Green Chemistry
Green Chemistry
DOI: 10.1039/C3GC41908H
I.D., 0.25 ꢁm film thickness, J&W Scientific Inc., Folsom,
CA, USA) was used as a secondꢀdimension column. The
1
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3
S.V. Vassilev, D. Baxter, L.K. Andersen, C.G. Vassileva and T.J.
Morgan, Fuel, 2012, 94, 1.
ꢀ
1
carrier gas was helium at a constant flow rate of 2.0 mL min .
The primary oven temperature was programmed from 35 ºC to
6
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5
0
ꢀ
1
P. Foley, A. Kermanshahi pour, E.S. Beach and J.B. Zimmerman,
Chem. Soc. Rev., 2012, 41, 1499.
5
0
5
0
5
0
5
50 ºC (0.2 min) at a heating rate of 2 ºC min , then to 220 ºC
ꢀ
1
(
14 min) at a heating rate of 5 ºC min ; the secondary oven
temperature was programmed from 50 ºC to 65 ºC (0.2 min) at
(a) K. J. Zeitsch, The Chemistry and Technology of Furfural and Its
Many By-Products, Elsevier, The Netherlands, 2000; (b) D.T. Win,
ꢀ
1
a heating rate of 2 ºC min , then to 235 ºC (14 min) at a
ꢀ
1
heating rate of 5 ºC min . The MS transfer line temperature
and the MS source temperature were 250 ºC. The modulation
time was 5 s, and the modulator temperature was kept at 20 ºC
offset (above primary oven). The ToFMS was operated at a
Au Journal of Tech., 2005,
C. Kim, I.T. Hwang, N.ꢀJ. Park, Y.K. Hwang, J.ꢀS. Chang and J.ꢀS.
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8, 185; (c) A.S. Mamman, J.ꢀM. Lee, Y.ꢀ
1
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2
2
3
3
2
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1
4
(a) M. Mascal and E.B. Nikitin, Green Chemistry, 2010, 12, 370; (b)
M. Mascal and E.B. Nikitin, Angew. Chem. Int. Ed., 2008, 47, 7924ꢀ
spectrum storage rate of 100 spectra s . The mass
spectrometer was operated in the EI mode at 70 eV using a
range of m/z 33ꢀ500 and the detector voltage was 1626 V. 75
Total ion chromatograms (TIC) were processed using the
automated data processing software ChromaTOF (LECO) at a
signalꢀtoꢀnoise threshold of 100. Contour plots were used to
evaluate the separation general quality and for manual peak
identification; a signalꢀtoꢀnoise threshold of 50 was used. Two
7926; (c) M. Mascal and E. B. Nikitin, ChemSusChem, 2009,
23ꢀ426; (d) G.J.M. Gruter , EP2487170 A1, 2012; (e) M. Chia and
J. A. Dumesic, Chem. Commun., 2011, 47, 12233ꢀ12235; (f) J.
Zhang, S. Wu, B. Li and H. Zhang, ChemCatChem, 2012, , 1230ꢀ
237; (g) A.P. Groves, C. Morley, J. Smith and P.A. Stevenson,
2,
4
4
1
8
8
9
0
5
0
US20050144835 A1, 2005; (h) L.E. Manzer, US20050210738 A1,
2005; (i) E. Christensen, A. Williams, S. Paul, S. Burton and R.L.
McCormick, Energy Fuels, 2011, 25, 5422; (j) G.J.M. Gruter and F.
Dautzenberg, US8338626 B2, 2012; (k) G.ꢀJ. Gruter and E. de Jong,
Biofuels Technology, 2009, 11; (l) R.J. Haan and J.P. Lange
US8372164 B2, 2013.
commercial databases (Wiley 275 and US National Institute of
Science and Technology (NIST) V. 2.0 ꢀ Mainlib and Replib)
were used. The majority (62% and 87% for Hmf and FA
catalytic systems, respectively) of the identified compounds
showed mass spectral similarity matches > 800. Furthermore,
a manual inspection of the mass spectra was done, combined
with the use of additional data, such as the retention index (RI)
value, which was determined according to the Van den Dool
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(a) P. Che, F. Lu, J. Zhang, Y. Huang, X. Nie, J. Gao and J. Xu,
2
1
and Kovats RI equation. For the determination of the RI, a
C ꢀC ꢀalkane was used, and as some volatile compounds
were eluted before C , the solvent
Bioresour. Technol., 2012, 119, 433ꢀ436; (b)
E. R. Sacia and A.T. Bell, Green Chem., 2012, 14, 1626; (c) M.I.
Alam, S. De, S. Dutta and B. Saha, RSC Adv., 2012, , 6890; (d) P.
