Purification of EMIMOAc used in the acetylation of lignocellulose

Article abstract of DOI:10.1021/je300330t

Up to now, several methods of purifying ionic liquids (ILs), such as the extraction with supercritical carbon dioxide, crystallization, column chromatography, and so forth were reported. The IL that was used in the acetylation of lignocellulose with the help of acetic anhydride contains an elevated amount of acetic acid. In this paper our investigations on the separation of acetic acid from synthetic mixtures with 1-ethyl-3- methylimidazolium acetate (EMIMOAc) are described. The separation was performed by evaporation, extraction, and esterification. While impurities like ethyl acetate, n-propyl acetate, isopropyl acetate, and tetrahydrofuran (THF) can easily be evaporated from EMIMOAc, it is difficult to remove acetic acid from EMIMOAC or EMIMCl by evaporation below certain concentration levels. In extraction tests acetic acid could be separated from EMIMOAc to some degree, especially with extractants immiscible with EMIMOAc having a high value of E_T(30) and a dielectric constant near that of acetic acid. The most successful removal of acetic acid was found to be an esterification of acetic acid at a large excess of alcohol, a long reaction time, and an intensive contact of the educts in the liquid phase at elevated temperature and pressure with subsequent evaporation of the produced acetic acid ester.

Full text of DOI:10.1021/je300330t

Article
pubs.acs.org/jced
Purification of EMIMOAc Used in the Acetylation of Lignocellulose
Jin-zhi Shi,†,‡,§ Jurgen Stein,*,‡ Stephan Kabasci,‡ and Hao Pang†
̈
†Key Laboratory of Cellulose and Lignocellulosics Chemistry, Guangzhou Institute of Chemistry, Chinese Academy of Sciences,
Guangzhou 510650, Guangdong, China
‡Fraunhofer Institute for Environmental, Safety and Energy Technology, UMSICHT, Oberhausen 46047, Germany
§Graduate University of the Chinese Academy of Sciences, Beijing 100049, China
ABSTRACT: Up to now, several methods of purifying ionic liquids (ILs), such as the
extraction with supercritical carbon dioxide, crystallization, column chromatography, and so
forth were reported. The IL that was used in the acetylation of lignocellulose with the help of
acetic anhydride contains an elevated amount of acetic acid. In this paper our investigations on
the separation of acetic acid from synthetic mixtures with 1-ethyl-3-methylimidazolium acetate
(EMIMOAc) are described. The separation was performed by evaporation, extraction, and
esterification. While impurities like ethyl acetate, n-propyl acetate, isopropyl acetate, and
tetrahydrofuran (THF) can easily be evaporated from EMIMOAc, it is difficult to remove acetic
acid from EMIMOAC or EMIMCl by evaporation below certain concentration levels. In
extraction tests acetic acid could be separated from EMIMOAc to some degree, especially with
extractants immiscible with EMIMOAc having a high value of ET(30) and a dielectric constant near that of acetic acid. The most
successful removal of acetic acid was found to be an esterification of acetic acid at a large excess of alcohol, a long reaction time,
and an intensive contact of the educts in the liquid phase at elevated temperature and pressure with subsequent evaporation of
the produced acetic acid ester.
lignocellulose in IL and only indicate possible methods of
recycling.
1. INTRODUCTION
The current energy and environmental crisis intensifies people’s
desire to find more renewable, as well as sustainable and more
environmentally friendly, resources as a substitute for
petroleum products. Cellulose as the most abundant renewable
organic material is the main constituent of natural materials
such as wood, cornhusk, bagasse, straw, and so forth. Cellulose
can be used as regenerated material for fibers, films, food
casings, membranes, sponges, and so forth; it can be modified
as cellulose derivatives, for example, cellulose ethers and esters,1
and additionally, it can be hydrolyzed to glucose, an important
raw material for biotechnological processes.
A big problem in the application of cellulose is that it is
difficult to bring cellulose to solution. Only a few solvents can
readily dissolve cellulose.2 Traditional cellulose solvents include
dimethyl sulfoxide/paraformaldehyde,3 N,N-dimethylacetamide
(DMAc)/LiCl,4 N-methylmorpholine-N-oxide (NMMO),5 al-
kali/urea or thiourea/H2O,6,7 NaOH/H2O,8 and so forth. All of
these solvents have a variety of disadvantages, especially the
requirement of activation before dissolution, instability, causing
serious environmental problems, side reactions, difficult
recycling, and high cost.
