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www.rsc.org/csr CRITICAL REVIEW

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Ionic liquid processing of cellulosew

Hui Wang, Gabriela Gurau and Robin D. Rogers*
Received 17th November 2011
DOI: 10.1039/c2cs15311d

Utilization of natural polymers has attracted increasing attention because of the consumption and
over-exploitation of non-renewable resources, such as coal and oil. The development of green
processing of cellulose, the most abundant biorenewable material on Earth, is urgent from the
viewpoints of both sustainability and environmental protection. The discovery of the dissolution
of cellulose in ionic liquids (ILs, salts which melt below 100 1C) provides new opportunities for
the processing of this biopolymer, however, many fundamental and practical questions need to be
answered in order to determine if this will ultimately be a green or sustainable strategy. In this
critical review, the open fundamental questions regarding the interactions of cellulose with both
the IL cations and anions in the dissolution process are discussed. Investigations have shown that
the interactions between the anion and cellulose play an important role in the solvation of
cellulose, however, opinions on the role of the cation are conflicting. Some researchers have
concluded that the cations are hydrogen bonding to this biopolymer, while others suggest they are
not. Our review of the available data has led us to urge the use of more chemical units of
solubility, such as ‘g cellulose per mole of IL’ or ‘mol IL per mol hydroxyl in cellulose’ to provide
more consistency in data reporting and more insight into the dissolution mechanism. This review
will also assess the greenness and sustainability of IL processing of biomass, where it would seem
that the choices of cation and anion are critical not only to the science of the dissolution, but to
the ultimate ‘greenness’ of any process (142 references).

Center for Green Manufacturing and Department of Chemistry,
The University of Alabama, Tuscaloosa, AL 35487, USA.
E-mail: rdrogers@as.ua.edu; Fax: (+) 1-205-348-0823
w Part of a themed issue covering the latest developments in green
chemistry.
1. Introduction
Cellulose is the most abundant organic compound found on
Earth and is known to have very attractive properties such as
biocompatibility, biodegradability, and thermal and chemical
stability;1 thus cellulose and its derivatives are extensively used

Dr Hui Wang received her Dr Gabriela Gurau received

doctoral degree from the her BS in 1998 from The
Institute of Process Engineering, University of Bucharest,
Chinese Academy of Sciences Romania, and her PhD in
and Graduate University of Chemistry from The University
the Chinese Academy of of Alabama (2007). Dr Gurau
Sciences in July, 2010. The is the CEO of 525 Solutions,
same year, Dr Wang joined Inc., a faculty start-up
Professor Robin D. Rogers’ company incubated in the
Group at The University of Bama Technology Incubator
Alabama as a postdoctoral on UA’s campus, and also a
research fellow. Her research Research Fellow in the
is focused on the application of Department of Chemistry and
ionic liquids in separations and Center for Green Manufacturing
Hui Wang biomass processing. Gabriela Gurau at The University of Alabama.
Her research focuses on the
use of Ionic Liquids as a basis for the design, development,
and delivery of pharmaceuticals, as well as applications in the
areas of agrochemicals, energetic materials, and biomass.

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1519–1537 1519
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Fig. 1 Intermolecular and intramolecular hydrogen bonds in cellulose.
in industries such as textiles, plastics, wood and paper products,
coatings, cosmetics, and pharmaceuticals, among others.2
Cellulose is the structural component of the primary cell wall of
green plants, and can also be produced by a large variety of living
organisms, such as algae, oomycetes, acetobacter, and rhizobium.3
The average cellulose content for all plant matter is about 33%
(e.g., the cellulose content of cotton is 90% and that of wood is
40–50%).4 Cellulose can be extracted from its raw biomass
materials and is potentially a virtually inexhaustible source of
renewable bioenergy. More and more attention is being paid to
the utilization of this biopolymer in the synthetic development of
environmentally friendly and biocompatible products and fuels.
However, cellulose is a polysaccharide consisting of a linear
chain of several hundred to over ten thousand b-(1-4)-linked
glucose repeating units,5 and there are numerous intermolecular
and intramolecular hydrogen bonds in cellulose (Fig. 1), which
result in the difficulty in dissolving cellulose in water and
common organic solvents, much less separating it from natural
lignocellulosic biomass.6 A few aqueous and nonaqueous
cellulose solvents were previously developed for the dissolution
of cellulose, but all of these solvents suffer drawbacks, such as high
cost, volatility, toxicity, generation of poisonous gas, difficulty in
solvent recovery, or insufficient solvation power for cellulose.7,8
Dr Robin D. Rogers obtained
both his BS in Chemistry
(1978, Summa Cum Laude)
and his PhD in Chemistry
(1982) at The University of
Alabama and currently serves
as Distinguished Research
Professor, Robert Ramsay
Chair of Chemistry, and
Director of the Center for
Green Manufacturing at UA.
His research interests cover the
use of ionic liquids and Green
Chemistry for sustainable
Robin D. Rogers technology through innovation
and include Materials
(advanced polymeric and composite materials from
biorenewables), Separations (novel strategies for separation
and purification of value added products from biomass), Energy
(new lubricant technologies and selective separations), and
Medicine (elimination of waste while delivering improved
pharmaceutical performance).
1520 Chem. Soc. Rev., 2012, 41, 1519–1537
At the same time, the molecular weights of the biopolymers are
often significantly reduced during such processing. Furthermore,
to fully dissolve cellulose, multi-step pretreatments are often
needed, followed by prolonged stirring.
Green chemistry, sustainability, and eco-efficiency are directing
the development of the next generation of industrial chemical
processes. It is clear that the current technologies used in obtaining
cellulose from raw biomass and in processing the cellulose once
obtained are mostly non-green and energy intensive. In recent
years, the comprehensive utilization of cellulose resources has
drawn much attention from the government and researchers, and
there is an increasing demand to develop new technologies to
obtain and dissolve cellulose to overcome the drawbacks of
traditional pulping and processing methods.
In 2002, our group reported that cellulose could be dissolved
without derivatization in high concentrations using ionic
liquids (ILs, commonly defined as salts which melt below
100 1C9), such as 1-butyl-3-methylimidazolium chloride
([C4mim]Cl),10 which led the development of a new class of
cellulose solvent systems. Since then studies on the application
of ILs in biomass chemistry have been widely carried out and
many kinds of ILs have been found to be able to dissolve
cellulose,11–20 to serve as the reaction medium to functionalize
cellulose,11,21–23 to prepare cellulose fibers, films, or
beads,16,24–28 and to make cellulose composite materials.29–31
It has also been reported that ILs can dissolve raw biomass
materials, such as wood, straw, shrimp shell,32–37 and others,
and that free biopolymers such as chitin, lignin, as well as
cellulose-rich pulp can be regenerated from the raw biomass.
Herein, we will specifically review the processing of cellulose
using ILs and discuss the interactions of cellulose with both
the cations and anions of the ILs. This critical review is not
meant to cover every published reference or aspect of the
processing of cellulose using ILs, rather, our opinions on some
fundamental questions in the dissolution of cellulose using ILs
are provided. Where possible, the greenness and sustainability
of the processing of biomass using ILs will also be analyzed,
although it must be recognized that such questions need
constant evaluation as new knowledge is developed.
2. Traditional processing methods of cellulose
The first attempts to dissolve cellulose or cellulose-containing
materials date back to the 1850s.38,39 Since then a variety of
cellulose solvent systems (Fig. 2) have been developed, such as
This journal is c The Royal Society of Chemistry 2012
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Fig. 2 Structures of traditional solvents for cellulose dissolution.
N-methylmorpholine oxide (NMMO),40 N,N-dimethylacetamide/
lithium chloride (DMAc/LiCl),41 1,3-dimethyl-2-imidazolidinone/
lithium chloride (DMI)/LiCl,42 N,N-dimethylformamide/nitrous
tetroxide (DMF/N2O4),43 dimethyl sulfoxide (DMSO)/tetrabutyl-
ammonium fluoride (TBAF),44 some molten salt hydrates, such as
LiClO4
3H2O,,45,46 LiSCN
2H2O,46 and some aqueous solutions
of metal complexes.47
The most important, and also the oldest process currently
used to manufacture cellulose fibers is the viscose process,
which involves first treating cellulose with sodium hydroxide,
and then derivatizing the cellulose with carbon disulfide leading
to a highly viscous sodium xanthogenate solution.48–50 This
solution is then later treated with acidic solution to reform the
cellulose. Despite continuous improvement in the past decades,
large quantities of carbon disulfide, sodium hydroxide, sulfuric
acid, and fresh water are required per ton of cellulose fiber
produced. Although ca. 70–75% of the carbon disulfide is
recyclable, waste water, alkali, acid, and exhaust air are causing
serious environmental problems. Another drawback of this
process is the degradation of the cellulose backbone.
Another more recent alternative for cellulose fiber production
is the NMMO process developed in the late 1960s and
commercialized in the early 1990s. In this process, cellulose
is dissolved to form a solution called dope, and then the
cellulose is reprecipitated in a water bath to produce a fiber.51
NMMO is a nonderivatizing solvent for cellulose, in which
cellulose is directly solvated to form a homogeneous polymer
solution. Despite many advantages, the NMMO process has
not replaced the viscose process to date, primarily due to cost
but also due to the nature of the fibrillating fiber produced
from the NMMO process compared to rayon.51 Moreover, the
use of NMMO, a thermally unstable solvent, requires a major
investment in safety technology.
Although the mechanism of the dissolution of cellulose in
these conventional solvents has not been fully determined, it is
widely speculated that breaking up the intra- and intermolecular
hydrogen bonds in cellulose is the key point in the dissolution of
this polymer.52 For example, it is considered that the highly
This journal is c The Royal Society of Chemistry 2012
polar N-O group in NMMO could readily form hydrogen bonds
with cellulose.53 In DMAc/LiCl, the Li+ ions interact with the
oxygen atoms of the carbonyl groups of the DMAc, while the
unencumbered Cl ions, as nucleophilic bases, play a major role
in breaking up the inter- and intramolecular hydrogen bonds
in cellulose.54 Similarly, N2O4 in the DMF/N2O4 system is
responsible for the dissolution of cellulose.55
3. Processing cellulose using ionic liquids
Ionic liquids refer to liquids composed of ions that are fluid
around or below 100 1C.56,57 The unique physicochemical
properties possible for many ILs, such as low vapor pressure,
high thermal stability, wide electrochemical window, wide
liquid range, and high solvation ability to dissolve various
organic and inorganic substances,58–60 have led to numerous
proposed applications in a variety of fields, including catalysis,61
extraction,62 electrochemistry,63 organic synthesis,64,65 and
polymer chemistry,66 among others. Furthermore, ILs can
be easily modified by changing the structure of the cations
or anions,67 and it is estimated that the number of potential
cation and anion combinations available reputedly equates to
1012 different ILs.68
3.1 Dissolution of cellulose
In 1934, Graenacher discovered that benzylpyridinium
chloride or N-ethylpyridinium chloride dissolved in suitable
solvents, such as nitrogen containing bases (Fig. 3), have the
ability to dissolve cellulose with the formation of solutions of
more or less viscosity.69 This work has been described in
hindsight in various ways such as ‘‘the first example of the
cellulose dissolution using ILs’’,70 or ‘‘a herald of what
scientists are trying to achieve nowadays using cellulose,’’71
however, we disagree with these characterizations and have
recently discussed the basis for our opinions.72
An examination of Graenacher’s results in the context of the
IL field does reveal some interesting similarities. The nitrogen
containing bases (e.g., pyridine) used to dissolve the chloride
Chem. Soc. Rev., 2012, 41, 1519–1537 1521
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Fig. 3 Structures of benzylpyridinium chloride, N-ethylpyridinium chloride, and pyridine.
salts have aromatic character providing compatibility with the
pyridinium cations, but it does not contain any strong hydrogen
bond donors to interact with the anions. Thus, a situation is set
up where again an essentially free chloride ion can disrupt the
hydrogen bonding within and between cellulose polymer chains.
In addition, the sizes of the cations and of the solvent are not
too different than those found for other cellulose solvents and
for the ILs discussed below.
Regardless of the debate on the history of the field, let’s take a
closer look at the science involved in IL dissolution of cellulose
which would also seems to be the subject of much debate. In
both areas, we would suggest a careful examination of the entire
literature, rather than a few reviews (even this one!).
Since the report on dissolving cellulose with ILs appeared
there has been a dramatic surge in interest from both the
scientific and industrial communities. This has included many
studies to find other IL or IL-like solvents for the dissolution of
cellulose. Table 1 gives an overview of the cellulose-dissolving
capacity of different ILs reported in the literatures.8–12,16–18,73–81
Table 1 shows that both the cation and anion of ILs influence
the dissolution of cellulose, however, while the role of the anion
would seem to be clear and the trends in solubility seem to
follow basicity, the same cannot be said of the influence of the
cations. The analysis of all of the literature data is complicated
by the different celluloses used, the different molecular weights,
the different dissolution conditions, and the real lack of analysis
of degradation vs. dissolution. We have also found that the use
of wt%, an engineering term, to describe solubility may mask
chemical trends within the data. This is compounded by the fact
that most of the literature uses the unit wt% when in reality it is
a mass ratio represented in percent. For example, 1.00 g cellulose
in 10.00 g IL, is 9.1 wt%, while the mass ratio is 0.10, or 10%.
Here we utilize the available data to discuss the differences and
possible roles of each ion in the dissolution of cellulose, but
strongly recommend that all future solubility data be reported in
terms of mass of cellulose dissolved per mol of IL.
Anions. There seems little debate that anions that are
good hydrogen bond acceptors, such as OAc , HCOO ,
(MeO)2PO2 , Cl , etc. are more effective in dissolving cellulose
(see Table 1). While, ILs containing low-basicity anions, such as
dicyanamide-based ILs, are not that efficient in dissolving
cellulose8 (although they are known to dissolve monosaccharides78)
and cellulose cannot be dissolved in ILs containing non-
coordinating anions, such as BF4 or PF6 .10
The current results suggest that the higher the hydrogen
bond basicity and dipolarity, the greater ability of salts of that
anion to dissolve cellulose. For example, since the hydrogen
bond basicity of the formate anion is 1.2 fold higher than that
of the chloride anion,82 a larger amount of cellulose could be
1522 Chem. Soc. Rev., 2012, 41, 1519–1537
dissolved in 1-allyl-3-methylimidazolium formate than in 1-allyl-
3-methylimidazolium chloride (Table 1, entry 26 (MCC, 85 1C)
vs. 36 (MCC, 100 1C)).
This trend is also clear from studies related to how difficult it
is to dissolve cellulose in ILs. The dissolution of microcrystalline
cellulose was investigated in different imidazolium phosphates
and phosphonates, such as [C2mim](MeO)2PO2, [C2mim]-
(MeO)MePO2, and [C2mim](MeO)HPO2, which exhibit higher
hydrogen bond basicities than chlorides.18 The phosphate and
phosphonate ILs were able to dissolve cellulose at 45–65 1C, a
temperature at which [C2mim]Cl is a solid (mp = 85 1C83).
Xu and coworkers also showed that the hydrogen bond
accepting ability of the anions is closely linked to the solubility
of cellulose.8 In their study, a series of ILs were prepared by
pairing the [C4mim]+ cation with Brønsted basic anions and
they concluded that the solubility of cellulose in these ILs
increased almost linearly with increasing hydrogen bond
accepting ability of the anions as determined by the authors
using solvatochromatic methods: OAc 4 HSCH2COO 4
HCOO 4 (C6H5)COO 4 H2NCH2COO 4
HOCH2COO 4 CH3CHOHCOO 4 DCA (Table 1,
entries 2, 25, 27, 31–34, and 64).
In this series of ILs, [C4mim]OAc was the most efficient
for the dissolution of cellulose, while cellulose was insoluble
in [C4mim][DCA]. This trend does not seem to correlate with
the established pKa values of the parent acids of HOAc:
4.75 4 (C6H5)COOH: 4.18 4 CH3CHOHCOOH: 3.87 4
HOCH2COOH: 3.83 4 HCOOH: 3.72 4 HSCH2COOH:
3.68 4 H2NCH2COOH: 2.35.84–86 However, it is important
to point out that three of these anions have hydrogen bond
donors which could interfere with the hydrogen bond acceptor
ability toward cellulose: H2NCH2COO , HOCH2COO , and
CH3CHOHCOO , and thus, the beta values obtained in the
solvatochromatic study may be a better indicator of ability to
dissolve cellulose than the pKa values.
Typically the dissolution of cellulose in a given IL is
provided in terms of mass percent; however, given the wide
distribution in formula weights for ILs, some consideration
should be given to solubility in terms of mass of cellulose per
mole of IL (Table 1, column 7). In the above example, the
order of solubility changes when ordered in this fashion to
(C6H5)COO 4 HSCH2COO 4 OAc 4 H2NCH2COO 4
HCOO 4 HOCH2COO 4 CH3CHOHCOO (Table 2).
This again is not in strict accordance with the established pKa
values or the beta values, however, it should be noted that the
anions which also contain hydrogen bond donors (and can thus
form interanion hydrogen bonds) do now appear at the lower
end of cellulose dissolving power. Based on this analysis, the
solubility of this type of cellulose at the temperature studied in
the formate IL seems lower than expected.
This journal is c The Royal Society of Chemistry 2012
 Table 1 Cellulose-dissolving capacity of different ionic liquids

