Ionic Liquids--Solvents of the Future?

Robin D. Rogers and Kenneth R. Seddon

Science 302, 792 (2003);
DOI: 10.1126/science.1090313

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PERSPECTIVES
pensation operates more quickly than Walker
et al.s thermostat; under todays conditions
the time scale is about 10,000 years (9).
Ridgwell et al. have identified a mechanism
by which CaCO3 compensation might have
gone awry, drawing down enough CO2 to explain the descent into the Snowball state.
The mechanism begins with a drop in sea
level. When continental crust is partially
flooded, as it is today, the ocean covers a large
area of shallow-water sea floor. If the sea level drops by a few hundred meters, the area of
shallow-water sea floor decreases dramatically, by about a factor of 10 in todays ocean.
Today, such a sea-level drop would shift the
burden of CaCO3 deposition from the shallow to the deep ocean. This was not an option
in the Neoproterozoic, when no organisms
secreted CaCO3 in the open ocean.
Ridgwell et al. (3) argue that deep-sea
burial of CaCO3 is more responsive to
changes in ocean pH than shallow-water
burial would be. CaCO3 solubility increases
with pressure. Today, the deep ocean straddles equilibrium (intermediate waters are
supersaturated, whereas the abyss is undersaturated). Hence, a change in pH alters the
boundary between supersaturated and undersaturated sea floor, driving a large
change in CaCO3 burial. In contrast, shallow waters are supersaturated almost everywhere. Shallow CaCO3 burial can therefore

only be enhanced by increasing the precipitation rate for CaCO3, which requires a
much larger pH change (see the figure).
Because the Neoproterozoic only had recourse to saturation stateinsensitive shallow-water CaCO3 deposition, a drop in sea
level would have driven a larger excursion in
ocean pH, and atmospheric CO2, than would
occur today. The mechanism identified by
Ridgwell et al. (3) would still require an initial kickperhaps a glaciationto lower sea
level, but would then amplify that cooling to
within reach of the runaway ice-albedo feedback. In the aftermath of the Snowball, after
Walker et al.s thermostat melted the ice, the
ocean would have relieved its CaCO3 burden
in newly flooded shallow seas, providing a
complementary or alternative explanation
for the observed cap carbonates.

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sheets reach some critical latitude, they reflect so much solar energy back into space
that the entire planet freezes over. In the
frozen world, weathering stops. Hydrothermal iron becomes more abundant than
weathering sulfur in the anoxic ocean, generating the first banded iron formations on
Earth in 1000 million years (2). Ultimately,
Walker et al.s thermostat overcomes the ice
albedo, because CO2 degassing from Earths
interior drives atmospheric pCO2 upward.
The ice melts abruptly, transforming Earth
into a hothouse, which the thermostat eventually ameliorates. In the process, weathering
consumes large amounts of CO2, generating
the cap carbonates.
There were two to four snowball glaciations during the Neoproterozoic (7). Why
did the thermostat break repeatedly during
this interval, but not at any other time?
Ridgwell et al. have identified a mechanism that may help to answer this question.
To understand their idea, we need to consider a second feedback mechanism in the
carbon cycle: CaCO3 compensation (8).
The balance this time is between weathering of CaCO3 and its burial in the ocean.
The homeostat switch is the pH of the ocean.
CaCO3 is a base and dissolves in acid. If the
rate of weathering exceeds that of burial, the
ocean becomes more basic, enhancing burial
until the two fluxes balance. CaCO3 com-

References
1. A. C. Doyle, Silver Blaze, in Strand Mag. (December 1892).
2. P. F. Hoffman, D. P. Schrag, Terra Nova 14, 29 (2002).
3. A. Ridgwell, M. J. Kennedy, K. Caldeira, Science 302,
859 (2003).
4. H. C. Urey, The Planets, Their Origin and Development
(Yale Univ. Press, New Haven, CT, 1952).
5. J. C. G. Walker, P. B. Hays, J. F. Kasting, J. Geophys. Res.
86, 9776 (1981).
6. R. A. Berner, Z. Kothavala, Am. J. Sci. 301, 182 (2001).
7. A. J. Kaufman, A. H. Knoll, G. M. Narbonne, Proc. Natl.
Acad. Sci. U.S.A. 94, 6600 (1997).
8. W. S. Broecker, T. H. Peng, Global Biogeochem. Cycles
1, 15 (1987).
9. D. Archer, H. Kheshgi, E. Maier-Reimer, Global
Biogeochem. Cycles 12, 259 (1998).

Ionic Liquids
Solvents of the Future?
Robin D. Rogers and Kenneth R. Seddon

esearch into ionic liquids is booming.

