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GreenꢀChemistryꢀ
Green Chemistry
ARTICLEꢀ
nd
Relative enzymatic activity for 2 cycle = (LGO conversion
f
AgroParisTech, UMR 782 GMPA, Site de Grignon, F-78850 Thiverval-
nd
st
cycle) x 100) / (LGO conversion (1 cycle))
(
2
Grignon, France.
g
INRA, UMR 782 GMPA, Site de Grignon, F-78850 Thiverval-Grignon,
DOI: 10.1039/C4GC01231C
rd
Relative enzymatic activity for 3 cycle = (LGO conversion France.
rd
3 cycle) x 100) / (LGO conversion (1 cycle))
st
§
(
these authors contributed equally to this work
*
and so on.
1
13
Electronic Supplementary Information (ESI) available: H & C NMR
GC-MS method
spectra, and FT-IR spectra of LGO, HBO, 2-LGO and 2-HBO. See
The GC-MS system consisted of an Agilent GC 5975 coupled DOI: 10.1039/b000000x/
with MS 7890 in electron impact mode with electron energy set
1
2
3
A. Corma, S. Iborra, A. Velty, Chem. Rev. 2007, 107, 2411
G. W. Huber, S. Iborra, A. Corma, Chem. Rev. 2006, 106, 4044
a) M. S. Miftakhov, F. A. Valeev, I. N. Gaisina, Russ. Chem. Rev. 1994,
at 70 eV and a mass range at m/z (30-350 amu), and equipped
with a HP5-MS (30 m × 0.25 mm i.d, 0.25 µm film thickness)
capillary column. The injector and transfer line temperatures
were both at 280 °C. GC was performed in split mode (40:1).
The temperature program was as follows: from 60 °C hold for 1
6
1
3, 869; b) A. V. Bridgwater, D. Meier, D. Radlein, Org. Geochem.
999, 30, 1479; c) Q . Lu, W. M. Xiong, W. Z. Li, Q. X. Guo, X. F. Zhu,
Bioresour. Technol. 2009, 100, 4871
-1
4
a) F. Shafizadeh, R. H. Furneaux, T. T. Stevenson and T. G. Cochran,
Carbohydr. Res. 1978, 61, 519; b) G. Dobele, T. Dizhbite, G.
Rossinskaja, G. Telysheva, D. Mier, S. Radtke and O. Faix, J. Anal.
Appl. Pyrolysis 2003, 68-69, 197; c) J. Zandersons, A. Zhurinsh, G.
Dobele, V. Jurkjane, J. Rizhikovs, B. Spince and A. Pazhe, J. Anal. Appl.
Pyrolysis, 2013, 103, 222
min, then to 325 °C at 20 °C.min , hold at 325 °C for 5 min.
-1
The flow rate of hydrogen was set at 1.2 mL.min and the
injected volume was 1 µL. Mass detector was set as follows:
source temperature = 230 °C, quad temperature = 150 °C. A
calibration curve was performed each time, with pure lauric
-1
5
6
7
J. Jae, G. A. Tompsett, A. J. Foster, K. D. Hammond, S. M. Auerbach,
R. F. Lobo and G. W. Huber, J. Catal. 2011, 279, 257
acid (0.2-4.5 mg.mL ) in hexane. tr(lauric acid) = 7.22 min,
tr(1-propyl laurate) = 7.92 min.
G. R. Court, C. H. Lawrence, W. D. Raverty, A. J. Duncan,
th
WO2011/000030 January, 6 2011
HPLC method
a) V. L. Budarin, P. S. Shuttleworth, J. R. Dodson, A. J. Hunt, B.
Lanigan, R. Marriott, K. J. Milkowski, A. J. Wilson, S. W. Breeden, J.
Fan, E. H. K. Sin and J. H. Clark, Energy Environ. Sci. 2011, 4, 471; b)
X. Hu, L. Wu, Y. Wang, D. Mourant, C. Lievens, R. Gunawan and C. Z.
Li, Green Chem. 2012, 14, 3087
HPLC analyses were performed on a Thermofisher Ultimate
3
000 equipped with a DAD detector (220 nm) and a
Thermoscientific Syncronis aQ (250 x 4.6mm, 5µm) column.
Samples were prepared by diluting 10 µL of reaction mixture in
8
a) K. Tomioka, T. Ishiguro and K. Koga, J. Chem. Soc., Chem. Commun.
