Morin Crini2013

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JPPS-755; No. of Pages 25
Progress in Polymer Science xxx (2012) xxx–xxx
Contents lists available at SciVerse ScienceDirect
Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci
Environmental applications of water-insoluble

␤-cyclodextrin–epichlorohydrin polymers
Nadia Morin-Crini, Grégorio Crini ∗
Chrono-environnement, UMR 6249 usc INRA, Faculté des Sciences & Techniques, Place Leclerc 25030 Besançon cedex, France
a r t i c l e i n f o a b s t r a c t
Article history: Chemical cross-linking using epichlorohydrin as cross-linking agent is the most straightfor-
Received 19 March 2012 ward method to produce water-insoluble ␤-cyclodextrin-based polymers. The numerous
Received in revised form 23 June 2012
OH groups available on cyclodextrin (CD) molecules are active sites capable of forming a
Accepted 25 June 2012
number of linkages. Although this cross-linking reaction has been known for 50 years and is
Available online xxx
well documented, and relatively easy to use for the preparation of CD-based networks, some
This review is dedicated to Giangiacomo basic questions concerning the reaction still continue to interest the scientific community.
TORRI, G. Ronzoni Institute for Chemical and The main objectives of this review are (i) to describe the synthesis and characterization of
Biochemical Research, Milan, Italy. insoluble CD–epichlorohydrin polymers, (ii) to provide useful information on their most
important features, (iii) and to summarize the developments in the use of these materials
Keywords: for environmental purposes. In particular, the description of relevant environmental appli-
Cyclodextrin cations such as sorption-oriented processes, detoxification of wastewater, color removal,
Cross-linking reaction and concentration and purification of solutions is included. In this aim, an extensive pool of
Epichlorohydrin
data from the literature, from 270 papers, reviews, patents and books, has been compiled.
Polymeric network
The various interactions occurring between pollutants and CD–epichlorohydrin polymer in
Environmental applications
Pollutants the sorption processes are presented, and future research trends are discussed.
© 2012 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. General considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. Conventional and non-conventional materials for the removal of contaminants from water and wastewater . . . . . . . . . . 00
2.2. Why use ˇ-CD–epichlorohydrin polymer as a complexing material for environmental purposes? . . . . . . . . . . . . . . . . . . . . . . 00
3. Synthesis and characterization of water-insoluble ␤-cyclodextrin–epichlorohydrin polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1. Materials containing of cyclodextrin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2. Insoluble polymers prepared by direct cross-linking of cyclodextrin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2.1. Synthesis of water-insoluble ␤-cyclodextrin–epichlorohydrin polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2.2. Chemical modification of ECP materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2.3. Other cross-linking agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.3. Characterization of ␤-cyclodextrin–epichlorohydrin polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Water-insoluble ␤-cyclodextrin–epichlorohydrin polymers for environmental applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.1. History of water-insoluble ␤-cyclodextrin–epichlorohydrin polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
∗ Corresponding author. Tel.: +33 3 81 66 57 01; fax: +33 3 81 66 57 97.

E-mail addresses: nadia.crini@univ-fcomte.fr (N. Morin-Crini), gregorio.crini@univ-fcomte.fr (G. Crini).
0079-6700/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.progpolymsci.2012.06.005
Please cite this article in press as: Morin-Crini N, Crini G. Environmental applications of water-insoluble ␤-
cyclodextrin–epichlorohydrin polymers. Prog Polym Sci (2012), http://dx.doi.org/10.1016/j.progpolymsci.2012.06.005
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2 N. Morin-Crini, G. Crini / Progress in Polymer Science xxx (2012) xxx–xxx
4.2. A recent review of the literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

4.3. Control of performances in the sorption-oriented processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.4. Sorption mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.5. Personal remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1. Introduction natural molecules derived from starch [11,12]. These sub-

stances, and in particular ␤-cyclodextrin (beta-CD or ˇ-CD)
The use of water in domestic, industrial and agricul- and its derivatives, have a remarkable capacity to form
tural contexts implies its subsequent pollution: any activity inclusion complexes in solution or in the solid state with
using water produces effluents containing undesirable, other molecules through host–guest interactions [13–18].
and possibly toxic, pollutants. Nowadays, the discharge of The numerous and specific properties of ˇ-CD combined
chemicals into the environment is a serious problem affect- with its non-toxic character to humans have led to its
ing both water and soil quality. When present in discharge, use in pharmacy, in the biomedical sector, biotechnology
trace pollutants are released into the environment in forms or textile industry, as well as in toiletries, cosmetics, in
that are easily assimilated by fauna and flora. They can then packaging materials and food additives [19–23]. CDs can
accumulate in organisms, undergoing bio-magnification be employed in their native form or after modification.
through the food webs. Many pollutants exert toxic effects For example, ˇ-CD and its commercial derivatives such as
not only on the environment but also on humans. Thus, a hydroxypropyl-ˇ-CD and carboxymethyl-ˇ-CD (obtained
constant effort to protect water resources is being made by alkylation or by carboxymethylation) are widely applied
by the various governments, through the introduction of in pharmaceutical formulations to enhance the solubility,
increasingly strict legislation [1]. stability, and bioavailability of drugs. CDs are also used for
A multitude of wastewater treatment methods for liq- improving the taste and flavor of beverages, for dissolving
uid industrial effluents have been reported and tested. fragrances and suppressing their volatility, or for protect-
These methods include conventional treatment processes ing any components that are unstable when exposed to
(e.g. coagulation/flocculation, adsorption onto activated light or oxygen. The great significance of CDs both in indus-
carbons, etc.), established recovery technologies (oxida- trial applications and research mainly lies in their ability
tion, membrane filtration), and emerging removal methods to selectively form inclusion complexes with other sub-
such as advanced oxidation processes [2–5]. However, for stances.
economical reasons, many of the processes proposed can- Complexation phenomenon is also commercially
not be used on an industrial scale [1]. For example, small exploited for practical applications in analytical chem-
and medium-sized enterprises are not very enthusiastic istry, especially in separation processes. CDs have been
about the idea of investing in additional treatments such as successfully employed in liquid and gas chromatography
membrane filtration or advanced oxidation processes, due both on the laboratory and industrial scales; for example,
not only to their initial high costs, but also to their com- CDs play an important role in high-performance liquid
plicated maintenance. Another problem that must be also chromatography for chiral recognition. They also deserve
pointed out is that industrial wastewaters are very difficult particular attention in environmental science in terms
to treat because of their complex and variable composition. of making contaminants soluble, and in the enrichment
In fact, water generated by industrial sectors contains a and removal of organic pollutants and heavy metals from
complex and time-dependent mixture of organic and inor- soil, atmosphere and water [21,22]. A recent trend in the
ganic pollutants. The decontamination methods proposed development of new CD-based materials is characterized
and used by industrial sectors do not remove the whole by currently accelerated progress in developing practical
pollutant load. In practice, a combination of different pro- uses in the prevention of environmental pollution. Native
cesses is often used for pollutant removal to achieve the CDs and their hydrophilic, hydrophobic or ionic deriva-
desired water quality in the most economic way. This is due tives can be used in the decontamination of wastewater,
to the fact that there is, as yet, no single water treatment aquifers, air and soil to increase the stabilization, encap-
process that simultaneously removes all pollutants from sulation, separation and sorption of contaminants. This is
water to desirable levels. Another difficulty is the treatment mainly due to the fact that the hydrophobic cavity in their
of wastewater containing low concentrations of molecules structure can take up aromatics and other hydrophobic
and/or ions. Thus, there is a need to develop new treat- organic molecules, providing ideal binding sites. Currently
ments acceptable for industrial use that are effective for considerable attention is being devoted to the removal
a wide range of pollutants from poly-contaminated mix- of (organic) pollutants from water and wastewater by
tures, even at very low concentrations. CDs, and the growing interest can be seen through the
Much effort has recently been focused on various mate- increasing number of papers published each year on this
rials based on polysaccharides that can be obtained in large topic. Because of their solubility in water, CDs cannot
quantities and that are harmless to nature [6–10]. Special be used directly for separation and purification pur-
attention has been given to cyclodextrins (CDs) which are poses. It is thus necessary to produce insoluble CD-based
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N. Morin-Crini, G. Crini / Progress in Polymer Science xxx (2012) xxx–xxx 3
Table 1
Examples of sorbents used in sorption-oriented processes for pollutant
removal from water/wastewater with special attention to polysaccharide-
based sorbents (selected reviews).
