Elucidating enzymatic polymerisations: Chain-length selectivity of Candida antarctica lipase B towards various aliphatic diols and dicarboxylic acid diesters

Pellis, Alessandro; Comerford, James W.; Maneffa, Andrew J.; Sipponen, Mika H.; Clark, James H.; Farmer, Thomas J.

doi:10.1016/j.eurpolymj.2018.07.009

Cited by 49 publications

(54 citation statements)

References 24 publications

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“…Polypropylene beads are well-known supports for the efficient immobilization of hydrolytic enzymes [32,35,36]. Figure 1 shows the influence of different buffer systems for the immobilisation of lipase B form Candida antarctica (CaLB) on Accurel 1000. up to 94%, and molecular weights of around 13 kDa [29]. A combination of Novozym 435 and Lipozyme can catalyze the transesterification of rapeseed oil to biodiesel, using tert-Butanol as a water free reaction media [30].…”

Section: Lipase Immobilizationmentioning

confidence: 99%

“…Significantly lower conversion rates and molecular weights (M n ) were achieved when the reaction were performed at 1000 mbar compared to 70 mbar (Figure 3). This is caused by methanol, which is produced as byproduct during the reaction and if not removed from the reaction mixture causes: 1) the reversibility of the reaction (hydrolysis); and 2) inhibition of the enzyme [29]. At 70 mbar the methanol was readily removed, pushing the reaction to the right, and hence the polymerization process was more efficient.…”

Section: Polymerization Of Bio-based Polymersmentioning

confidence: 99%

“…Lipases especially show high activity in transesterification reactions performed under water free conditions like in organic solvents, where side reactions with water are eliminated [27], and the reaction media itself can involve a reactant like an alcohol [28]. CaLB is a suitable biocatalyst for the polymerization of aliphatic polyesters with substrates of carbon chain lengths between 4 and 10, leading to conversion rates of up to 94%, and molecular weights of around 13 kDa [29]. A combination of Novozym 435 and Lipozyme can catalyze the transesterification of rapeseed oil to biodiesel, using tert-Butanol as a water free reaction media [30].…”

Section: Introductionmentioning

confidence: 99%

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Efficient Physisorption of Candida Antarctica Lipase B on Polypropylene Beads and Application for Polyester Synthesis

et al. 2018

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In the present work, Candida antarctica lipase B (CaLB) was adsorbed onto polypropylene beads using different reaction conditions, in order to investigate their influence on the immobilization process and the enzyme activity of the preparations in polymerization reactions. In general, lower salt concentrations were more favorable for the binding of enzyme to the carrier. Polymerisation of dimethyl adipate (DMA) and 1,4-butanediol (BDO) was investigated in thin-film systems at 70 °C and at both atmosphere pressure (1000 mbar) and 70 mbar. Conversion rates and molecular masses of the reaction products were compared with reactions catalyzed by CaLB in its commercially available form, known as Novozym 435 (CaLB immobilized on macroporous acrylic resin). The best results according to molecular weight and monomer conversion after 24 h reaction time were obtained with CaLB immobilized in 0.1 M Na2HPO4\NaH2PO4 buffer at pH 8, producing polyesters with 4 kDa at conversion rates of 96% under low pressure conditions. The stability of this preparation was studied in a simulated continuous polymerization process at 70 °C, 70 mbar for 4 h reaction time. The data of this continuous polymerizations show that the preparation produces lower molecular weights at lower conversion rates, but is comparable to the commercial enzyme concerning stability for 10 cycles. However, after 24 h reaction time, using our optimum preparation, higher molecular weight polyesters (4 kDa versus 3.1 kDa) were obtained when compared to Novozym 435.

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Section: Lipase Immobilizationmentioning

confidence: 99%

Section: Polymerization Of Bio-based Polymersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Efficient Physisorption of Candida Antarctica Lipase B on Polypropylene Beads and Application for Polyester Synthesis

et al. 2018

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“…The solventless, enzyme-catalyzed synthesis of short aliphatic and aromatic oligoesters was conducted following previously published procedures [2,21,22]. Poly(1,4-butylene adipate) (PBA), poly(1,4-butylene isophthalate) (PBI), poly(1,4-butylene 2,5-furandicarboxylate) (PBF), and poly(1,4-butylene 2,4-pyridinedicarboxylate) (PBP) were successfully synthesized and their properties are shown in Table 1 in comparison to the same polyesters synthesized at 85 • C without enzymes [2,23]. In addition, the reactions were conducted at a lower reaction temperature compared to previous works on the topic, with the ambition of improving biocatalyst recyclability.…”

