Studies of lipase-catalyzed polyesterification of an unactivated diacid/diol system

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

doi:10.1002/(sici)1099-0518(19980915)36:12<2069::aid-pola13>3.0.co;2-4

Cited by 69 publications

(27 citation statements)

References 5 publications

(6 reference statements)

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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%

“…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%

“…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%

“…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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confidence: 99%

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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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Section: Discussionmentioning

confidence: 99%

Section: Polycondensation With Equimolar Quantities Of Diacid and Diolmentioning

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%

mentioning

confidence: 99%

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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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“…But the expensive materials make these processes non-viable commercially, to fit the commercial production demand the materials must be cheap and easily obtainable [17].From this aim we describe a chemo enzymatic route to synthesize a novel polymer poly3-hydroxypropionate in solvent-free system.…”

Section: Introductionmentioning

confidence: 99%

Chemo enzymatic Synthesis for Poly3-hydroxypropionate in Solvent-free System

Li¹,

Li²,

Yao³

et al. 2016

Proceedings of the 2016 6th International Conference on Mechatronics, Computer and Education Informationization (MCEI 2016)

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Enzymatic Polymerization

Kobayashi¹,

Uyama²

2001

Encyclopedia of Polymer Science and Technology

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This article deals with recent advances in enzymatic polymerizations, defined as chemical polymer synthesis in vitro (in test tubes) via nonbiosynthetic pathways catalyzed by an isolated enzyme. The principal target macromolecules via the enzymatic polymerization are polysaccharides, poly(amino acid)s, polyesters, polycarbonates, polyaromatics, and vinyl polymers. For synthesis of polysaccharides, poly(amino acid)s, polyesters, and polycarbonates, hydrolases are used as catalyst; hydrolases, enzymes catalyzing a bond‐cleavage reaction by water, induce the reverse reaction of hydrolysis, leading to polymer production by a bond‐forming reaction. Specific enzyme catalysis provides a novel synthetic route for not only natural biopolymers such as cellulose, xylan, and chitin, but also unnatural polysaccharides, polyesters, poly(amino acid)s, and polycarbonates, many of which are difficult to be synthesized by conventional methodologies. Oxidoreductases act as catalyst for oxidative polymerization of phenol, aniline, and their derivatives, for polymer modification via oxidative coupling, and for production of vinyl polymers. A new class of phenolic polymers are synthesized without use of toxic formaldehyde under mild reaction conditions. Enzyme‐model complexes also catalyze the synthesis of new phenolic polymer materials.

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Studies of lipase-catalyzed polyesterification of an unactivated diacid/diol system

Cited by 69 publications

References 5 publications

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

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

Chemo enzymatic Synthesis for Poly3-hydroxypropionate in Solvent-free System

Enzymatic Polymerization

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