1.5 mL of acetonitrile. Following conditions were applied:
injection 10 µL, oven temperature 30 °C, flow 0.8 mL/min,
1
979, 652; b) D. Enders, V. Lausberg, G. Del Signore and O. M. Berner,
Synthesis 2002, 515
9
1
E. Takashi, M. Katsuya, Y. Hajime, K. Koseki, H. Kawakami and H.
Matsushita, Heterocycles 1990, 31, 1585
elution method (water/acetonitrile): 0-5 min isocratic 85/15, 5-
1
0 min from 85/15 to 90/10, 10-15 min isocratic 90/10, 15-20
0
a) H. Hawakami, T. Ebata, K. Koseki, K. Statsumoto, H. Matsushita, Y.
Naoi and K. Itoh, Heterocycles, 1990, 31, 2041; b) R. Flores, A.
Rustullet, R. Alibes, A. Alvarez- Larena, P. de March, M. Figueredo and
J. Font, J. Org. Chem. 2011, 76, 5369; c) A. Diaz-Rodriguez, Y. S.
Sanghvi, S. Fernandez, R. F. Schinazi, E. A. Theodorakis, M. Ferreroa
and V. Gotor, Org. Biomol. Chem. 2009, 7, 1415
min 90/10 to 85/15. Retention times: tr(LGO) = 8.40 min,
tr(HBO) = 3.73 min, tr(FBO) = 3.87 min, tr(2H-LGO) = 8.40
min and tr(2H-HBO) = 3.61 min.
Acknowledgements
1
1
1
2
K. Koseki, T. Ebata, H. Kawakawmi, H. Matsushita, K. Itoh, Y. Naoi,
The authors are grateful to Circa Group for providing them with
industrial grade levoglucosenone, and to Région Champagne-
Ardenne, Conseil Général de la Marne and Reims Métropole
for financial support.
th
US 4,9947,585 Feb. 19 , 1991
a) C. Paris, M. Moliner, A. Corma, Green Chem. 2013, 15, 2101; b) P.
Rammohan, S. Taradas, K. Shampa, ARKIVOC 2012, 570; c) K. Tanabe,
W. F. Hölderich, App. Catal. A: Gen. 1999, 181, 399; d) J. H. Clark, Acc.
Chem. Res. 2002, 35, 791; e) Y. C. Sharma, B. Singh, J. Korstad,
Biofuels, Bioprod. Bioref. 2011, 5, 69
a) P. Carlqvist, R. Eklund, K. Hult, T. Brinck, J. Mol. Model. 2003, 9(3),
164; b) M. Y. Rios, E. Salazar, H. F. Olivo, Green Chem. 2007, 9, 459;
c) M. Y. Rios, E. Salazar, H. F. Olivo, J. Mol. Catal. B : Enzym. 2008,
54, 61 ; d) A. J. Kotlewska, F. van Rantwijk, R. A. Sheldon, I. W. C. E.
Arends, Green Chem. 2011, 13, 2154; e) A. Drozdz, A. Chrobok, S. Baj,
K. Szymanska, J. Mrowiec-Bialon, A. B. Jarzebski, Appl. Catal. A: Gen.
Notes and references
1
3
a
AgroParisTech, Chaire Agro-Biotechnologies Industrielles (ABI), 247
rue Paul Vaillant-Couturier F-51100 Reims, France.
b
AgroParisTech, UMR 1318 IJPB, Route de Saint-Cyr F-78026
Versailles, France.
c
INRA, UMR 1318 IJPB, Route de Saint-Cyr F-78026 Versailles,
2
013, 467, 163; f) G. Chavez, R. Hatti-Kaul, R. A. Sheldon, G. Mamo, J.
France.
d
Mol. Cat. B: Enzym. 2013, 89, 67
AgroParisTech, UMR 1145 GENIAL, 1 avenue des Olympiades, F- 14 a) F. Pion, F. A. Reano, P.-H. Ducrot, F. Allais, RSC Adv. 2013, 3, 8988;
b) F. Pion, P.-H. Ducrot, F. Allais, Macromol. Chem. Phys. 2014, 5, 431
15 Preliminar studies demonstrated that LGO was stable in the reaction
9
e
1744 Massy, France.
INRA, UMR 1145 GENIAL, 1 avenue des Olympiades, F-91744
medium (no degradation product) and that the only products obtained
through its oxidation were HBO and FBO.
Massy, France.
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