Solubilityd Solubilityd
Entry ILs a
Structure of ILs Cellulose typeb
Conditions (wt%) (g mol 1 IL) References
Cellulose NMc 420 434.0 72
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Eucalyptus
pre-hydrolysis NM 19.6 33.4 16
1 [C2mim]OAc sulfate pulp (569)
Avicel Heat (110 1C) 15 25.5 78
Avicel Heat (100 1C) 8 13.6 20
a-Cellulose Heat (90 1C) 45 48.5 75
Eucalyptus
pre-hydrolysis NM 18.9 37.5 16
2 [C4mim]OAc sulfate pulp (569)
MCC Heat (70 1C) 15.5 30.7 8
Avicel Heat (100 1C) 12 23.8 20

3 [Me(OEt)2-Et-Im]OAc Avicel Heat (110 1C) 12 31.0 78

4 [Me(OEt)3-Et-Im]OAc Avicel Heat (110 1C) 12 36.3 78

5 [Me(OEt)4-Et-Im]OAc Avicel Heat (110 1C) 10 34.6 78

6 [Me(OEt)3-Et3N]OAc Avicel Heat (110 1C) 10 30.7 78

7 [Me(OEt)2-Et3N]OAc Avicel Heat (110 1C) 10 26.3 78

8 [H(OEt)2-Me-Im]OAc Avicel Heat (110 1C) 5 11.5 78

9 [Me(OEt)7-Et-Im]OAc Avicel Heat (110 1C) 3 14.4 78

10 [H(OEt)3-Me-Im]OAc Avicel Heat (110 1C) 2 5.5 78

11 [C8mim]OAc Avicel Heat (110 1C) o1 o2.5 78

12 [Me(OEt)3-MeOEtOMe-Im]OAc Avicel Heat (110 1C) 0.5 1.8 78

13 [Me(OPr)3-Et-Im]OAc Avicel Heat (110 1C) 0.5 1.7 78

14 [Amm110]OAc Avicel Heat (110 1C) 0.5 — 78

15 [Me(OEt)3-Bu-Im]OAc Avicel Heat (110 1C) o0.5 o1.7 78

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1519–1537 1523
 Table 1 (continued )

Solubilityd Solubilityd
Entry ILs a
Structure of ILs Cellulose type b
Conditions (wt%) (g mol 1 IL) References
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16 [MM(EtOH)NH]OAc Avicel Heat (110 1C) o0.5 o0.8 78

17 [(MeOEt)2NH2]OAc Avicel Heat (110 1C) o0.5 o1.0 78

18 [MM(MeOEt)NH]OAc Avicel Heat (110 1C) o0.5 o0.8 78

19 [M(MeOEt)2NH]OAc Avicel Heat (110 1C) o0.5 o1.0 78

20 [C2mim](MeO)MePO2 MCC (250) Heat (55 1C) 10 22.0 18

MCC (250) Heat (45 1C) 10 20.6 18

21 [C2mim](MeO)HPO2 MCC (250) 25 1C 4 8.3 18

22 [C2mim](MeO)2PO2 MCC (250) Heat (65 1C) 10 23.6 18

Avicel Heat (100 1C) 10 22.2 20

23 [C1mim](MeO)2PO2 a-Cellulose Heat (90 1C) 45 411.1 75

24 [C2mim](EtO)2PO2 Avicel Heat (100 1C) 12–14 31.7–37.0 20

25 [C4mim]HSCH2COO MCC Heat (70 1C) 13.5 31.1 8

MCC (250) Heat (85 1C) B22 B37.0 17

26 [Amim]HCOO MCC (250) Heat (60 1C) B10 B16.8 17

MCC Heat (70 1C) 12.5 23.0 8

27 [C4mim]HCOO Avicel Heat (110 1C) 8 14.7 78

28 [Bu4P]HCOO Avicel Heat (110 1C) 6 18.3 78

29 [Bu4N]HCOO Avicel Heat (110 1C) 1.5 4.3 78

30 [Amm110]HCOO Avicel Heat (110 1C) 0.5 — 78

31 [C4mim](C6H5)COO MCC Heat (70 1C) 12 31.2 8

1524 Chem. Soc. Rev., 2012, 41, 1519–1537 This journal is c The Royal Society of Chemistry 2012
 Table 1 (continued )

Solubilityd Solubilityd
Entry ILs a
Structure of ILs Cellulose type b
Conditions (wt%) (g mol 1 IL) References
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32 [C4mim]H2NCH2COO MCC Heat (70 1C) 12 25.6 8

33 [C4mim]HOCH2COO MCC Heat (70 1C) 10.5 22.5 8

34 [C4mim]CH3CHOHCOO MCC Heat (70 1C) 9.5 21.7 8

Avicel (286) Heat (105 1C) 39 72.4 11,73

Spruce sulfite
Heat (105 1C) 37 68.7 11,73
pulp (593)
35 [C4mpy]Cl
Cotton linters
Heat (105 1C) 12 22.3 11,73
(1198)
a-Cellulose Heat (105 1C) 45 49.3 75
MCC Sonication 27 42.8 80
Pulp (650) Heat (80 1C) 14.5 23.0 12
Cotton linter Sonication 13 20.6 80
36 [Amim]Cl
MCC (250) Heat (100 1C) B10 B15.9 17
Kraft pulp Sonication 8 12.7 80
a-Cellulose Heat (90 1C) 45 47.9 75
Pulp cellulose Microwave
25 43.7 10
(1000) heating
Avicel Heat (100 1C) 20 34.9 20
Avicel Heat (100 1C) B20 B34.9 77
Avicel (286) Heat (83 1C) 18 31.4 11,73,74
Eucalyptus
pre-hydrolysis NMc 13.6 23.8 16
sulfate pulp (569)
Spruce sulfite
Heat (83 1C) 13 22.7 11,73,74
pulp (593)
Cotton linters
Heat (83 1C) 10 17.5 11,73,74
(1198)
Pulp cellulose
37 [C4mim]Cl Heat (100 1C) 10 17.5 10
(1000)
Avicel Heat (110 1C) 10 17.5 78
Cotton linter Sonication 10 17.5 80
Kraft pulp Sonication 9 15.7 80
MCC Sonication 8 14.0 80
a-Cellulose Heat (90 1C) 45 48.7 75
Pulp cellulose Heat (80 1C)
5 8.7 10
(1000) + sonication
Pulp cellulose Heat (130 1C) 43 45.2 76
Pulp cellulose
Heat (70 1C) 3 5.2 10
(1000)
Commercial Heat
1.8 3.1 81
cellulose (80–90 1C)
Eucalyptus
pre-hydrolysis NM 15.8 23.2 16
sulfate pulp (569)
Avicel Heat (100 1C) 10–14 14.7–20.5 20
Avicel (286) Heat (90 1C) 12 17.6 73,74
38 [C2mim]Cl Avicel Heat (100 1C) B10 B14.7 77
Spruce sulfite
Heat (90 1C) 6 8.8 73,74
pulp (593)
a-Cellulose Heat (90 1C) 45 47.3 75
Cotton linters
Heat (90 1C) 4 5.9 73,74
(1198)
Eucalyptus
pre-hydrolysis NM 12.8 24.2 16
sulfate pulp (569)
Avicel (286) NM 9 17.0 73,74
39 [C4dmim]Cl
Spruce sulfite
NM 6 11.3 73,74
pulp (593)
Cotton linters
NM 4 7.6 73,74
(1198)

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1519–1537 1525
 Table 1 (continued )

Solubilityd Solubilityd
Entry ILs a
Structure of ILs Cellulose type b
Conditions (wt%) (g mol 1 IL) References
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40 [C2OHmim]Cl NM Heat (70 1C) 6.8 11.1 79

Avicel (286) Heat (62 1C) 5 18.4 11,73

Spruce sulfite
Heat (62 1C) 2 7.4 11,73
41 BDTAC pulp (593)
Cotton linters
Heat (62 1C) 1 3.7 11,73
(1198)

