Selectivity of lipases for estolides synthesis

Todea, Anamaria; Frissen, A.E.; Otten, Linda G.; Arends, Isabel W. C. E.; Péter, Fráncisc; Boeriu, Carmen G.

doi:10.1515/pac-2014-0716

Cited by 17 publications

(14 citation statements)

References 23 publications

(31 reference statements)

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“…To the best of our knowledge, this is the first report about the biocatalytic copolymerization of ECL and HFAs. Three of the selected HFAs, specifically 16HHDA, 12HSA, and RCA, have been used in our previous study as substrates for the synthesis of estolides (homopolymers of HFA) catalyzed by lipases, but not for copolymers. Although the enzymatic synthesis of 10‐hydroxystearic acid (10HSA), starting from oleic acid and oleate hydratase from different sources was reported by several groups, 10HSA based polyester synthesis and characterization was not yet accomplished.…”

Section: Resultsmentioning

confidence: 99%

“…The biocatalyst with the best catalytic efficiency for the synthesis of the targeted copolymers was selected by screening four commercially available immobilized lipases: Novozym 435 (from Candida antarctica B), Lipozyme TL (from Thermomyces lanuginosus ), as well as two CLEA Pseudomonas stutzeri lipases (one specific for organic media and one with general applicability). Additionally, the native lipase from Pseudomonas fluorescens was also tested, based on our previous study which proved it as the best‐performing biocatalyst for estolides synthesis . The conversions were monitored by GC‐MS analysis, using hexadecane as internal standard.…”

Section: Resultsmentioning

confidence: 99%

“…Some drawbacks of the traditional chemical methods related to traces of metal catalysts, toxicity and high reaction temperatures can be avoided using the biocatalytic route . Our group reported the lipase‐catalyzed synthesis of several estolides, oligomers of hydroxy‐fatty acids derived from vegetable oils, in organic reaction media . Apart of lipase, cutinase, another lipolytic enzyme, was also found able to catalyze the homopolymerization of ω‐hydroxy acids, with different chain specificity than Novozym 435 .…”

Section: Introductionmentioning

confidence: 99%

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Biocatalytic Route for the Synthesis of Oligoesters of Hydroxy-Fatty acids and ϵ-Caprolactone

et al. 2018

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Developments of past years placed the bio-based polyesters as competitive substitutes for fossil-based polymers. Moreover, enzymatic polymerization using lipase catalysts has become an important green alternative to chemical polymerization for the synthesis of polyesters with biomedical applications, as several drawbacks related to the presence of traces of metal catalysts, toxicity and higher temperatures could be avoided. Copolymerization of ϵ-caprolactone (CL) with four hydroxy-fatty acids (HFA) from renewable sources, 10-hydroxystearic acid, 12-hydroxystearic acid, ricinoleic acid, and 16-hydroxyhexadecanoic acid, was carried out using commercially available immobilized lipases from Candida antarctica B, Thermomyces lanuginosus, and Pseudomonas stutzeri, as well as a native lipase. MALDI-TOF-MS and 2D-NMR analysis confirmed the formation of linear/branched and cyclic oligomers with average molecular weight around 1200 and polymerization degree up to 15. The appropriate selection of the biocatalyst and reaction temperature allowed the tailoring of the non-cyclic/cyclic copolymer ratio and increase of the total copolymer content in the reaction product above 80%. The catalytic efficiency of the best performing biocatalyst (Lipozyme TL) is evaluated during four reaction cycles, showing excellent operational stability. The thermal stability of the reaction products is assessed based on TG and DSC analysis. This new synthetic route for biobased oligomers with novel functionalities and properties could have promising biomedical applications.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Biocatalytic Route for the Synthesis of Oligoesters of Hydroxy-Fatty acids and ϵ-Caprolactone

et al. 2018

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“…Martin‐Arjol et al () synthesized 10(S)‐hydroxy‐8(E)‐octadecenoic acid mono‐estolides with Novozym 435 catalyst and obtained a maximum of 30% yield. Todea et al () synthesized estolides from 16 and 18 hydroxy fatty acids using several native immobilized lipases and obtained estolides with a degree of polymerization of up to 10 and a conversion of greater than 80%.…”

