Enzymatic synthesis of poly(ɛ-caprolactone) in supercritical carbon dioxide medium by means of a variable-volume view reactor

Rosso, Sibele R.; Bianchin, Emanuel; Oliveira, Débora de; Oliveira, J. Vladimir; Ferreira, Sandra R.S.

doi:10.1016/j.supflu.2013.02.009

Cited by 42 publications

(11 citation statements)

References 40 publications

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“…Polymerization reactions were conducted in a high‐pressure variable‐volume view cell, similar to those used by Rosso et al A magnetic stirrer bar provided agitation during reaction. Previously dried Novozym 435 (0.4 g), ω‐PDL (4.0 g), and the solvent (8.0 g) were weighed on a precision scale balance and placed inside the reactor, which was immediately closed.…”

Section: Methodsmentioning

confidence: 99%

“…To enable the use of solvents with boiling points below 70 °C, an apparatus or reactor that maintains the solvent in liquid form even if reaction temperature of the medium is higher than its boiling point can be used. This kind of reactor, called variable‐volume view reactor, is based on an equilibrium cell for phase‐equilibrium determinations and uses high pressures to maintain all solvent in liquid phase, has already been reported for polymerization of ε‐caprolactone . The reactor has a maximum internal volume of 27 mL, is equipped with a movable piston to allow pressure control and has two sapphire windows for visual observation of the reaction.…”

Section: Introductionmentioning

confidence: 99%

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Enzymatic ring opening polymerization of ω‐Pentadecalactone in different solvents in a variable‐volume view reactor

Polloni

Rebelatto

Veneral

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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The use of enzymes as catalyst in polyesters production enables the creation of new materials for use in biomedical applications. In this work, a polyester derived from xpentadecalactone was synthesized. The polymer synthesis was performed using lipase Novozym 435 as catalyst and several solvents at 70 8C. The use of a closed variable volume reactor allowed the use of solvents with a boiling point lower than the reaction temperature, without affecting the ratio of solvent to monomer. Yields above 49 wt% and high molecular weights were obtained for all tested solvents. Dichloromethane (DCM) and chloroform were used as solvents for the evaluation of water content on enzyme and reaction time over the properties of final polymer. The amount of water on enzyme has a direct influence on reaction yields though higher molecular weights were obtained in reactions with lower water content. Yields of around 90 wt% were obtained in 6 h of reaction and molecular weights up to 42,300 and 51,900 g mol 21 were obtained in 2 h of reactions using DCM and chloroform as solvents.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Enzymatic ring opening polymerization of ω‐Pentadecalactone in different solvents in a variable‐volume view reactor

Polloni

Rebelatto

Veneral

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…In addition to carrier design, the SCF technology is also used to synthesize certain biodegradable polymers by rapid depressurization at the end of polymerization. [ 100 ] Indeed, the SAS process is preferred to co-precipitate desired molecules of interest and is beneficial over other conventional methods. The plasticization phenomena of polymers in compressed SCF has a great impact on their physical and mechanical properties, which alters glass transition temperature of the polymer and allows to design advanced materials.…”

Section: Drug Deliverymentioning

confidence: 99%

Supercritical Fluid Technology: An Emphasis on Drug Delivery and Related Biomedical Applications

Kankala

Zhang

Wang

et al. 2017

Adv Healthcare Materials

225

184

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During the past few decades, supercritical fluid (SCF) has emerged as an effective alternative for many traditional pharmaceutical manufacturing processes. Operating active pharmaceutical ingredients (APIs) alone or in combination with various biodegradable polymeric carriers in high-pressure conditions provides enhanced features with respect to their physical properties such as bioavailability enhancement, is of relevance to the application of SCF in the pharmaceutical industry. Herein, recent advances in drug delivery systems manufactured using the SCF technology are reviewed. We provide a brief description of the history, principle, and various preparation methods involved in the SCF technology. Next, we aim to give a brief overview, which provides an emphasis and discussion of recent reports using supercritical carbon dioxide (SC-CO2) for fabrication of polymeric carriers, for applications in areas related to drug delivery, tissue engineering, bio-imaging, and other biomedical applications. We finally summarize with perspectives.

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“…Santos et al use fractional factorial design to evaluate the reaction conditions of enzymatic polymerization of ϵ‐caprolactone in scCO 2 and reported the highest M n of 7420 g mol ‐1 (PDI 1.96). The Ferreira group conducted the enzymatic ROP of ϵ‐caprolactone in scCO 2 and obtained PCL with M n up to 13 700 g mol ‐1 (90% yield, PDI 1.2–1.7); they also noted that the solvent/monomer ratio is a critical factor for controlling the molecular weight (1:2 ratio gave the highest molecular weights). The Oliveira group performed the enzymatic polymerization of ϵ‐caprolactone in liquified petroleum gas (LPG) and scCO 2 catalyzed by Novozym 435, and observed that the batch reaction in LPG gave PCL with M n up to 11 800 g mol ‐1 (68% yield and PDI 1.6) while in scCO 2 , the batch reaction afforded M n up to 15 000 g mol ‐1 (81% yield, PDI 1.2–1.7) and the Packed‐Bed Reactor produced M n up to 21 700 g mol ‐1 (60.1% yield, PDI 1.7–2.1).…”

Section: Enzymatic Rop In Co2mentioning

confidence: 99%

Enzymatic ring‐opening polymerization (ROP) of polylactones: roles of non‐aqueous solvents

Zhao

2017

J of Chemical Tech & Biotech

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Aliphatic polyesters such as polylactides (PLAs) and other polylactones are thermoplastic, biodegradable and biocompatible polymers with the potential to replace petro-chemical-based synthetic polymers. A benign route for synthesizing these polyesters is through the enzyme-catalyzed ring-opening polymerization (ROP) reaction; this type of enzymatic process is very sensitive to reaction conditions such as solvents, water content and temperature. This review systematically evaluates the crucial roles of different solvents (such as solvent-free/in bulk, organic solvents, supercritical fluids, ionic liquids, and aqueous biphasic systems) on the degree of polymerization and polydispersity. In general, many studies suggest that hydrophobic organic solvents with minimum water contents lead to efficient enzymatic polymerization and subsequently high molecular weights of polyesters; the selection of solvents is also limited by the reaction temperature, e.g. the ROP of lactide is often conducted at above 100 ∘ C, therefore, the solvent typically needs to have its boiling point above this temperature. The use of supercritical fluids could be limited by its scaling-up potential, while ionic liquids have exhibited many advantages including their low-volatility, high thermal stability, controllable enzyme-compatibility, and a wide range of choices. However, the fundamental and mechanistic understanding of the specific roles of ionic liquids in enzymatic ROP reactions is still lacking. Furthermore, the lipase specificity towards L-and D-lactide is also surveyed, followed by the discussion of engineered lipases with improved enantioselectivity and thermal stability. In addition, the preparation of polyester-derived materials such as polyester-grafted cellulose by the enzymatic ROP method is briefly reviewed.

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Enzymatic synthesis of poly(ɛ-caprolactone) in supercritical carbon dioxide medium by means of a variable-volume view reactor

Cited by 42 publications

References 40 publications

Enzymatic ring opening polymerization of ω‐Pentadecalactone in different solvents in a variable‐volume view reactor

Enzymatic ring opening polymerization of ω‐Pentadecalactone in different solvents in a variable‐volume view reactor

Supercritical Fluid Technology: An Emphasis on Drug Delivery and Related Biomedical Applications

Enzymatic ring‐opening polymerization (ROP) of polylactones: roles of non‐aqueous solvents

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