Integration of chemical and biological catalysis: Production of furylglycolic acid from glucose via cortalcerone

Article abstract of DOI:10.1021/cs400593p

Furylglycolic acid (FA), a pseudoaromatic hydroxy-acid suitable for copolymerization with lactic acid, can be produced from glucose via enzymatically derived cortalcerone using a combination of Bronsted and Lewis acid catalysts. Cortalcerone is first converted to furylglyoxal hydrate (FH) over a Bronsted acid site (HCl or Al-containing beta-zeolite), and FH is subsequently converted to FA over a Lewis acid site (Sn-beta zeolite). Selectivity for conversion of FH to FA is as high as 80% at 12% conversion using tetrahydrofuran (THF) as a solvent at 358 K. Higher conversion of FH leads to FA-catalyzed degradation of FH and subsequent deactivation of the catalyst by the deposition of carbonaceous residues. The deactivated catalyst can be regenerated by calcination. Cortalcerone can be produced from 10% glucose solution using recombinant Escherichia coli strains expressing pyranose 2-oxidase and aldos-2-ulose dehydratase from the wood-decay fungus Phanerochaete chrysosporium BKM-F-1767. This enzymatically derived cortalcerone is converted in one pot to FA in a methanol/water solvent over an Al-containing Sn-beta zeolite possessing both Bronsted and Lewis acid sites, achieving 42% selectivity to FA at 53% cortalcerone conversion.

Full text of DOI:10.1021/cs400593p

Research Article
pubs.acs.org/acscatalysis
Integration of Chemical and Biological Catalysis: Production of
Furylglycolic Acid from Glucose via Cortalcerone
Thomas J. Schwartz, Samuel M. Goodman, Christian M. Osmundsen, Esben Taarning,‡
†
∥
†
‡,§
∥
∥
∥
,†
Michael D. Mozuch, Jill Gaskell, Daniel Cullen, Philip J. Kersten, and James A. Dumesic*
†
Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States
Research & Development Division, Haldor Topsøe A/S, Lyngby, Denmark
‡
§
∥
Department of Physics, Technical University of Denmark, Lyngby, Denmark
Forest Products Laboratory, Forest Service, U.S. Department of Agriculture, Madison, Wisconsin 53726, United States
*
S Supporting Information
ABSTRACT: Furylglycolic acid (FA), a pseudoaromatic
hydroxy-acid suitable for copolymerization with lactic acid,
can be produced from glucose via enzymatically derived
cortalcerone using a combination of Brønsted and Lewis acid
catalysts. Cortalcerone is first converted to furylglyoxal hydrate
(
FH) over a Brønsted acid site (HCl or Al-containing beta-
zeolite), and FH is subsequently converted to FA over a Lewis
acid site (Sn-beta zeolite). Selectivity for conversion of FH to
FA is as high as 80% at 12% conversion using tetrahydrofuran
(
THF) as a solvent at 358 K. Higher conversion of FH leads to
FA-catalyzed degradation of FH and subsequent deactivation
of the catalyst by the deposition of carbonaceous residues. The
deactivated catalyst can be regenerated by calcination.
Cortalcerone can be produced from 10% glucose solution using recombinant Escherichia coli strains expressing pyranose 2-
oxidase and aldos-2-ulose dehydratase from the wood-decay fungus Phanerochaete chrysosporium BKM-F-1767. This
enzymatically derived cortalcerone is converted in one pot to FA in a methanol/water solvent over an Al-containing Sn-beta
zeolite possessing both Brønsted and Lewis acid sites, achieving 42% selectivity to FA at 53% cortalcerone conversion.
KEYWORDS: Sn-beta zeolite, MPVO reaction, hydride transfer, poly(lactic acid), whole-cell enzyme catalysis, pyranose-2-oxidase
INTRODUCTION
FA has an appropriate side chain to be used as a comonomer
with LA. Polyesters with a pendent furan ring, as an FA-LA
copolymer would be, have been reported to possess favorable
■
The development of biorenewable routes for the production of
value-added chemical intermediates is of interest for reasons of
both environmental and economic sustainability. Notable
among biorenewable chemicals is poly(lactic acid) (PLA), a
biodegradable polymer that has been in commercial-scale
production for several years. Copolymers of lactic acid (LA)
with another monomer are attractive targets for research,
because the final properties of the polymer can be tuned by
appropriate choice of comonomer. However, most copolymers
reported have been purely aliphatic,
pseudoaromatic hydroxy-acids have not yet been produced
from biomass. Vinyl-containing PLA-copolymers have also
8
1
characteristics. Such a copolymer may resemble polymande-
7
lide, which in turn has properties similar to polystyrene.
