Pseudomonas NCIMB

Sulfoxidations are not restricted to MOs but can also be carried out by dioxygenases. For example. Pseudomonas mutant strain UV4 producing a toluene dioxygenase (TOO) and Pseudomonas NCIMB 8859 expressing a naphthalene dioxygenase (NDO) were used to oxidize aryl sulfides to antipodal chiral sulfoxides [203]. 

Cyclopentanone monooxygenase Pseudomonas NCIMB 9872 1 3-4 identical subunits NADPH 200 (54-58 each) 1 FAD per subunit 7.7 [48]... 

Further studies also been performed on the bicydo[3.2.0]heptan-6-one series of compounds1124, 125]. These results are summarised in Fig. 16.5-35. Oxidation of this ketone with Pseudomonas NCIMB 9872 gave the (IS, 5 R)-lactone of low optical purity (23% ee) with only small amounts (5%) of the isomeric lactone, whereas its oxidation with an Acinetobacter sp. gave these lactones in a 9 1 ratio and a modest yield, a result quite different from the one described previously. However, oxidation of 7-mdo-methylbicydo[3.2.0]hept-2-en-6-one using either Pseudomonas sp. or Acinetobacter sp. produced optically pure (ee > 96 %) of both lactones in equal quantities... 

GubnCT R, Beech IB (2000) The effect of extracellular polymeric substances on the attachment of Pseudomonas NCIMB 2021 to AISI 304 and 316 stainless steel. Biofouling 15(1—3) 25—36... 

S. J. Yuan and S. O. Pehkonen, AFM study of microbial colonization and its deleterious effect on 304 stainless steel by Pseudomonas NCIMB 2021 and Desulfovibrio desulfuricans in simulated seawater, Corros. Set. 51 1372-1385 (2009). 

Purified CHMOs from Acinetobacter sp. NCIB 9871 and Pseudomonas NCIMB 10007 coupled with dehydrogenases to generate NADPH/NADH in situ was used to prepare (1R,5S)- and (i5, 5/ )-lactones [29,30]. These chiral lactones are important synthons used in the synthesis of prostaglandins. 

Gao X, CL Tan, CC Yeo, CL P (2005) Molecular and biochemical characterization of the x/ D-encoded 3-hydroxybenzoate 6 hydroxylase involved in the degradation of 2,5-xylenol via the gentisate pathway in Pseudomonas alcaligenes NCIMB 9S61. J Bacterial 187 7696-7702. 

Eernandez RE et al. (2004) Enzymatic assimilation of cyanide via pterin-dependent oxygenolytic cleavage to ammonia and formate in Pseudomonas fiuorescens NCIMB 11764. Appl Environ Microbiol 70 121-128. 

Wang C-S, DA Kunz, BJ Venables (1996) Incorporation of molecular oxygen and water during enzymatic oxidation of cyanide by Pseudomonas fluorescens NCIMB 11764. Appl Environ Microbiol 62 2195-2197. 

Best DJ, NC Floyd, A Magalhaes, A Bnrfield, PM Rhodes (1987) Initial steps In the degradation of alpha-pinene by Pseudomonas fluorescens NCIMB 11671. Biocatalysis 1 147-159. 

Althongh the prodnct from the transformation of toluene by mntants of Pseudomonas putida lacking dehydrogenase activity is the cis-2R,3S dihydrodiol, the cis-2S,3R dihydrodiol has been synthesized from 4-iodotoluene by a combination of microbiological and chemical reactions. P. putida strain UV4 was used to prepare both enantiomers of the di-dihydrodiol, and iodine was chemically removed nsing H2 -Pd/C. Incubation of the mixtnre of enantiomers with P. putida NCIMB 8859 selectively degraded the 2R,3S componnd to prodnce toluene cis-2S,3R dihydrodiol (Allen et al. 1995). 

Kunz DA, Nagappan O, Silva-Avalos J, et al. 1992. Utilization of cyanide as a nitrogenous substrate by Pseudomonas fluorescens NCIMB 11764 Evidence for multiple pathways of metabolic conversion. Appl Environ Microbiol 58(6) 2022-2029. 