Certain ionic liquids (ILs) have many attractive properties,
such as good chemical and thermal stability, nonflammability,
and an immeasurable low vapor pressure.9 Since it was found
that ILs can dissolve cellulose,10 the variety of advantages of
cellulose dissolved in ILs has attracted great interest from
researchers. However, research mainly focused on the
dissolution of cellulose in ILs. Up to now there have been
only a few papers focusing on IL recovery. Most of the
publications mainly focus on dissolving and transforming
Scurto et al.11 took supercritical CO2 (scCO2) as a separation
medium for IL/H2O mixtures and found that the solutions of
water and 1-butyl-3-methylimidazolium tetrafluoroborate
(BMIMBF4) can be induced to form three phases in the
presence of scCO2. They also revealed that CO2 can induce
separation of ILs and organic mixtures.12 Kroon et al.13 used
supercritical CO2 as an antisolvent to crystallize the organic
compound methyl-(Z)-α-acetamido cinnamate (MAAC) from
BMIMBF4 by either using a shift to higher concentrations of
CO2 at a constant temperature (antisolvent crystallization) or
by using a shift to lower temperatures at a constant
concentration of CO2 (thermal shift). Supercritical CO2 can
also directly extract organic compounds from IL-solutions, if
they can be dissolved in supercritical CO2; an example for this
is N-acetyl-(S)-phenylalanine methyl ester (APAM).14 Recrys-
tallization was used by Nockemann et al.15 to purify ILs.
Brennan et al.16 found that boronate complexes could extract
up to 90 % of mono- and disaccharides from aqueous IL
solutions, pure IL, and IL containing hydrolysates of corn
stover. Tan et al.17 used acetonitrile as an extractant to clean an
IL, which contains the 1-ethyl-3-methylimidazolium cation and
a mixture of alkylbenzenesulfonates with xylenesulfonate as the
main anion, sodium chloride, hydrochloric acid, and sodium
xylenesulfonate, from impurities. Earle et al.18 used a special
column which was packed with the following compounds: celite
Received: March 17, 2012
Accepted: December 4, 2012
© XXXX American Chemical Society
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on the bottom to trap charcoal particles, flash chromatographic
silica gel in the middle for decolorizing/removal of polar and
inorganic impurities, and charcoal on the top for decolorizing
to remove the chromophoric impurities. Tang et al.19 used
many different stationary phases, and they found that
octadecylsilyl (ODS) columns have the best efficiency in
separating the colored impurities from ILs. They used these
adsorbents especially to purify hydrogen-bonding anions
containing ILs. Jeapes et al.20 uncovered a new way to recover
the IL 1-methyl-3-ethylimidazolium chloride. They heated up
1-methyl-3-ethylimidazolium chloride to (200 to 300) °C
under reduced pressure, so that the IL decomposes to 1-
methylimidizole, 1-ethylimidizole, chloromethane, and chloro-
ethane. Then they separated the volatile products from the
impurities by distillation and collected the volatile products in a
cold trap. From this they regenerated 1-methyl-3-ethyl-
imidazolium chloride. A molecular sieve was used by Gnahm
and Kolb21 to purify ILs.
under vigorous mechanical stirring and nitrogen purging into
the mixture.
2.3. Extraction Experiments. A sample of 300 mL of
solvent was put into a 500 mL round-bottomed flask. Then 20
g of a mixture including about 80 % EMIMOAc and 20 % acetic
acid was added to the bottom of the continuous liquid−liquid
extractor (Figure 1). The solvent in the round-bottomed flask
All of the methods referred to above have their own
weaknesses, such as that supercritical CO2 extraction requests
the miscibility of the extracted material with supercritical CO2
or that it is difficult to pump ILs which are solid or highly
viscous at room temperature through a column during column
chromatography.18,19
Over the past years imidazolium-based ILs like 1-ethyl-3-
methylimidazolium acetate or chloride (EMIMOAc and
EMIMCl, respectively) were increasingly used as solvent and
derivatization media for lignocellulose, because of the
comparatively high amount of lignocellulose that can be solved
in these IL. Acetylation is a typical derivatization reaction of
lignocellulose, commonly using acetic anhydride as the
acetylation agent.