Sorbent Pollutants References
Activated carbon Phenolic compounds [28]

Agricultural waste Metals, dyes [29]
Algae Metals, radionuclides [30]
Alginates Metals, dyes, nitrophenols [31–34]
Alumina Arsenic [35]
Biomass Metals [36]
Cellulose Metals, dyes [37–40]
Chitin and chitosan Metals, dyes, phenols, fluorides [41–48]
Clays Dyes, surfactants [49]
Cyclodextrins Aromatics, dyes, metals, [50–54]
Fig. 1. Conventional sorbents for the removal of pollutants from
surfactants, detergents,
water/wastewater.
phthalates
Industrial waste Dyes [55]
materials using polymerization reactions or to immobilize Peat Phenols [56]
Sawdust Metals, organics [57]
CD molecules on a solid support by grafting. In the litera-
Silica gel Metals, anions, organics [58]
ture, there have been numerous studies on the preparation, Starch Dyes, metals, phenols, organics, [59–62]
characterization, properties and applications of water- anions
insoluble materials containing CD molecules. Among them, Zeolites Metals, dyes [63]
cross-linking polymers, obtained by (co)polymerization of
CD molecules and a coupling agent in alkaline medium,
have attracted great attention due to their facile synthesis, (Fig. 2) materials. Table 1 reports some examples of mate-
high sorption properties, and particular selectivity. Among rials used in sorption processes with special attention to
all the reactions proposed, chemical cross-linking using polysaccharide-based sorbents [28–63].
epichlorohydrin (EPI) as cross-linker agent is the most Most commercial systems currently use carbons and
straightforward method to produce water-insoluble CD resins, alone or in combined processes, as sorbents to
networks for environmental applications. remove pollutants from wastewaters because of their
Because of the extremely large number of publications excellent sorption and chelation abilities. However, unsur-
on CD-based materials, in this review, the discussion will prisingly, their widespread use is restricted due to high
be limited to ␤-cyclodextrin–epichlorohydrin-based mate- cost. The materials used for pollutant removal purposes
rials. The main objectives are: (i) to describe the synthesis may be also of natural origin. Some of those mentioned
and characterization of these polymers, (ii) to provide in the literature include peat, chitosan, starch, agricul-
useful information on their most important features, and tural wastes such as bagasse pith, and industrial waste
(iii) to summarize their developments for environmental products such as cotton-based materials. Recently, numer-
purposes. In particular, the description of relevant environ- ous approaches have been studied for the development of
mental applications such as sorption-oriented processes, cheaper and more effective materials containing cyclodex-
purification of solutions, detoxification of wastewater, and trins, an important class of starch derivatives.
color removal is included. To do so, an extensive list of data,
from about 270 papers, reviews, patents and books, has 2.2. Why use ˇ-CD–epichlorohydrin polymer as a
been compiled. complexing material for environmental purposes?
2. General considerations Cyclodextrins (CDs) or cycloamyloses are cyclic

oligomers consisting of 6–12 glucose units linked by
2.1. Conventional and non-conventional materials for ␣-1,4 linkages, formed by the action of an enzyme (␣-
the removal of contaminants from water and wastewater 1,4-glucan-glycosyltransferase for example) on starch.
Depending on the particular transferase, the nature of
Among all the treatments proposed, sorp- starch and the reaction conditions (e.g. the presence of
tion/adsorption onto solid materials is one of the more precipitating agent), different types of CDs result. Typical
popular methods for the removal of pollutants from native CDs contain six, seven or eight glucose units and
water and wastewater. These processes include adsorp- are denoted ␣-, ␤- and ␥-CDs, respectively (Fig. 3). The
tion, ion-exchange, and more simply, filtration. They are doughnut-shaped structure of CDs is characterized by
efficient, economical, and versatile using simple method- the presence of glucose residues in C1 conformation with
ologies. If the system used is designed correctly it will hydroxyl groups arranged around the outer rim. Due to
produce high-quality water [24–27]. The solids used as the chair conformer of the glucopyranose units, CD takes
sorbents/adsorbents can take a broad range of chemical the shape of a truncated cone or torus rather a perfect
forms and different geometrical surface structures. This is cylinder. The hydroxyl functions are oriented toward the
reflected in the range of their applications in industry, or cone exterior with the primary hydroxyl groups of the
utility in laboratory practices. Sorbents can be classified in sugar residues at the narrow edge of the cone and the
two categories: conventional (Fig. 1) and non-conventional secondary hydroxyl groups at the wider edge (Fig. 4).
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Fig. 2. Non-conventional sorbents for the removal of pollutants from wastewater.
Fig. 3. Chemical structure of alpha- (␣-CD), beta- (␤-CD) and gamma- (␥-CD) cyclodextrins.
The central cavity of the molecule is lined with skeletal features, CDs can encapsulate a variety of hydrophobic
carbons and ethereal oxygens of the glucose residue. The molecules or parts of molecules inside their cavity through
CD exterior is therefore hydrophilic whereas the central non-covalent interactions to form inclusion complexes
cavity is relatively hydrophobic. As a consequence of these of the host–guest type. CD complexation is a procedure
Fig. 4. Chemical structure (left) and shape (right) of the cyclodextrin molecule.
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of application of CDs is separation science. As already

described, CD molecules have a hydrophobic and non-
polar cavity that contains the oxygen-bridge and hydrogen
atoms. The interior of this cavity provides a relatively
hydrophobic environment in which a non-polar pollutant
can be trapped. Cyclodextrins are used as chiral selectors in
gas chromatography (GC), high-performance liquid chro-
matography (HPLC), supercritical fluid chromatography
(SFC), capillary electrophoresis (CE) and electrochromatog-
raphy (CEC). It is now recognized that CDs also represent an
interesting and attractive alternative as sorbents because
of their particular structure, chemical properties, high reac-
tivity and excellent selectivity toward a wide range of
substances. Hence, CD complexation is a procedure of
choice for decontamination techniques.
Another advantage must be noted. The removal of
toxic contaminants from water/wastewater remains a huge
challenge for water supplying companies and municipal-
ities. Both organic and inorganic contaminants are often
present in water distribution networks and industrial dis-
Fig. 5. A schematic representation showing the formation of an inclusion charges. However, there is at present no water treatment
complex between a cyclodextrin molecule and an aromatic solute. intervention that simultaneously removes both organic
and inorganic pollutants from water to desirable lev-
els. Cyclodextrin-based polymers could be such a system
of choice for analytical and complexation purposes capable of this because of their efficiency in pollutant
[64–66]. removal from poly-contaminated mixtures, even at low
␤-Cyclodextrin (ˇ-CD, cycloheptaamylose) is the most trace concentrations, and their high sorption capacities
studied and most frequently used owing to its cavity and interesting selectivity, with the additional advan-
with an internal diameter of 6.5 Å and a depth of 8 Å. tages of being cheap (the production of the materials is
As others CDs, the most characteristic feature of the ˇ- economically feasible and their synthesis is easy with rela-
CD molecule is its ability to form inclusion compounds tively inexpensive chemical reagents) and easily recyclable
with various molecules, ions and polymers (including (regeneration) or disposable (incineration).
aromatic derivatives, dyes, polycyclic aromatic hydrocar-
bons, volatile organic compounds, metals, etc.), through 3. Synthesis and characterization of
host–guest interactions (Fig. 5). Each substance which water-insoluble ␤-cyclodextrin–epichlorohydrin
presents a steric complementarity, even partial, with CD polymers
cavity might be included. In general, ˇ-CD constitutes a
good compromise as its hydrophobic cavity and its rather As already mentioned, native cyclodextrins are water
flexible macrocycle presents an intermediate size between soluble, and must therefore be processed into solid forms
␣-CD and ␥-CD. The greater complexation ability associ- before they can be implemented as usable separation and
ated with a lower cost (around 5, 45 and 80 US$ per kg sorption substrates. From the polymer chemist’s point
for ˇ-CD, ␣-CD and ␥-CD, respectively) explains why ˇ- of view, the chemical modification of cyclodextrin offers
CD is the CD of choice for environmental studies. The price enormous challenges.
will also depend on purity and technological grade of the
product. 3.1. Materials containing of cyclodextrin
Many review articles and books have been published
which give excellent overviews of detailed descriptions of One of the most important and useful features of ␤-
structural properties of CDs, CD complexation phenomena cyclodextrin (␤-CD) is its high chemical reactivity. ␤-CD
and CD applications. Because of the extremely large num- possesses 21 hydroxyl groups present at the 2-, 3- and
ber of CD publications, in references [67–88] only those 6-positions in the glucose unit as shown in Fig. 4, which
reviews and monographs are listed which contain the orig- can be modified chemically. These numerous OH groups
inal sources of the data displayed. Readers interested in a are available and reactive, able to form a number of link-
detailed presentation, description and applications on CD ages. The C6 -OH groups are the most reactive, and the
should refer to the excellent library database “Cyclodextrin C3 -OH groups the least reactive. The difference between
News” from CYCLOLAB Ltd. (Hungary) which is a peri- their reactivities is, however, not extremely high. More-
odical collecting all the cyclodextrin-related publications, over, it depends on the reaction conditions, in particular
patents, conferences and lectures, and is available in elec- temperature and alkalinity. The hydroxyl groups allow
tronic form. direct substitution reactions and/or chemical modifica-
CDs are among the most remarkable macrocyclic tions to different positions (primary face, secondary face or
molecules with significant theoretical and practical both faces) yielding different (nonionic, cationic or anionic)
impacts in chemistry and biology. An important field derivatives for specific domains of application.
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Fig. 6. Schematic structures of insoluble materials containing ␤-cyclodextrin (␤-CD) obtained by grafting (immobilized CD), polymerization (chain CD
polymer) or reticulation reactions (network CD polymer).
Products containing two or more covalently linked immobilization on insoluble supports can also be regarded
CD units are called cyclodextrin dimers and polymers. as an appropriate way to obtain insoluble CD materials with
Polymers are prepared by cross-linking the CD rings, by specific properties. Recently, other CD-based materials
polymerizing bifunctional substituents containing CDs or have been designed such as molecularly imprinted mate-
CD derivatives, or bonding CDs to other polymers. Fig. 6 rials, membranes and nanoparticles (Table 2) [103–113].
shows three schematic structures of insoluble materials Because this review does not intend to be a substitute for
containing ␤-CD obtained using grafting, polymeriza- detailed monographs, the list of references for the general
tion and reticulation reactions [89–91]. There have been literature on CD-based materials, summarized in Table 3, is
numerous studies on the preparation and characterization restricted to the most important sources, mainly reviews.
of materials containing cyclodextrin and information about
the most important features of these polymeric materials 3.2. Insoluble polymers prepared by direct cross-linking
can be found in the reviews of Mocanu et al. [21], Crini and of cyclodextrin
Morcellet [23], and Crini [61].
