Integration of Enzymatic and Heterogeneous Catalysis for One-Pot Production of Fructose from Glucose

Article abstract of DOI:10.1002/cssc.201800015

The search for efficient routes for the production of fructose from biomass-derived glucose is of great interest and importance, as fructose is a highly attractive substrate in the conversion of cellulosic biomass into biofuels and chemicals. In this study, a one-pot, multistep procedure involving enzyme-catalyzed oxidation of glucose at C2 and Ni/C-catalyzed hydrogenation of d-glucosone at C1 selectively gives fructose in 77 % yield. Starting from upstream substrates such as α-cellulose and starch, fructose was also generated with similar efficiency and selectivity by the combination of enzymatic and heterogeneous catalysis. This method constitutes a new means of preparing fructose from biomass-derived substrates in an efficient fashion.

Full text of DOI:10.1002/cssc.201800015

Accepted Article
Title: Integration of Enzymatic and Heterogeneous Catalysis for One-
pot Production of Fructose from Glucose
Authors: Jiankui Sun, Helong Li, Hongzhi Huang, Bo Wang, Ling-Ping
Xiao, and Guoyong Song
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10.1002/cssc.201800015
ChemSusChem
COMMUNICATION
Integration of Enzymatic and Heterogeneous Catalysis for One-
pot Production of Fructose from Glucose
Jiankui Sun,[a] Helong Li,[a] Hongzhi Huang,[b] Bo Wang,[a] Ling-Ping Xiao[a] and Guoyong Song*[a]
Abstract: The search for efficient routes for the production of
fructose from biomass-derived glucose is of great interest and
importance as fructose is a highly attractive substrate in the
conversion of cellulosic biomass to biofuels and chemicals. We
herein report a one-pot, multi-step procedure involving enzyme-
catalyzed oxidation of glucose at C2 position and Ni/C-catalyzed
hydrogenation of D-glucosone at C1 position selectively, thus giving
decreased and the glucose–fructose equilibrium shifted towards
fructose. In 2013, Riisager and coworkers reported a zeolite-
catalyzed multi-step reaction route involving isomerization,
methylation and hydrolysis, which gave 55% yield of fructose
finally (Scheme 1).[11] In 2016, Palkovits used (2-
(hydroxymethyl)phenyl)boronic acid (HMPBA) to covalently bond
fructose in a Na2HPO4/NaH2PO4 catalytic system, leading to
formation of fructose-HMPBA complexes, which can release
fructose up to 51% yield after acid extraction (Scheme 1).[9]
The integration of heterogeneous chemical and biological
catalysis has been regarded as an important strategy for
producing chemicals from biomass, especially in cascade-type
redox reactions.[12] For example, Froidevaux, Delcroix and
Dumeignil proposed that sorbitol generated from hydrogenation
of glucose by a chemcatalyst, can be oxidized into fructose in
the presence of a sorbitol dehydrogenase.[12g] It is well known
that glucose can be oxidized at C2 position with pyranose
oxidases[13] (or immobilized enzyme)[13b,14], leading to formation
of dicarbonyl D-glucosone, an important precursor for
biosynthesis of the antibiotic cortalcerone. Theoretically, it is
possible that D-glucosone can be hydrogenated into fructose
selectively at C1 position (aldehyde unit). Two patents have
confirmed such process by using a palladium catalyst[14] or
xylose reductase,[15] thus providing a new pathway to generate a
high yield of fructose by overcoming reaction equilibrium
between glucose and fructose.[12a] However, these two-step
reactions suffer from costly Pd or reductase catalyst and
complicated intermediate isolation. Alternatively，the low-cost
metal catalyst, such as Raney Ni, was also used for
hydrogenation of D-glucosone, which afforded fructose in a low
a
remarkable 77% yield of fructose. Starting from upstream
substrates such as α-cellulose and starch, fructose was also
generated with similar efficiency and selectivity by the combination
of enzymatic and heterogeneous catalysis. This method constitutes
a new protocol for preparation of fructose from biomass-derived
substrates in an efficient fashion.
