Part E | 28
706 Part E Marine Microbiology and Biotechnology
zymatic route of the biotransformation of phenylacetonitrile 1. First came the hydrolysis of the nitrile group
and later, hydroxylation (insertion of hydroxyl in the
ortho position of the aromatic ring), because the corresponding carboxylic acids 2a–5a were produced only
by hydrolysis of the cyano group. The biotransformation of nitriles is not trivial, and here we describe an
efficient method for the production of phenylacetic acid
derivatives under mild and environmentally-friendly
conditions.
The induced biotransformation of specific nitrile groups by whole mycelia of the marine fungus
A. sydowii CBMAI 934 was highly effective, using an
eco-friendly methodology. The enzymes produced by
this marine fungus showed substrate specificities typical of arylaliphatic and aliphatic nitrilases and hereto
(aromatic) nitrile hydratases. The enzymes present in
this catalyst system of the fungus A. sydowii CBMAI
934 exhibited activity only on addition of the inducer,
indicating that these enzymes are constructive. The biotransformation of nitriles 1–5, containing a cyano group
attached to an sp
3 carbon atom, to the corresponding
carboxylic acids 1a–5a was achieved with good yields.
The marine fungus A. sydowii CBMAI 934 is thus
a promising biocatalyst for the preparation of important
arylaliphatic and aliphatic carboxylic acids.
References
28.1
H.F. Castro, A.A. Mendes, J.C. Santos: Modificação
de óleos e gorduras por biotransformação, Quim.
Nova 27, 146–156 (2004)
28.2
F. Molinari, D. Romano, R. Gandolfi, R. Gualandris,
N. Ferrara: Biocatalysis for use in pharmaceutical
manufacturing, J. Biotechnol. 131, 98–121 (2007)
28.3
A. Liljeblad, L.T. Kanerva: Biocatalysis as a profound tool in the preparation of highly enantiopure
ˇamino acids, Tetrahedron Asymm. 62(25), 5831–
5854 (2006)
28.4
W.-D. Fessner, N.J. Turner, M.-X. Wang: Biocatalysis – A gateway to industrial biotechnology, Adv.
Synth. Catal. 353, 2189–2190 (2011)
28.5
U. Beshay, A. Moreira: Protease production from
marine microorganism by immobilized cells, Proc.
AIChE Annu. Meet. (Computer Optical, Austin 2004)
28.6
A.M. Vita-Marques, S.P. Lira, R.G.S. Berlinck,
M.H.R. Seleghim, S.R.P. Sponchiado, S.M.T. Tornisielo, M. Barata, C. Pessoa, M.O. Moraes,
B.C. Cavalcanti, G.G.F. Nascimento, A.O. Souza,
F.C.S. Galetti, C.L. Silva, M. Silva, E.F. Pimenta,
O. Thiemann, M.R.Z. Passarini, L.D. Sette: A multiscreening appoach for marine-derived fungal
metabolites and the isolation of cyclodepsipeptides from Beauveria felina, Quim. Nova 31, 1–5
(2008)
28.7
C.P. Loque: Fungos agrícolas associados à macroalgas do litoral do Paraná e Península Antártica
Dissertação (Mestrado em Ecologia e Ciências Biológicas (Instituto de Ciências Exatas e Biológicas
da Universidade Federal de Ouro Preto, Ouro Preto
2009)
28.8
T.S. Bugni, C.M. Ireland: Marine-derived fungi: A
chemically and biologically diverse group of microorganisms, Nat. Prod. Rep. 21, 143–163 (2004)
28.9
M.H. Kossuga, S. Romminger, C. Xavier, M.C. Milanetto, M.Z. Valle, E.F. Pimenta, R.P. Morais, E. Carvalho, C.M. Mizuno, L.F.C. Coradello, V.M. Barroso, B. Vacondio, D.C.D. Javaroti, M.H.R. Seleghim,
B.C. Cavalcanti, C. Pessoa, M.O. Moraes, B.L. Lima,
R. Gonçalves, R.C. Bonugli-Santos, L.D. Sette,
R.G.S. Berlinck: Evaluating methods for the isolation of marine-derived fungal strains and production of bioactive secondary metabolites, Braz.