There are several procedures reported for the conver- Due to the unique structure of the molecules combined
sion of ␤-CD into derivatives capable of interacting with with their polyfunctionality, ˇ-CD molecules have the abil-
pollutants from aqueous solutions and the methods can be ity to form cross-linked networks. ˇ-CD can be cross-linked
classified in two ways [21,23,89–92]. The first involves the by direct reaction between its hydroxyl groups with a
direct modification of ␤-CD by cross-linking which con- coupling agent to form water-soluble or water-insoluble
sists to bond the molecules to each other via the chains of polymeric structures. The primary product of the reaction
a coupling agent to form an insoluble three-dimensional of CD with a coupling agent such as epichlorohydrin in an
network. The properties of the polymers can be tailored alkaline medium is a heterogeneous mixture of various CD
according to the type of CD, the cross-linking spacer, or the glyceryl ethers: this is not a true polymer but a copolymer
molar ratio between the two. Controlling the experimental [114–123].
conditions such as base concentration, temperature, stir- Renard et al. [116,117] showed that the reaction
ring rate, and reaction time also fine-tunes the polymer of CD molecules with epichlorohydrin under controlled
produced. Chemical functionalization can also introduce conditions avoiding the gelation of the reaction mix-
reactive ligands onto the polymer particle surface. Intro- ture gave soluble polymers with hyperbranched struc-
duction of new groups into the hydrophilic CD molecule can tures consisting of CD moieties, linking bridges and
then cause extensive changes in its chemical properties, side-chain substituents (tails). The substitution patterns
which can then make it ionic and/or amphiphilic in nature. were determined by 13 C analysis and the formation
So, several materials with different characteristics in terms of side chains and bridges consisting of sequences of
of cross-link density, surface area, pore structure, chemical poly(2-hydroxypropyl)ether units was demonstrated by
properties, and sorption behavior can be obtained. electrospray ionization mass spectrometry and gas liq-
The second method relies on the covalent bonding of uid chromatography–mass spectrometry. Interestingly, the
ˇ-CD molecules to a pre-existing insoluble matrix such as CD cavities keep their complex-forming ability and the
highly cross-linked synthetic polymers [93], silica beads polymers obtained are much more soluble than the corre-
[94,95], zeolite [96], cellulose fibers [97], textiles [98], sponding CDs, and thus they have found pharmaceutical
alginate [99,100], or chitosan [101,102]. This kind of CD applications, for example for solubilizing drugs. Similar
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Table 2 conclusions were previously reported by Fenyvesi et al.

The main classes of cyclodextrin derivatives.
[114].
Cyclodextrin derivatives References If the degree of (co)polymerization is sufficiently high,
Modified native cyclodextrins
the matrix of the CD (co)polymers becomes insoluble in
Hydrophilic derivatives: methylated, [11–13,50,52,89–91] water [114,124–130]. These materials are obtained by con-
hydroxyalkylated and branched CDs densation using bi- or polyfunctional cross-linking agents
Hydrophobic derivatives: alkylated and such as aldehydes, ketones, isocyanates or epoxides such as
acylated CDs
epichlorohydrin. Insoluble derivatives can be hydrophobic,
Ionizable derivatives: anionic CDs,
cationic CDs hydrophilic, ionic, or amphiphilic in nature. An important
Cyclodextrin polymers feature must be pointed out: like soluble (co)polymers,
Linear polymers – linear CD tubes [50,52,89,90,103–107] in the insoluble (co)polymers, the CD units retain their
Cross-linked soluble polymers complex-forming capacity in the polymerized form.
(epichlorohydrin or ethylene glycol
bis-(epoxypropyl) ether derivatives)
Covalently cross-linked insoluble 3.2.1. Synthesis of water-insoluble
polymers (particles, beads, gels, ˇ-cyclodextrin–epichlorohydrin polymers
hydrogels, nanoparticles) Among the CD polymers, the most popular is an O-
Cyclodextrin-based materials
alkylated polymeric resin (abbreviated ECP or ECH in the
CD pendant synthetic polymers [50,52,85,89,90,
(polyesters, polyallylamines, 93–102,108–111] literature) produced by reaction of CDs with epichloro-
polymethacrylates, polyacrylic esters, hydrin (abbreviated EPI). EPI (1-chloro-2,3-epoxypropane)
preformed dendrimers, etc.) is the most common cross-linker used in polysaccharide
Polymeric products with CD content chemistry [23]. It is a bifunctional cross-linking agent
(cellulose-based fibers, textiles)
CD-immobilized by chemical bonding to
containing two reactive functional groups (Fig. 7), which
macromolecular supports (chitosan, can form bonds with ˇ-CD molecules (cross-linking step)
alginate, agarose) and/or itself (polymerization step). The resulting ECP
CD-based composites – CD-supported on materials are a mixture containing ˇ-CD units joined
solid surfaces or inert materials (silica
by repeating glyceryl linkers [124–127]. A number of
beads, zeolite)
Supramolecular assemblies (mono- or ˇ-CD rings are interconnected and a three-dimensional
polysubsituted amphiphilic CDs, (co)polymer network is formed (Fig. 8). The resulting link-
micelles, vesicles, nanoparticles) ages between CD moieties are relatively polar. Due to the
CD rotaxanes and polyrotaxanes – fact that the network is highly hydrophilic in nature and
CD-based catenanes
Molecularly imprinted functional
swells strongly in water, these (co)polymers are also called
materials gels or hydrogels (in this review we will use the terms
Membranes polymers, gels or ECP).
Polymers containing CDs [92,112,113] Cross-linking CDs with EPI is well-documented reac-
Hydrogels grafted with CD units
tion [21,23,114,116] and a relatively easy method for
Polymer inclusion membranes
preparing CD-based derivatives. However, although this
cross-linking reaction was developed 60 years ago, is well-
known and relatively easy to apply for the preparation
of water-insoluble ␤-cyclodextrin–epichlorohydrin-based
Table 3 networks, some basic questions concerning this reaction
Reviews of cyclodextrin-based materials (selected papers). and its numerous applications still continue to interest
Topics References the scientific community [1,61,128–130]. An analog of
CD–epichlorohydrin polymer is Sephadex® using dextran
Adsorption and adsorbents [1,21,23,53,61]
Analytical chemistry [11,20,67–70]
instead of CDs.
Biology and medicine [12,70,71] When the insoluble polymer is prepared by block poly-
Biotechnology [72,73] merization, the product has to be grounded to irregularly
Catalysis [17,74] shaped particles. Spherical beads are generally prepared by
Characterization [3,13,50]
polymerization in a heterogeneous phase. In the presence
Chromatography [75–78]
Cosmetics [51,79] of a surfactant, the alkaline solution of CD is dispersed as
Food industry [79–81] tiny droplets in a water-immiscible liquid phase. On addi-
Hydrogels [50,82] tion of the cross-linking reagent, the droplets are solidified
Inclusion compounds [61,83] to form polymer beads having the desired size and size
Industrial applications [13,14,18,50,64–66]
distribution [21,23].
Pharmaceuticals [52,70,84]
Remediation technologies [275]
Spectroscopy [1,23,61] 3.2.2. Chemical modification of ECP materials
Supramolecular chemistry [11,85] The chemical modification of an ECP network is an inter-
Synthesis [12,14,21,23,86]
esting step to introduce specific properties in order to
Textiles [87,88,274]
Toxicology [11,17] enlarge the field of its potential applications. In general,
Wastewater [1,16,21,23,51,61] the objectives are to improve pollutant sorption proper-
ties, to increase selectivity for target pollutants, and to
prepare insoluble amphoteric polymers. For example, the
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Fig. 7. Water-insoluble ␤-cyclodextrin–epichlorohydrin-based polymeric resin (abbreviated ECP in the literature) produced by reacting ␤-cyclodextrin
(ˇ-CD) with epichlorohydrin (abbreviated EPI).
functionalization of ECP materials can modify features of 3.2.3. Other cross-linking agents
this class of gel such as selectivity when forming inclusion Although widely used in chemical industries as inter-
complexes [23,50,64]. By replacing one or more OH groups mediates for the synthesis of many products (e.g.
at a “desired” position (the preparation of homogeneous, epoxy-resin, glycerin, polyurethane foam, surfactants,
selectively derivatized ECP is, however, not an easy task) drugs, etc.), the main disadvantage of EPI is its toxicity.
and with an oppositely designed substitution group, mul- This cross-linking agent is neither safe nor environmentally
tisite recognition systems can be obtained. Modification by friendly: it is considered to be hazardous environmental
charged functional units can improve the binding affinity pollutant and potential carcinogen, and there are serious
of CD molecules for oppositely charged guests. This can be concerns about EPI not only in the environment but also
explained by the fact that, because one of the main driv- when it comes into human contact. This has led many
ing forces for the formation of inclusion complexes by the workers to propose other cross-linking agents. However,
CD molecule in solution is hydrophobic interaction, a more it should be pointed that the presence of free unreacted
hydrophobic guest is apt to be accommodated in the CD EPI in materials is improbable since EPI is a very reactive
cavity [1]. Alternative approaches have focused on react- substance and suffers hydrolysis under alkaline conditions
ing EPI with a chemical such as NH4 OH: this method is of the cross-linking reactions. In addition, the gels are gen-
a convenient and inexpensive way to introduce weakly erally purified before use [23].
basic anion-exchange groups into the polymer network Because the ability of CD molecules to form com-
[59]. plexes is not affected when attached to water-insoluble
CH2O CH2 CHOH CH2O

CH2
CH2O ( CH2CHOHCH2O ) n
CH2
O OH
O O CHOH
CH2 CH2CHOHCH2O OH
CH2 CH2OH
CHOH
CHO CH2 CHOH CH2
CH2O
CH2 CH2O O
CH2 CH2
CHOH
O O CH2OH
CH2 CHOH CH2O O
CH2
CH2CHOHCH2O CH2
CHOH
CH2O (CH2 CHOH CH2 O)n
CH2 O OH
CHOH CH2
CH2OH CHOH
CH2OH
Fig. 8. A possible structure of a water-insoluble ␤-cyclodextrin–epichlorohydrin polymer.