Previous syntheses of FA have been laboratory-scale prepara-
9,10
tions.
While there are not obvious pathways to produce FA
2
from typical sugar dehydration products, it is possible to
produce this molecule using a combination of chemical and
biological catalysis.
The integration of chemical and biological catalysis is an
emerging field, which presents opportunities to produce
molecules that are not accessible by either discipline alone.
Much of the field has focused on the combination of
3
−5
because aromatic or
6
11
been recently reported using green feedstocks. Polymandelide
homogeneous organometallic catalysts with enzymes. Dy-
is a polylactide derivative based on mandelic acid, a hydroxy
acid which possesses an aromatic side chain. It has been7
reported to possess properties similar to those of polystyrene,
although mandelic acid has not been produced from biomass.
In this communication, we show that furylglycolic acid (FA), a
biomass-derived, pseudoaromatic hydroxy-acid, can be pro-
duced by the integration of chemical and biological catalysis.
namic kinetic resolution has been one of the most prominent
12
success stories, including the use of one-pot and cascade
13
schemes. Caiazzo and co-workers have demonstrated one-pot
Received: July 23, 2013
Revised: October 10, 2013
Published: October 11, 2013
©
2013 American Chemical Society
2689
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ACS Catalysis
Research Article
and cascade aminations, where the organometallic Pd catalyst
and the enzyme operate synergistically. It is also possible to
exploit synergies between enzymatic and heterogeneous
catalysis. For example, hydrogen peroxide, which is a byproduct
of many enzymatic oxidation reactions, can be used to perform
P. chrysosporium RP78, a homokaryotic strain derived from
BKM-F-1767 (ATCC 24725) was cloned, and the sequence
deposited in GenBank under accession number KF699142.
This 900 amino acid sequence differs at 4 positions from the
AUDH of P. chrysosporium ATCC 32629 reported by Claesson
14
30
catalytic epoxidations using zeolite catalysts. New synthetic
strategies can also be developed for molecules that can be
produced by traditional means, and the combination of
heterogeneous Sn catalysts with Candida rugosa lipase to
yield enantiomerically pure D- or L-LA from sugars is a good
et al. The BKM-F-1767 AUDH cDNA was commercially
synthesized with codon bias for optimized expression in E. coli
with plasmid pJexpress414 (DNA2.0, Menlo Park, CA, U.S.A.).
Transformed E. coli BL21(DE3) cells expressing BKM-F-1767
AUDH were used to produce cortalcerone from glucosone.
Anhydrous furylglyoxal, FH, and FA were synthesized
1
5
example. Kieboom and co-workers have combined in one pot
enzymatic oxidation, homogeneously catalyzed dehydration,
and hydrogenation over Pd/C to convert D-galactose to 4-
1
0,31
according to procedures described elsewhere.
beta and Al−Sn-beta,
Al-free Sn-
32−34
35
and bulk zirconia were prepared as
16
deoxy-D-glucose derivatives. More broadly, they suggest that
described in the literature. Other zeolite catalysts were
purchased from Zeolyst International (Conshohocken, PA).
Reactions were carried out in thick-walled glass batch reactors,
and products were analyzed using high performance liquid
chromatography. Thermodynamic calculations presented in the
combinations of chemical and biological catalysis can yield high
1
7,18
19,20
value products.
Shanks
has suggested that biological
catalysis can be used to generate platform molecules which are
subsequently upgraded using chemical catalysis. Our group has
recently employed such a strategy to produce high-value
chemicals from the biologically derived platform molecule
36
Supporting Information were carried out using Gaussian09
software. Full experimental details can be found in the
Supporting Information.
21
triacetic acid lactone.
In this work, we have explored the production of FA using
cortalcerone as an intermediate that can be produced
enzymatically from glucose, as previously described (see
RESULTS AND DISCUSSION
■
22
Initial studies examined two Al-containing zeolites (USY and
beta), zirconia, and Al-free Sn-beta for catalytic activity in
converting FH to FA. As shown in Table 1, the Al-containing
zeolites were not selective for the reaction (yielding other
products that were not identified), while zirconia achieves only
modest selectivity. Sn-beta showed the best performance for
conversion of FH to FA, achieving 64% selectivity at 18%
conversion (Entry 4, Table 1). Altering the Si/Sn ratio does not
Scheme 1). Cortalcerone is first dehydrated to form furylglyoxal
Scheme 1. Pathway for Conversion of Glucose to
a
Furylglycolic Acid (FA)
a
Table 1. Conversion of FH to FA over Al-Containing
Zeolites (USY and Al-beta), Zirconia, and Sn-beta Zeolite
Si/Al or
Si/Sn
conv.