In this work, we used some traditional methods such as
evaporation and extraction to remove the impurities from the
IL EMIMOAc. Probably, evaporation is the most common
method of purification of ILs, but documentation of
evaporation procedures in the literature is rare. The present
article focuses on the separation of acetic acid from synthetic
mixtures with EMIMOAc. As acetic acid is a main byproduct of
acetylation of lignocellulose with acetic anhydride (weight
fraction of acetic acid of about (10 to 15) % of the amount of
EMIMOAc in used IL mixtures), the described fundamental
work constitutes an integral part for the recycling of IL
solutions from lignocellulose treatment.
Figure 1. Continuous liquid−liquid extractor.
was kept at boiling point temperature for 5 h and continuously
extracted acetic acid from the EMIMOAc. After the extraction
procedure, the EMIMOAc raffinate was collected from the
bottom of the continuous liquid−liqiud extractor, and the
solvent content was separated by evaporation.
2. EXPERIMENTAL DETAILS
2.1. Materials. Toluene, ethyl acetate, tetrahydrofuran
(THF), n-heptane, diethyl ether, dioxane, acetic acid, ethanol,
methanol, n-propyl acetate, isopropyl acetate, Amberlyst, 1-
ethyl-3-methylimidazolium acetate (EMIMOAc), and 1-ethyl-3-
methylimidazolium chloride (EMIMCl) were purchased from
commercial sources, and all of the chemicals were used without
further purification. According to the supplier, the purity of the
used EMIMOAc is ≥ 95 %; before the experiments a water
content of 0.7 wt % was determined (Karl Fischer titration).
Amberlyst was dried under vacuum at 363 K for 8 h before
usage. Drying at higher temperatures runs the risk of losing
catalyst capacity due to gradual desulfonation.22
2.4. Esterification Experiments. A certain amount of IL
(EMIMOAc or EMIMCl), acetic acid, 15 mL of alcohol, and
dried Amberlyst as a catalyst were added into a 50 mL three-
necked round-bottom flask. Alcohol, which was in advance
added into a constant pressure funnel, was continuously
introduced into the three-necked round-bottom flask, and the
mixture was heated at (80 to 110) °C for 5 h under vigorous
mechanical stirring and nitrogen purging. After that, the
mixture was distilled at 130 °C under nitrogen for 5 h.
Some tests were performed in a pressure vessel with a
volume of 1 L. The quantities of EMIMOAc, acetic acid,
alcohol, and optionally Amberlyst as a catalyst were put into the
reactor, which was then prepressurized with nitrogen and
heated to 140 °C, so that the pressure reached (14 to 18) bar.
These conditions were kept over 16 h. Finally, the IL mixture
was distilled for 5 h at 130 °C while purging with nitrogen.
2.2. Evaporation Experiments. A certain amount of acetic
acid or other solvents and EMIMOAc (mixtures of a mass in all
about 20 g) was added into a three-necked round-bottom flask,
and the mixture was then heated to 130 °C for several hours
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2.5. Analytical Methods. The water content of EMIMOAc
was determined using a Karl Fischer titrator with model 795
KFT Titrino and 703 Ti stand from Metrohm. An Agilent 1200
high-performance liquid chromatograph equipped with a
column of phenomenex rezex ROH-organic acid H+ (300 ×
7.8 mm) was used to determine the concentrations in the liquid
samples of EMIMOAc and acetic acid.
acetic acid reached a nearly constant level of about 20 %, which
could not be reduced by prolonging the evaporation time. At
the same conditions acetic acid could be separated from a
mixture with EMIMCl to a mass content of about 8 %. It can be
concluded that, in contrast to common organic solvents or
water, acetic acid cannot easily be removed from ILs by
evaporation.
We believe that the possible reason is that acetic acid in these
ILs is dissociated to the anion H+ and the cation CH3COO−.
So in ILs the acetic acid with the form of anion and cation is
difficult to be evaporated by distillation.
Higher evaporation temperatures were not adopted because
further experiments showed that thermal decomposition of IL
becomes increasingly relevant at higher temperatures.
3.2. Separation of Acetic Acid from Mixtures with
EMIMOAc by Means of Extraction. As we have shown
above, it was difficult to reduce the mass fraction of acetic acid
in EMIMOAc to a level below 20 % by evaporation. Therefore,
we investigated liquid−liquid extraction as an alternative way to
purify acetic acid from ILs.