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Table 4 Table 5
Other commonly reported cross-linking agents used for the synthesis of Specific surface area from BET measurements for some sorbents studied
cross-linked cyclodextrin polymer (selected papers). in the literature and comparison with ECP polymer.
Cross-linking agent Reference(s) Sorbent Surface area (in Reference

m2 g−1 )
Acylated poly(ethylene glycol) [131]
Adipoyl chloride [132] Commercial activated carbon 1100 [151]
Citric acid [133–135] Mesoporous silica 737 [152]
Diphenyl carbonate [136] Bentonite 616.4 [153]
Ethyleneglycol diglycidylether [137] Commercial synthetic Zeolite 450 [154]
Glutaraldehyde [138] Alumina 250 [155]
Poly(acrylic) acid [138] Clay 71 [156]
Pyromellitate biacid [139,140] Sepiolite 50.5 [157]
Sebacoyl chloride [138] Fly ash 15.6 [158]
Succinic anhydride [141] Red mud 10.2 [159]
Succinyl chloride [142] Brown alga Fucus serratus 1.79 [160]
Terephthaloyl chloride [138] Chitosan 0.69 [161]
1,4-butanediol diglycidylether [125,126] Bark (Pinus pinaster) 0.374 [162]
1,4-phenyldiisocyanate [143] Calcite 0.277 [163]
1,5-naphthalene diisocyanate [144] ECP polymer (CD/EPI 1/35) 90.1a (pH 4.6) [246]
1,6-hexamethylene diisocyanate [145–148] ECP polymer (CD/EPI 1/35) 58.5a (pH 10.3) [246]
2,4-toluene diisocyanate [142,146–148] ECP polymer (CD/EPI 1/25) 52.1a (pH 4.6) [246]
4,4 -dicyclohexyldiisocyanate [143,144] ECP polymer (CD/EPI 1/25) 40.5a (pH 10.3) [246]
4,4 -diphenylmethane diisocyanate [138,144] Modified ECP polymer 8.01 [248]
1,2,4,5-benzenetetracarboxylic anhydride [149] ECP polymer 5.4391 [164]
3-(glycidoxypropyl)-trimethoxysilane [150] ECP polymer (CD/EPI 1/25) 4.7 [138]
ECP polymer 3.22 [248]
ECP polymer (CD/EPI 1/25) 2.4 [165]
polymeric chains there is also great interest in synthesizing ECP polymer 1.9 [166]
cross-linked CDs using chemicals other than EPI (Table 4) ECP polymer 0.75 [250]
ECP polymer 0.11 [167]
[131–150]. ‘Eco-friendly’ cross-linking agents such as poly-
a
carboxylic acids or citric acid derivatives can be used to give From dye-sorption estimation.
insoluble ˇ-CD-based networks. Diisocyanate derivatives
have also been proposed. In all cases, the reactions occur features of the products (e.g., degree of swelling, CD con-
between the hydroxyl groups of CD and the groups of the tent, etc.). A high polymerization temperature favored a
cross-linking agent. For example, Yamasaki et al. [146–148] high degree of polymer swelling. Similar conclusions were
prepared a series of cross-linked cyclodextrin particles reported by Romo et al. [128], Vélaz et al. [129], Sainz-Rozas
using diisocyanate-based cross-linkers. These materials, et al. [130], and Mohamed et al. [138]. Varying the synthe-
containing urethane groups, are interesting for environ- sis conditions (e.g. the amounts of the different reagents,
mental purposes because they are highly cross-linked and the CD/EPI molar ratio, NaOH concentration, reaction tem-
possess high surface areas and a heterogeneous non-polar perature, reaction time) it was possible to induce structural
network. It should also be pointed out, however, that modifications in the hydrogel networks in terms of surface
the temperature of the reaction must be relatively high area and porosity, and to obtain gels with different CD con-
(∼70–80 ◦ C), in comparison to EPI (∼30–50 ◦ C), because tents [124,125,138]. For example, Crini et al. [124] showed
of the lower reactivity of the diisocyanate cross-linkers. that changes in the relative mole ratio of CD (monomer A) to
Water-insoluble ␤-cyclodextrin polymer cross-linked by EPI (monomer B) alter the repeat structure of the monomer
citric acid was obtained through an environment-friendly units from an A–B to an A–Bn type copolymer; the lat-
synthesis procedure by Zhao et al. [133–135]. The synthe- ter type contains EPI rich domains that are hydrophilic in
sis can be performed at below 200 ◦ C without any organic nature.
solvents or harmful additives. The polymers can be prepared either as particles of
irregular shape or as regular beads. The specific sur-
3.3. Characterization of ˇ-cyclodextrin–epichlorohydrin face areas are in general extremely low (in the range
polymers 1–10 m2 g−1 ) (Table 5) compared to that of CAC or other
sorbents [151–167]. Recently, Pratt et al. [246] calculated
The structure of ECP gels was previously studied by surface areas from a dye-based method. The surface area
Szejtli and co-workers [17,50,73,90,114]. Polymers and of the ECP materials ranged between 40.5 and 90.1 m2 g−1 ,
copolymers were characterized by water-retention, den- depending both on the pH and composition (Table 5). For
sity, gel-bed volume, particle size, mechanical stability, conventional materials such as activated carbon the val-
and molecular weight. The products had a molecular ues were in agreement with those calculated from nitrogen
mass of over 20,000 Da and a structure with a three- porosimetry data. For ECP materials however, the dye-
dimensional network. The structure of an ECP gel was based method yielded lower values because the dye was
highly hydrophilic, swelled strongly in aqueous solutions, primarily included within the CD cavity.
and was insoluble in any (organic) solvents. The products Whereas the preparation and applications of ECP gels is
possessed a remarkably high swelling capacity in water. very well-known, relatively little attention has been paid
Crini’s group [61,124–127] showed that it was important to the nuclear magnetic resonance (NMR) characterization
to select optimal synthesis conditions to obtain the desired of these products [124,138,174]. To respond to that, Crini
ARTICLE IN PRESS
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et al. [124] investigated the structure of the polymers by suitable chromatographic supports for gel inclusion chro-
solid state NMR. Using cross-polarization magic angle spin- matography applications.
ning with dipolar decoupling (CPMAS) and high-resolution To improve the method introduced by Solms, Niels
magic angle spinning (HRMAS) spectra, they showed that, Wiedenhof and co-workers [174–178] proposed, in 1969,
in the materials, two kinds of structures existed: CD cross- two bead-polymerization processes in emulsion in a non-
linked by EPI due to the cross-linking reaction between polar organic solvent and in the presence of a nonionic
the CD molecules and epoxide, and polymerized EPI due to detergent with stirring control were developed. Different
the homopolymerization of EPI with itself. These two com- procedures, patented in 1971, give beads with excellent
ponents were analyzed in terms of relaxation parameters physical properties, uniform and regular shape: interest-
(13 C spin lattice relaxation, 1 H spin lattice relaxation in the ing features for chromatographic applications. The beads
rotating frame). The authors demonstrated that because, were easily wettable, insoluble in water and in organic sol-
CDs contain seven glucose units and hydroxyalkyl groups vents, and stable in aqueous alkaline solutions. In order
in the C6 position in the glucose units, the structure or the to obtain information about the place and the number of
polymer network was complicated since many units were the substituents, Wiedenhof et al. [174] also studied the
interconnected. When the degree of cross-linking was high, IR and NMR spectra of the beads. Only NMR results can
the sample was mostly amorphous and cross-linking was give such information [177]. Their results showed that ␣-
not homogeneous. Crini et al. [124] showed that ECP mate- ECP and ␤-CEP gels possessed a chromatographic behavior
rials contain many side chains and this can explain why comparable with that of Sephadex® G-25 resin in terms
the materials form less stable complexes than the acryloyl of swelling characteristics and heat resistance. Different
CD polymer, which is practically free of nonbridged side separations using phenol, benzoic acid, aniline, chloroben-
chains. However, for technical purposes, the preparation zoic acids, and tyrosine as solute were obtained and, again
of polymerizable CD derivatives such as acryloyl CD is too the results were mainly interpreted using the complexa-
expensive. Recently, Wilson’s group [138] reported similar tion phenomenon. For example, the separation of benzoic
NMR interpretations on ECP networks. acid and ortho-benzoic acid was possible, while it was
Cowie and Spence [168] showed that ECP gels contain- impossible using Sephadex® . The ability of the CD-resins
ing lithium, sodium and potassium triflate salts showed to separate different molecules was due to the fact that
interesting ion conduction properties. The CD network did the resin contained CD voids which were able to form
not participate greatly in the ion conduction process but inclusion compounds. Wiedenhof [175] also introduced the
had a more passive role. This can be interesting for the term inclusion isotherm instead of sorption isotherm.
formation of metal–CD complexes. In 1970, Hoffman [179–181], using the procedure
described by Solms and Egli [170], proposed materials with
4. Water-insoluble ␤-cyclodextrin–epichlorohydrin high CD contents for column chromatography. The gels
polymers for environmental applications were useful in the separation of nucleic acids, nucleotides,
nucleosides, and oligonucleotides. The results were inter-
4.1. History of water-insoluble preted not only in terms of inclusion complexation but also
ˇ-cyclodextrin–epichlorohydrin polymers by the presence of anion-exchange interactions. During the
same period, other studies on chromatographic separations
Water-insoluble ␤-cyclodextrin–epichlorohydrin poly- were proposed [182–185]. The results demonstrated that
mers (ECP) were proposed as “inclusion resins” in ECP materials were efficient to separate various positional
1964–1965 by the Swiss scientist Jürg Solms (Research isomers and optical isomers, and interpreted by the inclu-
Laboratory of the Nestlé group in Vevey, Switzeland), sion complex formation.