Fructose is widely used in the food industry, which contributes
many useful physical and functional attributes to food and
beverage applications.[1] In addition, recent investigations on
conversion of biomass to biofuels and fine chemicals confirmed
that fructose is a superior substrate compared to glucose.[2,3]
Currently, the isomerization of glucose to fructose for production
of high-fructose corn syrups (HFCS) has become the largest
immobilized biocatalytic manufacturing process worldwide,
reaching a global production as 8.5 million tons in 2015.[4] The
industrial isomerization of glucose to fructose is performed in
aqueous phase by using an immobilized enzyme (xylose
isomerase), which usually gives a mixture of 42% fructose, 50%
glucose and 8% other saccharides, because this isomerization
reaction is governed by thermodynamic equilibrium (Keq ≈ 1 at
298 K) (Scheme 1).[5] This entails the problem that enriching or
isolation of fructose from the reaction mixture needs the use of
elaborate and costly preparative column chromatography.[1]
As an alternative to enzyme catalysis, glucose can also be
isomerized to fructose in the presence of a chemical catalyst.[5d,6-
8]
Despite significant efforts have been devoted to designing
efficient chemical catalysts, including Lewis acid[6,7] and
Brønsted base[8] catalysts, the fructose yields were limited to
30–35% (Scheme 1), being inferior to enzymatic catalysts.
Recently, in situ complexation of fructose with borates,[9]
aluminates[10] or methanol[11] was reported as a new method to
improve the fructose yield in chemical catalysis, wherein the
concentration of fructose in the isomerization reaction mixture
[a]
Mr Jiankui Sun, Mr Helong Li, Dr Prof. Bo Wang, Dr. Ling-Ping Xiao,
Dr. Prof. Guoyong Song
Beijing Key Laboratory of Lignocellulosic Chemistry
Beijing Forestry University
No.35 Tsinghua East Road, Beijing, China
E-mail: songg@bjfu.edu.cn
[b]
Dr Hongzhi Huang
Novozymes (China) Investment Co. Ltd.
No.14 Xinxi Road, Beijing, China
Supporting information for this article is given via a link at the end of
the document.
Scheme 1. General procedures for preparation of fructose from glucose
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10.1002/cssc.201800015
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yield (30%) because of further hydrogenation of fructose.[14]
Herein, we reported a two-step procedure for synthesis of
fructose from glucose in a high yield, involving pyranose
oxidase-catalyzed oxidation of fructose at C2 position and Ni/C-
catalyzed hydrogenation of D-glucosone at C1 position. The
enzymatic and heterogeneous catalysis can be integrated into
one-pot procedure without any intermediate purification.
The first oxidative reaction step for the approaches shown in
Scheme 1 was carried out under citric acid butter (pH = 5) in air
at 30 oC, in which all of the enzymes were quite active. The
glucose 2-oxidase (EC 1.1.3.10, 620 U, 2 wt%), isolated from
Trametes hirsute, can efficient catalyze D-glucose (5% w/v) into
D-glucosone via selective C2 oxidation quantitatively in 24 h,
whereas oxygen acted as an oxidant and a catalase (2 wt%)
was used to convert H2O2. This reaction in O2 atmosphere is
faster than in air.[13e]
After successful achieving enzyme-catalyzed oxidation of
glucose, we then investigated the hydrogenation of D-glucosone
in the presence of a series of heterogeneous transition metal
catalysts including nickel, palladium, ruthenium and platinum.
On the treatment of D-glucosone with Ni/C (Ni content: 5 wt%,
1:15 Ni:D-glucosone molar ratio) and 1 atm H2 at 80 oC in EtOH
for 12 h, a complete conversion of D-glucosone was observed,
which gave a mixture of D-fructose (65.2%) via hydrogenation
aldehyde moiety (C1), D-glucose (17.2%) via hydrogenation
ketone moiety (C2), D-mannitol (12.6%) and D-sorbitol (3.6%)
via dual hydrogenation (Table 1, entry 1). A trace of D-mannose
(ca. 0.5%) was also detected in the mixture, which can be to
hydrogenate into mannitol rapidly.[16] Ethyl fructoside, possibly
generated from the reaction of D-fructose with EtOH,[17] was not
observed under current reaction conditions (SI). Nickel
supported on amorphous-silica-alumina (Ni/ASA)[18] also showed
a high activity, but gave a slight lower fructose yield (63%) under
similar reaction conditions (Table 1, entry 2). The precious metal
catalysts, such as Pd/C, Ru/C and Pt/C, were slight more
selective than Ni catalysts, gave D-fructose in 65.8–67.6% yields
in 9 h (Table 1, entries 3-5). Decreasing the dosage of Ni/C (Ni
content: 5 wt%) to 25 wt% (where molar ratio of Ni : D-
glucosone is 1:27) or employing a low Ni loading catalyst (Ni
content: 2 wt%, molar ratio of Ni : D-glucosone is 1:17) resulted
in a drop in activity, while the products distributions and
selectivity to fructose (62.6% and 62.1%, respectively) remain
unchanged (Table 1, entries 7-8). These yields compare well
with reports of fructose synthesis from glucose through
isomerization reaction using xylose isomerase[19] and chemical
catalysts.[7a] Taking account of the cost of catalyst, Ni/C was
chosen for subsequent investigation.