The most important point was to find a suitable solvent that
is not miscible with EMIMOAc in a large range of
concentration and has a miscibility gap with acetic acid. For
this purpose mixing experiments with some common solvents
and EMIMOAc were done; for the results compare Table 1.
Several physicochemical parameters are known to describe
the miscibility behavior of solvents at least to some extent. One
of them, the ET(30) value, empirically defines a solvent polarity
scale by using the solvatochromic visible absorption of betaine
dye no. 30 (2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)-
phenolate) as a solvent-dependent reference process.23,24
These ET(30) values are simply defined as the molar transition
energy of the standard betaine dye no. 30, measured in solvents
of different polarity at room temperature (25 °C) and normal
pressure (1 bar). High ET(30) values correspond to a high
solvent polarity. According to Doherty et al.,25 the ET(30) value
of EMIMOAc is 211 kJ·mol−1.
3. RESULTS AND DISCUSSION
3.1. Separation of Solvents from Mixtures with
EMIMOAc by Evaporation. It is widely believed that ILs
can easily be recycled, because they have no measurable vapor
pressure. Hence, volatile components are supposed to be easily
evaporated from mixtures with ILs. In our experiments with
acetic acid in EMIMOAc, we partly observed different results.
A comparative pretest with a mixture of an initial mass
fraction of water of 10 % in EMIMOAc showed that the
evaporation of water at 130 °C was within 3 h more efficient at
atmospheric pressure with nitrogen purging (final water
content of 0.2 wt %) than at a vacuum of 10 mbar (final
water content of 3.1 wt %). Therefore, the subsequent
evaporation tests with the aim to compare the evaporation
behavior of different solvents in mixtures with EMIMOAc were
made at atmospheric pressure under vigorous mechanical
stirring and nitrogen purging.
First, we investigated the separation of different organic
solvents from EMIMOAc by evaporation at the conditions
described above. As Figure 2 shows, ethyl acetate, n-propyl
From Table 1 we have come to the conclusion that the
change of miscibility behavior of EMIMOAc with different
solvents from miscible to not miscible correlates very well with
the dielectric constant and the ET(30) value of the solvents.
According to the experimental results the change of miscibility
takes place around a dielectric constant of 8 and an ET(30)
value of 160 kJ·mol−1.
The ET(30) value of acetic acid of 214.2 kJ·mol−1 is close to
that of EMIMOAc, which indicates a serious separation
challenge by extraction. The dielectric constant of acetic acid
is 6.15, and we also can find some solvents from Table 2 that
have a ET(30) value less than 160 kJ·mol−1 and a dielectric
constant near 6.15.
Table 2 shows some physicochemical data of solvents for
liquid−liquid extraction collected from literature26−28 and
various company publications.
Figure 2. Weight fraction of solvents in evaporation experiments with
partly different initial mass fractions (calculated from weight data of
the mixture with the assumption that the mass of the IL is constant in
the test).
Based on the principle of the dissolution in the similar
material structure and on the data of acetic acid for liquid−
liquid extraction, displayed above, solvents were chosen to test
the extraction efficiency of acetic acid from a mixture with
EMIMOAc, and the results are displayed in Table 3.
The results confirm the principle of the dissolution in the
similar material structure. The more the dielectric constant of
the solvent approaches the dielectric constant of acetic acid and
the closer the ET(30) value approaches 160 kJ·mol−1, the better
the solvent extracts acetic acid from EMIMOAc in the most
acetate, isopropyl acetate, and THF can easily and quickly be
removed from EMIMOAc. The mass fractions of these organic
solvents are reduced from 40 wt % to 5 wt % within less than 1
h.