(%)
sel. to
FA (%) rate
b
entry catalyst
solvent
1
2
3
4
USY
8
THF
THF
THF
THF
15
11
30
18
9
0.7
0.9
3.1
5.8
Al-beta
ZrO2
25
11
20
64
a
Conversion from glucose to glucosone to cortalcerone takes place
Sn-
beta
400
150
400
400
400
400
400
400
400
400
400
enzymatically, while dehydration of cortalcerone to furylglyoxal
hydrate (FH) requires a Brønsted acid and isomerization of FH to
FA takes place over a Lewis acid.
5
Sn-
beta
THF
THF
THF
water
36
47
48
80
10
18
17
41
54
53
40
9.0
1.5
6.0
0.7
2.5
1.8
3.4
4.6
1.7
3.1
c
c
c
6
Sn-
beta
39
hydrate (FH), which is then upgraded to FA through an
d
d
e
d
e
7
Sn-
beta
12
intramolecular Meerwein−Ponndorf−Verley−Oppenauer
(
MPVO) hydride shift. Dehydration of cortalcerone to FH
e
8
Sn-
beta
9
has been reported to take place using Brønsted acids such as
2
3
HCl. However, the MPVO isomerization of FH to FA is
heretofore unreported, although similar reactions have been
demonstrated to take place over aluminum-containing
zeolites and bulk zirconia, as well as Al-free Sn-containing
beta zeolite (Sn-beta).
production of FA from FH using Sn-beta, and we demonstrate
the production of FA from enzymatically derived cortalcerone
using a bifunctional Al-containing Sn-beta zeolite (Al−Sn-beta).
9
Sn-
beta
water
22
21
17
f
10
11
Sn-
beta
5% water/THF
2
4
25
f
2
6,27
Sn-
beta
2% water/THF
Herein we demonstrate the
g
g
g
1
2
Sn-
beta
THF
16
13
14
Sn-
beta
1:1 water/MeOH
9:1 water/MeOH
7
EXPERIMENTAL DETAILS
Sn-
beta
16
■
E. coli BL21(DE3) expressing pyranose 2-oxidase of Phaner-
ochaete chrysosporium in pET21a(+) (Novagen) as described
a
All reactions carried out with mass ratio of catalyst:FH = 0.5 for 4 h at
58 K except where indicated. Rate of FA formation (μmol g
min ). 24 h reaction. 3 h reaction. 338 K reaction. Vol %.
Catalyst reused after TGA analysis.
2
8,29
b
−1
previously
was used to oxidize glucose to glucosone. In
3
−1
c d e f
contrast to earlier studies, recombinant whole cells were used
for catalysis. Aldos-2-ulose dehydratase (AUDH) cDNA from
g
2
690
dx.doi.org/10.1021/cs400593p | ACS Catal. 2013, 3, 2689−2693

ACS Catalysis
Research Article
−
1
appear to affect selectivity (measured at 36−39% conversion).
Rather, a decrease in the Si/Sn ratio (i.e., an increase in the acid
site density) resulted in an increase in the reaction rate per
mass of catalyst, measured at 36−39% conversion (comparing
Entries 5 and 6, Table 1). As discussed below, the low
selectivity and depressed activity at high conversion (Entry 6,
Table 1) are a result of side reactions and deactivation of the
catalyst by deposition of carbonaceous residues.
mol . The fractional order is likely the result of the catalyst
operating at high surface coverage by organic species.
As shown in Figure 1, the selectivity to FA is dependent on
FH conversion, with higher conversion resulting in lower
selectivity, suggesting that FH and/or FA undergo degradation
at high FA concentrations. This idea is supported by the
addition of fresh catalyst after 24 h of reaction at 358 K,
followed by an additional 24 h of reaction. The selectivity to FA
decreases from 48% to 33%, and conversion of FH increases
from 40% to 59% during the second 24 h of reaction, indicating
that the addition of fresh catalyst does not produce an increase
in FA concentration due to degradation reactions at high FA
concentrations.
