Efficient production of l-menthol in a two-phase system with SDS using an immobilized Bacillus subtilis esterase

Abstract

Background

levo-Menthol is an important flavoring chemical, which can be prepared by enantioselective enzymatic hydrolysis of dl-menthyl esters. A recombinant esterase (BsE) cloned from Bacillus subtilis 0554 shows excellent enantioselectivity to dl-menthyl acetate and has been immobilized using cross-linked enzyme aggregates. Though BsE has relatively high substrate tolerance, the conversion of dl-menthyl acetate decreased sharply with the increase of substrate loading from 1 to 3 M in mono-aqueous system, which might be due to the severe inhibition of enzyme activity at extremely high load of substrate or product. In this work, enzymatic hydrolysis of dl-menthyl acetate with an extremely high load using the immobilized CLEA-BsE was investigated in an organic-aqueous biphasic system containing surfactant to establish a promising bioprocess for large-scale production of l-menthol.

Results

An efficient biphasic reaction system of pentanol-water containing sodium dodecyl sulfate (SDS) was developed for improving enantioselective hydrolysis of dl-menthyl acetate to produce l-menthol by immobilized BsE. Under the optimized reaction conditions, l-menthol was produced in >97% enantiomeric excess (ee) at a substrate load of up to 3.0 M with >40% conversion.

Conclusions

All the positive features demonstrate the potential applicability of the bioprocess for the large-scale production of l-menthol.

Keywords

l-Menthol / Enantioselective hydrolysis / Organic-aqueous biphasic system / dl-Menthyl acetate / Immobilized Bacillus subtilis esterase

References

[1.] Clark GS. Menthol. Perfum Flavor, 1998, 23: 33-46.

[2.] Clark GS. Aroma chemical profile: menthol. Perfum Flavor, 2007, 32: 38-47.

[3.] Rendler S, Auer G, Keller M, Oestreich M. Preparation of a privileged silicon-stereogenic silane: classical versus kinetic resolution. Adv Synth Catal, 2006, 348: 1171-1182.

[4.] Cattaruzza F, Fares V, Flamini A, Prosperi T (2006) Synthesis of enantiomeric menthol derivatives for forming and probing chiral surfaces. X-ray crystal and molecular structures of (+)-(1S,2R,5S)-1-(2-tricyanovinyl-1H-pyrrol-1-yl-methoxy)-2-isopropyl-5-methylcycl-ohexane. Tetrahedron-Asymmetry 17:1296–1300

[5.] Michael M. Hot market for a cool chemical. Chem Eng News, 2010, 88: 15-16.

[6.] Fleischer J, Bauer K, Hopp R (1976) Separating optically pure d-l-isomers of menthol, neomenthol and isomenthol. US Patent 3,943,181,ᅟ, p

[7.] Hopp R, Lawrence BM. Lawrence BM. Natural & synthetic menthol. Mint: the genus Mentha, 2006, Boca Raton: CRC, 389.

[8.] Tani K. Asymmetric isomerization of allylic compounds and the mechanism. Pure Appl Chem, 1985, 57: 1845-1854.

[9.] Akutagawa S. Enantioselective isomerization of allylamine to enamine: practical asymmetric synthesis of (−)-menthol by Rh–BINAP catalysts. Top Catal, 1997, 4: 271-274.

[10.] Akutagawa S. Asymmetric synthesis by metal BINAP catalysts. Appl Catal A-Gen, 1995, 128: 171-207.

[11.] Sumi K, Kumobayashi H. Rhodium/Ruthenium applications. Top Organomet Chem, 2004, 6: 63-95.

[12.] Chaplin JA, Gardiner NS, Mitra RK. Process for preparing (−)-menthol and similar compounds. US Patent 7,026,144, 2006, ᅟ: ᅟ.

[13.] Brad D, Reddy S, Mboniswa B, Steenkamp LH, Rousseau AL, Parkinson CJ, Chaplin J, Mitra RK, Moutlana T, Marais SF, Gardiner NS (2012) Biocatalytic enantiomeric resolution of l-menthol from an eight isomeric menthol mixture through transesterification. J Mol Catal B-Enzym 75:1–10

[14.] Xu JH, Kawamoto T, Tanaka A. Efficient kinetic resolution of dl-menthol by lipase-catalyzed enantioselective esterification with acid anhydride in fed-batch reactor. Appl Microbiol Biotechnol, 1995, 43: 402-407.

