Enzymatic ring‐opening polymerization of ε‐caprolactone by Yarrowia lipolytica lipase in ionic liquids

Abstract

Yarrowia lipolytica (YLL), Candida rugosa (CRL), and porcine pancreatic lipase (PPL) were employed successfully as catalysts in the enzymatic ring‐opening polymerization (ROP) of ε‐caprolactone in the presence of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([EMIM][BF4]), 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIM][BF4]), 1‐butylpyridinium tetrafluoroborate ([BuPy][BF4]), 1‐butylpyridinium trifluoroacetate ([BuPy][CF3COO]), 1‐ethyl‐3‐methylimidazolium nitrate ([EMIM][NO3]) ionic liquids. Poly(ε‐caprolactone)s (PCLs) with molecular weights (Mn) in the range of 300–9000 Da were obtained. 1H‐ and 13C‐NMR analyses on PCLs formed by YLL, CRL, and PPL showed asymmetric telechelic α‐hydroxy‐ω‐carboxylic acid end groups. Differences between CP‐MAS and MAS spectra are observed and discussed in terms of morphology. MALDI‐TOF spectra show the formation of at least seven species. Differential scanning calorimetry (DSC) and Wide Angle X‐Ray Scattering (WAXS) results demonstrate the high degree of crystallinity present in all the polyesters. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5792–5805, 2009

Effect of ionic liquids on the structural, thermal, and in vitro degradation properties of poly(ε‐caprolactone) synthesized in the presence of Candida antarctica lipase B

“…For PCL synthesized in [bmim][PF 6 ] at 60 °C and 80 °C, we found these values as: M n 2400 Da; M w /M n = 1.49 and M n 3000 Da; M w /M n =1.52, respectively. The curve profiles show multimodal distribution, confirming the presence of different species (either linear or cyclic oligomers) that are not in a fast equilibrium with each other . These results are consistent with those obtained by NMR and MALDI‐TOF analysis.…”

“…Figure (i) shows the MALDI‐TOF mass spectra of the synthesized PCL from ROP of CL using CALB as catalyst. The mass range below 1000 Da (removed from the spectra) was dominated with peaks resulted from matrix‐fragments and metal ions . The curve profiles indicated a bimodal distribution.…”

Predictors of an optimal clinical outcome with alcohol septal ablation for obstructive hypertrophic cardiomyopathy

“…Enzymes have been used extensively in organic chemistry for the synthesis of small molecules,1, 2 and in the past 2 decades the use of enzymes has expanded the toolbox for polymer chemists 3–9. The main advantages of enzyme catalysis include: high efficiency under mild conditions, biocompatibility along with high stereo‐ regio‐ and chemoselectivity 10, 11.…”

Enzymatic Ring‐Opening Polymerization of Lactones: Traditional Approaches and Alternative Strategies

“…Besides CAL-B, other lipases, such as Yarrowia lipolytica lipase (YLL), Candida rugosa lipase (CRL), and porcine pancreatic lipase (PPL) were also employed successfully as catalysts in the eROP of ɛ-CL in the presence of ionic liquids ( Table 5, Entry 2). [114] Poly-ɛ-CL with M n of 8000 Da was obtained catalyzed by YLL in 1-butylpyridinium tetrafluoroborate ([BuPy][BF 4 ]). Gumel et al investigated the use of IL together with ultrasonic irradiation for the eROP of ɛ-CL (Table 5, Entry 5).…”