who patented the chemical synthesis of these polymers, Research on CD polymers and copolymers acceler-
the methods of use and their applications [169–173]. In ated at the end of 1970s and the beginning of 1980s
1965, Solms with his colleague Egli published in detail with the interesting works of Szejtli and co-workers
the first procedure concerning the polymerization of CDs [16,17,50,51,64,72,114,186–197]. Their numerous publica-
in the presence of EPI in basic conditions [170]. Their tions and patents described the synthesis, characterization
results showed that polymers with irregularly shaped and applications of ECP materials. The first interesting
particles exhibited strong adsorptive properties toward result was the following: the authors showed that, when
various molecules such as aniline, nitrophenols, benzalde- the insoluble polymer was prepared by block polymer-
hyde, pyridine, iodine, Congo Red, and Methylene Blue. All ization, the particles had an irregular shape. It was much
the results were interpreted in terms of inclusion com- more advantageous to prepare the polymer in the form
plex formation. They compared their results with those of regular, spherical beads with specific properties, and in
obtained with a commercial cross-linking EPI–dextran particular with controlled swelling properties. In aqueous
polymer (Sephadex® ) with no inclusion properties. ECP solutions, these swelling beads were capable of form-
resins exhibited especially good selectivity compared with ing inclusion complexes with a wide variety of guest
the non-inclusion analog. The gels were also used in gel molecules. The stability of the complexes formed with
chromatography columns for the separation of phenylala- insoluble polymers was fairly high in comparison with
nine, tryptophan, nitrophenols (ortho and para isomers complexes formed in homogeneous solution. According to
cannot be separated on Sephadex® ), vitamins and per- kinetic studies the complex formation rate constant was
fumes [171]. For the first time, the results published by similar, but the dissociation rate constant was about two
Solms and Egli demonstrated that ECP materials were orders of magnitude lower than in homogeneous systems.
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The complex-forming capacity mainly depends on the a detailed discussion of the pharmaceutical applications
structure of the material: among the chemical character- should refer to the book by Frömming and Szejtli [216].
istics, the void concentration, the density of bridges and In the early 1980s, Shaw and co-workers [217–224]
the kind of cross-linking were the most important. Szejtli demonstrated that ␣- and ␤-ECP gels had an interesting
and co-workers showed that, incorporating a low molecu- potential for wide application in food processing because
lar weight glycol (such as ethylene glycol, propylene glycol they easily separated bitter components (naringin, limonin
or polyethylene glycol), gave a looser polymeric structure. and nomilin) from citrus juice according to their molecular
The size of the secondary cavities was increased, and this size and shape. The ˇ-CD gels were the best materials for
resulted in faster and higher swelling. Polymers and their the removal of both naringin and limonin from grapefruit
gel structures were also characterized by pollutant sorption juice and the results were better than those obtained using
isotherms. The methylation of ECP beads resulted in a poly- cross-linked polystyrene and Amberlite XAD-4 in terms of
mer containing very few free hydroxyl groups, nearly all efficiency and selectivity. However, their results indicated
of them being substituted with hydrophobic groups. Such that the method of polymerization, the cross-linking agent,
products did not swell in water, but swelled considerably and the particle size were important factors because they
in organic solvents and found specific chromatographic affected the capacity of the polymers to reduce levels of bit-
applications. Numerous significant results on the extrac- ter components in grapefruit juice and navel orange juice.
tion, concentration and purification of substances were In 1991, Su and Yang [225], studying the removal of natu-
obtained. Zsadon et al. [198–206] and Cserháti et al. ral food components (naringin, caffeine, theobromine) by
[207–211] showed that rigid structure of CDs and the sta- ECP gels, reported similar conclusions. In 1996, Hicks et al.
bility of the inclusion compounds formed in a solid phase, in [226] showed that the polymers could be used to inhibit
solution, or with a host present in a gaseous phase made it enzymatic browning of fresh raw apple, pear, and celery
possible to apply these selective inclusion processes widely juice.
in chromatographic methods. Among the numerous patents on CD-based polymers
ECP materials, prepared in block [169–171], film [174], used as resins, two other patents should be mentioned. All
bead [174,186] or fibrous form [186,187], make a variety of the attempts to prepare ECP gels resulted in products
of specific inclusion chromatographic separations possible, which either have only a moderate mechanical stability
and the first applications were mainly analytical for sep- or have a low CD content. In addition, the preparation
aration, extraction and concentration of substances. The can be difficult and expensive and this can rebut indus-
materials can be used as supports or stationary phases trial users. To overcome these problems, in 1988, Friedman
(column packing) in HPLC or GC, and as sorbents for solid- and West [227] patented a method for removing poly-
phase extraction (SPE). For example, Szejtli et al. [186–197], chlorinated biphenyl compounds from water efficiently
Zsadon et al. [198–206], and Cserháti et al. [207–211] by ECP materials using both batch and continuous tech-
showed that regular beads of medium swelling capacity niques. ECP beads exhibited high capacities toward these
can be used advantageously for inclusion chromatography. toxic molecules [228]. Vanzo [229] also patented in 1991
They swell rapidly even at ambient temperature, and can a commercial, industrial scale method for making spheri-
be readily packed and settled. The swollen particles do cal beads of cyclodextrin. These beads are simple to prepare
not deform and are elastic. They retain their original form, and possess a high CD content, and at the same time possess
dimensions and properties, even after repeated drying and improved mechanical properties compared with compara-
swelling. A further advantage is that they are resistant to ble ECP materials then known.
damage by microorganisms, even when moist, and can be At the same period, Kiji et al. [231], Chen and He [232],
stored for a long period without decomposition when wet. Murai et al. [233,234], and Shao et al. [235] published
From these results, there is no doubt that commercial ECP results of sorption of organic species on ECP gels. Murai
materials are useful as chromatographic supports for sepa- et al. [233,234], studying the sorption of nonionic surfac-
ration processes and their effectiveness of varying degrees tants, ionic surfactants and phthalic esters on ECP gels,
of success has been reported in numerous other publi- showed, for example, that 1 g of material was able to
cations [21,23]. However, it is important to note that no adsorb 85% of alkylphenol ethoxylate from a 150 mL solu-
practical technology was developed until the 1980s. This tion containing 200 ppm of nonionic surfactant. Both batch
can be explained by the fact that CD polymers in the form of and column sorption experiments gave similar interest-
gels presented low efficiency and poor mechanical strength ing sorption capacities. Another interesting feature is the
on prolonged use. For this reason, stationary phases with fact that the sorbents proposed can be easily regenerated.
CDs chemically bonded to silica gel were developed and to The results were interpreted by both the inclusion com-
success fully commercialized rapidly. plex formation and the presence of interactions through
ECP materials have been previously studied for specific the network polymer.
applications in chemistry (catalysis), pharmacy and in food At the end of the 1990s, our group [124,235–240], using
technology. They are effective tablet disintegrating agents the procedure described by Solms and Egli [170], and
in direct compression systems as well as in formulations improved by Hoffman [179–181], proposed several mate-
made by wet granulation [193], and they can also catalyze rials with different CD contents (ranging from 20% to 80%
certain reactions [212–215]. For example, Komiyama and w/w). We introduced some minor modifications consist-
Hirai [214,215] reported that the ECP gels were interesting ing in an increase of the amount of EPI in order to obtain
catalysts for the selective synthesis of 4-hydroxybenzoic mechanically stable materials. As the materials were rela-
acid and 4-hydroxybenzaldehyde. Readers interested in tively highly cross-linked, they can be used both in batch
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and column studies. The method proposed was interesting Table 6 lists some of the researchers whose results are pre-
and enlarged the potential applications of these materi- sented and the pollutants they investigated [241–277].
als because the use of ˇ-CD cross-linked gels in sorption Results published by Evans’s group [241,242] showed
columns in general presents restrictions due to hydrody- that ECP materials used as support in columns for trapping
namic limitations and column fouling. The gels were used organic pollutants in flowing water had practical appli-
as heterogeneous systems to adsorb pollutants such as cations in water remediation and water sampling. Their
chlorophenols, nitrophenols, naphthols, and benzoic acids. results clearly demonstrated that the CD-based supports
The gels also had a potential use in wastewater treatment were promising sorbents since they exhibited strong sorp-
from textile manufacturing as a result of the ability of ˇ- tion capacities, with the additional benefit of recovering the
CD to form inclusion complexes with many dye molecules polymers for recycling. The saturated sorbents were easily
(acid, direct, mordant and reactive dyes). Favorable ion- regenerated by extraction and the complexing abilities of
exchange properties can be also conferred on insoluble CD the sorbent remained unchanged after many regeneration
materials by the introduction of appropriate substituents, cycles.
e.g. carboxymethyl or amino groups. A correlation between The effectiveness of ECP materials as sorbents for pollu-
the polymer structure and its sorption properties was pro- tant removal has also been intensively investigated by Isasi
posed using solid state NMR data. and co-workers [128,142,167,262–264]. The pollutants
studied were dibenzofuran [167], naphthalene [142,262],
4.2. A recent review of the literature and phenol derivatives [142,264], and the parameters
influencing the sorption performances were the variables
The idea of preparing ECP materials for analytical pur- of the experimental conditions used for ECP synthesis
poses (e.g. inclusion chromatography) has been the center [128], polymer structure [167], cross-linking density and
of attention of scientists worldwide during the last 60 years, degree of swelling [128], CD content [128], pollutant struc-
but the most intensive studies on their use as sorbents in ture [262], particle size [128] and temperature behavior
wastewater treatment for toxic pollutant removal started [167]. Significant results were obtained: ECP gels exhibited
only in the last two decades [240]. strong sorption properties and selectivity. All the results
In the 1990s, the reviews and books published on were interpreted mainly by the formation of inclusion com-
CDs and their practical applications stimulated numerous plexes, confirming the interpretation previously published
works on CD-based materials and their use for environ- by Crini’s group [61,125–127]. When compared with con-
mental applications [11–23,50–52]. The fact that many ventional sorbents used to extract pollutant from water
CD derivatives were available and employed in numer- (activated carbons, macroporous organic resins), ECP poly-
ous commercial applications provided a stimulus to create mers showed better sorption properties and features [264].
