chiral specificity of PHA synthases enables the synthesis of isotactic polymers.…”

Section: Perspectivementioning

confidence: 99%

Toward the production of block copolymers in microbial cells: achievements and perspectives

Matsumoto

2024

Appl Microbiol Biotechnol

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The microbial production of polyhydroxyalkanoate (PHA) block copolymers has attracted research interests because they can be expected to exhibit excellent physical properties. Although post-polymerization conjugation and/or extension have been used for PHA block copolymer synthesis, the discovery of the first sequence-regulating PHA synthase, PhaCAR, enabled the direct synthesis of PHA–PHA type block copolymers in microbial cells. PhaCAR spontaneously synthesizes block copolymers from a mixture of substrates. To date, Escherichia coli and Ralstonia eutropha have been used as host strains, and therefore, sequence regulation is not a host-specific phenomenon. The monomer sequence greatly influences the physical properties of the polymer. For example, a random copolymer of 3-hydroxybutyrate and 2-hydroxybutyrate deforms plastically, while a block copolymer of approximately the same composition exhibits elastic deformation. The structure of the PHA block copolymer can be expanded by in vitro evolution of the sequence-regulating PHA synthase. An engineered variant of PhaCAR can synthesize poly(d-lactate) as a block copolymer component, which allows for greater flexibility in the molecular design of block copolymers. Therefore, creating sequence-regulating PHA synthases with a further broadened substrate range will expand the variety of properties of PHA materials. This review summarizes and discusses the sequence-regulating PHA synthase, analytical methods for verifying block sequence, properties of block copolymers, and mechanisms of sequence regulation. Key points • Spontaneous monomer sequence regulation generates block copolymers • Poly(D-lactate) segment can be synthesized using a block copolymerization system • Block copolymers exhibit characteristic properties Graphical abstract

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Section: Perspectivementioning

confidence: 99%

Toward the production of block copolymers in microbial cells: achievements and perspectives

Matsumoto

2024

Appl Microbiol Biotechnol

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“…Aliphatic polyesters are promising materials with good material properties, degradability, and/or recyclability as alternatives to commodity plastics, such as polyethylene. The major synthetic methods for polyesters are ring-opening polymerization (ROP), , polycondensation, and enzymatic polymerization using bacterial polyhydroxyalkanoate (PHA) synthases (PhaCs). The advantages of PhaC-catalyzed polymerization are as follows: (i) the high molecular weight of the polymerized products, which can reach 10 7 ; , (ii) the robustness unimpeded by water and other impurities, which renders the dehydration and purification processes unnecessary; and (iii) the enantiospecificity, leading to the strict recognition of ( R )-3-hydroxyacyl-coenzyme As (CoAs) as substrates; etc.…”

Section: Introductionmentioning

confidence: 99%

Engineering of the Long-Main-Chain Monomer-Incorporating Polyhydroxyalkanoate Synthase PhaC_AR for the Biosynthesis of Poly[(R)-3-hydroxybutyrate-co-6-hydroxyhexanoate]

Hozumi,

Hachisuka,

Tomita

et al. 2024

Biomacromolecules

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Polyhydroxyalkanoate (PHA) synthases (PhaCs) are useful and versatile tools for the production of aliphatic polyesters. Here, the chimeric PHA synthase PhaC AR was engineered to increase its capacity to incorporate unusual 6-hydroxyhexanoate (6HHx) units. Mutations at positions 149 and 314 in PhaC AR were previously found to increase the incorporation of an analogous natural monomer, 3-hydroxyhexanoate (3HHx). We attempted to repurpose the mutations to produce 6HHxcontaining polymers. Site-directed saturation mutants at these positions were applied for P(3HB-co-6HHx) synthesis in Escherichia coli. As a result, the N149D and F314Y mutants effectively increased the 6HHx fraction. Moreover, the pairwise NDFY mutation further increased the 6HHx fraction, which reached 22 mol %. This increase was presumably caused by altered enzyme activity rather than altered expression levels, as assessed based on immunoblot analysis. The glass transition temperature and crystallinity of P(3HB-co-6HHx) decreased as the 6HHx fraction increased.