Section: Enzymatic Synthesis Of Aliphatic and Aromatic Oligoestersmentioning

confidence: 99%

“…In addition, the reactions were conducted at a lower reaction temperature compared to previous works on the topic, with the ambition of improving biocatalyst recyclability. Despite most studies in the literature reporting the synthesis of polyesters using CaLB at temperatures around 85 • C [2,23], it is widely known that lower reaction temperatures ensure the preservation of the enzyme's activity over repeated reaction cycles [12]. With the immobilized biocatalyst being the most expensive component of the system, its recyclability is a key parameter to consider when conducting polycondensation reactions [24].…”

Section: Enzymatic Synthesis Of Aliphatic and Aromatic Oligoestersmentioning

confidence: 99%

Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters

et al. 2020

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The enzymatic synthesis of polyesters in solventless systems is an environmentally friendly and sustainable method for synthetizing bio-derived materials. Despite the greenness of the technique, in most cases only short oligoesters are obtained, with limited practical applications or requiring further chemical processing for their elongation. In this work, we present a catalyst-free thermal upgrade of enzymatically synthesized oligoesters. Different aliphatic and aromatic oligoesters were synthesized using immobilized Candida antarctica lipase B (iCaLB) as the catalyst (70 • C, 24 h) yielding poly(1,4-butylene adipate) (PBA, M w = 2200), poly(1,4-butylene isophthalate) (PBI, M w = 1000), poly(1,4-butylene 2,5-furandicarboxylate) (PBF, M w = 600), and poly(1,4-butylene 2,4-pyridinedicarboxylate) (PBP, M w = 1000). These polyesters were successfully thermally treated to obtain an increase in M w of 8.5, 2.6, 3.3, and 2.7 folds, respectively. This investigation focused on the most successful upgrade, poly(1,4-butylene adipate), then discussed the possible effect of di-ester monomers as compared to di-acids in the thermally driven polycondensation. The herein-described two-step synthesis method represents a practical and cost-effective way to synthesize higher-molecular-weight polymers without the use of toxic metal catalysts such as titanium(IV) tert-butoxide, tin(II) 2-ethylhexanoate, and in particular, antimony(IV) oxide. At the same time, the method allows for the extension of the number of reuses of the biocatalyst by preventing its exposure to extreme denaturating conditions.

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Unraveling The Impact of Isomerism on Enzymatic Polymerization of Furanic Polyesters

Silvianti,

Maniar,

Agostinho

et al. 2024

Advanced Sustainable Systems

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As awareness of the environmental impact of fossil‐based polymers grows, the demand for biobased alternatives rises. In this context, combining eco‐friendly synthesis techniques with renewable resources is important to produce polymers efficiently and sustainably. Furandicarboxylic acid (FDCA) is one of the key building blocks for producing biobased polymers. However, most studies predominantly focus on 2,5‐FDCA, while FDCA encompasses other noteworthy isomers, namely, 2,4‐ and 3,4‐FDCA. The polymers derived from these two isomers have recently gained attention due to their promising properties. In this study, an environmentally friendly approach for producing biobased polyesters from 2,5‐, 2,4‐, and 3,4‐FDCA dimethyl ester isomers is proposed. The synthesis is conducted under greener conditions, utilizing Candida antarctica lipase B (CALB) enzyme as a biocatalyst. The performance of the enzyme is assessed, revealing CALB preference for polymerizing 2,5‐FDCA over 2,4‐ and 3,4‐FDCA dimethyl ester, which is elucidated by docking analysis. Moreover, CALB shows varying rates of cyclic oligomer formation for each isomer, favoring 2,5‐FDCA cyclization. The structure‐property relationship, encompassing the variation in isomeric structure, is evaluated through structural characterization, thermal analysis, and surface properties. This study primarily emphasized enzymatic polymerization and highlighted its versatility in accommodating different monomer isomeric substitutions.

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Elucidating enzymatic polymerisations: Chain-length selectivity of Candida antarctica lipase B towards various aliphatic diols and dicarboxylic acid diesters

Cited by 49 publications

References 24 publications

Efficient Physisorption of Candida Antarctica Lipase B on Polypropylene Beads and Application for Polyester Synthesis

Efficient Physisorption of Candida Antarctica Lipase B on Polypropylene Beads and Application for Polyester Synthesis

Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters

Unraveling The Impact of Isomerism on Enzymatic Polymerization of Furanic Polyesters

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