A range of solvents were screened in the hydrogenation of D-
glucosone with Ni/C under H2 atmosphere and the results are
summarized in Figure 1 and Table S1. The hydrogenation
i
reactions in MeOH, PrOH and H2O proceeded to give complete
o
conversions of D-glucosone in 12 h at 80 C with Ni/C. It looks
that the selectivity towards D-fructose increased with the solvent
polarity.[20] For example, water having a high ET(30)[20] value
(63.1 kcal mol-1) enabled high selectivity to D-fructose (67.5%)
and D-glucose (20%), wherein the yield of D-mannitol decreased
to 6.2%, probably because the formation of D-mannose was
suppressed in water.[6c,21] EtOH (ET(30) = 51.9 kcal mol-1) gave
D-fructose in 65.2% yield, in which low yields of D-glucose
(17.2%) and sorbitol (3.6%) were observed. In the case of iPrOH
with ET(30) value as 48.4 kcal mol-1, a significant drop of D-
fructose (58.7%) and a raise of D-mannitol (12.3%) were
observed. Therefore, we focused on the study of binary solvent
mixture of EtOH and H2O. Further screening indicated that the
mixed EtOH/H2O in 7: 1 (v/v) as the best choice,[22] in which
fructose yield was improved to 78.5%, together with the
formation of glucose (13.2%), mannitol (6.7%) and sorbitol
(1.1%) as byproducts.
Table 1. Hydrogenation D-glucosone over various catalysts[a]
yields (mol %)b
time Con.
entry
catalyst
(h)
(%)
fructose glucose mannitol sorbitol
1
2
3
4
5
6
7
8
Ni/C
12
100
100
100
100
100
94.6
92.1
90.3
65.2
63.0
66.8
67.6
65.8
60.3
57.6
56.1
17.2
18.1
17.1
16.5
17.3
15.9
15.6
15.7
12.6
13.5
12.6
12.3
13.1
13.6
14.1
14.0
3.6
4.6
2.8
2.6
2.9
4.3
4.1
4.1
fructose
glucose
mannitol
sorbitol
Ni/ASA
Pd/C
12
9
80
70
60
50
40
30
20
10
0
Ru/C
Pt/C
9
9
Ni/C[c]
Ni/C[d]
Ni/C[e]
24
48
48
i
H
O
EtOH
EtOH/H
7:1
O
EtOH/H O EtOH/H O
2 2
MeOH
PrOH EtOH/H O
2
2
2
1:1
4:1
9:1
[a] Reaction conditions: D-glucosone (0.28 mmol, 50 mg), catalyst (50 mg),
EtOH (5 mL), H2 (1 atm); The metal content in catalysts is 5 wt % in entries 1-
7. D-fructose exists in different conformations which vary with the polarity of
the reaction medium and the open-chain form is depicted here. [b] Determined
by HPLC and ion chromatography by comparison with authentic samples. [c]
25 mg 5 wt % Ni/C was used. [d] 13 mg 5 wt % Ni/C was used. [e] 50 mg 2
wt % Ni/C was used.