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“…16 We first investigated the diphenyl phosphate (DPP)catalyzed ROP of M1, since DPP is a good catalyst for the living ROP of lactones under mild conditions by the monomer/chain-end dual activation mechanism. 9,15,55,56 The polymerization was conducted in toluene ([M1] 0 = 1 M) with benzyl alcohol (BnOH) as an initiator at 30 S4, entry 1). The polymerization was slow, and complete monomer consumption was reached after 54 h. The purified polymer was characterized by 1 H NMR (Figure 1A), MALDI-ToF MS (Figure 1B), 13 C NMR (Figure S9), and SEC (Figure S10, M n = 10.5 kDa, Đ = 1.03) measurements, verifying that the obtained polyester PM1 is a linear polymer initiated by BnOH (BnO-[M] n -H).…”

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confidence: 99%

Photochemical [2 + 2] Cycloaddition Enables the Synthesis of Highly Thermally Stable and Acid/Base-Resistant Polyesters from a Nonpolymerizable α,β-Conjugated Valerolactone

Yang,

Wu,

et al. 2024

ACS Macro Lett.

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We report a simple strategy to transform a nonpolymerizable six-membered α,β-conjugated lactone, 5,6dihydro-2H-pyran-2-one (DPO), into polymerizable bicyclic lactones via photochemical [2 + 2] cycloaddition. Two bicyclic lactones, M1 and M2, were obtained by the photochemical [2 + 2] cycloaddition of tetramethylethylene and DPO. Ring-opening polymerization (ROP) of M1 and M2 catalyzed by diphenyl phosphate (DPP), La[N(SiMe 3 ) 2 ] 3 , and 1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris (dimethylamino) phosphoranylidenamino]-2λ 5 , 4λ 5 -catenadi(phosphazene) ( t Bu-P 4 ) were conducted. M1 is highly polymerizable, either DPP or La[N(SiMe 3 ) 2 ] 3 could catalyze its living ROP under mild conditions, affording the well-defined PM1 with a predictable molar mass and low dispersity. M2 could only be polymerized with t Bu-P 4 as the catalyst, also generating the same polymer PM1. PM1 has high thermal stability, with a T d,5% being up to 376 °C. Ring-opening copolymerization (ROcP) of M1 and δ-valerolactone (δ-VL) catalyzed by La[N(SiMe 3 ) 2 ] 3 afforded a series of random copolymers with enhanced thermal stabilities. Both PM1 and the copolymer containing 10 mol % M1 exhibited excellent resistance to acidic and basic hydrolysis. Our results demonstrate that direct photochemical [2 + 2] cycloaddition of α,β-conjugated valerolactone is not only a strategy to tune its polymerizability, but also allows for the synthesis of highly thermally stable aliphatic polyesters, inaccessible by other methods.

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Sourcing, thermodynamics, and ring-opening (co)polymerization of substituted δ-lactones: a review

Abstract: Environmental concerns have escalated due to the extensive production of polymers from fossil resources and the resultant issues in waste management and environmental pollution. With the increased demand for more...

Cited by 4 publications

References 132 publications

Toward the production of block copolymers in microbial cells: achievements and perspectives

Toward the production of block copolymers in microbial cells: achievements and perspectives

Engineering of the Long-Main-Chain Monomer-Incorporating Polyhydroxyalkanoate Synthase PhaC_AR for the Biosynthesis of Poly[(R)-3-hydroxybutyrate-co-6-hydroxyhexanoate]

Photochemical [2 + 2] Cycloaddition Enables the Synthesis of Highly Thermally Stable and Acid/Base-Resistant Polyesters from a Nonpolymerizable α,β-Conjugated Valerolactone

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Sourcing, thermodynamics, and ring-opening (co)polymerization of substituted δ-lactones: a review

Abstract: Environmental concerns have escalated due to the extensive production of polymers from fossil resources and the resultant issues in waste management and environmental pollution. With the increased demand for more...

Cited by 4 publications

References 132 publications

Toward the production of block copolymers in microbial cells: achievements and perspectives

Toward the production of block copolymers in microbial cells: achievements and perspectives

Engineering of the Long-Main-Chain Monomer-Incorporating Polyhydroxyalkanoate Synthase PhaCAR for the Biosynthesis of Poly[(R)-3-hydroxybutyrate-co-6-hydroxyhexanoate]

Photochemical [2 + 2] Cycloaddition Enables the Synthesis of Highly Thermally Stable and Acid/Base-Resistant Polyesters from a Nonpolymerizable α,β-Conjugated Valerolactone

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Engineering of the Long-Main-Chain Monomer-Incorporating Polyhydroxyalkanoate Synthase PhaC_AR for the Biosynthesis of Poly[(R)-3-hydroxybutyrate-co-6-hydroxyhexanoate]