new materials, including insoluble CD-based polymers, for Isasi and co-workers concluded that ECP were efficient
pollutant removal using in particular sorption-oriented materials for environmental applications.
processes. Numerous CD-based materials were proposed A new solid-phase extraction technique based on the
and developed such as cross-linked polymers or hydro- formation of an inclusion complex with ECP polymer was
gels, CD-based composites, CD-immobilized by chemical proposed by Moon et al. [259–261]. Steroidal compounds
bonding to various supports, and more recently, CD-based tests on the entrapped polymer were extracted with
membranes and molecularly imprinted functional mate- tetrahydrofuran and the overall recoveries ranged from
rials. Among these materials, ECP gels play an important 82% to 112% for 77 steroids in urine. Comparison with a
role. conventional hydrophobicity-based cartridge showed that
The list of pollutants investigated on ECP gels is very the extraction efficiency of polar steroids was significantly
large and includes dye molecules, aromatics, chlorophe- increased in the CD experiment due to its multi-functional
nols, naphthalene derivatives, dibenzofuran molecules, mechanism derived from molecular inclusion and chemical
polychlorinated biphenyls, pesticides (herbicides, fungi- interactions.
cides, insecticides, acaricides, etc.), nonionic (alkylphenols) Using batch experiments, Li et al. [166,249–251]
and ionic surfactants (dodecylbenzenesulfonic acid), deter- showed that ECP materials exhibited high sorption
gents (lithium dodecylsulfate, 2-naphthalene carboxylate), capacities toward 4-chlorophenol, 2,4-dichlorophenol and
metals and also rare earth metal ions [50,51]. ECP materials aniline. The kinetics were rapid (2–2.5 h for reaching equi-
were also used for the removal of odor-causing compounds librium) and the values of sorption capacities high (up to
from water samples and in the enrichment of different 24.4 mg g−1 when initial concentration of pollutant was
species from aqueous solutions. Again the potential use of a 140 mg L−1 at 283 K). The sorption capacities were also
support containing CD molecules in the reduction of envi- pH-independent. The polymers were easily recovered by
ronmental pollution is based in all cases on the formation of ethanol as washing solvent.
inclusion complexes between CDs and the unwanted sub- Recently, Wilson’s group [138,244–246] studied the
stances. The term “inclusion” means that a specific spatial sorption of naphthenic acids (NAs) onto a series of
interaction occurs, in which the molecule of a guest, or at cyclodextrin particles cross-linked by EPI or isocyanate
least part of it, is included in the cavity of the host with derivatives. The best removal efficiency was obtained by
attainment of minimal energy for the system [61]. the CD cross-linked with EPI. Although the proposed mate-
In this part, due to the large number of groups work- rials possess low surface areas as compared to that of
ing around the world, we make a selection from the most commercial activated carbons, the authors concluded that
significant results on ECP materials for pollutant removal. they were suitable for the removal of NAs, especially at
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Table 6
Authors of recent research on pollutant removal by water-insoluble ␤-epichlorohydrin polymers.
Country Corresponding author Contaminant(s) Reference(s)
Canada Evans CH 2-naphthol [241,242]

Canada Hausler R Nonylphenol ethoxylate [243]
Canada Wilson LD Naphthenic acids [138,244–246]
China Ji H Cinnamaldehyde, benzaldehyde [247]
China Cai X Pesticides [248]
China Li N 4-chlorophenol, aniline [249–251]
China Zhang XM Fuchsin [252]
France Crini G Phenol, benzoic acid, p-nitrobenzoic acid, chlorophenols, ␤-naphthol, [124–127,230,236,240]
acid blue 15, acid blue 25, basic blue 3, basic blue 9, basic green 4, basic
violet 10, reactive blue 19, disperse blue 3, direct red 81
France Fourmentin S Linalool, camphor [253,254,275]
France Mallard Favier Toluene [255]
France Martel B Acid red 1, acid blue 15, mordant black 11, mordant yellow 30, reactive [235]
black 5, reactive blue 7
Germany Kleine R Polycyclic aromatic hydrocarbons [276]
Hong Kong Yu JC p-Hydroxybenzaldehyde, p-aminobenzoic acid, benzene, pyridine, [256]
p-nitrophenol
Hungary Gruiz K Bisphenol A, nicotine [277]
Italy Vecchi C Phenol, p-nitrophenol, benzoic acid, p-nitrobenzoic acid, [237]
chlorophenols, ␤-naphthol
Japan Kitaoka M Bisphenol A [257]
Japan Murai S 4-nonylphenol, 4-nonylphenol ethoxylates, bisphenol [233,234,258]
Korea Choi MH Androgens, estrogens, corticoids [259–261]
Spain González-Gaitano G Dibenzofuran [130,262]
Spain Isasi JR Phenol, 1-naphtol, 1-naphthyl acetate, 2-acetylnaphthalene, cresols, [128,167,263,264]
dibenzofuran, 2-hydroxy-dibenzofuran, 2-methoxy-dibenzofuran,
3-amino-2-methoxy-dibenzofuran
Spain Martínez-Ohárriz MC Gemfibrozil [265]
Spain Peñas FJ Phenol, toluene [266,267]
Spain Vélaz I Phenolphthalein, terbinafine [129,268,269]
Spain Zornoza A Pindolol, propanolol, indole, 4-methoxyindole, ebastine [270,271]
USA Oskouie AK Geosmin [272]
lower pH conditions [244]. The sorption results for carbons In our group, experiments are being conducted to
ranged from 100 to 160 mg NAs per g of sorbent whereas evaluate the possibility of using ˇ-CD-based mate-
the polymeric materials ranged from 20 to 30 mg NAs per g rials as sorbents in industrial wastewater treatment
of material over the experimental conditions investigated. [23,53,61,124–127,165,235–240]. We propose the use of
The authors concluded that differences in the performances these polymers as new cross-linked materials to adsorb
between standard granular carbon and the CD-based poly- both organic and inorganic pollutants from real effluents
mers were related to differences in the surface areas of using batch methods and column tests. These experiments
the materials and in their chemical nature. Similar conclu- showed that ECP gels were able to interact efficiently with
sions were reported using p-nitrophenol as model solute organic compounds (phenol, ␤-naphthol, etc.) and dye
[138]. In another work, Mohamed et al. [245] demonstrated molecules. In particular, the ␤-CD-based polymers were
that dye-based sorption represented a facile and versatile very efficient at removing acid, direct, disperse and reactive
analytical method for the evaluation of the inclusion site dyes from solutions. The surface area and pore structure
accessibility of ECP polymers providing useful insights into characteristics were important physicochemical proper-
the sorption properties of sorbent materials containing CD ties. It is well-known that these characteristics affect the
molecules. All these studies [138,241,245,263] showed that sorption properties of porous polymeric materials, partic-
the CD macrocyle is a key component in designing materi- ularly for amorphous and non-templated materials. We
als since the surface accessibility of the binding sites affects interpreted our results by the predominance of inclusion
their sorption properties. complex formation. Beside the physical sorption on the sur-
Polymerization of ˇ-CD with EPI in the presence of face and inside the pores of the ECP gel structure inclusion
carboxymethylcellulose (CMC) was recently proposed by complex formation in the CD cavities plays the most impor-
Bonenfant et al. [243] and led to interesting sorbents tant role in the mechanism. Similar conclusions have been
for removal of nonionic surfactants (such as alkylphenol previously reported by Fenyvesi et al. [193–195]. ECP poly-
ethoxylate – NPEO) from aqueous solutions. The experi- mers can be easily regenerated, and column sorption and
ments were performed using mixtures containing 500 mg desorption tests showed that the pollutants adsorbed on
of ECP polymer and aqueous NPEO solutions at concentra- cross-linked polymer were successfully released by vari-
tions of 12–82 mg L−1 . The results showed that the removal ous kinds of aqueous alcohol solutions. Zhang et al. [252]
was rapid and the polymer exhibited high NPEO sorption also reported that ˇ-CD-sorbents possess specific inclu-
capacities (1.1–6.8 mg of NPEO per g of polymer). Similar sion recognition capabilities with dye molecules. Also the
conclusions were previously reported by Murai et al. [233] mechanisms for the sorption of dyes on ECP materials pro-
using ECP gels. posed by these authors were both physical sorption in the
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polymer network and the formation of a host–guest inclu- the presence of NH4 OH at moderate temperature. Dur-
sion complex, this interaction playing the most important ing the cross-linking step with BUDGE, polymer chains
role. were cationized with EPTAC. The cross-linked polymer
The chemical modification of ECP gels continues to obtained contains both hydroxyl, tertiary amino and
attract the attention of researchers because it can be used quaternary ammonium groups with different degrees of
to introduce the desired properties in order to enlarge substitution. The material also possesses useful surface
the range of pollutants trapped [23,59]. An improvement areas (100–150 m2 g−1 ), an amphiphilic character, and a
can be obtained by introducing groups able to coordinate remarkably high swelling capacity in water due to the
metals or fluoride ions as recently shown by Sancey et al. hydrophilic nature of its cross-linked units. The aminoethy-
[165], in addition to complexing target dyes [126,127,252] lation and carboxymethylation of cationic cross-linked
or phenol derivatives [243]. For example, it is known that materials enable the preparation of amphoteric derivatives
ECP polymers without modification had a low affinity for for possible use in the treatment of wastewater containing
cationic dyes. In order to extend their sorption proper- metals from surface-treatment industries, dyes from tex-
ties, Crini’s group [126,127] proposed chemical grafting tile industries or organic matter from the paper industry.