Avicel Heat (100 1C) B6.5 B13.2 77

Avicel Heat (100 1C) 6 12.2 20
42 [C6mim]Cl Pulp cellulose
Heat (100 1C) 5 10.1 10
(1000)

Avicel Heat (100 1C) 5 10.8 20

43 [C7mim]Cl Avicel Heat (100 1C) B5 B10.8 77

Avicel Heat (100 1C) 4 9.2 20

Avicel Heat (100 1C) B4 B9.2 77
44 [C8mim]Cl Pulp cellulose Slightly
Heat (100 1C) — 10
(1000) soluble

Avicel Heat (100 1C) B2.5 B6.1 77

45 [C9mim]Cl Avicel Heat (100 1C) 2 4.9 20

46 [Me(OEt)2-Et-Im]Cl Avicel Heat (110 1C) 2 4.7 78

Avicel Heat (100 1C) B1.5 B2.8 77

47 [C5mim]Cl Avicel Heat (100 1C) 1 1.9 20

48 [H(OEt)2-Me-Im]Cl Avicel Heat (110 1C) 1 2.1 78

Avicel Heat (100 1C) B0.5 B0.8 77

49 [C3mim]Cl Avicel Heat (100 1C) Insoluble — 20

50 [C10mim]Cl Avicel Heat (100 1C) B0.5 B1.3 77

51 [Amm110]Cl Avicel Heat (110 1C) 0.5 — 78

Avicel (286) NM 12 26.1 74

Spruce sulfite
NM 4 8.7 74
52 [Admim]Br pulp (593)
Cotton linters
NM 4 8.7 74
(1198)

Pulp cellulose Microwave

5–7 11.0–15.3 10
(1000) heating
53 [C4mim]Br Avicel Heat (100 1C) 2–3 4.4–6.6 20

Commercial Heat
54 [Cyanomim]Br 3.4 6.4 81
cellulose (80–90 1C)

1526 Chem. Soc. Rev., 2012, 41, 1519–1537 This journal is c The Royal Society of Chemistry 2012
 Table 1 (continued )

Solubilityd Solubilityd
Entry ILs a
Structure of ILs Cellulose type b
Conditions (wt%) (g mol 1 IL) References
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55 [C2mim]Br Avicel Heat (100 1C) 1–2 1.9–3.8 20

Avicel Heat (100 1C) 1–2 2.1–4.1 20

Commercial Heat
56 [C3mim]Br 1.7 3.5 81
cellulose (80–90 1C)

57 [C5mim]Br Avicel Heat (100 1C) 1–2 2.3–4.7 20

58 [C6mim]Br Avicel Heat (100 1C) 1–2 2.5–4.9 20

59 [C7mim]Br Avicel Heat (100 1C) 1 2.6 20

60 [C8mim]Br Avicel Heat (100 1C) 1 2.8 20

61 [C4mim]I Avicel Heat (100 1C) 1–2 2.7–5.3 20

62 [C2mim]F Avicel Heat (100 1C) 2 2.6 20

Pulp cellulose Microwave

63 [C4mim]SCN 5–7 9.9–13.8 10
(1000) heating

Avicel Heat (110 1C) 1 2.1 78

64 [C4mim]DCA MCC Heat (70 1C) 0 0 8

65 [P66614]DCA Avicel Heat (110 1C) o0.5 o2.8 78

66 [Amm110]DCA Avicel Heat (110 1C) o0.5 — 78

67 [C4mim]NTf2 Avicel Heat (110 1C) o0.5 o2.1 78

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1519–1537 1527
 Table 1 (continued )

a
C2mim: 1-ethyl-3-methylimidazolium; OAc: acetate; C4mim: 1-butyl-3-methylimidazolium; Me(OEt)2-Et-Im: 1-(3,6-dioxaheptyl)-3-ethylimidazolium;
Me(OEt)3-Et-Im: 1-(3,6,9-trioxadecyl)-3-ethylimidazolium; Me(OEt)4-Et-Im: 1-(3,6,9,12-tetraoxatridecyl)-3-ethylimidazolium; Me(OEt)3-Et3N: N,N,N-
triethyl-3,6,9-trioxadecylammonium; Me(OEt)2-Et3N: N,N,N-triethyl-3,6-dioxaheptylammonium; H(OEt)2-Me-Im: 1-(3,6-dioxahexyl)-3-methylimida-
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zolium; Me(OEt)7-Et-Im: 1-(3,6,9,12,15,18,21-heptaoxadocosyl)-3-ethylimidazolium; H(OEt)3-Me-Im: 1-(3,6,9-trioxanonyl)-3-methylimidazolium;

C8mim: 1-octyl-3-methylimidazolium; Me(OEt)3-MeOEtOMe-Im: 1-(3,6-dioxaheptyl)-3-(3,6,9-trioxadecyl)imidazolium; Me(OPr)3-Et-Im: 1-(4,8,12-
trioxatridecyl)-3-ethylimidazolium; [Amm110]Cl: AMMOENGt 110; Me(OEt)3-Bu-Im: 1-(3,6,9-trioxadecyl)-3-butylimidazolium; MM(EtOH)NH:
N,N-dimethylethanolammonium; [(MeOEt)2NH2]: N,N-bis(2-methoxyethyl)ammonium; MM(MeOEt)NH: N,N-dimethyl-2-methoxyethylammonium;
M(MeOEt)2NH: N-methyl-N,N-bis(2-methoxyethyl)ammonium; (MeO)MePO2: methyl methylphosphonate; (MeO)HPO2: methylphosphonate;
(MeO)2PO2: dimethylphosphate; C1mim: 1-methyl-3-methylimidazolium; (EtO)2PO2: diethylphosphate; Amim: 1-allyl-3-methylimidazolium; HCOO: formate;
Bu4P: tetrabutylphosphonium; Bu4N: tetrabutylammonium; C4mpy: 3-methyl-N-butylpyridinium; C4dmim: 1-butyl-2,3-dimethylimidazolium; C2OHmim:
1-(2-hydroxyethyl)-3-methylimidazolium; BDTAC: benzyldimethyl(tetradecyl)ammonium chloride; C6mim: 1-hexyl-3-methylimidazolium; C7mim:
1-heptyl-3-methylimidazolium; C9mim: 1-nonyl-3-methylimidazolium; C5mim: 1-pentyl-3-methylimidazolium; C3mim: 1-propyl-3-methylimidazolium;
C10mim: 1-decyl-3-methylimidazolium; Admim:1-allyl-2,3-dimethylimidazolium; SCN; thiocyanate; DCA: dicyanamide; P66614: trihexyltetradecyl phos-
phonium; NTf2: bis-(trifluoromethanesulfonyl)imide; b The numbers in brackets correspond to the degree of polymerization values; Pulp: lignocellulosic
fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops, or waste paper; Avicel: a microcrystalline
cellulose powder; MCC: microcrystalline cellulose; c NM: not mentioned. d The data in column 7 has been calculated from the data provided in each
reference. It is not entirely clear in the published literature that all papers report solubility of cellulose in ILs in the same way. Some reports seem to indicate
g cellulose per g of IL while using the unit wt%. In the calculations provided in column 7, we have assumed that all values reported as ‘wt%’ are in fact
‘g cellulose/g IL’. The differences in the resulting calculations are minor, however, it will be important to clear this up in future reports.

Table 2 Mass of microcrystalline cellulose dissolved per mole of IL8 Table 3 Dissolution of Avicel cellulose at 110 1C78

Solubilitya Solubility Mole of IL/ Solubility Solubility Mol IL/

IL (wt%) (g mol 1 IL) mol OH ILs (wt%) (g mol 1 IL) mol OH
[C4mim]OAc 15.5 30.7 1.8 [Me(OEt)3-Et-Im]OAc 12 36.3 1.5
[C4mim]HSCH2COO 13.5 31.1 1.7 [Me(OEt)4-Et-Im]OAc 10 34.6 1.6
[C4mim]HCOO 12.5 23.0 2.3 [Me(OEt)2-Et-Im]OAc 12 31.0 1.7
[C4mim](C6H5)COO 12 31.2 1.7 [Me(OEt)3-Et3N]OAc 10 30.7 1.8
[C4mim]H2NCH2COO 12 25.6 2.1 [Me(OEt)2-Et3N]OAc 10 26.3 2.0
[C4mim]HOCH2COO 10.5 22.5 2.4 [C2mim]OAc 15 25.5 2.1
[C4mim]CH3CHOHCOO 9.5 21.7 2.5 [Bu4P]HCOO 6 18.3 3.0
a [C4mim]Cl 10 17.5 3.1
Dissolution T = 70 1C. [C4mim]HCOO 8 14.7 3.7
[Me(OEt)7-Et-Im]OAc 3 14.4 3.8
[H(OEt)2-Me-Im]OAc 5 11.5 4.7
If we consider cellobiose and its 6 hydroxyl groups as the [H(OEt)3-Me-Im]OAc 2 5.5 9.8
repeating unit of cellulose, we can also calculate the ratio of [Me(OEt)2-Et-Im]Cl 2 4.7 11.5
the number anions to the number of hydroxyl groups. This [Bu4N]HCOO 1.5 4.3 12.5
[H(OEt)2-Me-Im]Cl 1 2.1 26.1
analysis (Table 2) indicates 1.5–2.5 anions per hydroxyl group [C4mim]DCA 1 2.1 26.4
near the solubility limit; that is, an excess of anions is needed. [P66614]DCA o0.5 o2.8 419.7
As the number of anions to hydroxyl groups approaches 1 : 1, [C8mim]OAc o1 o2.5 421.3
steric considerations must also be considered when comparing [C4mim]NTf2 o0.5 o2.1 425.7
[Me(OEt)3-MeOEtOMe-Im]OAc 0.5 1.8 29.9
the ability of the anions to promote cellulose dissolution. [Me(OPr)3-Et-Im]OAc 0.5 1.7 31.4
One difficulty in making more in depth comparison with the [Me(OEt)3-Bu-Im]OAc o0.5 o1.7 432.8
available data arises from the variable conditions used in these [M(MeOEt)2NH]OAc o0.5 o1.0 452.0
studies. The cellulose source, degree of polymerization, heating [(MeOEt)2NH2]OAc o0.5 o1.0 455.7
[MM(MeOEt)NH]OAc o0.5 o0.8 465.9
method (e.g., oil bath, microwave, sonication), time, and [MM(EtOH)NH]OAc o0.5 o0.8 472.1
temperature vary widely. Let us here then compare some of
the data in Table 1 collected under similar conditions (Table 3).
salts of that anion to dissolve cellulose. For example, in the
Table 3 indicates that OAc is a better anion in dissolving
study of Vitz et al.,20 [C4mim]Cl shows a higher ability to
cellulose than Cl ([Me(OEt)2-Et-Im]OAc vs. [Me(OEt)2-Et-Im]Cl;
dissolve cellulose than [C4mim]OAc (Table 1, entry 37, Avicel,
[H(OEt)2-Me-Im]OAc vs. [H(OEt)2-Me-Im]Cl), and both Cl
100 1C vs. entry 2, Avicel, 100 1C), and data in Table 3 indicate
and HCOO are better than DCA or NTf2 -based ILs.
that [C4mim]Cl is better than [C4mim]HCOO in dissolving
(The data in Table 3 also seem to show that the dissolving
cellulose. These conflicting results deserve further study to
ability of HCOO is lower than that of Cl , however, see
determine if variances in technique, the presence of impurities
below). The capabilities of the anions in Table 3 to dissolve
in ILs, etc., might explain the results.
cellulose appear to decrease in the order: OAc 4 Cl 4
HCOO 4 DCA or NTf2 . Note again, that the highest Mechanistic studies. Experimental studies on the mechanism
solubilities are reached with an anion/OH ratio of between of the dissolution of cellulose in ILs have confirmed the
1–2, however, it is never 1 : 1 or lower. interactions between the anion of ILs and cellulose. In our first
Some of the data in Table 1 seem not to support the conclusion publication on cellulose dissolution using ILs, we attributed the
that the higher the hydrogen bond basicity, the greater ability of solvation to the interaction of the chloride ions with the

