Studies leading to the large scale synthesis of polyesters using enzymes

Binns, Falmai; Harffey, P.; Roberts, Stanley M.; Taylor, A.

doi:10.1039/a904889h

Cited by 93 publications

(96 citation statements)

References 28 publications

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“…Considering the data reported in literature, it must be noted that results in terms of molecular weight of polymerization products might be affected by detachment and dispersion of the enzyme when not covalently supported as demonstrated in previous studies [64]. In addition to adsorbed preparation with consequently problematic leaching, the mechanical strength of CLEAs preparations still has to be demonstrated on an industrially relevant scale [65].…”

Section: Cutinases As Biocatalysts For Polymerization Reactionsmentioning

confidence: 99%

Nature Inspired Solutions for Polymers: Will Cutinase Enzymes Make Polyesters and Polyamides Greener?

et al. 2016

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Abstract:The polymer and plastic sectors are under the urge of mitigating their environmental impact. The need for novel and more benign catalysts for polyester synthesis or targeted functionalization led, in recent years, to an increasing interest towards cutinases due to their natural ability to hydrolyze ester bonds in cutin, a natural polymer. In this review, the most recent advances in the synthesis and hydrolysis of various classes of polyesters and polyamides are discussed with a critical focus on the actual perspectives of applying enzymatic technologies for practical industrial purposes. More specifically, cutinase enzymes are compared to lipases and, in particular, to lipase B from Candida antarctica, the biocatalyst most widely employed in polymer chemistry so far. Computational and bioinformatics studies suggest that the natural role of cutinases in attacking natural polymers confer some essential features for processing also synthetic polyesters and polyamides.

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Section: Cutinases As Biocatalysts For Polymerization Reactionsmentioning

confidence: 99%

Nature Inspired Solutions for Polymers: Will Cutinase Enzymes Make Polyesters and Polyamides Greener?

et al. 2016

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“…The early stage of the reaction can be interpreted by Binns's proposal. 21,22 However at the later stage of the reaction, the carboxyl terminated product was preferred through transesterification. Even for the reaction conducted under the condition of excess diacid, the early stage took the hydroxyl terminated polyester and then it changed to the carboxyl terminated one at the later stage.…”

Section: Discussionmentioning

confidence: 99%

“…The initial stage of the reaction has been proposed by Binns et al 21,22 First, the enzyme reacted with A, that is Enz-O-A was formed. This process corresponds to the Scheme 1(1) (n = 0).…”

Section: Model Mechanism Of Enzymatic Esterificationmentioning

confidence: 99%

“…Binns et al proposed the reaction mechanism for polycondensation of aliphatic diacid (abbreviated as A) and diol (abbreviated as B) in solvent free system. 21,22 According to their result, AB unit plays a key roll to make the chain grow. The enzyme-substrate complex (Enz-O-AB) is attacked by B, and then the oligomer consists of hydroxyl terminated products such as BAB, B(AB) 2 , B(AB) 3 , and so on.…”

Section: Polycondensation With Equimolar Quantities Of Diacid and Diolmentioning

confidence: 99%

“…19,20 Binns et al investigated the polycondensation in stoichiometric adipic acid and butane-1,4-diol system. 21,22 They proposed a step-growth mechanism following the sequential addition of a unit of diaciddiol. It was shown that the predominant product is hydroxyl terminated oligomers.…”

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Enzyme-Catalyzed Polymerization Mechanism of Aliphatic Polyester Investigated by 1H NMR and MALDI-TOF Mass Spectrum