J. Pharmacogn. 22(2), 257–267 (2012)
28.10 C. Zhan, S.-K. Kim: Research and application of
marine microbial enzymes: Status and prospects,
Mar. Drugs 8, 1920–1934 (2010)
28.11 A. Howden, G.M. Preston: Nitrilase enzymes and
their role in plant-microbe interactions, Microb.
Biotechnol. 2, 441–451 (2009)
28.12 K. Faber: Biotransformations in Organic Chemistry
(Springer, Heidelberg 2011)
28.13 Y. Kato, R. Ooi, Y. Asano: Distribution of aldoxime
dehydratase in microorganisms, Appl. Environ. Microbiol. 66, 2290–2296 (2000)
28.14 A. Banerjee, R. Sharma, U.C. Banerjee: The nitriledegrading enzymes: Current status and future
prospects, Appl. Microbiol. Biotechnol. 60, 33–44
(2002)
28.15 D. Johnson, A. Zabelinskaja-Mackova, H. Griengl:
Oxynitrilases for asymmetric C–C bond formation,
Curr. Opin. Chem. Biol. 4, 103–109 (2000)
28.16 J. Chen, R.-C. Zheng, Y.-G. Zheng, Y.-C. Shen: Microbial Transformation of nitriles to high-value
acids or amides, Adv. Biochem. Eng. Biotechnol.
113, 33–77 (2009)
28.17 D. Zhu, C. Mukherjee, Y. Yang, B.E. Rios, D.T. Gallagher, N.N. Smith, E.R. Biehl, L. Hua: A new nitrilase from Bradyrhizobium japonicum USDA 110
gene cloning, biochemical characterization and
substrate specificity, J. Biotechnol. 133, 327–333
(2008)
28.18 P. Kielbasinski, M. Rachwalski, M. Mikolajczyk, M. Szyrej, M.W. Wieczorek, R. Wijtmans,
F.P.J.T. Rutjes: Enzyme-promoted desymmetrisation of prochiral bis(cynomethyl)sulfoxide, Adv.
Synth. Catal. 349, 1387–1392 (2007)
706 Part E Marine Microbiology and Biotechnology
zymatic route of the biotransformation of phenylacetonitrile 1. First came the hydrolysis of the nitrile group
and later, hydroxylation (insertion of hydroxyl in the
ortho position of the aromatic ring), because the corresponding carboxylic acids 2a–5a were produced only
by hydrolysis of the cyano group. The biotransformation of nitriles is not trivial, and here we describe an
efficient method for the production of phenylacetic acid
derivatives under mild and environmentally-friendly
conditions.
The induced biotransformation of specific nitrile groups by whole mycelia of the marine fungus
A. sydowii CBMAI 934 was highly effective, using an
eco-friendly methodology. The enzymes produced by
this marine fungus showed substrate specificities typical of arylaliphatic and aliphatic nitrilases and hereto
(aromatic) nitrile hydratases. The enzymes present in
this catalyst system of the fungus A. sydowii CBMAI
934 exhibited activity only on addition of the inducer,
indicating that these enzymes are constructive. The biotransformation of nitriles 1–5, containing a cyano group
attached to an sp
3 carbon atom, to the corresponding
carboxylic acids 1a–5a was achieved with good yields.
The marine fungus A. sydowii CBMAI 934 is thus
a promising biocatalyst for the preparation of important
arylaliphatic and aliphatic carboxylic acids.
References
28.1
H.F. Castro, A.A. Mendes, J.C. Santos: Modificação
de óleos e gorduras por biotransformação, Quim.
Nova 27, 146–156 (2004)
28.2
F. Molinari, D. Romano, R. Gandolfi, R. Gualandris,
N. Ferrara: Biocatalysis for use in pharmaceutical
manufacturing, J. Biotechnol. 131, 98–121 (2007)
28.3
A. Liljeblad, L.T. Kanerva: Biocatalysis as a profound tool in the preparation of highly enantiopure
ˇamino acids, Tetrahedron Asymm. 62(25), 5831–
5854 (2006)
28.4
W.-D. Fessner, N.J. Turner, M.-X. Wang: Biocatalysis – A gateway to industrial biotechnology, Adv.