1528 Chem. Soc. Rev., 2012, 41, 1519–1537 This journal is c The Royal Society of Chemistry 2012
 hydroxyl protons of the cellulose.10 Then, cooperating with
Prof. G. Moyna, we studied the mechanism of dissolution of
cellulose in chloride-based IL using NMR spectroscopy87 which
indicated that the solvation of cellulose by [C4mim]Cl involves
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stoichiometric hydrogen-bonding between the hydroxyl protons
of the solute and the chloride ions of the IL. Later, the solvation
of carbohydrates in [C2mim]OAc, [C4mim]Cl, and [Amim]Cl
was studied to evaluate the effects of cation and anion
structure on the solvation mechanism.88 In all cases, the
35/37
Cl and 13C relaxation rates of chloride ions and acetate
ion carbon atoms, respectively, exhibited a strong dependency
on carbohydrate content, indicating that the dissolution of
cellulose is mainly due to the interactions between the IL
anions and the carbohydrate. More importantly, there was no
change in the solvation mechanism regardless of the structure
of the anion. These results were corroborated by Hardacre
et al., who examined the solvation of glucose in [C1mim]Cl.89
Zhang and coworkers also used NMR spectroscopy to study
the solvation of cellobiose, the repeating unit in cellulose, in
[C2mim]OAc under various cellobiose concentrations and
temperatures.90 NMR data of this model system suggested
that hydrogen bonding is formed between hydroxyls of cellobiose
and the anion of [C2mim]OAc. The acetate anions favor the
formation of hydrogen bonds with hydrogen atoms of hydroxyls
in cellobiose, while after acetylation of all hydroxyls in cellobiose,
the interactions between cellobiose octaacetate and [C2mim]OAc
became weaker, implying that hydrogen bonding is the major
reason for the dissolution of cellobiose in this IL. (This study also
suggested that the cation was interacting directly with the cellulose
as discussed below, however, it was later suggested that flaws exist
in the design of this study and in the interpretation of the
data,91,92 thus there is some room for doubt in this conclusion.)
Apart from the experimental evidence, molecular dynamics
simulations have been conducted to understand the interactions
of cellulose with ILs.93,94 An all-atom force field for [C2mim]OAc
was developed by Liu et al., and the behavior of cellulose in this
IL was examined using molecular dynamics simulations of a
series of (1-4) linked-D-glucose oligomers with different
molecular weights.93 The proposed dissolution mechanism
involves the formation of hydrogen bonds between the IL
anions and the hydroxyl group protons of the glucose. A
computer modeling study by Novoselov et al. also showed that
the intermolecular hydrogen bond between hydrogen and
oxygen in cellobiose is broken in formation of a solvate complex
with the solvent and new bonds are formed between hydroxyl
hydrogen atoms in cellobiose and the chloride in [C4mim]Cl.94
All the studies on the mechanism of the cellulose dissolution
in ILs agree that the interactions between the anions of the ILs
and the hydroxyls of cellulose play an important role in this
process. The requirement of hydrogen bonding acceptor ability
(or basicity) of the anion has also been borne out by published
experimental work on screening ILs for cellulose dissolution
with a variety of anions of different hydrogen bonding basicity.18
As discussed below, the same cannot be said for the role of the
IL cation on cellulose dissolution.
Cations. Although the role of the anion seems clear, it is
equally clear that the cation must play some role in the ability
of a given IL to dissolve cellulose. There is not a single anion
This journal is c The Royal Society of Chemistry 2012
where it can be said that all liquid salt forms of that anion will
dissolve cellulose or dissolve it in the same amount (compare
for example the admittedly limited data in Table 3 for the
OAc anion). Let us examine here the various cations used in
ILs to dissolve cellulose and some of the ongoing controversy
about their specific roles.
Ionic Liquids containing imidazolium, pyridinium, ammonium,
and phosphonium cations have been observed to dissolve cellulose
when paired with a strongly basic, hydrogen bond accepting
anion (Table 1). The aromatic imidazolium and pyridinium
cations seem to work the best, however it is apparent that
these are also the most widely studied ones, most likely due to
the fact that imidazolium salts were the first ionic liquids used
to dissolve cellulose and much less attention has been paid
to cation choice. Thus, it is not yet clear that sufficient data
exist to declare these cation classes superior to the quaternized
ammonium or phosphonium cations.
The high ability of pyridinium- and imidazolium-based
ILs to dissolve cellulose might be related to the aromatic
nature of these cations and their ability to shield the dissolved
anion/cellulose polymer complexes. On one hand, the aromatic
rings are more polarizable as indicated by a Raman study,95
while on the other hand, the aromatic-based ILs present lower
relative interaction strengths between the cations and anions
because of reduction of the electrostatic strength due to the
charge delocalization in the aromatic rings.96 In the latter case,
it is easier for the anion to form hydrogen bonds with cellulose.
Studies, including the patent by Graencher, also show that
cellulose can be dissolved in the solutions of these salts when
basic solvents such as pyridine are present to dissolve the
salt.69,97 This might help us to understand the higher ability
of [C4mpy]Cl to dissolve cellulose (Table 1, entry 35), which
may be caused by the presence of unreacted starting material
(pyridine) from the synthesis of this IL.
When the alkyl chain length in the cation is increased, the
solvent power of ILs for cellulose seems to decrease, e.g., [C6mim]Cl
or [C8mim]Cl vs. [C4mim]Cl (Table 1, entries 42, 44 vs. 37,
pulp cellulose (1000), 100 1C). The lower solubility of cellulose
in ILs containing long chain length cations may be due to the
reduced effective chloride concentration or the hydrophobic
interactions between cations which might reduce their ability
to screen the anion/cellulose complexes.10
Size and polarizability may not be the only factors involved.
The effect of alkyl chain length from C2 to C10 of 1-alkyl-3-
methylimidazolium chloride was systematically investigated
by Erdmenger et al.77 A strong odd-even effect was observed
for the small alkyl chains. Cellulose was more soluble in
1-alkyl-3-methylimidazolium-based ILs with even-numbered
alkyl chains compared to odd-numbered alkyl chains, below
six carbon units. Marsh et al. attributed this even-odd effect to
the additional polarity in the heteroatomic substituents on the
imidazolium ring,98 however, packing effects in the liquid state
should also be considered.
When alkyloxy or alkyloxyalkyl groups are appended to an
imidazolium ring, the melting points and viscosity of the
corresponding ILs are lowered, however, some of those ILs do
not tend to dissolve cellulose.78 [Me(OEt)3-MeOEtOMe-Im]OAc,
[Me(OPr)3-Et-Im]OAc, and [Me(OEt)3-Bu-Im]OAc (Table 1,
entries 12, 13, 15) do not efficiently dissolve cellulose probably
Chem. Soc. Rev., 2012, 41, 1519–1537 1529
 due to the large size of the cation, however, the presence of
basic oxygen atoms in the side chains of the cations may also
interfere with the efficient hydrogen bonding of the anion to all
of the cellulose hydroxyl groups.78 These results suggest one
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might also need to consider a mechanism where the role of the
cation is simply to solvate and separate the cellulose polymers
which might be considered polyanionic with direct interactions
to many anions.
Other functional groups on the cation can also influence the
dissolution of cellulose. The presence of a hydroxyl end-group
in the cation decreases the solubility of cellulose in the
corresponding ILs, presumably by competing with cellulose
for hydrogen bond donation to the anion. This was demon-
strated for ILs containing a hydroxylated alkylalkoxy cation
(Table 1, entry 10), which exhibited low solubility of cellulose
compared to its counterpart containing no hydroxyl-end
group (Table 1, entry 4).78 While the hydroxyl group in the
cation can interact with the anions and compete with cellulose
in forming hydrogen bonds, thus decreasing the cellulose
solubility, Luo79 and Feng14 reported that the solubility of
cellulose in [C2OHmim]Cl was 11.1 g mol 1 IL at 70 1C,79
while [C2mim]Cl could not dissolve cellulose at this temperature
because of its high melting point (85 1C).83 Feng et al.,14
suggested that the hydroxyl group in the cation side chain
could form hydrogen bonds with cellulose hydroxyl groups,
thus enhancing the dissolution of cellulose and allowing more
to be dissolved. This seems counter-intuitive given the much
greater basicity (hydrogen bond acceptor ability) of the anions
vs. the cellulose hydroxyl groups and thus needs further study.
The above mentioned studies appear to prove opposite
conclusions, however, we do note that the chain lengths
containing the hydroxyl group and the number of hydrogen
bond donating hydroxyl groups are quite different in the ILs
studied: [H(OEt)3-Me-Im]OAc which did not dissolve cellulose
well78 and [C2OHmim]Cl which did dissolve cellulose well.79
It is possible that the much longer chain length in [H(OEt)3-
Me-Im]OAc provides more flexibility in allowing the formation
of intermolecular hydrogen bonds with its anions, while the
hydroxyls on the much shorter chain in [C2OHmim]Cl would
be more sterically congested leading to fewer interactions with
anions and availability to hydrogen bond to cellulose. It is also
possible that the differences are a result of the fact that
[H(OEt)3-Me-Im]+ simply has more OH groups to interact
with the acetate anion than does [C2OHmim]+.
Perhaps due to contradictory observations such as those
mentioned above, the exact role of the cation in dissolving
cellulose is the subject to competing theories. Most reports in
the literatures suggest that the IL anions disrupt the hydrogen
bonding in and between cellulose chains. The cation, on the
Table 4 Solubility of cellulose in [C2mim]OAc16,20,72,75,78
Cellulose type Temperature
a
Cellulose NM
Eucalyptus pre-hydrolysis sulfate pulp (569) NM
Avicel 100 1C
Avicel 100 1C
a-Cellulose 90 1C
a
NM: not mentioned.
1530 Chem. Soc. Rev., 2012, 41, 1519–1537
other hand, has been suggested to have anywhere from no
interactions to strong direct hydrogen bonding to cellulose.
Given the nature of the cations typically studied and the lack
of any strong hydrogen bond donors or acceptors, we wonder
how the cation could directly interact with cellulose to an
appreciable degree.
In our own NMR study with Prof. Moyna, the experimental
data indicated only a slight variation in the relaxation times of
the carbon nuclei of the IL cations, [C4mim]+, [C2mim]+, and
[Amim]+, with solute concentration, consistent with the only
moderate increase in solution viscosity.87,88 It was concluded
that no specific interactions exist between the cations and the
cellulose solute. Simulation studies by Novoselov and colleagues
also indicated that binding of the cation of [C4mim]Cl with the
hydroxyl oxygen atoms in cellulose is difficult due to steric
hindrances, and in this IL, the cation remains associated with
the Cl anion, but this association becomes weaker with
increased cellulose concentration.94
However, in a study of the dissolution mechanism of
cellobiose by Zhang et al.,90 they found that when the amount
of [C2mim]OAc increases, the peaks of the hydroxyls in
cellobiose merge into one broad peak and gradually move
downfield. The significant broadening of these proton resonances
was attributed to the interaction of oxygen atoms of the hydroxyls
in cellobiose with the acidic protons in the imidazolium cation.
They concluded that hydrogen bonds are formed between the
hydroxyls of cellobiose and both the anion and cation of
[C2mim]OAc. Their results indicated the stoichiometric ratio of
[C2mim]OAc/hydroxyl to be between 3 : 4 and 1 : 1 in the primary
solvation shell, suggesting that there should be one anion or
cation to form hydrogen bonds with two hydroxyl groups
simultaneously. However, if the solubility of cellulose in
[C2mim]OAc from the literature is related to the molar ratio of
IL to the OH group in cellulose, this molar ratio is higher than
1.5 (Table 4, column 5). Thus, there is some discrepancy between
the stoichiometric ratio of [C2mim]OAc/hydroxyl obtained by
Zhang et al. and the reported solubility of cellulose in this IL.
A subsequent paper by Moyna commented directly on the
above results and indicated that the chemical shift perturbation
(Dd) data are too vague to be attributed to specific interactions
between the IL and the sugar with any confidence since Dd is
only a good indicator of changes in the chemical environment
of nuclei. In addition, the authors simply used the concentration
of the IL at which some of the cellobiose 13C Dds reached a
plateau to determine the interaction stoichiometries between
cellobiose and [C2mim]OAc, which Moyna pointed out to be
inadequate for performing this type of study as the influence
of DMSO solvent is not taken into account. Thus, these
conclusions need to be considered with care.91,92
1
Solubility (wt%) Solubility (g mol IL) Mol IL/mol OH
420 434.0 41.6
19.6 33.4 1.6
15 25.5 2.1
8 13.6 4.0
45 48.5 6.4
This journal is c The Royal Society of Chemistry 2012
 Other molecular dynamics studies of the interactions of
cellulose with [C2mim]OAc by Liu et al. showed that some of
the cations were found to be in close contact with the poly-
saccharides through hydrophobic interactions.93 This supports
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the role of the cation is needed. We would suggest that an open
mind be kept and that other reasonable theories also be
considered.
For example, as indicated above cellulose is reported to be