It is noteworthy that, in contrast to mammalian systems, the majority of bacterial strains exhibited sufficient activity even when the cells were grown under non-optimized conditions. Since enzyme induction is still a largely empirical task, cells were grown on standard media in the absence of inducers. Furthermore, all attempts to induce epoxide hydrolase activity in Pseudomonas aeruginosa NCIMB 9571 and Pseudomonas oleovorans ATCC 29347 by growing the cells on an alkane (decane) or alkene (1-octene) as the sole carbon source failed [27]. 

More recently, the degradation of a-pinene by Pseudomonas jluorescens NCIMB 11671 was described [97,98]. A novel pathway for the microbial breakdown of a-pinene (119) was proposed, Fig. (23). The attack is initiated by enzymatic oxygenation of the 1,2-double bond to form the epoxide (127). This epoxide then undergoes rapid rearrangement to produce a novel diunsaturated aldehyde, occurring as two isomeric forms. The primary product of the reaction (Z)-2-methyl-5-isopropylhexa-2,5-dien-l-al (trivial name isonovalal) (128) can undergo chemical isomerisation to the -form (novalal) (129). Isonovalal, the native form of... 

Whole-cell enantioselective oxidation of sulfides is in fast development and of preparative interest. Additional examples with Acinetobacter sp NCIMB 9871, Pseudomonas sp. NCIMB 9872, and Xanthobacter autotrophicus DSM 431 have been reported [113,114]. 

Gagnon R, Grogan G et al (1995) Enzymatic Baeyer-Villiger oxidations of some bicyclo [2.2.1]heptan-2-ones using monooxygenases from Pseudomonas putida NCIMB 10007 enantioselective preparation of a precursor of azadirachtin. J Chem Soc Perkin Trans 1 1505-1511... 

Dorr, P. and Knowles, C. 1989. Cyanide oxygenase and cyanase activities of Pseudomonas fluorescens NCIMB 11764. FEMS Microbiology Letters, 60 289-94. 

El-Sayed AK, Hothersall J, Cooper SM, Stephens ER, Simpson TJ, Thomas CM. Characterization of the mupirocin biosynthesis gene cluster from Pseudomonas fluorescens NCIMB 10586. Chem. Biol. 2003 10 419-430. 

It has been noted in Section 4.4.1.1 that naphthalene dioxygenase from a strain of Pseudomonas sp. also carries out enantiomeric monooxygenation of indan and dehydrogenation of indene (Gibson et al. 1995), and the stereospecific hydroxylation of (R)-l-indanol and (S)-l-indanol to rfs-indan-l,3-diol and trans (lS,3S)-indan-l,3-diol (Lee et al. 1997) the indantriols are also formed by further reactions. Essentially comparable reactions have been observed with Rhodococcus sp. strain NCIMB 12038 (Allen et al. 1997). 

However, production of 2,6-difluorobenzamide (Scheme 12.1-18) was effected in 99.5% n-heptane using the nitrile hydratase from Rhodococcus sp. NCIMB 12 21 81841. The enzymatic reaction was found to be activated by light (see 12.1.3.4). More recently, Layh and Willetts have studied nitrile transformations in various organic solvents and biphasic mixtures using a nitrilase from Pseudomonas sp. DSM 11387 and a nitrile hydratase from Rhodococcus sp. DSM 113971 51. The enzymes exhibited good stabilities in biphasic mixtures with hydrophobic solvents when dispersed in... 

All these degradation pathways were shown to involve a Baeyer-Villiger oxidation of a cycloalkanone that led to formation of the corresponding lactone. Further degradation then occured via hydrolysis of this lactone by a lactone hydrolase which has, in some cases, been isolated. As an example, the reaction sequence for the degradation of cyclopentanol by Pseudomonas sp. NCIMB 98721351 is shown in Fig. 16.5-7. 

Figure 16.5-11. Metabolism of both enantiomers of camphor by Pseudomonas putida Cl (=NCIMB 10007 = ATCC 17453).

Whilst the whole-cell approach has proved invaluable, the associated problems of overmetabolism and side reactions can be encountered. Another way to counter the problems of high cost in using isolated BVMOs is to use an NADH dependent enzyme, as NADH retails at approximately one tenth of the cost of NADPH. The Type 2 DKCMOs from Pseudomonas putida ATCC 17453 (= NCIMB 10007) are NADH dependent, and Grogan et al. were successftd in applying a complement of these enzymes, termed MOl, to the transformation of bicyclo[3.2.0]hept-2-en-6-one, to yield another enantiodivergent mix of lactones enantiomeric to those obtained... 

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