Figure 1. Influences of solvents of Ni/C-catalyzed hydrogenation of D-
glucosone
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The hydrogenation reaction of D-glucosone was further
carried out over Ni/C at different reaction temperature in
EtOH/H2O (7: 1) under 1 atm H2 atmosphere, and the results
were summarized in Figure 2 and Table S3. In the case of a low
reaction temperature, a drop in activity was observed as seen in
The hydrogenation of D-glucosone over Ni/C as a function of
time by HPLC was monitored under the optimized conditions (80
oC, 1 atm H2, 7:1 EtOH/H2O). Over the first 11 h of the reaction,
98.8% conversion was observed in Figure 4, where fructose,
glucose, mannitol and sorbitol were generated steadily over time
to reach 77.1%, 10.8%, 8.1% and 1.2% yields, respectively. The
production of D-fructose was much faster than the formation of
other products. The formation of fructose follows first order
o
the case of 50 oC (19.2% conversion, 24 h) and 70 C (90.1%
conversion, 20 h), while the selectivity towards D-fructose
remained high (71.4% and 76.2%, respectively). Increasing the
temperature to 100 oC led to an obvious decreased fructose
yield (41.5%), together with the observation of increasing of D-
mannitol (32.8%) and D-sorbitol (10.3%). The influence of H2
pressure in the range of 1−20 atm was also investigated. As
shown in Figure 3 and Table S2, the distribution of D-fructose
was decreased obviously, while the yields of D-glucose, D-
mannitol and D-sorbitol were increased under high H2 pressure.
Hydrogenation of D-glucosone at C2 position (ketone unit)
leading to the formation of D-glucose probably features higher
energy profile than the formation of D-fructose at C1 position
due to steric hindrance. Therefore, the high H2 pressure and/or
high temperature are favorable for generation D-glucose and
other byprodcts through further hydrogenation. In the absence of
H2, no transfer hydrogenation of D-glucosone was observed.
kinetics at 60-80 oC
, consistent with the hydrogenation
process.[23] The rate constants were measured at 60 oC (k =
0.0102 h-1), 65 oC (k = 0.0267 h-1), 70 oC (k = 0.0399 h-1), 75 oC
(k = 0.0595 h-1) and 80 oC (0.234 h-1) (SI). Obviously, at
temperature of 60-75 oC, the increase in reaction rate with
increase in temperature is limited, while at 80 oC a sudden
increase in the reaction rate was observed, probably because of
the attenuation of mass transport limitation.[23b]
D-glucosone
100
fructose
glucose
mannitol
80
sorbitol
60
80
60
40
20
0
fructose
glucose
mannitol
sorbitol
40
20
0
0
2
4
6
8
10
reaction time / h
Figure 4. Time profile of the hydrogenation of D-glucosone under optimized
conditions.
50
100
70
80
reaction temperature / oC
The recycling stability of the metal catalysts is important for
their potential applications in industry. Initially, the spent Ni/C
was subjected to simple washing and was used directly in the
Figure 2. Effect of reaction temperature of Ni/C-catalyzed hydrogenation of D-
glucosone.
following cycle, which showed
a
decreased activity in
hydrogenation of D-glucosone (85% conversion). In such a case,
the selectivity towards D-fructose remained unaltered (75%). To
recuperate the catalyst, a H2-thermal treatment was conducted
at 400 oC for 2 h. As a result, performing this H2-treatment
almost recovered the performance of the spent Ni/C in 10st run,
80
fructose
glucose
mannitol
60
40
20
0
sorbitol
which gave
a complete conversion of D-glucosone with
observation of 73.2% yield of D-fructose (Table S4). The Ni
contents were determined as 4.8 wt % after ten cycles based on
ICP analysis, close to the initial Ni content 5.0 wt %.
Based on above results, a one-pot procedure for preparation
D-fructose was tested on a large scale (Scheme 2). Treatment
of 5 g D-glucose with glucose 2-oxidase (100 mg, 2 wt%) in a
citric acid butter under air for 24 h gave D-glucosone aqueous
solution. After concentration and addition of EtOH and Ni/C, D-
glucosone (0.28 M in 7:1 EtOH/H2O), without prior isolation, was
then hydrogenated into D-fructose in 77% yield under 1 atm H2.
Obviously, the residuary citric acid and enzyme do not affect the
0
5
10
15
20
H pressure / atm
2
Figure 3. Effect of H2 pressure of Ni/C-catalyzed hydrogenation of D-
glucosone.
activity and selectivity of hydrogenation reaction.