Afterward, mixtures of different concentrations of acetic acid
in EMIMOAc were evaporated at the same conditions, and the
results are presented in Figure 2. In the tests with a high initial
concentration of acetic acid (≥ 50 % by weight) in the mixture,
the concentration of acetic acid decreased rapidly in the first
two hours to a level around 30 %. After 4 h the concentration of
C
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Table 1. Miscibility Behavior of Different Solvents with EMIMOAc (Sequence According the Value of Dielectric Constant)
ET(30)
solvent
n-heptane
dielectric constant
kJ·mol−1
85 wt % IL
25 wt % IL
20 wt % IL
15 wt % IL
10 wt % IL
5 wt % IL
1.90
2.00
130.2
a
a
a
a
a
b
a
a
b
b
b
b
b
b
a
a
a
a
a
b
a
a
b
b
b
b
b
b
a
a
a
a
a
b
a
a
b
b
b
b
b
b
a
a
a
a
a
b
a
a
b
b
b
b
b
b
a
a
a
a
a
b
a
a
b
b
b
b
b
b
a
a
a
a
a
b
a
a
b
b
b
b
b
b
petroleum ether
p-dioxane
2.20
150.6
141.8
144.8
163.6
159.4
156.5
187.2
176.6
217.5
192.5
188.3
264.0
toluol
2.38
diethyl ether
chloroform
ethyl acetate
tetrahydrofuran
dichloromethane
acetone
4.34
4.80
6.02
7.30
9.10
20.70
24.30
37.50
46.68
78.54
ethanol
acetonitrile
dimethylsulfoxide
water
a
b
Immiscible. Miscible.
mass fraction of acetic acid from (15.3 to 12.1) wt %. In the
extraction test with 2-pentanone the mass of EMIMOAc
decreased from initially (5 to 3) g in the IL-rich phase, which
means that an appreciable amount of EMIMOAc is transferred
to the 2-pentanone phase. In the extraction tests with other
solvents the mass loss of EMIMOAc was in general lower in
comparison to the 2-pentanone tests. Although all solvents
tested showed an extraction ability for acetic acid, the mass
transfer always was quite small taking the severe extraction
conditions (long time and high solvent volume) into account.
Therefore, it is difficult to use liquid−liquid extraction for acetic
acid removal, too.
3.3. Separation of Acetic Acid from Mixtures with
EMIMOAc by Esterification. As it is shown in Figure 2, ethyl
acetate can easily be removed from EMIMOAc by evaporation.
Additionally, higher fractions of ethyl acetate do not dissolve in
EMIMOAc and form a second liquid phase which can easily be
decanted from the IL (compare extraction tests). Therefore, we
concluded that if we were able to esterify the acetic acid in IL to
an acetic acid ester, this would be a possible way to purify
EMIMOAc from acetic acid.
Pretests with mixtures of an initial mass fraction of acetic acid
of not more than 20 wt % at atmospheric pressure showed that
the esterification with ethanol needs a long reaction time and
alcohol in high excess. Table 4 presents the purity of
EMIMOAc after esterification of alcohol with acetic acid in
EMIMOAc and subsequent evaporation of the reactants and
products from EMIMOAc at 130 °C under nitrogen for up to 5
h.
Experiments 4 to 6 were made at a temperature of 140 °C in
a pressurized vessel, so that the alcohol does not evaporate and
there is an excess of alcohol in contact with the acid for the
whole reaction time. We can see that the results of these trials
are very good. The mass concentration of acetic acid was
decreased to a very low level, especially when using methanol
for esterification (experiment 6).
Table 2. Physicochemical Data of Solvents for Liquid−
a
Liquid Extraction
μ
δmedium
ET(30)
solvent
BMIMOAc
ε
10−30 Cm MPa1/2
kJ·mol−1
206
[RMIMO]+X−
10−12
1.9
200.8−230.1
129.2
n-hexane
0.1
14.9
15.3
n-heptane
1.99
2.0
130.2
petroleum ether
p-dioxane
2.2
0.5
0.3
1.0
1.1
1.2
20.5
18.2
19.6
16.3
15.6
150.6
141.8
toluol
2.4
propylamine
diethyl amine
diethyl ether
3.1
3.6
148.1
144.8
145.3
4.3
MTBE (methyl terbutyl
ether)
4.5
anisole
4.5
19.5
18.9
18.6
155.3
163.6
chloroform
n-butyl amine
ether
4.8
1.2
1.4
1.7
1.5
1.2
1.8
1.9
1.5
1.6
1.8
2.0
4.9
5.5
161.5
156.9
148.6
156.9
159.4
214.2
151.5
156.5
156.5
172.0
183.7
172.1
197.1
176.6
217.5
233
chlorobenzene
piperidine
5.6
19.6
20.2
5.8
propyl acetate
ethyl acetate
acetic acid
6.0
6.0
18.2
21.4
6.2
1,1,1-trichlorethane
tetrahydrofuran
1-chloropropane
dichloromethane
t-butanol
7.5
7.6
19.5
15.6
7.7
9.1
12.5
15.4
16.6
21.5
24.6
33.8
37.5
46.7
80.4
1.7
2-pentanone
2-butanol
1.7
2.7
1.7
1.6
22.2
19.9
26.5
29.6
acetone
ethanol
methanol
acetonitrile
dimethyl sulfoxide
water
192.5
188.3
264
4. CONCLUSIONS
1.8
47.8
The separation of acetic acid from a mixture with EMIMOAc
by evaporation, liquid−liquid extraction, and esterification
followed by evaporation was investigated. In contrast to other
volatile organic liquids like ethyl acetate, n-propyl acetate, i-
propyl acetate, and THF, acetic acid cannot be evaporated
a
ε: dielectric constant, μ: dipole moment, δ: solubility parameter.