of carboxyl groups onto cyclodextrin as a means of con- The hydrogels obtained possess typical amphoteric char-
ferring the ability to adsorb cationic dyes onto polymer acteristics, due to the protonation and deprotonation of
beads. These organic sorbents were prepared by reticu- the backbone tertiary amine and pendant carboxyl groups
lation in the presence of CMC. Because of the OH and in the polymer network. For example, we proposed these
COOH groups in the polymer network, the material was new amphiphilic cross-linked CD polymers as complexing
hydrophilic, easily swelled by water, and possesses ion- resins for the removal of organic matter (characterized by
exchange properties. The results showed that modified the chemical oxygen demand or COD parameter), metals,
ECP gels exhibited more specific and higher sorption of boron and fluoride ions from industrial wastewater [165].
pollutants from water samples than other traditional ECP The gels can be used over a wide pH range due to their par-
materials. Zhang et al. [252], studying the sorption of ticular electrical character. Fig. 9 compares industrial water
fuchsin on ECP containing carboxymethyl groups, reported discharged in the natural environment without additional
similar conclusions. They also noted that the mechanism post-treatment (before sorption) and the same discharged
should integrate not only the presence of inclusion due water treated by sorption (after sorption). These results
to CD cavities but also the effects of electrostatic inter- showed that sorption onto cross-linked CD material having
actions and van der Waals forces due to the presence ion-exchange properties is an interesting process to simul-
of new reactive groups on the surface particles. Bonen- taneously remove cations, anions, and organics, and to
fant et al. [243] also demonstrated that ECP gel prepared abate more pollution before release into the environment.
in the presence of CMC was able to interact efficiently After use, the materials can be eliminated by incineration,
with alkylphenols from aqueous solutions. These authors thus avoiding the need for fastidious and expensive regen-
showed that the presence of CMC can enhance both accessi- eration.
bility and mobility of the ˇ-CD in the polymer by promoting A few studies have shown that polymeric sorbents also
the swelling of the material in water. However, they present a facility of regeneration. After this treatment, the
concluded that the sorption of nonylphenol ethoxylate sorption capacities remain unchanged showing both the
was highly concentration dependent, and the ECP poly- chemical stability of the insoluble polymers and the repro-
mer adsorbed much more pollutant at low concentration. ducibility of the values [125,166,233–237,241,247,272].
Fenyvesi et al. [193–195] previously reported that, when Murai et al. [234] concluded that the repeated cycling of
ionic groups such as COOH sites were linked covalently to ECP material was more advantageous than that of commer-
the (co)polymer, the interactions between the matrix and cial activated carbon in practical use. Similar conclusions
the contaminants were supplemented with salt formation, were reported by Li et al. [166] and Yang et al. [247].
with different kinds of interactions acting simultaneously Finally, recent studies on the applications of ECP gels in
(e.g. inclusion, chemisorption, physical sorption by the the enrichment of different species from aqueous solutions,
polymer network). for the removal of polluting components from the gaseous
pH-responsive hydrogels are a kind of gel that can phase, or for the removal of odor-causing compounds
respond to changes in ambient pH and alter their volume [253–255,272] should also be pointed out. For example,
accordingly. These materials are particularly interesting Rashmawi et al. [272] proposed ECP gels to remove taste
for pharmaceutical applications, for example for con- and odor causing compounds; more interesting removal
trolled drug delivery systems. In recent years, particular efficiencies were obtained as compared to commercial car-
interest has been devoted to amphoteric pH-sensitive bons. Fourmentin’s group [253,254] studied the inclusion
polysaccharide-based hydrogels that possess both posi- interactions of ECP with linalool and camphor in essential
tive and negative charges and are therefore capable of oils. Mallard Favier et al. [255] proposed for the first time
swelling in both acidic and basic media, without requir- cross-linked CD-based materials for VOC trapping from
ing modification of the pH. Crini [273] recently patented gaseous phase. They concluded that ECP were promising
a new route for preparing cross-linked polysaccharides for organic pollutant remediation. However, although the
and oligosaccharides with ionic functional groups. The results were interpreted using the formation of inclusion
polymer or oligomer was mixed with an epoxy cross- complexes, further investigations were needed to define
linking agent (1,4-butanediol diglycidylether, BUDGE) and the role of the structure of the polymer and to study the
2,3-epoxypropyltrimethylammonium chloride (EPTAC) in dynamic VOC trapping.
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Fig. 9. Effect of sorption onto CD-based sorbent on [Al], [F], [B] and COD for effluents discharged from surface-treatment industries. Comparison between
water discharged into the natural environment without additional post-treatment (before sorption) and the same discharged water treated by sorption
(after sorption) (dotted red line represents the legal limit for Al, F and COD). (For interpretation of the references to color in this figure legend, the reader
is referred to the web version of the article.)
It appears clearly from this literature survey of about capacities but also interesting selectivity. Table 7 reports
110 recent papers that cross-linked ˇ-CD polymers might some significant sorption capacities of ECP for a range of
be a promising material as sorbents for extraction and pollutants. The reader is encouraged to refer to the original
removal of toxic organic and mineral pollutants from aque- papers for complete information on experimental condi-
ous solutions. ECP materials exhibit not only high sorption tions in the sorption-oriented processes used.
Table 7
Recently reported maximum sorption capacities (qmax ) of water-insoluble ␤-cyclodextrin–epichlorohydrin polymers for a range of pollutants (the reader
is encouraged to refer to the original articles for all information on experimental conditions).
Pollutant Sorbent Experimental conditions in the sorption-oriented process used qmax Reference
p-Nitrophenol ECP m = 0.2; V = 7; pH 4.6; CT = 1440; 22 ◦ C 387 ␮mol g−1 [246]

p-Nitrophenol ECP m = 0.2; V = 7; pH 10.3; CT = 1440; 22 ◦ C 294 ␮mol g−1 [246]
2,4-dichlorophenol ECP m = 0.1; V = 50; C0 = 0.67 mM; CT = 120; pH 7; 30 ◦ C 160 ␮mol g−1 [250]
␣-Naphthol ECP m = 0.15; V = 50; CT = 150; 25 ◦ C 140.2 ␮mol g−1 [142]
␤-Naphthol ECP m = 0.05; V = 5; C0 = 0.5 mM; pH 11; CT = 240; 25 ◦ C 105 ␮mol g−1 [236]
Phenol ECP m = 0.15; V = 50; CT = 90; 25 ◦ C 33.6 ␮mol g−1 [142]
Benzene ECP m = 0.3; pH 5; CT = 30; 20 ◦ C 0.82 ␮mol g−1 [256]
Basic green 4 Modified ECP m = 0.15; V = 100; C0 = 40 mg L−1 ; pH 8; CT = 120; 25 ◦ C 91.9 mg g−1 [127]
Acid blue 25 ECP m = 0.1; V = 20; C0 = 0.03 mM; pH 5.2; NaCl = 0.1 M; CT = 120; 25 ◦ C 88 mg g−1 [125]
Bisphenol A ECP m = 0.5; C0 = 0.2 mM; pH 7; CT = 120; 20 ◦ C 84 mg g−1 [257]
Fuchsin Modified ECP m = 0.1; V = 50; C0 = 250 mg L−1 ; pH 5.2; CT = 120; 20 ◦ C 54.6 mg g−1 [252]
Basic violet 10 ECP m = 0.1; V = 100; C0 = 40 mg L−1 ; pH 8; NaCl = 0.1 M; CT = 120; 25 ◦ C 53.2 mg g−1 [126]
Basic blue 3 ECP m = 0.1; V = 100; C0 = 40 mg L−1 ; pH 8; NaCl = 0.1 M; CT = 120; 25 ◦ C 42.4 mg g−1 [126]
Naphthenic acids ECP m = 0.2; pH = 5; 25 ◦ C 39.5 mg g−1 [244]
Basic violet 3 ECP m = 0.1; V = 100; C0 = 40 mg L−1 ; pH 8; NaCl = 0.1 M; CT = 120; 25 ◦ C 35.8 mg g−1 [126]
Fuchsin ECP m = 0.1; V = 50; C0 = 250 mg L−1 ; pH 5.2; CT = 120; 20 ◦ C 32.3 mg g−1 [252]
Naphthenic acids ECP m = 0.2; pH 9; 25 ◦ C 29.1 mg g−1 [244]
p-Chlorophenol ECP m = 0.1; V = 50; C0 = 140 mg L−1 ; CT = 240; pH 7; 30 ◦ C 24.4 mg g−1 [166]
Nonylphenol ethoxylate Modified ECP m = 0.5; V = 50; C0 = 12–60 mg L−1 ; CT = 480; 25 ◦ C 1.1–6.8 mg g−1 [243]
m = mass of sorbent in g.
V = volume of solution in mL.
C0 = initial concentration.
CT = contact time in min.