A
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10.1002/cssc.201800015
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COMMUNICATION
complementary reaction by using D-glucose-13C6 as a substrate
was conducted by this one-pot process, which gave D-fructose-
13C6 in 77.6% yield. In the 13C NMR spectrum (CD3OD/D2O), the
C2 of α-D-fructofuranose, β-D-fructofuranose and β-D-
fructopyranose resonate characteristically at δ = 104.9 (dd, J =
49.2, 49.3 Hz), 102.2 (dd, J = 49.5, 46.8 Hz) and 98.5 (dd, J =
48.1, 48.2 Hz) ppm, respectively, in line with typical values
reported for 13C-labelled D-fructose.[24] The C1 of D-glucose
selectivity, respectively.[16] These results may explain the reason
of low yield of D-mannose and relative higher yield D-mannitol
compared to D-sorbitol in Ni/C-catalyzed D-glucosone
hydrogenation.
Since D-glucose is available from starch or cellulose via
hydrolysis, we then explored the direct conversion of upstream
substrates into D-glucose by combination of enzymatic and
heterogeneous catalysis in a one-pot manner. This procedure
resonate as doublets at 96.6 (J = 46.4 Hz) and 92.7 (J = 44.6 Hz) involved treatment of α-cellulose with cellulase (7 wt%), glucose
ppm, ascribed to β-D-glucopyranose and α-D-glucopyranose
tautomers (SI).
2-oxidase (2.5 wt%) and catalase (2.5 wt%) in citric acid butter
(pH = 5) at 50 C under air for 48 h, followed by further 12 h
o
hydrogenation reaction with Ni/C under optimized conditions,[27]
without separation of D-glucose and D-glucosone intermediates.
As a consequence, fructose was obtained in 74.1% yield,
together with the formation of with glucose (15.3%), mannitol
(7.3%), sorbitol (2.1%) and mannose (0.6%) as byproducts
(Scheme 4). Starting from starch, D-fructose was also obtained
in 74.3% yield via hydrolysis, oxidation and hydrogenation with
similar activity and selectivity (SI).
Scheme 2. One-pot production of fructose from glucose
To understand the products distribution in hydrogenation of D-
glucosone process, we carried out a series of reactions with
Ni/C in EtOH/H2O at 80 oC (Scheme 3). No isomerization
reaction between D-glucose and D-fructose or D-glucose and D-
mannose[20] were detected with Ni/C, differing with the acidic or
basic heterogeneous catalysts.[5,7] Hydrogenation of D-glucose
gave sorbitol exclusively. Obviously, the activity of this
transformation was affected by H2 pressure, whereas only 4%
conversion was obtained under 1 atm H2, versus 99% yield
under 40 atm H2.[23c,25] In the case of D-fructose, 45% sorbitol
and 55% mannitol were generated after hydrogenation, albeit in
the difference activities, consistent with previous reports.[26]
Treatment of D-mannose under 1 atm and 40 atm H2 with Ni/C
resulted in D-mannitol in 23% and 99% yields with 100%
Scheme 4. Direct conversion of α-cellulose into fructose by combination of
enzymatic and heterogeneous catalysis.
In summary, we demonstrated a one-pot, two-step reaction
procedure involving enzyme-catalyzed oxidation of D-glucose
and Ni/C-catalyzed hydrogenation of D-glucosone, thus giving
D-fructose in 77% yield on a large scale. Direct use of upstream
substrates such as α-cellulose and starch was also applicable in
this integrated system. This constitutes an efficient protocol to
produce D-fructose from biomass-derived substrates, being
superior to enzyme or chemicals-catalyzed isomerization
reactions in terms of efficiency and the reduction of purification.
The influences on reaction temperature, time and H2 pressure
together with a series of catalytic hydrogenation reactions
offered important information for understanding the distribution
of hydrogenation products from D-glucosone.
Acknowledgements
This work was supported by Fundamental Research Funds for
the Central Universities (No. 2017ZY25), the National Natural
Science Foundation of China (No. 2177060769) and National
Program for Thousand Young Talents of China.
Scheme 3. Reactivities and selectivity of hydrogenation of sugars with Ni/C.
Keywords: glucose • fructose • glucose 2-oxidase • Ni/C •
biomass
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10.1002/cssc.201800015
ChemSusChem
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Jiankui Sun, Helong Li, Hongzhi Huang,
Bo Wang, Ling-Ping Xiao and Guoyong
Song*
Page No. – Page No.
Integration of Enzymatic and
Heterogeneous Catalysis for One-pot
Production of Fructose from Glucose
The combination of enzymatic and heterogeneous catalysis provides a new
protocol for preparation fructose up to 77% yield from biomass-derived substrates
in a one-pot manner.
This article is protected by copyright. All rights reserved.