M. Balakrishnan,
n
20
8
n
ꢀhexane was used as C6
8
2
standard. The experimentally calculated RI values were
compared, when available, with values reported in the
literature for similar chromatographic columns employed as
the first dimension.
Lanzafame, D.M. Temi, S. Perathoner, G. Centi, A. Macario, A.
Aloise and G. Giordano, Catal. Today, 2011, 175, 435; (e) L. Bing,
Z. Zhang and K. Deng, Ind. Eng. Chem Res., 2012, 51, 15331; (f)
K.S. Arias, S.I. AlꢀResayes, M.J. Climent, A. Corma and S. Iborra,
Acknowledgements
ChemSusChem, 2013,
ChemSusChem, 2012,
6
, 123; (g) S. De, S. Dutta and B. Saha,
We are grateful to Fundação para a Ciência e a Tecnologia 95
5, 1826; (h) X. Hu, R. Gunawan, D. Mourant,
(
FCT), Programa Operacional Ciência e Inovação (POCI)
C. Lievens, X. Li, S. Zhang, W. Chaiwat and C.ꢀZ. Li, Fuel, 2012,
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5
2010, Orçamento do Estado (OE), Fundo Europeu de
Desenvolvimento Regional (FEDER) for general funding
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, 512; (i) S. Saravanamurugan and A. Riisager, Catal. Commun.
,
2
012, 17 71ꢀ75; (j) G. J.M. Gruter and L.E. Manzer,
,
(
project POCTI/QUI/56112/2004), and to CICECO (Pestꢀ
US20100058650 A1, 2010.
(a) G. M. G. Maldonado, R. S. Assary, J. A. Dumesic and L. A.
Curtiss, Energy Environ. Sci., 2012, , 8990ꢀ8997; (b) Z.H. Zhang,
C/CTM/LA0011/2011) and QOPNA (Research Unit 62/94,
project PEstꢀC/QUI/UI0062/2011). We acknowledge the FCT
for postꢀdoctoral grants to P.N. (SFRH/BPD/73540/2010),
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00
05
10
15
6
5
M.M.A.
SFRH/BPD/79910/2011) and S.L. (SRFH/BPD/23765/2005).
The authors thank Magda Santos for the assistance in the
GC GCꢀToFMS analyses.
(SFRH/BPD/89068/2012),
P.A.R
K. Dong and Z.B. Zhao, ChemSusChem, 2011, 4, 112; (c) P. Neves,
S. Lima, M. Pillinger, S.M. Rocha, J. Rocha and A.A. Valente,
Catal. Today, 2013 (http://dx.doi.org/10.1016/j.cattod.2013.04.035).
S. Saravanamurugan, O.N. Van Buu and A. Riisager,
(
×
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ChemSusChem, 2011,
(a) J.P. Lange, W.D. van de Graaf and R.J. Haan, ChemSusChem
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Notes and references
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a
Department of Chemistry, CICECO, University of Aveiro, Campus
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2
Universitário de Santiago, 3810-193 Aveiro, Portugal
R.R. Mukminov and U.M. Whemilev, Russ. J. Appl. Chem., 2007,
80, 1687; (c) W.D.V. de Graaf and J.P. Lange, US7265239 B2,
b
Institute for Biotechnology and Bioengineering, Centre for Biological and
Chemical Engineering, Instituto Superior Técnico, Av. Rovisco Pais,
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007; (d) B.C. Redmon, US2763665, 1956.
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c
04900, Lisboa, Portugal
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(a) R. Rinaldi and F. Schueth, Energy Environ. Sci., 2009,
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26; (b) A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107
411; (c) P. MaekiꢀArvela, B. Holmbom, T. Salmi and D. Y.
Department of Chemistry, QOPNA, University of Aveiro, Campus
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,
Universitário de Santiago, 3810-193 Aveiro, Portugal
Corresponding author: (A.A. Valente) Tel.: 00351-234-370603; fax:
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Electronic Supplementary Information (ESI) available: [Includes Figs
S1ꢀS4, and Tables S1 and S2]. See DOI: 10.1039/b000000x/
1
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Green Chem., 2013, 00, 1-10 | 9