[15.] Ngo-Thi MT, Yin JG, Pan J, Zheng GW, Xu JH. Enantioselective hydrolysis of dl-menthyl benzoate by cell-free extract of newly isolated Acinetobacter sp. ECU2040. Appl Biochem Biotechnol, 2013, 170: 1974-1981.

[16.] Wang DL, Nag A, Lee GC, Shaw JF (2002) Factors affecting the resolution of dl-menthol by immobilized lipase-catalyzed esterification in organic solvent. J Agric Food Chem 50:262–265

[17.] Vorlova S, Bornscheuer UT, Gatfield I, Hilmer JM, Bertram HJ, Schmid RD. Enantioselective hydrolysis of D, L-menthyl benzoate to L-(−)-menthol by recombinant Candida rugosa lipase L1P1. Adv Synth Catal, 2002, 344: l152-1155.

[18.] Yu LJ, Xu Y, Wang XQ, Yu XW (2007) Highly enantioselective hydrolysis of DL-menthyl acetate to L-menthol by whole-cell lipase from Burkholderia cepacia ATCC25416. J Mol Catal B-Enzym 47:149–154

[19.] Meng Y, Wu JP, Xu G, Yang LR (2010) Production of L-menthol by immobilized enzyme-catalyzed diastereoselective transesterification. Chin J Bioprocess Eng 8:39–44

[20.] Ren MY, Bai S, Sun Y. Resolution of (±)-menthol in ionic liquid catalyzed by immobilized lipase on magnetic microspheres. Chin J Bioprocess Eng, 2009, 7: 16-20.

[21.] Xu JH, Zhu J, Takuo K, Atsuo T, Hu Y. Comparison of acid anhydrides with carboxylic acids in enantioselective enzymatic esterification of racemic menthol. Chin J Biotechnol, 1997, 13: 387-393.

[22.] Xu G, Li M, Sun MM, Wu JP, Yang LR. Screening of stereoselective lipase and its application in resolution of menthol. Chin J Bioprocess Eng, 2013, 11: 1-4.

[23.] Zheng GW, Yu HL, Zhang JD, Xu JH (2009) Enzymatic production of l-menthol by a high substrate concentration tolerable esterase from newly isolated Bacillus subtilis ECU0554. Adv Synth Catal 351:405–414

[24.] Zheng GW, Pan J, Yu HL, Ngo-Thi MT, Li CX, Xu JH (2010) An efficient bioprocess for enzymatic production of l-menthol with high ratio of substrate to catalyst using whole cells of recombinant E. coli. J Biotechnol 150:108–114

[25.] Zheng GW, Yu HL, Li CX, Pan J, Xu JH (2011) Immobilization of Bacillus subtilis esterase by simple cross-linking for enzymatic resolution of dl-menthyl acetate. J Mol Catal B-Enzym 70:138–143

[26.] Zhang ZJ, Pan J, Liu JF, Xu JH, He YC, Liu YY (2011) Significant enhancement of (R)-mandelic acid production by relieving substrate inhibition of recombinant nitrilase in toluene-water biphasic system. J Biotechnol 152:24–29

[27.] Li YG, Xing JM, Xiong XC, Li WL, Gao HS, Liu HZ. Improvement of biodesulfurization activity of alginate immobilized cells in biphasic systems. J Ind Microbiol Biotechnol, 2008, 35: 145-150.

[28.] Liu YY, Xu JH, Hu Y. Enhancing effect of Tween-80 on lipase performance in enantioselective hydrolysis of ketoprofen ester. J Mol Catal B-Enzym, 2000, 10: 523-529.

[29.] Chen CS, Fujimoto Y, Girdaukas G, Sih CJ. Quantitative analyses of biochemical kinetic resolutions of enantiomers. J Am Chem Soc, 1982, 104: 7294-7299.

[30.] Wang LJ, Li CX, Ni Y, Zhang J, Liu X, Xu JH (2011) Highly efficient synthesis of chiral alcohols with a novel NADH-dependent reductase from Streptomyces coelicolor. Bioresour Technol 102:7023–7028

[31.] Ni Y, Li CX, Wang LJ, Zhang J, Xu JH. Highly stereoselective reduction of prochiral ketones by a bacterial reductase coupled with cofactor regeneration. Org Biomol Chem, 2011, 9: 5463-5468.

[32.] Mori S, Yumoto H, Matsumi R, Nishigaki T, Ebara Y, Ueji S. A method to greatly improve the enantioselectivity of lipase-catalyzed hydrolysis using sodium dodecyl sulfate (SDS) as an additive. Tetrahedron: Asymmetry, 2005, 16: 3698-3702.