the concept that the cation may play a role in the dissolution of virtually insoluble in [C3mim]Cl (insoluble; Table 1, entry 49)
cellulose by [C2mim]OAc, but not one of hydrogen bonding. or [C5mim]Cl (Table 1, entry 47),20 while ILs with an even
Heinze et al. also investigated the interactions of IL number of carbons in their alkyl chain substituent exhibit
cations using simple cellulose model systems (cellooligomers, higher capacities for cellulose dissolution compared to those
DP = 6–10).99 They found that one of the carbon signals of having an odd number.77 [C4mim]Cl is reported to be more
the glucose unit disappeared after dissolution in [C2mim]OAc. efficient than [C6mim]Cl in solvation of cellulose.10 These
On the basis of these results, the authors suggested that a studies might suggest that the role of the cation is in solvating
covalent bond was formed between the carbon of the reducing and keeping dispersed the anionic hydrogen bonded cellulose

end of the glucose unit and the carbon of the imidazolium anionn moieties. If this theory were true, then the ability of the
core. Ebner et al. verified this assumption by means of cations to organize in solution to shield the negative charges
13
C-isotopic labeling and fluorescence labeling experiments, and still pack well with other cations would be important. This
which indicated the formation of a covalent bond between the might explain the odd-even effect noted above and perhaps
C2 carbon of 1-alkyl-3-methylimidazolium IL and the reducing other of the various data reported in Table 1.
end of cellulose.100 It was pointed out that this bond formation
is strongly catalyzed by bases, and can be suppressed by the Influence of viscosity of ILs. It has also been noted that IL
absence of bases.100 viscosity may play a role in cellulose solvation, where it is
The possible reactivity of the C2 proton in dialkylimidazolium generally considered that ILs with low viscosity are more
cations is well known in nitrogen heterocycle carbene chemistry, efficient in dissolving cellulose.12,17,18 Some of the most efficient
where base catalyzed reactions are well documented.101 We have ILs to dissolve cellulose and their viscosity are listed in Table 5.
also recently demonstrated that some carbene exists in ILs of The conflicting data in Table 5 suggest that perhaps viscosity
sufficiently basic anions such as acetate. For example, the same is not a key factor in the dissolution of cellulose in a given
IL used to dissolve cellulose, [C2mim]OAc, will react directly IL. It is true, however, that ILs with lower viscosity are
with S or CO2. Reaction of [C2mim]OAc with elemental sulfur easier to handle, but it still seems that the basicity and polarity
or selenium at room temperature leads to the corresponding of the anions is a better indicator of their ability to dissolve
imidazole-2-chalcogenones via a carbene route, even in the cellulose.
absence of additional external sources of base.102 Bubbling
CO2 through [C2mim]OAc at atmospheric pressure and ambient Microwave irradiation and sonication. Impressive results
temperature, leads to the crystallization of the corresponding have been obtained when microwave irradiation or sonication
neutral imidazolium carboxylate ([C2mim+-COO ]) cocrystallized were used to dissolve cellulose instead of thermal heating.10,80
with a [C2mim]+ cation, and an anion that can best be The solubility of cellulose in one mole of [C4mim]Cl increases
described as [H(OAc)2] .103 Nonetheless, this reactivity when to 43.7 g with microwave heating, compared to only 17.5 g
dissolving cellulose appears to only occur under extreme with general heating.10 (CAUTION: Care must be taken when
conditions, such as under heating and in the presence of bases, using microwave heating because ILs are efficient microwave
as might be expected from the known chemistry of the absorbers and heating occurs rapidly which can easily lead to
[C2mim]+ cation. degradation of the ILs and cellulose, or even explosions of
Based on all of the experimental results, it does seem that sealed systems.) The solubility of Kraft pulp in [Amim]Cl
the cations of ILs play a role in the dissolution of cellulose. reached 12.7 g mol 1 IL when the solution was sonicated for
However, given the competing theories and different inter- only 5 min, and that of MCC in [Amim]Cl reached 42.8 g mol 1
pretations of essentially the same data, further clarification of IL in 27 min.80
Our studies have also shown that microwave is more
Table 5 Viscosity vs. solubility of various ILs efficient than oil-bath heating in dissolving raw lignocellulosic
biomass (e.g., pine trees)33 or chitinous biomass (e.g. shrimp
Solubility of
Viscosity Solubility of Cellulose shells).37 Longer and more pure biopolymers can be extracted
IL (mPa
s)a Cellulose (wt%) (g mol 1 IL)
b from raw biomass using microwave irradiation leading to the
ability to spin fibers directly from the extraction solutions.29,37
[C4mim]Cl 147 (80 1C)72 20 (100 1C) 34.9
[C2mim]Cl 62 (80 1C)104 14 (100 1C) 20.5 Microwave heating also assisted in the preparation of IL
[C2mim]OAc 10 (80 1C)72 420 (NM)c 434.0 solutions used to spin cellulose-magnetite composite fibers.29
[C4mim]OAc 26 (80 1C)105 15.5 (70 1C) 30.7
[C2mim](MeO)HPO2 107 (25 1C)18 10 (45 1C) 20.6 3.2 Regeneration of cellulose
[C2mim](MeO)MePO2 510 (25 1C)18 10 (55 1C) 22.0
[C2mim](MeO)2PO2 265 (25 1C)18 10 (65 1C) 23.6 Cellulose dissolved in ILs can be easily precipitated from the
[Amim]HCOO 66 (25 1C)17 B22 (85 1C) B37.0 cellulose/IL solution by adding anti-solvents, such as water,
10 (60 1C) 16.8
ethanol, methanol, acetone, acetonitrile, etc.8,10,12,20,80,82 The
a
The numbers in brackets correspond to temperatures at which the macroscopic morphology of the regenerated cellulose depends
viscosity is measured. b The numbers in brackets correspond to tem-
on how the cellulose/IL solution contacts the regeneration
peratures at which the solubility is measured. c NM: not mentioned.
solvent. Rapid mixing of the IL solution with an aqueous