Given that the enzymatic production of cortalcerone takes
37
place in aqueous medium and Sn-beta has been demonstrated
to be a water-tolerant Lewis acid, we examined the conversion
of FH to FA in water. As shown in Table 1 (Entries 8 and 9),
high selectivity for conversion of FH to FA is not possible in
purely aqueous medium, regardless of reaction temperature.
Indeed, even the presence of small amounts of water decreases
the selectivity for conversion of FH to FA (comparing Entries
Reuse of the Sn-beta catalyst recovered after reaction for 24 h
led to only 9% FA selectivity at 18% FH conversion after
reaction for 4 h at 358 K. Thermogravimetric analysis (TGA) of
the same catalyst revealed 2.5% mass loss over the range of 400
to 700 K, with a maximum rate of loss at 534 K (see Supporting
Information, Figure S4). Reuse of the catalyst after TGA
analysis yields 54% selectivity at 16% conversion, with a rate
comparable to that of the fresh catalyst (Entry 12, Table 1),
indicating that activity can be recovered by calcination. The
observed mass loss indicates formation of carbonaceous
deposits on the catalyst, which would be consistent with
deposition of residues from the degradation of FH and/or FA
at high FA concentrations.
1
0 and 11 with Entry 4, Table 1). As discussed below, this
behavior is the result of FA-catalyzed degradation of FH, which
takes place in water regardless of the presence of the Sn-beta
catalyst. Neutralizing the acid functionality of FA by performing
the reaction in mixtures of methanol and water resulted in
substantial improvements in selectivity compared to reactions
carried out in pure water (comparing Entries 13 and 14 with
Entry 9 in Table 1).
The highest selectivities for production of FA were observed
for reactions in tetrahydrofuran (THF) solvent, where
selectivity as high as 80% can be obtained at 12% FH
conversion, although selectivity decreases with increasing
conversion (see Table 1, Figure 1). Given the improvement
As shown in Table 2, FH is stable in water and FA is not,
regardless of the presence of the Sn-beta catalyst. Moreover, it
a
Table 2. Stability of FH and FA under Reaction Conditions
FH only
FA only
FA and FH
solvent
conv (%) conv (%) FH conv (%) FA conv (%)
b
water
THF
2
21
38
21
30
4
c
4
n.d.
n.d.
6
THF + TFA
:1 water/MeOH
10
n.d.
1
n.d.
9
a
b
3
58 K for 4 h. Reaction of FA in water in the presence of Sn-beta
c
resulted in 23% conversion. Not detected.
appears that FA can catalyze the degradation of FH because
significant degradation of FH occurs when FA is also present in
solution. Given that FA is a Brønsted acid, this observed
instability suggests that FH and FA are susceptible to Brønsted-
acid catalyzed degradation in water. Indeed, FH is stable in the
presence of FA in a 1:1 mixture of methanol and water,
although there is still a small amount of FA degradation due to
the presence of water. The acid-catalyzed degradation of FH
potentially involves ring hydrolysis and subsequent condensa-
tion, as has been proposed for the acid-catalyzed degradation of
5-hydroxymethylfurfural (see Supporting Information, Figure
S7). The resulting high molecular-weight condensation
products would be deposited on the catalyst, consistent with
the observed catalyst deactivation.
While hydrolysis and condensation describe the behavior of
FH and FA in water, they do not account for the decrease in
selectivity observed at high conversions in THF solvent.
Importantly, while FH and FA are both stable independently in
THF (see Table 2), degradation of FH occurs in the presence
of FA, whereas FA is stable in THF with or without the
presence of FH. This behavior suggests that FH degradation is
catalyzed by FA when FA is present at high concentrations, and
it shows that degradation of FA requires the presence of water.
Figure 1. Influence of FH conversion on selectivity to FA for reactions
carried out with Sn-beta (Si/Sn = 400) at 348 K (○) and 358 K (●).
in selectivity observed for reactions carried out in THF, the use
of a biphasic reactor could be a promising reaction system;
however, the partition coefficient of FH in aqueous/organic
systems is not favorable using nonpolar solvents (see
Supporting Information, Table S1). Additionally, the use of
long-chain alcohols for the organic phase is precluded by the
formation of either hemiacetals, which would be too large to fit
into the pores of Sn-beta, or diacetals which are sterically
hindered and unreactive for MPVO reactions.