Section: Synthesis Of Fatty Acid Estolidesmentioning

confidence: 99%

“…It is concluded that the selectivity of lipases was strongly dependent on the position of the hydroxyl group in the hydroxy fatty acid chain, slightly on the hydroxy acid chain length, and on lipase concentration. Hayes and Kleiman (1995) Todea et al (2015) synthesized estolides from 16 and 18 hydroxy fatty acids using several native immobilized lipases and obtained estolides with a degree of polymerization of up to 10 and a conversion of greater than 80%.…”

Section: Lipasesmentioning

confidence: 99%

Fatty Acid Estolides: A Review

Chen

Biresaw

Cermak

et al. 2020

J Americ Oil Chem Soc

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Estolides are bio‐based oils synthesized from fatty acids or from the reaction of fatty acids with vegetable oils. Estolides have many advantages as lubricant base oils, including excellent biodegradability and cold flow properties. Promising applications for estolides include bio‐lubricant base oils and in cosmetics. In this review, the synthesis of estolides from fatty acids using four different types of catalysts, namely, mineral acids, solid acids, lipases, and ionic liquids, is summarized. The summary includes the yield of estolide obtained from varying synthetic conditions (time, temperature, catalyst). Also reviewed are studies comparing the physical properties of estolides synthesized from refined fatty acids against those synthesized from fatty acid mixtures obtained from vegetable oils such as coconut, castor, Physaria, etc. By varying the structure of the fatty acids, estolides with a wide range of pour point, cloud point, and viscosity are synthesized to meet a wide range of application requirements. Currently, estolide products are being commercialized for personal care and lubricant base oils for automotive, industrial, and marine applications. The application areas and the demand for estolides is expected to grow as the drive for switching from petroleum to bio‐based products keeps growing.

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The Role of Reactive Natural Deep Eutectic Solvents in Sustainable Biocatalysis

Buzatu,

Todea,

Peter

et al. 2024

ChemCatChem

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Deep eutectic solvents (DES) advanced in the past decade as the new generation of green and sustainable extraction and reaction media in biorefineries and in a multitude of chemical and biotechnological processes. Particularly, enzyme catalyzed reactions benefit from the specific properties of DESs, which not only ensure good substrate solubility but also enhance enzyme stability and operational efficiency. Recent studies showed that natural deep eutectic solvents comprising choline chloride or betaine as hydrogen bond acceptor and a large spectrum of natural compounds, such as carbohydrates, polyols carboxylic acids, as hydrogen bond donors, can have multiple functions, acting simultaneously as extraction solvent, reaction medium, source of substrate and source as catalyst. This novel approach for the utilization of multifunctional reactive natural deep eutectic solvents (R‐NADES) in catalytic conversions opens the way to the development of greener biocatalytic and chemo‐catalytic processes, with simpler downstream processing and minimal discarded wastes, which will speed up their durable implementation in industry. This paper reviews the innovative applications of R‐NADES in biocatalytic reactions for the synthesis of a large diversity of high value chemicals and materials, including biosurfactants, flavors, biobased building blocks and biobased polymers, with highlight on esterification, transesterification, glycerolysis, polymerization, and redox reactions.

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Selectivity of lipases for estolides synthesis

Cited by 17 publications

References 23 publications

Biocatalytic Route for the Synthesis of Oligoesters of Hydroxy-Fatty acids and ϵ-Caprolactone

Biocatalytic Route for the Synthesis of Oligoesters of Hydroxy-Fatty acids and ϵ-Caprolactone

Fatty Acid Estolides: A Review

The Role of Reactive Natural Deep Eutectic Solvents in Sustainable Biocatalysis

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