Synthesis of lactate (LA)-based poly(ester-urethane) using hydroxyl-terminated LA-based oligomers from a microbial secretion system

Utsunomia, Camila; Saito, Tatsuya; Matsumoto, Ken’ichiro; Hori, Chiaki; Isono, Takuya; Satoh, Toshifumi; Taguchi, Seiichi

doi:10.1007/s10965-017-1325-1

Cited by 13 publications

(5 citation statements)

References 17 publications

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“…Notably, the direct secretion of lactate‐based oligomers enabled us to establish a shortcut for producing poly(lactide) (PLA) via the ring‐opening polymerization of lactide converted from the lactate‐based oligomers . Secreted lactate‐based oligomers end‐capped with DEG were also functionally used to synthesize poly(ester‐urethane) . However, the mechanism underlying lactate‐based oligomer generation has not been clearly elucidated.…”

Section: Introductionmentioning

confidence: 99%

Microbial Secretion Platform for 3‐Hydroxybutyrate Oligomer and Its End‐Capped Forms Using Chain Transfer Reaction‐Mediated Polyhydroxyalkanoate Synthases

Miyahara

Hiroe

Tsuge

et al. 2019

Biotechnology Journal

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The biodegradable polyester 3‐hydroxybutyrate (3HB) polymer [P(3HB)] is intracellularly synthesized and accumulated in recombinant Escherichia coli. In this study, native polyhydroxyalkanoate (PHA) synthases are used to attempt to microbially secrete 3HB homo‐oligomers (3HBOs), which are widely distributed in nature as physiologically active substances. High secretory production is observed, especially for the two PHA synthases from Aeromonas caviae and Bacillus cereus YB4. Surprisingly, an ethyl ester at the carboxy terminus (ethyl ester form) of 3HBOs is identified for most of the PHA synthases tested. Next, 3HBOs with a functional carboxyl group (carboxyl form of 3HBO) are obtained by using the alcohol dehydrogenase gene (adhE)‐deficient mutant strain, suggesting that the endogenous ethanol produced in E. coli acts as a chain transfer (CT) agent in the generation of 3HBOs. Furthermore, an in vitro polymerization assay reveals that CT agents such as ethanol and free 3HB are involved in the generation of ethyl ester and carboxyl form of 3HBO, respectively. The microbial platform established herein allows the secretion of 3HBOs with desirable end structures by supplementation with various CT agents. The obtained 3HBOs and their end‐capped forms may be used as physiologically active substances and building blocks for polymeric materials.

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Section: Introductionmentioning

confidence: 99%

Microbial Secretion Platform for 3‐Hydroxybutyrate Oligomer and Its End‐Capped Forms Using Chain Transfer Reaction‐Mediated Polyhydroxyalkanoate Synthases

Miyahara

Hiroe

Tsuge

et al. 2019

Biotechnology Journal

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“…Solid‐state polymerization (SSP) 13,14 and chain‐extension reactions (CERs) following direct polymerization are promising methods for the synthesis of HMW‐PLA 15–21 . CERs are useful not only for easily increasing the molecular weight of low‐molecular‐weight (LMW) PLA (i.e., M w below 100 × 10 3 ) but also for expanding the range of polymers to include block copolymers containing PLA segments connected to different types of polymers or oligomers 22 . In addition, CERs can be potentially applied to mechanical recycling or repair to restore the molecular weight, which decreases during the service life of HMW‐PLA 23 …”

Section: Introductionmentioning

confidence: 99%

“…[15][16][17][18][19][20][21] CERs are useful not only for easily increasing the molecular weight of low-molecular-weight (LMW) PLA (i.e., M w below 100 Â 10 3 ) but also for expanding the range of polymers to include block copolymers containing PLA segments connected to different types of polymers or oligomers. 22 In addition, CERs can be potentially applied to mechanical recycling or repair to restore the molecular weight, which decreases during the service life of HMW-PLA. 23 Difunctional compounds such as diisocyanates, 15-19 bisoxazolines, 16,24,25 diepoxides, 26 diacid chlorides, 27,28 acid anhydrides, 27 bislactams, 24 and carbodiimides 21 are commonly used as chain extenders for polyesters including PLA.…”

