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13
13
13
Fig. 6
C NMR spectrum of CO
C-labeled glycerol after 10 h of oxidation by TEMPO-NH
A) and in the presence of OxDC (B).
2
trapped in the form of Na
2 3
CO from
1
3
9 E. Ricca, B. Brucher and J. H. Schrittwieser, Adv. Synth. Catal., 2011,
53, 2239–2262.
1
2
in the absence
3
(
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2
glycerol by enzymatic reaction. Knowing that TEMPO-NH is just
able to oxidize glycerol to mesoxalic acid, we can conclude from 12 T. Matsumoto, S. Shimada, K. Yamamoto, T. Tanaka and A. Kondo,
Fuel Cells, 2013, 13, 960–964.
3 Z. Zhu, T. Kin Tam, F. Sun, C. You and Y. H. Percival Zhang, Nat.
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5 D. P. Hickey, M. S. McCammant, F. Giroud, M. S. Sigman and
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this result that a decarboxylation of mesoxalic acid was catalysed
by OxDC and we have confirmed above that those products are
oxidized completely to CO2.
We have shown that recombinant OxDC from Bacillus
subtilis can be used as an attractive alternative to commercially
1
1
1
6 A. Dijksman, A. Marino-Gonzalez, A. Mairata
I. W. C. E. Arends and R. A. Sheldon, J. Am. Chem. Soc., 2001, 123,
826–6833.
´
i
Payeras,
available OxOx from barley in combination with TEMPO-NH
part of a hybrid electrocatalytic cascade capable of the complete
oxidation of glycerol to CO . Use of the non-redox enzyme,
2
as
6
1
7 L. De Luca, G. Giacomelli, S. Masala and A. Porcheddu, J. Org.
Chem., 2003, 68, 4999–5001.
2
OxDC, allows for the collection of additional electrons from the 18 P. L. Bragd, H. van Bekkum and A. C. Besemer, Top. Catal., 2004, 27,
4
9–66.
oxidation of formic acid by TEMPO-NH compared to the use of
2
1
2
9 M. B. Lauber and S. S. Stahl, ACS Catal., 2013, 3, 2612–2616.
0 J. R. Fish, S. G. Swarts, M. D. Sevilla and T. Malinski, J. Phys. Chem.,
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OxOx. The use of OxDC as an alternative to OxOx increases
current density 8 times and also avoids the formation of H O
2
2
2
2
1 M. F. Semmelhack, C. R. Schmid and D. A. Cort ´e s, Tetrahedron Lett.,
2
which can alter the redox properties of TEMPO-NH . In addition,
1986, 27, 1119–1122.
OxDC was expressed in E. coli which allows for the possibility to
modify the enzyme by protein engineering. This advantage could
allow for the creation of optimized OxDC with higher activity for
mesoxalic acid and/or an enzyme with broader substrate range
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2
2
with the possibility to use other fuels such as carboxylic acids and 25 V. J. Just, C. E. M. Stevenson, L. Bowater, A. Tanner, D. M. Lawson
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larger carbohydrates.
2
The authors would like to thank the Professor Steve Ealick
from Cornell University for sharing the OxDC gene and Army 27 P. Moussatche, A. Angerhofer, W. Imaram, E. Hoffer, K. Uberto,
C. Brooks, C. Bruce, D. Sledge, N. G. J. Richards and E. W. Moomaw,
Research Office MURI (#W911NF1410263) grant for funding.
Arch. Biochem. Biophys., 2011, 509, 100–107.
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2
Notes and references
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M. J. Moehlenbrock, T. K. Toby, A. Waheed and S. D. Minteer, J. Am.
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30 S. E. Carpenter and D. J. Merkler, Anal. Biochem., 2003, 323, 242–246.
Chem. Commun.
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