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 1519–1537 1531
 stream results in precipitation of cellulose as a powdery floc.10
By extrusion of the cellulose/IL solution into an anti-solvent,
thin fibers and rods can be prepared.10,16,25,27 If the cellulose/IL
solution is cast onto a glass plate, thin cellulose films can be
obtained.12,24,26 In addition, nanofibrillar cellulose aerogels can
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be prepared if the regenerated gel is washed with liquid carbon
dioxide prior to drying under supercritical conditions.76
The reconstructed celluloses exhibit typically lower degrees
of crystallinity than native cellulose after being dissolved in ILs,
and the results show that after dissolution and regeneration,
the X-ray diffraction pattern of regenerated cellulose changes
from cellulose I (diffraction pattern of native cellulose) to
cellulose P.12 These regenerated celluloses have lower or no
crystallinity and are thus much easier to be enzymatically
hydrolyzed to glucose.106
The ready ability to reconstitute the dissolved cellulose into
a variety of structural forms is one of the advantages of
working with ILs for cellulose dissolution. However, the
removal of the anti-solvent from the IL such that the IL can
be reused is a process which can require considerable energy
and expense. We will discuss this below as we consider the
‘greenness’ of an IL process to dissolve cellulose.
4. Dissolution of lignocellulosic biomass using ionic
liquids: the pros and cons
The depletion of the world’s petroleum supply and environ-
mental issues associated with crude oil usage increase demand
for developing alternative, environmental-friendly and non-
petroleum dependent energy sources.107 Lignocellulosic biomass,
an alternative and sustainable energy source for the future, can be
used as a feedstock for bioconversion into fermentable sugars, an
intermediate which is eventually converted into biofuels. However,
current processes to convert lignocellulosic biomass into useful
materials are highly inefficient. For example, the production of
paper from wood, the most efficient conversion process, shows a
biomass utilization of only 35%,108 and the rest of the ligno-
cellulosic biomass is burned to produce heat or ends up as waste.
The highly crystalline structure of cellulose in lignocellulosic
biomass is embedded in a matrix of the polymers lignin and
hemicellulose.109 Overcoming this recalcitrance, the resistance
of plant cell walls to deconstruction, is a key step in the
conversion of lignocellulosic biomass to fuels and valuable
chemicals. The dissolution and pretreatment of lignocellulose
using ILs as the solvents offers several attractive features, and
have been widely studied. In 2006, Fort et al. first demonstrated
that the IL [C4mim]Cl is capable of dissolving untreated wood
with varying hardness.32 Later, we showed that [C2mim]OAc is
a better solvent to dissolve wood than [C4mim]Cl under the
same operation conditions,33 and [C2mim]OAc can also be used
to dissolve bagasse.36 Our work has also demonstrated that
polyoxometalate, [PV2Mo10O40]5 , is an effective catalyst for
the dissolution and delignification of wood in [C2mim]OAc.34
Other sources of lignocellulosic biomass, e.g., bamboo, can
also be dissolved in ILs, such as 3-(1-methylimidazolium-
3-yl)propane-1-sulfonate.110 After such dissolution processes,
cellulose-rich materials and free lignin can be recovered by
the addition of precipitating solvents, such as the mixture of
acetone and H2O.32–34,36,110
1532 Chem. Soc. Rev., 2012, 41, 1519–1537
Several ILs have now been used to pretreat wheat, triticale, and
rice straw, flaxshives and poplar wood, among other biomass
sources.35,111–114 The regenerated cellulosic materials have a more
amorphous macrostructure and their enzymatic hydrolysis rates
are thus improved significantly, however, a possible limitation in
using ILs for the treatment of biomass is that some ILs can
inactivate cellulases which might be used to convert cellulose into
fuels such as ethanol. Turner and coworkers found that the
hydrolytic rate of cellulose by T. reesei cellulase was poor,115 which
could be attributed to the high concentration of the Cl ion that
leads to irreversible unfolding and inactivation of the enzymes.
Interestingly, the structure of lignin and hemicellulose are essen-
tially unaltered after treatment with ILs.114 Thus, the IL processing
of lignocellulosic biomass could have tremendous advantages over
current technologies by enabling the recovery of all three of the
major natural lignocellulosic biopolymers.72 This would open the
door to an integral usage of this feedstock, and allow the direct use
of the regenerated polymers in composites, advanced materials, or
conversion into useful chemicals. For instance, lignin is considered
as the major aromatic resource of the bio-based economy,116 and
theoretically can be converted into valuable platform chemicals,
such as phenol, benzene, toluene, and xylene.
Upcoming research in this area is expected to further
contribute to the fulfillment of the ‘‘biorefinery’’ concept, which
may constitute the basis of a sustainable chemical industry
based on biorenewable resources and environmentally friendly
processing.72 The most promising investigations will include the
potential use of hemicellulose and lignin, the development of
ILs based on biorenewable resources that could be used in the
biomass area, and lower energy processing. Nonetheless, it is
important to keep in mind that sustainability will be determined
by the entire process, the chemicals used, and energy costs. Let
us now examine the potential greenness for such processes.
5. ‘‘Degree of Green’’ analysis of processing using
ionic liquids
Green Chemistry is defined as the ‘‘design of chemical products
and processes to reduce or eliminate the use and generation of
hazardous substances’’.117,118 The field seeks to reduce and prevent
pollution at its source, and it is distinct from environmental
chemistry which focuses on chemical phenomena in the environ-
ment. The twelve principles of Green Chemistry were introduced
in 1998 by Anastas and Warner,117 to help to explain what the
definition of Green Chemistry means in practice. These principles
include (1) Prevention; (2) Atom Economy; (3) Less Hazardous
Chemical Synthesis; (4) Design Safer Chemicals; (5) Safer Solvents
and Auxiliaries; (6) Design for Energy Efficiency; (7) Use of
Renewable Feedstock; (8) Reduce Derivatives; (9) Catalysis;
(10) Design for Degradation; (11) Real Time Analysis for Pollution
Prevention; (12) Inherently Safer Chemistry for Accident
Prevention. In this section, the ‘greenness’ of the processing of
cellulose using ILs will be analyzed in the context of the above
principles of Green Chemistry.
5.1 Greenness analysis from the principles
Prevention. Waste prevention is the first of the twelve principles
of Green Chemistry. It is better to prevent the formation of
waste rather than to clean it up after its production. In the first
This journal is c The Royal Society of Chemistry 2012
 literatures related to the dissolution of cellulose using ILs, it was
reported that no chemical reactions occur between the IL and
cellulose and that ILs are nonderivatizing solvents for cellulose.10–12
If this is true, no waste or byproduct would be produced in this
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process and the IL would be infinitely recycled. However, it
has also been reported that when bases such as imidazole or
1-methylimidazole are present (e.g., as unreacted starting
materials), 1-alkyl-3-methylimidazolium cations can react at
the C2 position with cellulose at its reducing end, forming a
carbon–carbon bond.100 It is pointed out in the same paper
that the amount of cellulose reacting with the ILs is rather
minor, and that this side reaction can be suppressed by the
absence of bases and reaction or contact times of less than 2 h.
While minor amounts of byproducts can be produced and
this should be considered, current research indicates that the
amount of waste (byproducts, water, chemicals, etc.) generated
in the processing of cellulose using ILs is much less when
compared with traditional pulping processes such as Kraft
pulping or cellulose forming processes such as the viscose
process.119 Both Kraft pulping and the viscose process have
high chemical loads and energy and water usage.50
Atom economy. The term atom economy was introduced by
Trost in the 1990s, and refers to the concept of maximizing the
use of raw materials so that the final product contains the
maximum number of atoms from the reactants.120 The ideal
reaction would incorporate all of the atoms of the reactants. In
the ideal IL process, cellulose would be regenerated from the
IL solutions using anti-solvents, and the ILs, as well as the
anti-solvents would be recycled. By reducing the number of
chemicals needed for this processing to as low as two (IL and
anti-solvent), the potential losses of chemicals can be reduced.
If the ILs themselves could be produced from the biomass
value-added chemicals, this would be even better.
Process and product toxicity. The products of a green
process should pose little or no toxicity to human beings
and the environment. If we consider the ability of ILs to
process cellulose into many useful advanced materials, then
there is little concern for the toxicity of the products, either the
cellulose itself or derivative such as cellulose acetate, carboxy-
methylated cellulose, etc. These are already useful and widely
used products in coatings, membranes, composites, separation
media, as well as in medical applications.98 They are considered
non-toxic and non harmful to our health or the environment.
That leaves us with the need to improve the attributes of the ILs
and anti-solvents used which could include lower toxicity and
improved biodegradability as discussed below.
Solvent safety. Perhaps the biggest concern will be the
toxicity of the IL solvent and any anti-solvents used in the
processing. While the relevant Green principle suggests it is
better to use no solvents or auxiliaries in a process when it is
possible, or when they are unavoidable to be used it goes on to
state that they should be innocuous to humans and the
environment. Solventless systems, water, and supercritical
fluids are often noted as ‘‘green’’,121 although these get their
fair share of criticism.
Let’s consider here first the IL and then the anti-solvent. At
present there are no ‘solventless’ methods to treat cellulose and
This journal is c The Royal Society of Chemistry 2012
keep its molecular structure and molecular weight intact. ILs
have emerged as a nonderivatizing solvent that will truly
‘dissolve’ cellulose rather than degrade it and it is this property
that makes them useful in this field. The original IL used to
dissolve cellulose, [C4mim]Cl, is however somewhat toxic. The
median lethal dose (LD50) of [C4mim]Cl ranges from 50 mg
kg 1 to 300 mg kg 1,122 and this IL was also shown to be toxic
to mice at maternally toxic dosages.123
It is quite well known that there is a near infinite variety of
combinations of ions that will lead to salts which can be defined
as ILs. Common knowledge also seems to suggest that ILs can
dissolve anything. However, what is sometimes forgotten is that it
is not a single IL that can dissolve everything, but rather that a
specific IL can be found to dissolve many, many solutes. Thus, the
search for a better cellulose solvent cannot rely on only picking
non-toxic or biodegradable ions; but picking the combination of
these ions which will still efficiently dissolve cellulose.
As discussed earlier, it was determined that the primary
mechanism of cellulose dissolution by ILs was the basicity of
the anion which disrupts the inter- and intramolecular hydrogen
bonds in cellulose.8,17 With this knowledge, BASF screened
hundreds of potential ILs as cellulose solvents and found some
favorable properties in the IL [C2mim]OAc.124 They found
that the use of [C2mim]OAc has many advantages over our original
use of [C4mim]Cl due to the acetate salt’s lower melting point
(o 20 1C vs. 70 1C), lower viscosity (10 mPa
s vs. 147 mPa
s, at
80 1C), lower corrosivity (very little vs. strong), lower toxicity (LD50
B2000 mg kg 1 vs. 50–300 mg kg 1), and higher dissolution
ability for cellulose (cellulose solubility 420% vs. B20%).72,122,124
However, current ILs for cellulose dissolution are not
biodegradable. Biodegradation is a natural process involving
a collective effort of different microorganisms to break down
the complex organic molecules into biomass and/or inorganic
compounds, such as CO2 and water.125 Hence, a biodegradable,
but toxic, substance may exert an acute effect upon exposure
to it, but will be rendered non-toxic upon its biodegradation.
It is clear that the biodegradability of the ILs can still be
improved and the search for ILs made from natural materials
is a major research driver in the field. For example, Fukumoto
et al. synthesized a series of ILs from natural amino acids,
which are said to be useful for a variety of applications, such
as solvents, biodegradable materials, etc.126
In addition to the IL, one also must consider the anti-solvent
which is needed to coagulate the cellulose and recover the IL.
Here the choices for a relatively benign medium are more
plentiful and the two most common regeneration solvents are
water and ethanol. The anti-solvent must hydrogen bond the IL
anion more strongly than cellulose and solvate both IL ions.
Typically ILs that dissolve cellulose will be water soluble and
thus anti-solvents such as water, ethanol, methanol, acetone,
acetonitrile, etc.10,70 have been explored. Water as a solvent
would seem safe, environmentally-benign, and inexpensive, to
not pose any hazards, and thus green, however, as will be
discussed below, the greenness of recovering the water for reuse
