Characterised Flavin-Dependent Two-Component Monooxygenases from the CAM Plasmid of Pseudomonas putida ATCC 17453 (NCIMB 10007): ketolactonases by Another Name
Abstract
:1. Introduction
2. Early Research at the University of Illinois
3. Post-Gunsalus Research at the University of Aberystwyth
4. A New Millennium and a New Perspective—The Ketolactonases as fd-TCMOs
5. Structural Studies of the Ketolactonases
6. Chemo-, Regio-, and Enantioselectivity of the Ketolactonases: Natural and Xenobiotic Substrates, Plus Biocatalytic Applications
Funding
Acknowledgments
Conflicts of Interest
References
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Cofactor | Moles/Mole Enzyme |
---|---|
Total iron | 1.01 |
Heme iron | 0.015 |
Flavin (FMN) | 0.094 |
Molybdenum | <0.001 |
Copper | 0.076 |
Substrate | 2,5-DKCMO-Generated Oxygenated Product(s) | 3,6-DKCMO-Generated Oxygenated Product(s) | ||
---|---|---|---|---|
7-endo-methylbicyclo[3.2.0]hept-2-en-6-one | (1S,5R)-3-oxa-lactone | (1R,5S)-2-oxa-lactone | (1S,5R)-3-oxa-lactone | (1R,5S)-2-oxa-lactone |
>95%, e.e. | >80%, e.e. | 5%, e.e. | 10%, e.e. | |
100% conversion | 100% conversion | |||
7,7-dimethylbicyclo[3.2.0]hept-2-en-6-one | (1S,5R)-3-oxa-lactone | (1R,5S)-2-oxa-lactone | racemic 3-oxa-lactone | no 2-oxa-lactone detected |
>80%, e.e. | >95%, e.e. | |||
100% conversion | 100% conversion | |||
methyl-para-tolyl sulfide | (S)-sulfoxide | (S)-sulfoxide | ||
75%, e.e. | 40%, e.e. | |||
20% conversion | 30% conversion |
Substrate | Enzyme | |||
---|---|---|---|---|
2,5-DKCMO-1 a | 2,5-DKCMO-2 b | 2,5-DKCMO-1 + 2 c | 3,6-DKCMO d | |
(A) | ||||
(+)-camphor product(s) | 2-oxa-lactone | 2-oxa-lactone | 2-oxa-lactone | none |
conversion % | 100 | 100 | 100 | 0 |
e.e.% | >97 | >97 | >95 | n.a. |
(−)-camphor product(s) | none | none | none | 6-oxa-lactone |
conversion % | n.a. | n.a | n.a | 100 |
ee% | n.a. | n.a | n.a | >97 |
2,5-diketocamphane product(s) | n.t | n.t | OTE(indirect) | none |
conversion% | 100 | n.a. | ||
e.e.% | n.a. | n.a. | ||
3,6-diketocamphane product(s) | n.t | n.t | none | OTE(indirect) |
conversion % | n.a. | 100 | ||
e.e.% | n.a. | n.a. | ||
(+)-fenchone product(s) | none | none | none | none |
conversion % | n.a. | n.a | n.a | n.a |
ee% | n.a. | n.a. | n.a. | n.a. |
(−)-fenchone product(s) | none | none | none | none |
conversion % | n.a | n.a | n.a | n.a |
e.e.% | n.a. | n.a. | n.a | n.a. |
(+)-nopinone product(s) | none | none | n, t | none |
conversion % | n.a. | n.a | n.a | |
ee% | n.a. | n.a | n.a. | |
(rac)-bicyclo[2.2.1]heptan-2,5-dione product(s): | 2-oxa-lactone | n.t | n.t. | 2-oxa-lactone |
conversion % | 94 | 26 | ||
e.e.% | n.t | n.t. | ||
6-oxo-cineole product(s) | n.t | n.t | 6-oxa-lactone | n.t |
conversion% | 25 | |||
e.e.% | n.t | |||
(rac)-bicyclo[3.2.0]hept-2-en-6-one product(s) | i. (+)-2-oxa-lactone (1R,5S) | i. (+)-2-oxa-lactone (1R,5S) | i. (+)-2-oxa-lactone (1R,5S) | i. (+)-2-oxa-lactone (1R,5S) |
ii. (+)-3-oxa-lactone (1S,5R) | ii. (+)-3-oxa-lactone (1S,5R) | ii. (+)-3-oxa-lactone (1S,5R) | ii. (+)-3-oxa-lactone (1S,5R) | |
conversion % | i. 55 | i. 50 | i. 43 | i. 18 |
ii. 35 | ii.50 | ii. 57 | ii. 22 | |
e.e.% | i. 77 | i. 87 | i. 89 | i. 33 |
ii. 99 | ii. 97 | ii. 100 | ii. 82 | |
(rac)- bicyclo[2.2.1]heptan-2-one(norcamphor) product(s) | i. (−)-2-oxa-lactone (1R,5S) | i. (−)-2-oxa-lactone (1R,5S) | (−)-2-oxa-lactone (1R,5S) | (−)-2-oxa-lactone (1R,5S) |
