Enzymatic synthesis supercritical carbon dioxide

Dumont, T. Barth, D. Perrut, M. Continuous Synthesis of Ethyl Myristate by Enzymatic Reaction in Supercritical Carbon Dioxide. J. Supercrit. Fluids 1993, 6, 85-89. 

Kamat, S. Critchley, G. Beckman, E. J. Russell, A. J. Biocatalytic Synthesis of Acrylates in Organic Solvents and Supercritical Fluids HI. Does Carbon Dioxide Covalently Modify Enzymes Biotechnol. Bioeng. 1995, 46, 610-620. Kamihira, M. Taniguchi, M. Kobayashi, T. Synthesis of Aspartame Precursors by Enzymatic Reaction in Supercritical Carbon Dioxide. Agric. Biol. Chem. 1987, 51, 3427-3428. 

Kumar, R., G. Madras and J. Modak, Enzymatic Synthesis of Ethyl Palmitate in Supercritical Carbon Dioxide, Industrial Engineering Chemistry Research, 43, 1568-1573 (2004). 

Reetz, M.T., W. Wiesenhofer, G. Francio and W. Leitner, Continuous Flow Enzymatic Kinetic Resolution and Enantiomer Separation Using Ionic Liquid/Supercritical Carbon Dioxide Media, Advanced Synthesis Catalysis, 345, 1221-1228 (2003). 

The present work reports results and observations on the enzymatic synthesis of oleyl oleate (which is a synthetic analogue of jojoba oil) in supercritical carbon dioxide. Special stress was laid on the comparison between batch and continuous systems for the above mentioned synthesis. Influence of different reaction parameters on the reaction yield and initial reaction rates was studied. 

Reaction performance. Supercritical carbon dioxide was used as a reaction media for the enzymatic synthesis of oleyl oleate directly from oleic acid and oleyl alcohol. Reaction was catalyzed by immobilized lipase from Rhizomucor miehei-Ltpozyme IM. Reactions were carried out in the high pressure batch and continuous reactor. 

Habulin, M., Sabeder, S., Sampedro, M.A., and Knez, Z. 2008. Enzymatic synthesis of citronellol laurate in organic media and in supercritical carbon dioxide. Biochemical Engineering Journal, 42 6-12. 

Romero, M.D. Calvo, L. Alba, C. Habulin, M. Primozic, M. Knez, Z. Enzymatic synthesis of isoamyl acetate with immobilized Candida ant-arc tica lipase in supercritical carbon dioxide. J. Supercritic. Fluids 2005, 33 (1), 77-84. 

Ikushima Y, Salto N, Yokoyama T, Hatakeda K, Ito S, Aral M, Blanch HW. Solvent effects on enzymatic ester synthesis in supercritical carbon dioxide. Chem Lett 1993 109-112. 

Hernandez FJ, de los Rios AP, Gomez D, Rubio M, ViUora G. A new recirculating enzymatic membrane reactor for ester synthesis in ionic liquid/supercritical carbon dioxide biphasic systems. Appl Catal B 2006 67 121-126. 

Ionic Liquids/Supercritical Carbon Dioxide as Advantageous Biphasic Systems in Enzymatic Synthesis... 

Fig. 8.1 Experimental set-up of the recirculating enzymatic membrane reactor used for the synthesis of butyl propionate from vinyl propionate and 1-butanol catalysed by Candida antarctica lipase B in supercritical carbon dioxide and supercritical carbon dioxide/ionic liquid biphasic system [17]...

Hemdndez FJ, de los Rfos AP, Gomez D et al (2007) Understanding the chemical reaction and mass-transfer phenomena in a recirculating enzymatic membrane reactor for green ester synthesis in ionic Uquid/supercritical carbon dioxide biphasic systems. J Supercrit Flitids 43 303-309... 

Heise, Palmans, de Geus, Villarroya and their collaborators (17,41,42) have been working on a chemoenzymatic cascade synthesis to prepare block copolymers. They combine enzymatic ring-opening polymerization (eROP) and atom transfer radical polymerization (ATRP). The synthesis of block copolymers was successful in two consecutive steps, i.e., eROP followed by ATRP. In the one-pot approach, block copolymers could be obtained by sequential addition of the ATRP catalyst, but side reactions were observed when all components were present from at the onset of reactions. A successful one-pot synthesis was achieved by conducting the reaction in supercritical carbon dioxide. 