must also be considered and this is currently energy intensive.
In looking for other anti-solvents, one might first consider
the toxicity. The toxicities of 21 organic compounds were
estimated by Na"e˛cz-Jawecki and Sawicki,127 and the toxicities
of the tested compounds varied over 4 orders of magnitude.
Chem. Soc. Rev., 2012, 41, 1519–1537 1533
 The least toxic compounds were methanol, ethanol, acetone,
DMF, acetonitrile, and isopropanol; all potential anti-solvents
for the regeneration of cellulose from the IL solutions.
Nonetheless, a further consideration could play a major role
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in selecting an appropriate anti-solvent; the anti-solvent/IL
solution must be separated and each component recycled and
reused, both from an environmentally-benign standpoint, but
also a cost competitive one.
Energy. This Principle of Green Chemistry suggests that the
required energy of any process should be minimized, and the
design of chemical reactions or systems that are not energy
intensive is highly desirable.121 (We might point out in today’s
society this also makes great economic sense.) Processing of
cellulose using ILs is usually performed under mild heating
conditions, but the time and temperature needed for an
optimum process has yet to be determined. We, for example,
have looked at higher temperatures, but much shorter times to
expand the available processing options.36 We also noted that
highly concentrated cellulose/IL solution can be obtained in a
few minutes under microwave irradiation or sonication,10,80
and such processing methods need to be closely compared.
Others, have even tried to change the IL and lower the
temperature needed for dissolution, for example, it has even
been reported that cellulose could be dissolved in phosphonate-
based ILs, such as [C2mim][(MeO)HPO2], at room temperature
(25 1C) and ambient pressure.18 Nonetheless, the temperature of
dissolution must be balanced against the efficiency of dissolution
and the capacity of the dissolving solvent.
It may, however, be the energy required in the IL and anti-
solvent recycling step that ultimately determines the greenness
and economic viability of an IL process for biomass. It is clear
that the ILs used for dissolving cellulose can be separated from
water at high purity and both the IL and water reused. The IL
can be obtained with little degradation. However, the current
methods for removing the IL completely from the cellulose
involve extensive washing steps and those for separating the
water from the IL involve energy intensive evaporative steps.
The energy demands from such steps need to be reduced and
this has inspired a variety of research efforts. Interesting
approaches are now being considered which involve the use
of solvent mixtures128 or even ‘switchable solvents’ which
change form based on a chemical or physical stimulus.129
Renewable feedstocks. Certainly, the cellulose feedstock
itself is renewable and the water if used as anti-solvent, but
the currently contemplated ILs are not. Some research has
been published in developing ILs from renewable chemicals,
however, to date none of these will dissolve cellulose. This is
an interesting topic of research that continues to be explored.
Reduce derivatives. The only possible derivatives in the
dissolution of cellulose with ILs might be the product of the
reaction between the 1-alkyl-3-methylimidazolium cations at
its C2 position with the reducing end of cellulose.100 As
mentioned previously, the amount of this kind of byproduct
is rather minor and this side reaction can be minimized by the
absence of bases and shorter reaction times. Typically, this
principle is directed toward more synthetic methodologies, for
example, the use of protective groups in organic synthesis.
1534 Chem. Soc. Rev., 2012, 41, 1519–1537
Catalysis. To recover the three major natural biopolymers
cleanly from woody biomass, it is necessary to cleave certain
covalent linkages. Our recent work has shown that the dissolution
of wood in [C2mim]OAc can be enhanced when polyoxometalates
(POMs) are used as catalysts.34 The use of POMs does lead to
additional degradation of the lignin and lower lignin recovery,
however, the yield of cellulose-rich material is comparable to or
higher than that obtained from Kraft pulping processes. POM
can be recovered with [C2mim]OAc after evaporation of the
reconstitution solvent and can be reused, although with some
loss of POM and catalytic activity under current conditions. More
work on this catalytic process needs to be done, such as the
development of more efficient and selective catalysts, and this
represents a very interesting and fruitful line of future research.
Design for degradation. The currently designed ILs for
biomass treatment are not biodegradable and this has raised
concerns over the sustainability of an IL process. On the other
hand, the high stability of many ILs makes them recyclable.59
Reports show that 99.5% of the ILs used in cellulose processing
can be recovered with high purity and can be reused,119 which is
a positive indicator for their durability in use.
Biodegradable ILs are indeed attracting more and more
attention. A number of ILs have been identified to be ‘‘readily
biodegradable’’ using CO2 headspace tests (ISO14593).125,130
With such studies ongoing, we feel the goal of biodegradable ILs
will be reachable, however they must still be able to dissolve
cellulose to be useful for this application. Designing in one feature
of an IL, often leads to designing out another useful property.
Online analytics. It is necessary to monitor a reaction and act
immediately upon it to prevent unwanted byproducts.121 In situ
monitoring of a reaction has significant advantages where action
can be taken immediately to prevent formation of byproducts,
and pretreatment of the samples can be avoided. As to the
dissolution of cellulose using ILs, in situ FT-IR might be a good
choice and could be connected with the reactor, in which solution
samples could enter the reactor tank of the FT-IR equipment at
specific reaction times. By examining the absorbance of the
reaction solution, we could know if there is any side reaction
between the ILs and cellulose. FT-IR analysis could be
performed in few minutes, thus, real time monitoring can be
realized. At the moment, however, even though scale-up of
IL-based biorefineries is being contemplated and even under
development, little attention has been paid to this area.
Safer chemistry and accident prevention. A green process
should have minimum potential for chemical accidents. Many
ILs do possess properties which could indeed help make a
process safer compared to the use of volatile organic solvents.
These include low vapor pressure, low flammability, high
thermal stability, etc. All of these can decrease the potential
for chemical accidents of processing of cellulose, such as
chemical releases, explosions, and fires. However, it should be
pointed out that not all ILs possess all of these properties and
one must continue to evaluate all of the physical and chemical
properties of potential ILs. For example, we demonstrated that
not all ILs are non-volatile or nonflammable,131 while Earle and
coworkers demonstrated that some ILs can be distilled at low
pressure without decomposition.132 We have also shown that
This journal is c The Royal Society of Chemistry 2012
 perfluorinated anions can be hazardous due to hydrolytic
instability; for instance, [PF6] can decompose to the dangerous
HF(g).133 Thus, as with any IL chosen for a particular application,
care must be taken to not over generalize the properties from
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one IL to another, but rather to carefully consider the
chemistry of each ion and chemical utilized.
5.2 Is biomass processing using ionic liquids green or not?
Some ILs, but not all are toxic, corrosive, and flammable.
Recent investigations have led to ILs comprised of ions
Generally Recognized As Safe components (e.g., saccharin
and acesulfame),134–136 and other ILs such as benzalkonium
ibuprofenate and lidocainium docusate are made from active
pharmaceutical ingredients or food grade ions.137–139 Studies
have shown that some ILs can be generally orders of magnitude
less toxic than conventional organic solvents.140 But the cautionary
note again, is to not over generalize the properties of one IL to
another. ILs can practically be comprised of any targeted ions
where the choice of ions is driven by the desire to obtain a
particular physical, chemical, or biological property.
Wise choices need to be made in the choice of IL, but the
choice of IL is not the deciding factor. One must consider the
entire processing of cellulose and all of the Principles brought
into balance before one can determine if any given process is
indeed ‘‘green.’’ We might also add that the greenest process in
the World will never be implemented if one cannot make a
profit and sustain a business based on it.
6. Conclusions and prospects
The ability of ILs to dissolve cellulose has attracted intense
academic and industrial interest in a relatively short period
of time. The ability to dissolve cellulose in ILs with no
derivatization under mild conditions, and then regenerate
the same molecular weight cellulose with any given shape,
rheology, or function, provides a platform for a wide variety
of new advanced materials. In addition, dissolved cellulose
provides opportunities for homogeneous modification of the
cellulose polymer.21–23 However, perhaps one area where inter-
est has been quite intense is the application of ILs to the concept
of a ‘biorefinery’.72
Recently, the application of ILs has been extended to not
only the processing of other biopolymers, such as lignin,
hemicellulose, chitin, and wool, but to the direct extraction
of the biopolymers from raw biomass (e.g., wood, shrimp
shell).32,33,37 Biomass is regarded as a permanent and woefully
underutilized source of renewable feedstock on the planet for
both material and energy,141 and it is an intensively studied
alternative and sustainable source for chemicals, materials,
and fuels. Development of a technology platform, which could
facilitate the access to natural biopolymers and subsequent
enabling of the production of biofuels based on renewable
sources, is a major step towards sustainability.
ILs do provide a new and powerful platform for the
conversion of biomass into valuable chemicals, either as a
‘pretreatment process’ or as a conversion solvent. However, in
this arena, the current focus is squarely on the utilization of
cellulose, e.g., its hydrolysis and fermentation to ethanol or
biofuels. The use of lignin, hemicellulose, or chitin seems to
This journal is c The Royal Society of Chemistry 2012
be neglected. A much broader range of value-added products
and chemicals is possible using ILs in a true biorefinery, where
fuels are only one aspect of the production processes.
While the number of publications on the use of ILs in the
biomass field has increased significantly in recent years, work
is needed in several key areas to further understand the process
and to meet the sustainability and green chemistry requirements
for the development of the next generation of industrial
chemical processes. First, the roles of the cation and anion in
the treatment of biomass in ILs should be clarified in order to
design the next generation of biomass solvents. In addition, the
development of much more efficient and energy-saving methods
for the recycling of ILs is required. The current methods to
recycle ILs in biomass processing mainly center on evaporation
of the anti-solvents, which can consume a lot of energy,
especially in the case of IL/water solutions. Finally, data on
the corrosivity, toxicity, biodegradability, and environmental
fate of ILs have to be enriched.
In summary, while ILs offer tremendous possibilities as
the basis for a revolutionary technological platform for the
development of a sustainable industry related to biomass, this field
is still new and it requires a better fundamental understanding
of the mechanisms of dissolution and a more comprehensive
database on the physicochemical properties of the ILs. Much
of this work is now underway around the world. We fully
expect great progress in this area as this technique may offer
less energy and chemical intensive processes and significantly
improved environmental benefits when compared with traditional
processes.
Nonetheless, any major new chemical process which will
require tons of a new chemical will, and should, generate
debate. Is the outcome worth the production of tons of a new
chemical of any type, green or not? Ultimately this should be
decided by the benefits of the process. In the current context,
ILs are of concern because ILs are viewed as unknown
expensive chemicals with energy intensive recycling technol-
ogies. However, with the intense worldwide study on ILs for
biomass processing, we and others142 believe that IL prices will
continue to be dramatically lowered, recycling with energy-
saving methods will be realized, and any toxic properties of
the ILs be engineered out of the proper choice of IL solvent.
The key will be if the ILs can truly do something valuable
that no other system can reasonably accomplish. Only time
will tell.
Acknowledgements
We would like to thank 525 Solutions for recent support of
our biomass efforts through a U.S. Department of Energy
SBIR Award (Grant No. DE-SC0004198).
References
1 C. Tsioptsias, A. Stefopoulos, I. Kokkinomalis, L. Papadopoulou
and C. Panayiotou, Green Chem., 2008, 10, 965–971.
2 K. J. Edgar, C. M. Buchanan, J. S. Debenham, P. A. Rundquist,
B. D. Seiler, M. C. Shelton and D. Tindall, Prog. Polym. Sci.,
2001, 26, 1605–1688.
3 P. R. Chawla, I. B. Bajaj, S. A. Survase and R. S. Singhal,
Food Technol. Biotechnol., 2009, 47, 107–124.
Chem. Soc. Rev., 2012, 41, 1519–1537 1535
 4 A. H. Conner, in Handbook of Size Exclusion Chromatography,