ii (−)-3-oxa-lactone (1R,5S) | ii (−)-3-oxa-lactone (1R,5S) | |||
conversion % | i. 48 | i. 35 | 20 | 37 |
ii. 16 | ii. 25 | |||
e.e.% | i. 40 | i. 58 | 60 | >90 |
ii. 57 | ii. 20 | |||
(rac)-5-exo-hydroxybicyclo[2.2.1]heptan-2-one product(s) | n.t. | n.t. | none | (−)-2-oxa-lactone (1R,5S) |
conversion % | n.a | 33 | ||
ee | n.a. | >95 | ||
(rac)-5-exo-acetoxybicyclo[2.2.1]heptan-2-one product(s) | n.t. | n.t | (−)-2-oxa-lactone (1R,5S) | none |
conversion % | 35 | n.a. | ||
e.e.% | >95 | n.a | ||
(B) | ||||
Cyclobutanone product(s) | none | n.t. | n.t. | 2-oxa-lactone |
conversion % | n.a. | 13 | ||
e.e.% | n.a. | n.a. | ||
Cyclopentanone product(s) | none | n.t | n.t | 2-oxa-lactone |
conversion % | n.a. | 24 | ||
e.e.% | n.a. | n.a. | ||
2-methylcyclopentanone product(s) | none | none | n.t. | none |
conversion % | n.a. | n.a. | n.a. | |
e.e.% | n.a. | n.a. | n.a. | |
2-n-hexylcyclopentanone product(s) | (+)-2-oxa-lactone | (+)-2-oxa-lactone | n.t. | none |
conversion % | 6 | 3 | ||
E. | 12 | 5 | ||
2-cyclopenten-1-one product(s) | n.t. | n.t. | n.t. | none |
conversion % | n.a. | |||
e.e.% | n.a. | |||
3-methyl-2-cyclopenten-1-one product(s) | n.t. | n.t. | n.t. | none |
conversion % | n.a. | |||
e.e.% | n.a | |||
2,3,4,5-tetramethyl-2-cyclopenten-1-one product(s) | n.t. | n.t. | n.t. | none |
conversion % | n.a. | |||
e.e.% | n.a. | |||
Cyclohexanone product(s) | none | n.t. | n.t. | 2-oxa-lactone |
conversion % | n.a. | 3 | ||
e.e.% | n.a. | n.a. | ||
2-cyclohexen-1-one product(s) | n.t. | n.t. | n.t. | none |
conversion % | n.a. | |||
e.e.% | n.a. | |||
2-methylcyclohexanone product(s) | (+)-2-oxa-lactone | (+)-2-oxa-lactone | n.t. | (+)-2-oxa-lactone |
conversion % | 8 | 4 | 2 | |
E | 3.2 | 3.1 | 3.2 | |
2-ethylcyclohexanone product(s) | (+)-2-oxa-lactone | (+)-2-oxa-lactone | n.t. | none |
conversion % | 11 | 6 | n.a. | |
E | 43 | 22 | n.a. | |
2-n-propylcyclohexanone product(s) | (+)-2-oxa-lactone | (+)-2-oxa-lactone | n.t. | none/trace |
conversion % | 18 | 13 | n.a. | |
E | 19 | 8.5 | n.a. | |
2-phenylcyclohexanone product(s) | (−)-2-oxa-lactone | (−)-2-oxa-lactone | n.t. | (rac)-2-oxa-lactone |
conversion % | 11 | 6 | 2 | |
E | 43 | 22 | n.a. | |
4-methylcyclohexanone product(s) | (−)-2-oxa-lactone | (−)-2-oxa-lactone | n.t. | trace |
conversion % | 8 | 5 | n.a. | |
e.e.% | 27 | 55 | n.a. | |
4-ethylcyclohexanone product(s) | (−)-2-oxa-lactone | (−)-2-oxa-lactone | n.t. | (+)-2-oxa-lactone |
conversion % | 29 | 10 | 3 | |
e.e.% | 71 | 89 | 87 | |
4-n-pentylcyclohexanone product(s) | (−)-2-oxa-lactone | trace | n.t. | trace |
conversion % | 2 | n.a. | n.a | |
e.e.% | 26 | n.a. | n.a. | |
4-tert-butylcyclohexanone product(s) | (+)-2-oxa-lactone | trace | n.t. | none |
conversion % | 5 | n.a. | n.a | |
e.e.% | 61 | n.a. | n.a. | |
3-methyl-2-cyclohexene-1-one product(s) | none | n.t. | n.t. | none |
conversion % | n.a. | n.a. | ||
e.e.% | n.a. | n.a. | ||
3,5,5-trimethyl-2-cyclohexene-1-one product(s) | none | n.t. | n.t. | none |
conversion % | n.a. | n.a. | ||
e.e.% | n.a. | n.a | ||
(C) | ||||
Progesterone product(s) | none | n.t. | n.t. | n.t |
conversion % | 0 | |||
e.e.% | n.a. | |||
2-decanone product(s) | none | n.t. | n.t. | n.c. |
conversion % | 0 | 11 | ||
e.e.% | n.a. | n.a. | ||
Acetophenone product(s) | none | n.t. | n.t. | n.c. |
conversion % | 0 | 80 | ||
e.e.% | n.a. | n.a. | ||