Section: Introductionmentioning

confidence: 99%

Diisocyanate‐based chain extension via Mg(II) catalyzed amide formation to high‐molecular‐weight poly(lactic acid)

Kawashima

Usugi

Ogawa

2023

Journal of Polymer Science

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A simple chain‐extension reaction using diisocyanate as a chain extender was adopted to increase the molecular weight of low‐molecular‐weight (LMW) poly(lactic acid) (PLA) synthesized via direct polycondensation and to recover the molecular weight of commercial PLA after service life. The slow reaction between diisocyanate and the carboxylic acid terminus of PLA was successfully accelerated using a Mg(II) catalyst, affording a linear chain‐extended PLA (cePLA) connected through amide bonds. To increase the number of amide bonds, which exhibit higher thermal stability than the urethane bonds that are formed in the more common chain‐extension reactions between isocyanates and the hydroxy terminus of PLA, a telechelic LMW‐PLA having carboxylic acid groups at both termini was prepared. Subsequent reaction of this LMW‐PLA with diisocyanate in the presence of a Mg(II) catalyst afforded a cePLA with high molecular weight (Mw > 180 × 103 g/mol) and enhanced stability against thermal degradation, while showing identical mechanical properties and biodegradability as commercial PLA.

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“…Recently, the antibacterial activity of a 3HBO and an application of this oligomer (as a textile fiber) were also reported [21,23]. 3HBOs are expected to have utility as bioactive compounds and macromonomers for various polymers, such as polyurethanes [17,24].…”

Section: Introductionmentioning

confidence: 99%

Enhanced Production of (R)-3-Hydroxybutyrate Oligomers by Coexpression of Molecular Chaperones in Recombinant Escherichia coli Harboring a Polyhydroxyalkanoate Synthase Derived from Bacillus cereus YB-4

et al. 2022

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The biodegradable polyester poly-(R)-3-hydroxybutyrate [P(3HB)] is synthesized by a polymerizing enzyme called polyhydroxyalkanoate (PHA) synthase and accumulates in a wide variety of bacterial cells. Recently, we demonstrated the secretory production of a (R)-3HB oligomer (3HBO), a low-molecular-weight P(3HB), by using recombinant Escherichia coli expressing PHA synthases. The 3HBO has potential value as an antibacterial substance and as a building block for various polymers. In this study, to construct an efficient 3HBO production system, the coexpression of molecular chaperones and a PHA synthase derived from Bacillus cereus YB-4 (PhaRCYB4) was examined. First, genes encoding enzymes related to 3HBO biosynthesis (phaRCYB4, phaA and phaB derived from Ralstonia eutropha H16) and two types of molecular chaperones (groEL, groES, and tig) were introduced into the E. coli strains BW25113 and BW25113ΔadhE. As a result, coexpression of the chaperones promoted the enzyme activity of PHA synthase (approximately 2–3-fold) and 3HBO production (approximately 2-fold). The expression assay of each chaperone and PHA synthase subunit (PhaRYB4 and PhaCYB4) indicated that the combination of the two chaperone systems (GroEL-GroES and TF) supported the folding of PhaRYB4 and PhaCYB4. These results suggest that the utilization of chaperone proteins is a valuable approach to enhance the formation of active PHA synthase and the productivity of 3HBO.

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Synthesis of lactate (LA)-based poly(ester-urethane) using hydroxyl-terminated LA-based oligomers from a microbial secretion system

Cited by 13 publications

References 17 publications

Microbial Secretion Platform for 3‐Hydroxybutyrate Oligomer and Its End‐Capped Forms Using Chain Transfer Reaction‐Mediated Polyhydroxyalkanoate Synthases

Microbial Secretion Platform for 3‐Hydroxybutyrate Oligomer and Its End‐Capped Forms Using Chain Transfer Reaction‐Mediated Polyhydroxyalkanoate Synthases

Diisocyanate‐based chain extension via Mg(II) catalyzed amide formation to high‐molecular‐weight poly(lactic acid)

Enhanced Production of (R)-3-Hydroxybutyrate Oligomers by Coexpression of Molecular Chaperones in Recombinant Escherichia coli Harboring a Polyhydroxyalkanoate Synthase Derived from Bacillus cereus YB-4

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