Nakaoki

Danno

Kurokawa

2003

Polym J

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ABSTRACT:Enzyme-catalyzed polymerization mechanism of adipic acid and hexanediol was investigated by proton nuclear magnetic resonance ( 1 H NMR) and MALDI-TOF mass spectra. When the stoichiometric substrates were used for the reaction, 1 H NMR measurements showed that the hydroxyl terminated product was preferentially formed at the early stage, then with reaction time it changed to carboxyl terminated product. This process was also confirmed by MALDI-TOF mass spectra. First the chain propagation follows the step-growth mechanism accompanying the sequential addition of a diacid-diol unit. In this case, an enzyme-substrate complex is attacked by hydroxyl group of substrates, and as a result the hydroxyl terminated product was preferentially formed. And at the later stage of the reaction, the transesterification plays an important role to form the carboxyl terminated product. When an excess diacid was used, the end group structure showed the same behavior as the stoichiometric condition, i.e., the predominant end group is consisted of the hydroxyl group at the initial stage then it rapidly changed to the carboxyl group although the time to change to carboxyl terminated product became shorter. In case of the condition of an excess diol, the reaction was avoided at the early stage because no enzyme forms a complex with diacid.KEY WORDS Enzyme / Polycondensation / End Structure / Polyester / Nuclear Magnetic Resonance (NMR) / MALDI-TOF Mass Spectrum / Enzyme-catalyzed polymerization in organic media has been extensively investigated during the last decade. Generally lipases are known to catalyze esterification and transesterification. Enzymatic ring opening polymerization such as lactones has been wellestablished by many researches. In 1993, Kobayashi et al. succeeded to polymerize different lactones using some lipases. 1 The advantage of this polymerization is that a leaving group is not produced and high molecular weight product is obtained. Lots of investigations on different ring size of lactones, solvent effect, and an enzymatic activity of lipases immobilized on different matrix have been carried out. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] In case of condensation of diol and diacid with aliphatic chain, the high molecular weight polyester can be obtained by removing a leaving group. Klibanov et al. have explored the enzymatic catalyzed asymmetric polymerization of aliphatic diol and diacid. 17 They observed the formation of hydroxyl terminated oligomers, as an excess diol was used. Morrow et al. recognized the importance of stoichiometry and studied polycondensation using equimolar quantities of diol and diacid. 18 They succeeded to prepare polyester with a several thousands of molecular weight. They also showed that the early stage of polymerization followed relatively rapid formation of hydroxyl terminated polyester and slower † To whom correspondence should be addressed.formation of carboxyl terminated one. Enzymatic synthesis of aliphatic polyester in solvent-free system was studied by Uyama e...

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Lipase-catalyzed polymerization of fluorinated lactones and fluorinated hydroxycarboxylic acids

Runge

O’Hagan

Haufe

2000

J. Polym. Sci. A Polym. Chem.

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Lipase‐catalyzed ring‐opening polymerization of 10‐fluorodecan‐9‐olide (1a), 11‐fluoroundecan‐10‐olide (1b), 12‐fluorododecan‐11‐olide (1c) and 14‐fluorotetradecan‐13‐olide (1d) gave optically active products with Mw of 3.000 to 8.000, while 10‐fluoroundecan‐11‐olide (3a) gave an optically inactive polymer with Mw = 11.000. On the other hand, Candida antarctica lipase‐catalyzed polymerization of 10‐ to 14‐membered ω‐fluoro‐(ω‐1)‐hydroxyalcanoic acids gave optically inactive oligomers with Mw of 3.000 to 11.000 in the presence of molecular sieves, while reactions without molecular sieves gave oligomers with lower molecular weight, but with small optical rotations. 9‐Fluoro‐10‐hydroxydecanoic acid, on the other hand, gave an optically inactive polyester with Mw = 7400. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2004–2012, 2000

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Studies leading to the large scale synthesis of polyesters using enzymes

Cited by 93 publications

References 28 publications

Nature Inspired Solutions for Polymers: Will Cutinase Enzymes Make Polyesters and Polyamides Greener?

Nature Inspired Solutions for Polymers: Will Cutinase Enzymes Make Polyesters and Polyamides Greener?

Enzyme-Catalyzed Polymerization Mechanism of Aliphatic Polyester Investigated by 1H NMR and MALDI-TOF Mass Spectrum

Lipase-catalyzed polymerization of fluorinated lactones and fluorinated hydroxycarboxylic acids

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