Synth. Catal. 353, 2189–2190 (2011)
28.5
U. Beshay, A. Moreira: Protease production from
marine microorganism by immobilized cells, Proc.
AIChE Annu. Meet. (Computer Optical, Austin 2004)
28.6
A.M. Vita-Marques, S.P. Lira, R.G.S. Berlinck,
M.H.R. Seleghim, S.R.P. Sponchiado, S.M.T. Tornisielo, M. Barata, C. Pessoa, M.O. Moraes,
B.C. Cavalcanti, G.G.F. Nascimento, A.O. Souza,
F.C.S. Galetti, C.L. Silva, M. Silva, E.F. Pimenta,
O. Thiemann, M.R.Z. Passarini, L.D. Sette: A multiscreening appoach for marine-derived fungal
metabolites and the isolation of cyclodepsipeptides from Beauveria felina, Quim. Nova 31, 1–5
(2008)
28.7
C.P. Loque: Fungos agrícolas associados à macroalgas do litoral do Paraná e Península Antártica
Dissertação (Mestrado em Ecologia e Ciências Biológicas (Instituto de Ciências Exatas e Biológicas
da Universidade Federal de Ouro Preto, Ouro Preto
2009)
28.8
T.S. Bugni, C.M. Ireland: Marine-derived fungi: A
chemically and biologically diverse group of microorganisms, Nat. Prod. Rep. 21, 143–163 (2004)
28.9
M.H. Kossuga, S. Romminger, C. Xavier, M.C. Milanetto, M.Z. Valle, E.F. Pimenta, R.P. Morais, E. Carvalho, C.M. Mizuno, L.F.C. Coradello, V.M. Barroso, B. Vacondio, D.C.D. Javaroti, M.H.R. Seleghim,
B.C. Cavalcanti, C. Pessoa, M.O. Moraes, B.L. Lima,
R. Gonçalves, R.C. Bonugli-Santos, L.D. Sette,
R.G.S. Berlinck: Evaluating methods for the isolation of marine-derived fungal strains and production of bioactive secondary metabolites, Braz.
J. Pharmacogn. 22(2), 257–267 (2012)
28.10 C. Zhan, S.-K. Kim: Research and application of
marine microbial enzymes: Status and prospects,
Mar. Drugs 8, 1920–1934 (2010)
28.11 A. Howden, G.M. Preston: Nitrilase enzymes and
their role in plant-microbe interactions, Microb.
Biotechnol. 2, 441–451 (2009)
28.12 K. Faber: Biotransformations in Organic Chemistry
(Springer, Heidelberg 2011)
28.13 Y. Kato, R. Ooi, Y. Asano: Distribution of aldoxime
dehydratase in microorganisms, Appl. Environ. Microbiol. 66, 2290–2296 (2000)
28.14 A. Banerjee, R. Sharma, U.C. Banerjee: The nitriledegrading enzymes: Current status and future
prospects, Appl. Microbiol. Biotechnol. 60, 33–44
(2002)
28.15 D. Johnson, A. Zabelinskaja-Mackova, H. Griengl:
Oxynitrilases for asymmetric C–C bond formation,
Curr. Opin. Chem. Biol. 4, 103–109 (2000)
28.16 J. Chen, R.-C. Zheng, Y.-G. Zheng, Y.-C. Shen: Microbial Transformation of nitriles to high-value
acids or amides, Adv. Biochem. Eng. Biotechnol.
113, 33–77 (2009)
28.17 D. Zhu, C. Mukherjee, Y. Yang, B.E. Rios, D.T. Gallagher, N.N. Smith, E.R. Biehl, L. Hua: A new nitrilase from Bradyrhizobium japonicum USDA 110
gene cloning, biochemical characterization and
substrate specificity, J. Biotechnol. 133, 327–333
(2008)
28.18 P. Kielbasinski, M. Rachwalski, M. Mikolajczyk, M. Szyrej, M.W. Wieczorek, R. Wijtmans,
F.P.J.T. Rutjes: Enzyme-promoted desymmetrisation of prochiral bis(cynomethyl)sulfoxide, Adv.
Synth. Catal. 349, 1387–1392 (2007)