The first industrial process involving
ionic liquids was announced in
March 2003, and the potential of ionic liquids for new chemical technologies is beginning to be recognized. The burgeoning
interest in the field was obvious at the recent American Chemical Society (ACS)
meeting in New York, where ionic liquids
were the focus of 10 sessions (1).
Ionic liquids are composed entirely of
ions. For example, molten sodium chloride is
an ionic liquid; in contrast, a solution of sodium chloride in water (a molecular solvent) is
an ionic solution. The term ionic liquids
has replaced the older phrase molten salts

R. D. Rogers is at the Center for Green Manufacturing,

The University of Alabama, Tuscaloosa, AL 35487,
USA. E-mail: rdrogers@bama.ua.edu K. R. Seddon is
with Queens University Ionic Liquid Laboratories
(QUILL), The Queens University of Belfast, Belfast
BT9 5AG, UK. E-mail: k.seddon@qub.ac.uk

792

(or melts), which suggests

that they are high-temperature, corrosive, viscous media (like molten minerals).
The reality is that ionic liquids can be liquid at temperatures as low as 96C.
Furthermore, room-temperature ionic liquids are frequently colorless, fluid, and
easy to handle. In the patent
and academic literature, the
term ionic liquids now
refers to liquids composed
entirely of ions that are fluid
around or below 100C.
One of the primary driving forces behind research
into ionic liquids is the perceived benefit of substituting
traditional industrial solvents, most of which are

31 OCTOBER 2003

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SCIENCE

volatile organic compounds (VOCs), with

nonvolatile ionic liquids. Replacement of
conventional solvents by ionic liquids would
prevent the emission of VOCs, a major
source of environmental pollution. Ionic liquids are not intrinsically greensome are
extremely toxicbut they can be designed to
be environmentally benign,
with large potential benefits
for sustainable chemistry (2).
There are four principal
strategies to avoid using
conventional organic solvents: No solvent (heterogeneous catalysis), water, supercritical fluids, and ionic
liquids. The solventless option is the best established,
and is central to the petrochemical industry, the least
polluting chemical sector.
The use of water can also be
advantageous, but many organic compounds are difficult to dissolve in water, and
disposing of contaminated
aqueous streams is expensive. Supercritical fluids,
The BASIL reactor. Upper phase, which have both gas- and
the solvent-free pure product; liquid-like properties, are
highly versatile solvents for
lower phase, ionic liquid.
www.sciencemag.org

CREDIT: PHOTO REPRODUCED BY COURTESY OF BASF

C H E M I S T RY

chemical synthesis (3). This technology

was recently commercialized by Thomas
Swan & Co., Ltd., in a chemical plant designed for multipurpose synthesis. Together
with ionic liquids (46), these alternative
solvent strategies (sometimes referred to as
alternative reaction media or green solvents) provide a range of options to industrialists looking to minimize the environmental impact of their chemical processes.
What are the advantages of using a
room-temperature ionic liquid in an industrially relevant catalytic process? As noted
above, ionic liquids have no detectable vapor pressure, and therefore contribute no
VOCs to the atmosphere. But this is not the
only reason for using ionic liquids. Another
is that at least a million binary ionic liquids,
and 1018 ternary ionic liquids, are potentially possible (7). (For comparison, about 600
molecular solvents are in use today.)
This diversity enables the solvent to be
designed and tuned (2) to optimize yield, selectivity, substrate solubility, product separation, and even enantioselectivity. Ionic liquids can be highly conducting (8), dissolve
enzymes (9), form versatile biphasic systems
for separations (10), can form both polymers
and gels for device applications (8), are media for a wide range of organic and inorganic reactions (46), and are the basis for at
least one industrial process, called the
BASIL process (see the figure) (11).
The BASIL process was developed and
is operated by BASF. At the meeting,
Matthias Maase (BASF) revealed that use
of the BASIL process increases the productivity of their alkoxyphenylphosphine formation process by a factor of 80,000 compared with the conventional process. Other
companies are also pursuing the use of ionic liquids. Bernd Weyershausen (Degussa)
presented an ionic liquidbased process for
the synthesis of organosilicon compounds.
Use of an ionic liquid solvent enabled the
catalyst to be easily recycled and reused
without further treatment after separation
from the product at the end of the reaction.
Christian Mehnert (ExxonMobil) described
biphasic hydroformylation with rhodium
catalysts in ionic liquids.
Because research into ionic liquids is at
an early stage, many of their properties remain to be elucidated. Nonetheless, ionic
liquids have already provided access to
new chemical processes. Recent papers describe their potential application as embalming fluids (12), in ion drives for space
travel (13), for desulfurization of fuels
(14), and as lubricants (15).
Ionic liquids have already found many
laboratory applications in synthesis, catalysis, batteries, and fuel cells (46, 8, 16),
and numerous new combinations of ionic
liquid solvent properties are available or

predicted. The next decade should see ionic liquids being used in many applications
where conventional organic solvents are
used today. Furthermore, ionic liquids will
enable new applications that are not possible with conventional solvents. In the future, solvents will be designed to control
chemistry, rather than the chemistry being
dictated by the more limited range of molecular solvents currently used.
References and Notes
1. ACS Fall Meeting, 7 to 11 September 2003, New York.
The Ionic Liquids symposium was sponsored by the
ACS Division of Industrial and Engineering Chemistry,
the Green Chemistry and Engineering Subdivision, the
Separation Science and Technology Subdivision, and
the Green Chemistry Institute.
2. M. Freemantle, Chem. Eng. News 76, 32 (30 March
1998).
3. M. Poliakoff, J. M. Fitzpatrick, T. R. Farren, P. T. Anastas,
Science 297, 807 (2002).
4. R. D. Rogers, K. R. Seddon, Eds., Ionic Liquids as Green
Solvents: Progress and Prospects (ACS Symp. Ser. 856,
American Chemical Society, Washington, DC, 2003).
5. R. D. Rogers, K. R. Seddon, Eds., Ionic Liquids: Industrial
Applications for Green Chemistry (ACS Symp. Ser.
818, American Chemical Society, Washington, DC,
2002).
6. P. Wasserscheid, T. Welton, Eds., Ionic Liquids in
Synthesis (Wiley-VCH, Weinheim, Germany, 2003).