Measurement of the apparent reaction kinetics for the
reaction in THF, using the initial rate of FA formation, (see
Supporting Information, Figures S2 and S3) gave a reaction
order of 0.22 ± 0.07 with respect to the FH concentration. The
apparent activation energy was determined to be 71.6 ± 3.5 kJ
38
2
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ACS Catalysis
Research Article
a
Table 3. Conversion of Cortalcerone to FA with Bifunctional Al−Sn-beta
b
entry
catalyst
Al-beta
Si/Al
Si/Sn
solvent
conv. (%)
sel. to FH (%)
sel. to FA (%)
c
1
2
3
4
5
6
7
8
9
50
--
water
water
15
28
7
20
n.d.
27
n.d.
8
n.d.
Sn-beta
--
400
--
n.d.
n.d.
n.d.
36
Al-beta
50
1:1 water/MeOH
1:1 water/MeOH
1:1 water/MeOH
1:1 water/MeOH
1:1 water/MeOH
1:1 water/MeOH
1:1 water/MeOH
1:9 water/MeOH
9:1 water/MeOH
Sn-beta
--
400
400
400
200
200
200
200
200
33
40
14
15
53
Al-beta + Sn-beta
Al−Sn-beta
Al−Sn-beta
Al−Sn-beta
Al−Sn-beta
Al−Sn-beta
Al−Sn-beta
50
50
21
21
5
11
50
32
200
200
200
200
42
d
d
d
76
3
34
1
0
1
20
56
1
47
17
1
5
a
b
All reactions carried out with mass ratio of catalyst:cortalcerone = 0.25 for 0.5 h at 358 K except where indicated. FA is analyzed via HPLC as a
c
d
combination of ester and free acid. Not detected. Catalyst:cortalcerone = 0.5.
Furthermore, addition of a stoichiometric amount of trifluoro-
Entries 6−8 in Table 3 show that the highest yield of FA
acetic acid (TFA) to FH in THF results in an amount of
degradation comparable to that observed in the presence of FA,
confirming that FH is unstable in the presence of Brønsted
acids. Similar addition of TFA to FA in THF has no effect,
indicating that the degradation reactions involve the hydrated
glyoxal group of FH. For example, two FH molecules can
dimerize through nucleophilic addition, as has been described
(42% selectivity at 53% conversion) can be achieved using Al−
Sn-beta with a high Si/Al ratio and a low Si/Sn ratio,
corresponding to a low Brønsted acid site density and high
Lewis acid site density (as confirmed by FTIR spectra of
adsorbed pyridine, Supporting Information, Table S2). For the
two catalysts with low Si/Al ratio (Entries 6 and 7, Table 3),
the high Brønsted acid site density results in increased FH
degradation and deposition of carbonaceous residues on the
catalyst, leading to low overall activity. Similar behavior is
observed when cortalcerone is reacted over pure Al-beta, where
conversion is low because of deposition of carbonaceous
resides, as revealed by TGA (Supporting Information, Figure
S6). Correspondingly, the overall catalyst activity improves
when the Si/Al ratio is increased and the number of Brønsted
acid sites is decreased (Entry 8, Table 3). Decreasing the Si/Sn
ratio increases the number of water-tolerant Lewis acid sites,
and increases the selectivity to FA. Additionally, as observed
above, the selectivity to FA appears to depend on conversion,
with decreasing selectivity at high conversion (Entry 9, Table
3
9,40
for the dimerization of methylglyoxal
(see Supporting
Information, Figure S8 for more detail). This behavior would
also take place in water, which could further explain the above-
noted conversion of FH in the presence of FA in water. Thus,
FH is unstable in the presence of Brønsted acids in both THF
and water, whereas FA is susceptible to acid-catalyzed
degradation in water only.
The degradation of FH observed at high FA concentrations
suggests that it would be desirable to convert cortalcerone to
FA over a bifunctional catalyst containing Brønsted and Lewis
acid sites, thereby minimizing the FH concentration. This
approach also has the benefit of simpler processing, as both
reactions can be performed in one pot without the need for
intermediate separations. Brønsted acid sites are required to
convert cortalcerone to FH, because the Lewis acid sites on Sn-
beta do not catalyze this dehydration reaction (see Table 3). In
this respect, an Al-containing beta zeolite (Al-beta), a
heterogeneous Brønsted acid, is active for dehydration of
cortalcerone to FH, achieving 20% selectivity to FH at 15%
cortalcerone conversion (see Table 3).