4-phenyl-2-butanone | none | n.t. | n.t. | n.c. |
conversion % | 0 | 48 | ||
e.e.% | n.a. | n.a. | ||
(D) | ||||
Methyl-p-tolyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 12 | 57 | ||
e.e.% | 62 | 32 | ||
p-methoxyphenyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 29 | 65 | ||
e.e.% | 71 | 25 | ||
p-bromophenyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 29 | 65 | ||
e.e.% | 71 | 25 | ||
p-chlorophenyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 5 | 15 | ||
e.e.% | 45 | 27 | ||
p-fluorophenyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (R)-sulfoxide |
conversion % | 9 | 72 | ||
e.e.% | 39 | 30 | ||
n-pentyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (rac)-sulfoxide |
conversion % | 28 | 90 | ||
e.e.% | 32 | n.a. | ||
n-hexyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 19 | 50 | ||
e.e.% | 37 | 19 | ||
n-heptyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 10 | 43 | ||
e.e.% | 30 | 20 | ||
n-octyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 6 | 20 | ||
e.e.% | 36 | 16 | ||
n-nonyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (R)-sulfoxide |
conversion % | 2 | 9 | ||
e.e.% | 16 | 8 | ||
n-decyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (R)-sulfoxide |
conversion % | 1 | 9 | ||
e.e.% | 5 | 9 | ||
n-octyl ethyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 3 | 14 | ||
e.e.% | 21 | 14 | ||
methyl phenyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (S)-sulfoxide |
conversion % | 9 | 53 | ||
e.e.% | 35 | 9 | ||
ethyl phenyl sulphide product(s) | n.t. | n.t. | (R)-sulfoxide | (rac)-sulfoxide |
conversion % | 5 | 25 | ||
e.e.% | 2 | n.a. | ||
n-propyl phenyl sulphide product(s) | n.t. | n.t. | (R)-sulfoxide | (S)-sulfoxide |
conversion % | 8 | 20 | ||
e.e.% | 8 | 19 | ||
isopropyl phenyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (R)-sulfoxide |
conversion % | 11 | 21 | ||
e.e.% | 20 | 24 | ||
n-butyl phenyl sulphide product(s) | n.t. | n.t. | (R)-sulfoxide | (S)-sulfoxide |
conversion % | 5 | 14 | ||
e.e.% | 11 | 43 | ||
benzyl methyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (R)-sulfoxide |
conversion % | 29 | 85 | ||
e.e.% | 30 | 4 | ||
benzyl ethyl sulphide product(s) | n.t. | n.t. | (S)-sulfoxide | (R)-sulfoxide |
conversion % | 20 | 41 | ||
e.e.% | 2 | 9 | ||
2,3-dihydrobenzo-thiophene product(s) | n.t. | n.t. | (S)-sulfoxide | (R)-sulfoxide |
conversion % | 18 | 24 | ||
e.e.% | 38 | 41 | ||
1-thiatetrahydro-naphthalene product(s) | n.t. | n.t. | (S)-sulfoxide | (R)-sulfoxide |
conversion % | 15 | 28 | ||
e.e.% | 17 | 7 |
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Share and Cite
Willetts, A. Characterised Flavin-Dependent Two-Component Monooxygenases from the CAM Plasmid of Pseudomonas putida ATCC 17453 (NCIMB 10007): ketolactonases by Another Name. Microorganisms 2019, 7, 1. https://doi.org/10.3390/microorganisms7010001
Willetts A. Characterised Flavin-Dependent Two-Component Monooxygenases from the CAM Plasmid of Pseudomonas putida ATCC 17453 (NCIMB 10007): ketolactonases by Another Name. Microorganisms. 2019; 7(1):1. https://doi.org/10.3390/microorganisms7010001
Chicago/Turabian StyleWilletts, Andrew. 2019. "Characterised Flavin-Dependent Two-Component Monooxygenases from the CAM Plasmid of Pseudomonas putida ATCC 17453 (NCIMB 10007): ketolactonases by Another Name" Microorganisms 7, no. 1: 1. https://doi.org/10.3390/microorganisms7010001