Characterization of Polyesters Obtained by Enzyme-Catalyzed Ring-Opening Polymerization of Pentadecanolide at high Temperature

Herrera‐Kao, Wilberth; Cervantes-Uc, M.; Lara-Ceniceros, Tania E.; Aguilar‐Vega, Manuel

doi:10.1557/opl.2015.224

Cited by 3 publications

(3 citation statements)

References 14 publications

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“…Although the eROP reactions have been tested and optimized, , the conditions for eRC reactions are not well examined. To study the feasibility of performing a double esterification for eRC in one synthetic step using iCALB, the eRC reactions of simpler macrocyclic structures (28 and 56 atoms, monomers 3 and 4 , Scheme ) without a bulky moiety were tested.…”

Section: Resultsmentioning

confidence: 99%

“…The use of lipases is an alternative for the synthesis of polyesters, and the activity of such enzymes as catalysts has been extensively investigated. , Several isoforms are now commercially available in the pure and immobilized forms. They are known to hydrolyze triglycerides in the body, but the reaction is reversible and may be used to perform esterification and transesterification reactions under laboratory conditions. − In fact, they have been particularly useful for the ROP of various monomers. − …”

Section: Introductionmentioning

confidence: 99%

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Two-Step Enzymatic Synthesis of Biocompatible Polymers Made from Cholic Acid

Champagne

Lévaray

Zhu

2016

ACS Sustainable Chem. Eng.

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Polyesters are known biodegradable materials that are frequently used for biomedical applications that require biocompatibility. Their synthesis usually requires transition metal catalysts, which may become a source of contamination. In addition, using such compounds translates to extensive purification procedures, which do not agree with green chemistry principles. In addition to being renewable, enzymes such as lipases are milder for biological systems, and were studied for both ring-closure and ring-opening reactions. Here, Candida antarctica lipase B was used in ring-closure, reducing a two-step synthesis to a single step with 58% yield. The bile acid-containing macrocycles were subsequently polymerized with the same enzyme; relatively high molar masses (40 000 g/mol) were obtained. The conditions for the enzymatic ring-closure and ring-opening reactions were established through the reaction of thapsic acid with 1,10-decanediol. The di- and tetralactones afforded semicrystalline polymers with relatively high molar masses. Therefore, lipases were successfully used for both ring-closing reactions and ring-opening polymerizations of large rigid moieties as well as more flexible structures. The use of enzymes for the multistep syntheses shows their utility as a simple and green method for monomer and polymer synthesis with better biocompatibility and tunable properties.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Two-Step Enzymatic Synthesis of Biocompatible Polymers Made from Cholic Acid

Champagne

Lévaray

Zhu

2016

ACS Sustainable Chem. Eng.

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show abstract

“…Recently, oligomers of PPDL were obtained at 70 and 90 °C for 24 h [84]. PPDL can be also synthesized in the presence of HEMA initiator [85], in order to obtain methacrylated aliphatic polyester, which in further studies can be used for formation of macroporous matrices for tissue scaffolds [86].…”

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confidence: 99%

Candida antarctica Lipase B as Catalyst for Cyclic Esters Synthesis, Their Polymerization and Degradation of Aliphatic Polyesters

et al. 2017

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Thiazolium as Single‐Group Bifunctional Catalyst for Selectively Bulk Melt ROP of Cyclic Esters

et al. 2019

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Novel single-group bifunctional hydrogen-bonding catalysts based on thiazolium were developed. The integration of hydrogen-bonding donor and acceptor in a single thiazolium ring not only amplified synergetic effect, but also enhanced the stability and the controllability for catalysis, and hence prompt thiazolium an efficient metal-free catalyst for melt ROP of cyclic esters. More interestingly, thiazolium may form a compacted active center with monomer and initiator (or propagating chain end), thus enabling it to selectively activate lower sterically encumbered substrates in ROP.Ring-opening polymerization (ROP), as one of the most effective strategy to prepare aliphatic polyesters and aliphatic polycarbonates, is critical for biodegradable technology aiming at new generation of biomedical or environmental applications. [1] Comparing with those conventional organometallic coordination catalysts for ROP, [2] the development of metal-free organic catalysts has attracted tremendous attentions in recent years owing to the zero metal residue in polymerized product, which is especially important for applications such as in-vivo implantation, drug delivery and food package. [3] Typical metal-free catalyst, such as enzymes, [4] nucleophilic bases (e. g. NHCs, phosphazene bases), [5] monofunctional hydrogen-bonding systems (e. g. DBU, MTBD), [6] and bifunctional hydrogen-bonding systems (e. g. thioureas/bases, phenols/amines) [7] were widely studied. Among these catalyst systems, bifunctional hydrogenbonding catalysts (Scheme 1A) have been demonstrated to be one of most versatile category. [8] Benefitting from the diversity of their chemical structures, ingeniously designed bifunctional hydrogen-bonding catalysts enabled to be stereoselective, switchable, and reaction process controllable. [9] Bifunctional single-molecule hydrogen-bonding catalyst (Scheme 1B) which integrating hydrogen-bonding donor and acceptor group together in one molecule provided a strategy to amplify the synergetic effect between donor and acceptor of catalyst, and thus allows for the use of mild bases as acceptor. [10] Despite significance progresses have been made, there remains a major challenge for application of metal-free catalysts that few organocatalyst could be applied in an industrial scale of polymerization, which generally performed in bulk-molten state at the temperature higher than the melting point of the resulting polymer. [12] Catalytic activity of typical organic catalysts come from extreme acidity or alkalinity, which is responsible for the instability of them at relatively high temperature. Although some of bifunctional hydrogen-bonding catalysts approximate overall neutrality, they still involve separated acidic donor or basic acceptor, thus leading to undesirable side reaction, such as denaturation and deactivation, and poor controllability of ROP at relatively high temperature. Moreover, the incompatibility between catalyst and cyclic ester monomer also limit their solvent-free application. In this work, bio-derived t...

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Characterization of Polyesters Obtained by Enzyme-Catalyzed Ring-Opening Polymerization of Pentadecanolide at high Temperature

Cited by 3 publications

References 14 publications

Two-Step Enzymatic Synthesis of Biocompatible Polymers Made from Cholic Acid

Two-Step Enzymatic Synthesis of Biocompatible Polymers Made from Cholic Acid

Candida antarctica Lipase B as Catalyst for Cyclic Esters Synthesis, Their Polymerization and Degradation of Aliphatic Polyesters

Thiazolium as Single‐Group Bifunctional Catalyst for Selectively Bulk Melt ROP of Cyclic Esters

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