7. K. R. Seddon, in The International George

Papatheodorou Symposium: Proceedings, S.
Boghosian et al., Eds. (Institute of Chemical
Engineering and High Temperature Chemical
Processes, Patras, Greece, 1999), pp. 131135.
8. H. Ohno, Ed., Ionic Liquids: The Front and Future of
Material Developments (CMC, Tokyo, 2003).
9. R. A. Sheldon, R. M. Lau, M. J. Sorgedrager, F. van
Rantwijk, K. R. Seddon, Green Chem. 4, 147 (2002).
10. K. E. Gutowski et al., J. Am. Chem. Soc. 125, 6632
(2003).
11. K. R. Seddon, Nature Mater. 2, 363 (2003).
12. P. Majewski, A. Pernak, M. Grzymislawski, K. Iwanik, J.
Pernak, Acta Histochem. 105, 135 (2003).
13. M. Gamero-Castano, V. Hruby, J. Propulsion Power 17,
977 (2001).
14. A. Bosmann et al., Chem. Commun., 2494 (2001).
15. W. M. Liu, C. F. Ye, Q. Y. Gong, H. Z. Wang, P. Wang,
Tribol. Lett. 13, 81 (2002).
16. R. D. Rogers, K. R. Seddon, S. Volkov, Eds., Green
Industrial Applications of Ionic Liquids (Kluwer,
Dordrecht, Netherlands, 2002), vol. 92.
17. R.D.R. acknowledges financial support from the U.S.
Environmental Protection Agency; NSF; Air Force
Office of Scientific Research; U.S. Department of
Energy, Environmental Management Science Program and Office of Basic Energy Sciences, Office of
Energy Research; National Renewable Energy Laboratory; and the PG Research Foundation. QUILLs industrial sponsors include Avecia, bp, Chevron, C-Tri,
Cytec, Eastman, ICI, Merck, Novartis, SASOL, Shell,
and UOP.

MOLECULAR BIOLOGY

MeCP2 Repression
Goes Nonglobal
Robert Klose and Adrian Bird

fter replication, mammalian DNA

becomes marked by the addition of
methyl groups to certain cytosine
bases, almost exclusively those in the sequence 5CpG. Just how the resulting pattern of methylated and nonmethylated cytosines is converted into biological outcomes is now starting to become clear.
Methyl-CpG has emerged as a gene silencing signal that usually ensures the longterm shutdown of gene expression. Likely
mediators of this effect are the methyl-CpG
binding domain (MBD) proteins that recruit transcriptional silencing machinery to
the DNA. One of these proteins, MeCP2, is
of particular interest because about 80% of
patients with a profound neurological condition called Rett syndrome carry a mutation in their MECP2 gene (1). Mice lacking
the Mecp2 gene exhibit several features of
Rett syndrome. Furthermore, targeted deletion of Mecp2 in mouse brain causes a Rettlike phenotype that is virtually indistinguishable from the phenotype of mice in
which every tissue lacks MeCP2. Global

The authors are at the Wellcome Trust Centre for Cell

Biology, University of Edinburgh, The Kings Buildings,
Edinburgh EH9 3JR, UK. E-mail: a.bird@ed.ac.uk

www.sciencemag.org

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VOL 302

microarray analyses designed to search for

target genes that are derepressed in the
brains of MeCP2-deficient mice, and thus
might be causally implicated in Rett syndrome, have not yielded any clear candidates (2). The existence of a genuine target
gene is now highlighted on pages 885 (3)
and 889 (4) of this issue. Chen et al. (3) and
Martinowich et al. (4) describe their discovery that normal MeCP2 regulates expression of the gene encoding brain-derived neurotrophic factor (BDNF), a secreted protein that is essential for neural plasticity, learning, and memory. Their new
findings, together with recent work in the
amphibian Xenopus laevis (5), confirm that
MeCP2 is a methyl-CpGdependent transcriptional repressor and reveal its unexpected role in the induction of gene expression in the nervous system.
Belonging to a set of proteins synthesized in response to neuronal activity, BDNF
is thought to be essential for converting transient stimuli into long-term changes in brain
activity (6). Understanding how BDNF is
regulated in neurons is important if we are to
comprehend brain development, learning,
and memory. There are four BDNF promoters, one of which (promoter III) responds

31 OCTOBER 2003

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PERSPECTIVES

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