We investigated the chemoenzymatic synthesis of block copolymers combining eROP and ATRP using a bifunctional initiator. A detailed analysis of the reaction conditions revealed that a high block copolymer yield can be realized under optimized reaction conditions. Side reactions, such as the formation of PCL homopolymer, in the enzymatic polymerization of CL could be minimized to < 5 % by an optimized enzyme (hying procedure. Moreover, the structure of the bifunctional initiator was foimd to play a major role in the initiation behavior and hence, the yield of PCL macroinitiator. Block copolymers were obtained in a consecutive ATRP. Detailed analysis of the obtained polymer confirmed the presence of predominantly block copolymer structures. Optimization of the one-pot procedure proved more difficult. While the eROP was compatible with the ATRP catalyst, incompatibility with MMA as an ATRP monomer led to side-reactions. A successfiil one-pot synthesis could only be achieved by sequential addition of the ATRP components or partly with inert monomers such as /-butyl methacrylate. One-pot block copolymer synthesis was successful, however, in supercritical carbon dioxide. Side reactions such as those observed in organic solvents were not apparent. 

Mori T, Kobayashi A, Okahata Y (1998) Biocatalytic esterification in supercritical carbon dioxide using a Upid-coated lipase. Chem Lett 9 921-922 Mori M, Gomez Garcia R, BeUeviUe MP (2005) A new way to conduct enzymatic synthesis in an active membrane using ionic liquids as catalyst support. Catal Today 104 313-317 Morley KL, Kazlauskas RJ (2005) Improving enzyme properties when are closer mutations better TIBTECH 23(5) 231-237... 

Hernandez, F. J., A. P. de los Rfos, D. Gomez, M. Rubio, and G. Vfllora. 2006. A New Recirculating Enzymatic Membrane Reactor for Ester Synthesis in Ionic Liquid/ Supercritical Carbon Dioxide Biphasic Systems. Applied Catalysis B Environmental Cl (1-2) 121-126. 

Romero, M. D., L. Calvo, C. Alba, M. Habulin, M. Primozic, and Z. Knez. 2005. Enzymatic Synthesis of Isoamyl Acetate with Immobilized Candida Antarctica Lipase in Supercritical Carbon Dioxide. Journal of Supercritical Fluids 33 (l) 77-84. 

Rathore, V., and G. Madras. 2007. Synthesis of Biodiesel from Edible and Non-Edible Oils in Supercritical Alcohols and Enzymatic Synthesis in Supercritical Carbon Dioxide. Fuel 86 (17-18) 2650-2659. 

Methyl oleate (biodiesel) was synthesized by methanolysis of triolein using immobilized C. antarctica lipase B (Novozym 435) (Figure 3.26) [36]. The operational stability of the immobilized lipase was improved by coating with ILs such as 1-methyl-3-octadecylimidazolium hexafluorophosphate A continuous enzymatic reactor for biodiesel synthesis in supercritical carbon dioxide at 60°C and 180 bar was eralu-ated. This provided up to 82% biodiesel yield after 12 cycles at 4 h per cycle... 

P. Lozano,. M. Bernal, M. Vaultier, Towards continuous sustainable processes for enzymatic synthesis of biodiesel in hydrophobic ionic liquids/supercritical carbon dioxide biphasic systems, Fuel 90 (2011) 3461-3467. 

Rathore, V., Madras, G., 2007. Synthesis of biodiesel fiom edible and non-edible oils in supercritical alcohols and enzymatic synthesis in supercritical carbon dioxide. Fuel 86, 2650-2659. 

Chapters are also included on yeast-mediated stereoselective biocatalysis, stereoselective synthesis of steroids, chemo-enzymatic synthesis of enantiopure arylpropionic acids, supercritical carbon dioxide as a solvent in enzyme catalysis, state-of-the-art techniques in enzyme immobilization, biocatalysis by polyethylene glycol-modified enzymes, and enzymatic deprotection techniques in organic synthesis. 

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