cases. n-Propyl acetate can reduce the mass fraction of acetic
acid from (20.3 to 15.4) wt %, while 2-pentanone reduces the
D
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a
Table 3. Fraction of Components in EMIMOAc after Extraction by Various Solvents and Evaporation
extractants
components in mixture
toluene
MTBE
n-heptane
anisole
diethyl ether
ethyl acetate
EMIMOAc (wt %)
acetic acid (wt %)
78.1
21.8
78.6
21.2
79.6
20.1
80.0
79.7
80.7
20.0
19.3
18.9
dioxane
diethyl carbonate
1,1,1-trichloroethane
tetrahydrofuran
n-propyl acetate
2-pentanone
EMIMOAc (wt %)
acetic acid (wt %)
80.8
18.6
83.1
16.8
83.8
16.0
83.7
15.7
84.5
15.4
87.8
12.1
a
The initial weight fraction of EMIMOAc is about 79 % with the exception of the experiment with 2-pentanone (84.1 %). The initial fraction of
acetic acid is about 20 % with the exception of the test with 2-pentanone (15.3 %).
Table 4. Change of Concentration of EMIMOAc by Esterification with Alcohol (Tests 1 to 3 at Atmospheric Pressure, Tests 4
to 6 at an Elevated Pressure of (14 to 18) bar)
after esterification and
reaction conditions
before esterification
EMIMOAc acetic acid
distillation
mass of alcohol
g
mass of mixture
mass of Amberlyst
g
temperature
time
h
EMIMOAc
acetic acid
%
probe
g
°C
%
%
%
a
1
2
3
4
5
6
6.04
20.17
20.5
0.20
0.41
0.38
0
120
110
105
140
140
140
1.5
5
76.0
65.8
76.1
75.8
76.4
75.7
20.00
30.73
19.87
20.2
80.80
76.00
80.24
91.5
18.80
24.00
17.11
6.2
a
54.66
b
65.42
20.23
62.76
62.49
62.71
5
a
200
16
16
16
a
200
0.65
0.75
19.6
87.2
5.9
b
200
20.3
90.2
−0.3
a
b
Ethanol was used. Methanol was used.
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completely from EMIMOAc and EMIMCl. Several solvents
were used to extract acetic acid from EMIMOAc. The closer
the dielectric constant of solvents comes to the dielectric
constant of acetic acid, and the ET(30) value approaches 160
kJ·mol−1, the better the separation efficiency of acetic acid is.
The best results for the purification of EMIMOAc were found
by esterification with subsequent evaporation of the ester when
the esterification took place with alcohol in large excess at
elevated pressure, thus keeping the alcohol in the liquid phase,
and long reaction time. The presented experiences in
separation of acetic acid from mixtures with EMIMOAc form
a valuable basis for purification and recycling of ILs used in the
acetylation of cellulose.
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AUTHOR INFORMATION
■
(10) Swatloski, R. P.; Spear, S. K.; Holbrey, J. D.; Rogers, R. D.
Dissolution of cellose with ionic liquids. J. Am. Chem. Soc. 2002, 124
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Corresponding Author
*Tel.: +49-20885981128; e-mail: juergen.stein@umsicht.
fraunhofer.de.
(11) Scurto, A.; Aki, S.; Brennecke, J. Carbon dioxide induced
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The authors declare no competing financial interest.
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