Because the biological production of cortalcerone takes place
in water, it would be attractive to convert cortalcerone to FA in
an aqueous/organic solvent system. Thus, initial reactions
combining the use of both Brønsted and Lewis acid catalysts
were carried out using a mixture of 50% w/w methanol in water
as the solvent and lyophilized, enzymatically derived cortalcer-
one as the reactant. Methanol was chosen to favor the
formation of FA as its methyl ester, thereby preventing the acid
group from catalyzing undesirable degradation reactions of FH
and FA, and water was included in the solvent mixture to
moderate the formation of acetals with FH. This solvent system
was studied first using a physical mixture of Al-beta and Sn-
beta, achieving 36% selectivity to FA at 40% cortalcerone
conversion, with only 8% selectivity to FH. This result
demonstrates that FA can be produced from enzymatically
derived cortalcerone when both Brønsted and Lewis acid sites
are present. We subsequently studied this solvent system using
bifunctional catalysts containing both Sn and Al.
3
). TGA measurements of this spent catalyst again confirmed
the presence of carbonaceous deposits (see Supporting
Information, Figure S5).
Increasing the methanol content of the solvent (Entry 10,
Table 3) results in a decrease in catalytic activity, which is
possibly a side effect of reaction of the hydroxyl groups of
cortalcerone with methanol. In spite of the lower activity, the
selectivity to FA remains high because of the high methanol
content. Indeed, the selectivity is only marginally higher than
that observed in 1:1 water/methanol, indicating that high
methanol concentrations are not necessary to obtain the best
observed selectivity. Conversely, decreasing the methanol
content results in lower selectivity because of increased
degradation of FH and FA (Entry 11, Table 3), indicating
that methanol is important for prevention of FA-catalyzed
degradation.
CONCLUSIONS
■
We have demonstrated the conversion of FH to FA using tin-
containing beta zeolites. Conversion of FH in THF over Al-free
Sn-beta can achieve 80% selectivity to FA at 12% conversion,
although selectivity decreases with increasing conversion
because of Brønsted acid catalyzed degradation reactions of
FH. While the catalyst undergoes deactivation from deposition
of carbonaceous residues, the catalyst can be fully regenerated
by calcination. Further, bifunctional catalysts containing both
2
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ACS Catalysis
Research Article
Brønsted and Lewis acid sites (i.e., beta-zeolite containing both
Al and Sn) are effective for conversion of enzymatically derived
cortalcerone to FA in one pot in a methanol−water solvent
system, achieving 42% selectivity at 53% conversion.
(16) Schoevaart, R.; Kieboom, T. Tetrahedron Lett. 2002, 43, 3399−
3
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2
(
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ASSOCIATED CONTENT
■
*
S
Supporting Information
(
19) Nikolau, B. J.; Perera, M.; Brachova, L.; Shanks, B. Plant J. 2008,
Complete experimental methods, details of cortalcerone
synthesis, partition coefficient measurements, apparent reaction
kinetics measurements, thermogravimetric analysis of spent
catalysts, details of potential FH and FA degradation pathways,
and catalyst characterization by FTIR spectroscopy of adsorbed
pyridine. This material is available free of charge via the
Internet at http://pubs.acs.org.
5
(
(
4, 536−545.
20) Shanks, B. H. ACS Chem. Biol. 2007, 2, 533−535.
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AUTHOR INFORMATION
(24) West, R. M.; Holm, M. S.; Saravanamurugan, S.; Xiong, J.;
Beversdorf, Z.; Taarning, E.; Christensen, C. H. J. Catal. 2010, 269,
■
Corresponding Author
E-mail: dumesic@engr.wisc.edu.
1
(
22−130.
25) Chia, M.; Dumesic, J. A. Chem. Commun. (Cambridge, U. K.)
2011, 47, 12233−12235.
26) Corma, A.; Domine, M. E.; Valencia, S. J. Catal. 2003, 215,
94−304.
27) Bermejo-Deval, R.; Assary, R. S.; Nikolla, E.; Moliner, M.;
*
Notes
(
2
(
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Roman-Leshkov, Y.; Hwang, S.-J.; Palsdottira, A.; Silverman, D.; Lobo,
R. F.; Curtiss, L. A.; Davis, M. E. Proc. Natl. Acad. Sci. U. S. A. 2012,
109, 9727−9732 S9727/1-S9727/19.
This work was supported in part by the Advanced Biofuel
Intermediates program of the U.S. Forest Service and in part by
the Agriculture and Food Research Initiative Grant No. 2011-
(28) de Koker, T. H.; Mozuch, M. D.; Cullen, D.; Gaskell, J.; Kersten,
P. J. Appl. Environ. Microbiol. 2004, 70, 5794−5800.
6
7009-20056 from the USDA National Institute of Food and
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