ed. Wu and Chi-san, Chromatographic Science Series, Marcel
Dekker, New York, 1995.
5 D. M. Updegraff, Anal. Biochem., 1969, 32, 420–424.
6 H. Ohno and Y. Fukaya, Chem. Lett., 2009, 38, 2–7.
Published on 20 January 2012. Downloaded by Chalmers Tekniska Hogskola on 10/5/2023 10:41:09 AM.
7 T. Heinze and T. Liebert, Prog. Polym. Sci., 2001, 26, 1689–1762.
8 A. R. Xu, J. J. Wang and H. Y. Wang, Green Chem., 2010, 12,
268–275.
9 R. D. Rogers and K. R. Seddon, ACS Symposium Series 818,
American Chemical Society, Washington D. C., 2002.
10 R. P. Swatloski, S. K. Spear, J. D. Holbrey and R. D. Rogers,
J. Am. Chem. Soc., 2002, 124, 4974–4975.
11 T. Heinze, K. Schwikal and S. Barthel, Macromol. Biosci., 2005,
5, 520–525.
12 H. Zhang, J. Wu, J. Zhang and J. S. He, Macromolecules, 2005,
38, 8272–8277.
13 Q. Ren, J. Wu, J. Zhang, J. S. He and M. L. Guo, Acta Polym. Sin.,
2003, 3, 448–451.
14 L. Feng and Z. L. Chen, J. Mol. Liq., 2008, 142, 1–5.
15 M. Mazza, D. A. Catana, C. Vaca-Garcia and C. Cecutti,
Cellulose, 2009, 16, 207–215.
16 B. Kosan, C. Michels and F. Meister, Cellulose, 2008, 15, 59–66.
17 Y. Fukaya, A. Sugimoto and H. Ohno, Biomacromolecules, 2006,
7, 3295–3297.
18 Y. Fukaya, K. Hayashi, M. Wada and H. Ohno, Green Chem.,
2008, 10, 44–46.
19 W. Lan, C. F. Liu, F. X. Yue, R. C. Sun and J. F. Kennedy,
Carbohydr. Polym., 2011, 86, 672–677.
20 J. Vitz, T. Erdmenger, C. Haensch and U. S. Schubert, Green Chem.,
2009, 11, 417–424.
21 S. Kohler and T. Heinze, Cellulose, 2007, 14, 489–495.
22 J. Wu, J. Zhang, H. Zhang, J. S. He, Q. Ren and M. L. Guo,
Biomacromolecules, 2004, 5, 266–268.
23 S. Bose, D. W. Armstrong and J. W. Petrich, J. Phys. Chem. B,
2010, 114, 8221–8227.
24 M. Bagheri, H. Rodrı́guez, R. P. Swatloski, S. K. Spear, D. T. Daly
and R. D. Rogers, Biomacromolecules, 2008, 9, 381–387.
25 S. L. Quan, S. G. Kang and I. J. Chin, Cellulose, 2010, 17,
223–230.
26 M. B. Turner, S. K. Spear, J. D. Holbrey and R. D. Rogers,
Biomacromolecules, 2004, 5, 1379–1384.
27 T. Cai, H. H. Zhang, Q. H. Guo, H. L. Shao and X. C. Hu,
J. Appl. Polym. Sci., 2010, 115, 1047–1053.
28 K. F. Du, M. Yan, Q. Y. Wang and H. Song, J. Chromatogr., A,
2010, 1217, 1298–1304.
29 N. Sun, R. P. Swatloski, M. L. Maxim, M. Rahman, A. G. Harland,
A. Haque, S. K. Spear, D. T. Daly and R. D. Rogers, J. Mater.
Chem., 2008, 18, 283–290.
30 M. G. Ma, N. Jia, S. M. Li and R. C. Sun, Iran. Polym. J., 2011,
20, 413–421.
31 S. S. Rahatekar, A. Rasheed, R. Jain, M. Zammarano,
K. K. Koziol, A. H. Windle, J. W. Gilman and S. Kumar,
Polymer, 2009, 50, 4577–4583.
32 D. A. Fort, R. C. Remsing, R. P. Swatloski, P. Moyna, G. Moyna
and R. D. Rogers, Green Chem., 2007, 9, 63–69.
33 N. Sun, M. Rahman, Y. Qin, M. L. Maxim, H. Rodrı́guez and
R. D. Rogers, Green Chem., 2009, 11, 646–655.
34 N. Sun, X. Y. Jiang, M. L. Maxim, A. Metlen and R. D. Rogers,
ChemSusChem, 2011, 4, 65–73.
35 T. A. D. Nguyen, K. R. Kim, S. J. Han, H. Y. Cho, J. W. Kim,
S. M. Park, J. C. Park and S. J. Sim, Bioresour. Technol., 2010,
101, 7432–7438.
36 W. Y. Li, N. Sun, B. Stoner, X. Y. Jiang, X. M. Lu and
R. D. Rogers, Green Chem., 2011, 13, 2038–2047.
37 Y. Qin, X. M. Lu, N. Sun and R. D. Rogers, Green Chem., 2010,
12, 968–971.
38 G. Audemars, British Patent, 1855, 283.
39 T. Liebert, ACS Symposium Series, American Chemical Society,
Washington D.C., 2010.
40 H. P. Fink, P. Weigel, H. J. Purz and J. Ganster, Prog. Polym. Sci.,
2001, 26, 1473–1524.
41 C. L. McCormick and T. R. Dawsey, Macromolecules, 1990, 23,
3606–3610.
42 N. Tamai, D. Tatsumi and T. Matsumoto, Biomacromolecules,
2004, 5, 422–432.
1536 Chem. Soc. Rev., 2012, 41, 1519–1537
43 R. B. Hammer and A. F. Turbak, Abstracts of Papers of the
American Chemical Society, 1977, 173, 8–8.
44 G. T. Ciacco, T. F. Liebert, E. Frollini and T. J. Heinze, Cellulose,
2003, 10, 125–132.
45 S. Fischer, W. Voigt and K. Fischer, Cellulose, 1999, 6, 213–219.
46 S. Fischer, H. Leipner, K. Thümmler, E. Brendler and J. Peters,
Cellulose, 2003, 10, 227–236.
47 K. Saalwachter, W. Burchard, P. Klufers, G. Kettenbach,
P. Mayer, D. Klemm and S. Dugarmaa, Macromolecules, 2000,
33, 4094–4107.
48 C. F. Coss and D. C. Spruance, US Patent, 763266, 1904.
49 H. Lyncke, GB Patent, 190808023, 1908.
50 F. Hermanutz, F. Gähr, E. Uerdingen, F. Meister and B. Kosan,
Macromol. Symp., 2008, 262, 23–27.
51 T. Rosenau, A. Potthast, H. Sixta and P. Kosma, Prog. Polym. Sci.,
2001, 26, 1763–1837.
52 A. L. Dupont, Polymer, 2003, 44, 4117–4126.
53 B. Duchemin, PhD thesis, University of Canterbury Christchurch,
New Zealand, 2008.
54 A. M. Striegel, J. Chil. Chem. Soc., 2003, 48, 73–77.
55 N. A. Portnoy and D. P. Anderson, ACS Symp. Ser., 1977, DOI:
10.1021/bk-1977-0058.ch005.
56 R. D. Rogers and K. R. Seddon, Science, 2003, 302, 792–793.
57 K. R. Seddon, J. Chem. Technol. Biotechnol., 1997, 68, 351–356.
58 J. Dupont, R. F. de Souza and P. A. Z. Suarez, Chem. Rev., 2002,
102, 3667–3691.
59 T. Welton, Chem. Rev., 1999, 99, 2071–2083.
60 M. Kosmulski, J. Gustafsson and J. B. Rosenholm, Thermochim.
Acta, 2004, 412, 47–53.
61 H. Hagiwara, Y. Sugawara, K. Isobe, T. Hoshi and T. Suzuki,
Org. Lett., 2004, 6, 2325–2328.
62 A. Bosmann, L. Datsevich, A. Jess, A. Lauter, C. Schmitz and
P. Wasserscheid, Chem. Commun., 2001, 2494–2495.
63 M. Galinski, A. Lewandowski and I. Stepniak, Electrochim. Acta,
2006, 51, 5567–5580.
64 C. J. Adams, M. J. Earle, G. Roberts and S. R. Seddon,
Chem. Commun., 1998, 2097–2098.
65 T. Fischer, A. Sethi, T. Welton and J. Woolf, Tetrahedron Lett.,
1999, 40, 793–796.
66 P. Snedden, A. I. Cooper, K. Scott and N. Winterton, Macro-
molecules, 2003, 36, 4549–4556.
67 H. Matsumoto, M. Yanagida, K. Tanimoto, M. Nomura,
Y. Kitagawa and Y. Miyazaki, Chem. Lett., 2000, 29, 922–923.
68 S. A. Forsyth, J. M. Pringle and D. R. MacFarlane, Aust. J.
Chem., 2004, 57, 113–119.
69 C. Graenacher, US Patent, 1943176, 1934.
70 S. D. Zhu, Y. X. Wu, Q. M. Chen, Z. N. Yu, C. W. Wang,
S. W. Jin, Y. G. Ding and G. Wu, Green Chem., 2006, 8, 325–327.
71 N. V. Plechkova and K. R. Seddon, Chem. Soc. Rev., 2008, 37,
123–150.
72 N. Sun, H. Rodrı́guez, M. Rahman and R. D. Rogers, Chem.
Commun., 2011, 47, 1405–1421.
73 O. A. El Seoud, A. Koschella, L. C. Fidale, S. Dorn and
T. Heinze, Biomacromolecules, 2007, 8, 2629–2647.
74 S. Barthel and T. Heinze, Green Chem., 2006, 8, 301–306.
75 M. Zavrel, D. Bross, M. Funke, J. Büchs and A. C. Spiess,
Bioresour. Technol., 2009, 100, 2580–2587.
76 O. Aaltonen and O. Jauhiainen, Carbohydr. Polym., 2009, 75,
125–129.
77 T. Erdmenger, C. Haensch, R. Hoogenboom and U. S. Schubert,
Macromol. Biosci., 2007, 7, 440–445.
78 H. Zhao, G. A. Baker, Z. Song, O. Olubajo, T. Crittle and
D. Peters, Green Chem., 2008, 10, 696–705.
79 H. M. Luo, Y. Q. Li and C. R. Zhou, Polym. Mater. Sci. Eng.,
2005, 21, 233–235.
80 J. P. Mikkola, A. Kirilin, J. C. Tuuf, A. Pranovich, B. Holmbom,
L. M. Kustov, D. Y. Murzin and T. Salmi, Green Chem., 2007, 9,
1229–1237.
81 H. Lateef, S. Grimes, P. Kewcharoenwong and B. Feinberg,
J. Chem. Technol. Biotechnol., 2009, 84, 1818–1827.
82 P. Mäki-Arvela, I. Anugwom, P. Virtanen, R. Sjöholm and
J. P. Mikkola, Ind. Crops Prod., 2010, 32, 175–201.
83 J. S. Wilkes, J. A. Levisky, R. A. Wilson and C. L. Hussey,
Inorg. Chem., 1982, 21, 1263–1264.
84 M. Namazian and S. Halvani, J. Iran. Chem. Soc., 2005, 2, 65–70.
This journal is c The Royal Society of Chemistry 2012
 85 R. K. Bansal, Organic reaction mechanism, Tata McGraw-Hill
Publishing Company Limited, 1998.
86 Y. Kim, T. Kim and W. Lee, Rapid Commun. Mass Spectrom.,
1997, 11, 863–868.
87 R. C. Remsing, R. P. Swatloski, R. D. Rogers and G. Moyna,
Published on 20 January 2012. Downloaded by Chalmers Tekniska Hogskola on 10/5/2023 10:41:09 AM.
Chem. Commun., 2006, 1271–1273.
88 R. C. Remsing, G. Hernandez, R. P. Swatloski, W. W. Massefski,
R. D. Rogers and G. Moyna, J. Phys. Chem. B, 2008, 112,
11071–11078.
89 T. G. A. Youngs, C. Hardacre and J. D. Holbrey, J. Phys. Chem. B,
2007, 111, 13765–13774.
90 J. M. Zhang, H. Zhang, J. Wu, J. Zhang, J. S. He and J. F. Xiang,
Phys. Chem. Chem. Phys., 2010, 12, 1941–1947.
91 R. C. Remsing, I. D. Petrik, Z. W. Liu and G. Moyna,
Phys. Chem. Chem. Phys., 2010, 12, 14827–14828.
92 J. M. Zhang, H. Zhang, J. Wu, J. Zhang, J. S. He and J. F. Xiang,
Phys. Chem. Chem. Phys., 2010, 12, 14829–14830.
93 H. B. Liu, K. L. Sale, B. M. Holmes, B. A. Simmons and S. Singh,
J. Phys. Chem. B, 2010, 114, 4293–4301.
94 N. P. Novoselov, E. S. Sashina, V. E. Petrenko and M. Zaborsky,
Fibre Chem., 2007, 39, 153–158.
95 A. R. Ferreira, M. G. Freire, J. C. Ribeiro, F. M. Lopes,
J. G. Crespo and J. A. P. Coutinho, Ind. Eng. Chem. Res.,
2011, 50, 5279–5294.
96 A. M. Fernandes, M. A. A. Rocha, M. G. Freire, I. M.
Marrucho, J. A. P. Coutinho and L. M. N. B. F. Santos,
J. Phys. Chem. B, 2011, 115, 4033–4041.
97 Z. Liu, H. Wang, Z. X. Li, X. M. Lu, X. P. Zhang, S. J. Zhang
and K. B. Zhou, Mater. Chem. Phys., 2011, 128, 220–227.
98 A. Pinkert, K. N. Marsh, S. S. Pang and M. P. Staiger, Chem. Rev.,
2009, 109, 6712–6728.
99 T. Heinze, S. Dorn, M. Schoebitz, T. Liebert, S. Koehler and
F. Meister, Macromol. Symp., 2008, 262, 8–22.
100 G. Ebner, S. Schiehser, A. Potthast and T. Rosenau, Tetrahedron
Lett., 2008, 49, 7322–7324.
101 S. Sowmiah, V. Srinivasadesikan, M. C. Tseng and Y. H. Chu,
Molecules, 2009, 14, 3780–3813.
102 H. Rodrı́guez, G. Gurau, J. D. Holbrey and R. D. Rogers,
Chem. Commun., 2011, 47, 3222–3224.
103 G. Gurau, H. Rodrı́guez, S. P. Kelley, P. Janiczek, R. S. Kalb
and R. D. Rogers, Angew. Chem., Int. Ed., 2011, 50,
12024–12026.
104 T. Chen, M. Chidambaram, Z. P. Liu, B. Smit and A. T. Bell,
J. Phys. Chem. B, 2010, 114, 5790–5794.
105 S. Fendt, S. Padmanabhan, H. W. Blanch and J. M. Prausnitz,
J. Chem. Eng. Data, 2011, 56, 31–34.
106 S. H. Lee, T. V. Doherty, R. J. Linhardt and J. S. Dordick,
Biotechnol. Bioeng., 2009, 102, 1368–1376.
107 J. van Spronsen, M. A. T. Cardoso, G. J. Witkamp, W. de Jong
and M. C. Kroon, Chem. Eng. Process., 2011, 50, 196–199.
108 Kirk–Othmer, Encyclopedia of Chemical Technology, John Wiley
& Sons, Inc., Hoboken (NJ), USA, 5th edn, 2007.
109 G. Brodeur, E. Yau, K. Badal, J. Collier, K. B. Ramachandran
and S. Ramakrishnan, Enzyme Research, 2011, DOI: 10.4061/
2011/787532.
110 N. Muhammad, Z. Man, M. A. B. Khalil and Y. A. Elsheikh,
J. Appl. Sci., 2010, 10, 1090–1096.
111 D. B. Fu, G. Mazza and Y. Tamaki, J. Agric. Food Chem., 2010,
58, 2915–2922.
112 Q. Li, Y. C. He, M. Xian, G. Jun, X. Xu, J. M. Yang and L. Z. Li,
Bioresour. Technol., 2009, 100, 3570–3575.
113 I. P. Samayam and C. A. Schall, Bioresour. Technol., 2010, 101,
3561–3566.
This journal is c The Royal Society of Chemistry 2012
114 C. E. Wyman, B. E. Dale, R. T. Elander, M. Holtzapple,
M. R. Ladisch, Y. Y. Lee, C. Mitchinson and J. N. Saddler,
Biotechnol. Prog., 2009, 25, 333–339.
115 M. B. Turner, S. K. Spear, J. G. Huddleston, J. D. Holbrey and
R. D. Rogers, Green Chem., 2003, 5, 443–447.
116 J. Zakzeski, P. C. A. Bruijnincx, A. L. Jongerius and B. M.
Weckhuysen, Chem. Rev., 2010, 110, 3552–3599.
117 P. T. Anastas and J. C. Warner, Green Chemistry: Theory and
Practice, Oxford University Press, New York, 1998.
118 I. Horvath and P. T. Anastas, Chem. Rev., 2007, 107, 2167–2168.
119 F. Hermanutz, F. Meister and E. Uerdingen, Chemical Fibers
International, 2006, 6, 342–343.
120 B. M. Trost, Science, 1991, 254, 1471–1477.
121 P. Anastas and N. Eghbali, Chem. Soc. Rev., 2010, 39, 301–312.
122 BASF report, Ionic liquids—An introduction: http://www.inter
mediates.basf.com/chemicals/web/en/function/conversions:/publish/
images/products-and-industries/ionic-liquids/Ionic_Liquids.pdf, last
accessed December 26, 2011.
123 M. M. Bailey, M. B. Townsend, P. L. Jernigan, J. Sturdivant,
W. L. Hough-Troutman, J. F. Rasco, R. P. Swatloski, R. D.
Rogers and R. D. Hood, Green Chem., 2008, 10, 1213–1217.
124 BASF, personal communication.
125 J. R. Harjani, J. Farrell, M. T. Garcia, R. D. Singer and
P. J. Scammells, Green Chem., 2009, 11, 821–829.
126 K. Fukumoto, M. Yoshizawa and H. Ohno, J. Am. Chem. Soc.,
2005, 127, 2398–2399.
127 G. Na"e˛cz-Jawecki and J. Sawicki, Chemosphere, 1999, 38, 3211–3218.
128 Y. Qin, R. D. Rogers, D. T. Daly, PCT Int. Appl., WO
2010141470 A2, 2010.
129 I. Anugwom, P. Mäki-Arvela, P. Virtanen, P. Damlin,
R. Sjöholm and J. P. Mikkola, RSC Adv., 2011, 1, 452–457.
130 J. R. Harjani, R. D. Singer, M. T. Garcia and P. J. Scammells,
Green Chem., 2008, 10, 436–438.
131 M. Smiglak, W. M. Reichert, J. D. Holbrey, J. S. Wilkes, L. Y. Sun,
J. S. Thrasher, K. Kirichenko, S. Singh, A. R. Katritzky and
R. D. Rogers, Chem. Commun., 2006, 2554–2556.
132 M. J. Earle, J. M. S. S. Esperança, M. A. Gilea, J. N. C. Lopes,
L. P. N. Rebelo, J. W. Magee, K. R. Seddon and J. A. Widegren,
Nature, 2006, 439, 831–834.
133 R. P. Swatloski, J. D. Holbrey and R. D. Rogers, Green Chem.,
2003, 5, 361–363.
134 E. B. Carter, S. L. Culver, P. A. Fox, R. D. Goode, I. Ntai,
M. D. Tickell, R. K. Traylor, N. W. Hoffman and J. H. Davis,
Chem. Commun., 2004, 630–631.
135 P. Nockemann, B. Thijs, K. Driesen, C. R. Janssen, K. V. Hecke,
L. V. Meervelt, S. Kossmann, B. Kirchner and K. Binnemans,
J. Phys. Chem. B, 2007, 111, 5254–5263.
136 W. L. Hough-Troutman, M. Smiglak, S. Griffin, W. M. Reichert,
I. Mirska, J. Jodynis-Liebert, T. Adamska, J. Nawrot, M. Stasiewicz,
R. D. Rogers and J. Pernak, New J. Chem., 2009, 33, 26–33.
137 W. L. Hough and R. D. Rogers, Bull. Chem. Soc. Jpn., 2007, 80,
2262–2269.
138 J. Stoimenovski, D. R. MacFarlane, K. Bica and R. D. Rogers,
Pharm. Res., 2010, 27, 521–526.
139 G. D. Elliott, R. Kemp and D. R. MacFarlane, ACS Symp. Ser.,
2009, 1030, 95–105.
140 S. Murugesan and R. J. Linhardt, Curr. Org. Synth., 2005, 2,
437–451.
141 M. Graziani and P. Fornasiero, Renewable Resources and Renewable
Energy, A Global Challenge, CRC Press/Taylor & Francis Group
LLC, Boca Raton, 2007.
142 D. Klein-Marcuschamer, B. A. Simmons and H. W. Blanch,
Biofuels, Bioprod. Biorefin., 2011, 5, 562–569.
Chem. Soc. Rev., 2012, 41, 1519–1537 1537