Please cite this article in press as: Morin-Crini N, Crini G. Environmental applications of water-insoluble ˇ-
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4.3. Control of performances in the sorption-oriented available CD than those with 65% CD: the authors explained
processes this by the higher degree of cross-linking of the CD-rich
polymer. However, in this study, the CD content in the
From the literature data, the parameters controlling the materials was determined by elemental analysis [129]. But,
extent of sorption properties of CD polymers and playing both CD molecules and bridges, as well as side chains in
an important role in the mechanism, are the cross-link the material contain only C, O and H. From calculations
density, hydrophilicity, degree of swelling, CD content, based on elemental analysis, it seems to be controversial
CD accessibility, and also the presence of ligands on the that higher degree of cross-linking results in higher CD con-
polymer network [21,23,61,166]. It is known and widely tent, especially because the concentration of accessible CD
reported in the literature that the cross-link density (i.e., is not in accordance with these results. Recently, Liu et al.
frequency of inter-strand bridges) is the main parameter [248], using multivariate regression analysis in order to
influencing the properties of the final material. However, distinguish between the quantitative contributions of the
there is a debate on its precise role. properties of CD-based polymers to their sorption poten-
In general, ECP materials used for sorption-oriented tial, showed that the apparent sorption potential of the
processes possess a remarkably high swelling capacity in polymer was related mainly to CD content.
water and, consequently, their networks are sufficiently Effects of pH and ionic strength are also another area
expanded to allow fast diffusion of the studied adsor- of debate. Shao et al. [235], studying the sorption of dyes
bate. Crini’s group [23,124–127,236,237] showed that it onto ECP polymers, showed that the influence of pH was
was important to control and characterize the condi- rather low whilst that of ionic strength was prominent on
tions of the cross-linking reaction since they modulate the sorption rate. The addition of anionic surfactants and
the cross-linking density and the degree of swelling. They salts had either a positive or a negative effect on sorption.
observed that high polymerization temperatures favored a Surfactants and salts such as SDS and NaCl are dyeing aux-
high degree of polymer swelling, and hence the sorption iliaries often used in industrial dyeing processes. NaCl was
properties, confirming the results previously published by found to have a positive effect on ECP performance while
Wiedenhof et al. [174,175]. Self-polymerization of EPI was SDS decreased sorption drastically. This was interpreted
also favored at high temperatures and the amount of EPI by the insulation of the dye molecule inside the surfactant
incorporated into the ECP polymer increased for high NaOH micelle and by the predominance of an inclusion complex
concentrations, in accordance with the results of Szejtli between SDS and CD molecules. In this case micellar dis-
et al. [186–190]. Using NMR data, Crini’s group also showed solution and competition with SDS were the reasons for
that longer hydroxypropyl ether segments between CD the lower sorption of the dye molecules on ECP polymer. Li
molecules favored the expansion of the macromolecular et al. [166], studying the sorption of chlorophenol deriva-
network and consequently produced higher degrees of tives onto ECP polymers, showed that NaCl produced a
swelling [124]. Sorption results demonstrated that the per- slight increase of the performance of ECP, due to the fact
formance decreased as cross-linking frequency increased. that the salt can minimize electrical charge on the surface.
At higher levels of cross-linking, the gels had a lower Pratt et al. [246] recently reported that the removal effi-
swelling capacity and the accessibility and diffusion of pol- ciencies of ECP polymer depended on both amount and
lutants into the polymer network decreased as a result of nature of sorbent, temperature, pollutant concentration,
the denser three-dimensional network and the increased and pH. Greater removal efficiencies occurred for polymers
hydrophobic character. For the control of polymer swelling, with increased cross-linking density. The performances
they showed that the most important factor was mainly were also greater at elevated pH and this was attributed
the CD/EPI molar ratio, followed by the stirring speed dur- to potential swelling of the framework because of electro-
ing the reaction and the concentration of NaOH. Similar static repulsions of the material as partial deprotonation of
conclusions were reported by Romo et al. [128]. the CD hydroxyl groups occurred at alkaline pH. In contrast
The cyclodextrin content is also an important factor to this, Crini’s group [125–127] reported that the sorption
although contrasting conclusions have been published. For capacity of the gels depends on ionic strength more than
example, Crini [125], Romo et al. [128], and Yu et al. [256] on pH. In particular, the presence of sodium chloride mini-
showed that a higher CD content was responsible for higher mized electrical charges on the surface of the ECP polymer
sorption capacity, whereas lower CD loadings, in some [166] and thus increased its performance. Differences in
cases, favored better sorption as recently reported by Vélaz materials and methodology, however, make the compar-
et al. [129] or previously reviewed by Mocanu et al. [21], ison of results difficult, and much work is necessary to
and Crini and Morcellet [23]. Romo et al. [128] showed understand the role of pH and ionic strength for this kind
that ECP gels with lower CD content yielded smaller parti- of CD-based material.
cles and degrees of swelling. In general, an increase in the Some interesting differences were published by Romo
amount of CD corresponded to an increase in the sorption et al. [128], studying the sorption of dibenzofuran (DBF)
capacity, corroborating the fact that inclusion phenomena and phenol onto ECP polymers. The differences were also
played the most important role in the mechanism. Vélaz related to the different structures and polarities of aromatic
et al. [129] demonstrated that polymers with similar CD compounds themselves. DBF was more susceptible to being
contents can show different structural characteristics, and trapped in the hydrophobic CD cavity than phenol, pro-
particularly different degrees of swelling due to differ- ducing a less stable inclusion complex (the stability of the
ences in degree of cross-linking used in the synthesis of the phenol–CD complex was quite low because this solute was
polymers. Insoluble polymers with 74% CD possessed less small for the CD cavity). However, in the case of polymers
ARTICLE IN PRESS
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with lower CD content and greater degrees of swelling (due [171]. Similar conclusions were reported by Wiedenhof and
to the presence of hydroxypropyl ether segments of greater Trieling [177] and Hoffmann [179–181], from the inter-
lengths) the sorption of phenol in the polymer network, action isotherms for the isomers of chlorobenzoic acid
by means of hydrophobic and/or hydrogen bonds, can be or nucleotides with ECP polymers. For example, from the
greater than that of DBF. In this case, the sorption of phenol slopes of the isotherms, m-chlorobenzoic acid interacted
was mainly determined by its interaction with the polymer most strongly, whereas p- and o-chlorobenzoic acids inter-
network. acted differently but both substantially less. In addition,
the stronger interaction with ␤-ECP gel than with ␣-ECP
4.4. Sorption mechanism gel corresponded to the inclusion mechanism which was
governed by the size of the cavity in the CD ring. The data
The relative stabilities of the CD inclusion compound confirmed a strong interaction with the ␤-ECP gel and the
are governed by different factors such as hydrogen bond- fact that o-chlorobenzoic acid could be separated from ben-
ing, hydrophobic interactions, solvatation effects in liquid zoic acid, whereas the peaks of the two components overlap
media, and the space-filling ability of the molecule. The sta- on Sephadex® .
bility of the inclusion depends on the size and polarity of the On the basis of these data, a general conclusion was
host molecule and its shape, in relation to the dimension made by Zsadon et al. [198,199], studying separations of
of the CD cavity [13,14,50,66]. During complex formation, aromatic amino acids on ECP polymer, about an increased
no covalent bonds are formed or broken which stresses the affinity of CD toward aromatic molecules and a steric
physical rather than the chemical nature of the process. specificity toward their isomers. Their conclusions were
Nevertheless, the driving forces binding host and guest confirmed by comparing the chromatograms obtained with
molecules (e.g. pollutants or drugs) which have been com- ␤-ECP polymer and Sephadex® under identical condi-
monly proposed to justify the complex formation include tions. The most important interaction was due to the
electrostatic interactions, hydrogen bonds, hydrophobic inclusion phenomenon. In another work, studying the
interactions, van der Waals forces, and the release of “high separation of indole alkaloids on ECP and Sephadex®
energy water” [65,66]. This explains the fact that substan- gels, Zsadon et al. [200] concluded, however, that the
tial differences in binding behavior can be observed for a mechanism of the interaction was governed by inclusion
series of structurally related sorbates present in a mixture. complex formation or a combined effect of inclusion and
This is the basis of the use of CD derivatives in separation sorption, depending of the polymer structure and solute
processes [11,12,50,75,76]. studied.
For the interpretation of the interactions between Szejtli’s group [186–189] previously reported that
water-insoluble CD polymers in the form of gels and com- cross-linked cyclodextrin polymers can retain different
pounds, three main mechanisms were proposed which organic molecules by forming inclusion complexes with
involve (1) interactions in the CD cavities (i.e., the for- CDs and also by adsorbing them externally onto their
mation of inclusion compounds), (2) interactions in the network. The mechanism and in particular the complex-
internal pores of polymeric pearls and (3) interactions forming capacity mainly depend on the ECP structure,
on the surface (physical sorption). In general, physical and its degree of cross-linking, in accordance with the
sorption plays a little role in the interaction between results published by Solms and Egli [170], Wiedenhof et al.
ECP and pollutants because CD-based materials have a [177], and Hoffmann [179–181]. Szejtli’s group [186–189]
very small surface area [21,23,256], and the results are demonstrated that CD rings can easily be reached by the
mainly explained by the formation of inclusion complexes. guest molecules in a loose structure. If the secondary cavi-
However, this is a source of debate in the literature. ties formed by the cross-linking agent are commensurable
Mohamed et al. [138,244] recently showed that physic- with the rings, further guest molecules can be inserted into
ochemical and texture properties (i.e., surface area and them. This phenomenon results in a higher host–guest ratio
pore structure) played an important role in the sorption for the ECP gels than for the CD and its non-polymer deriva-
mechanism. Studying the sorption of naphthenic acids tives. However, in the case of highly cross-linked polymers,
onto an ECP polymer, they showed that the sorption only the outer surface of the particles can take part in
capacity increased as the surface area of the polymer the formation of the complex. The guest molecules cannot
increased. penetrate into the network. This is the reason underlying
The three mechanisms, described above and com- the lower host–guest ratio for such polymers as compared
pared with Sephadex® gels as non-inclusion analogs, have with CD or its non-polymer derivatives. However, Shao
become the basis of gel inclusion chromatography. The et al. [235], studying the sorption of dyes on ECP arrived at
first example given by Solms and Egli [170] was illustra- contrasting conclusions. No clear correlation was observed
tive: they compared the interaction isotherms for two gels, between the performance of the gels and their respec-
Sephadex® and ECP with different solutes (aniline, ben- tive degree of cross-linking. They found that certain dye
zaldehyde, pyridine, nitrophenols). Great differences were molecules did not present specific interactions with ␤-
found in all these cases, confirming the inclusion charac- CD in the solution (no modification of the visible spectra)
ter of interactions with the CD polymer. It follows from the but they could still be adsorbed efficiently by ECP gel. The
shape of the isotherms of o- and p-nitrophenol that these authors explained that the sorption of dyes by gels was not
guest molecules cannot be separated on Sephadex, whereas due to the host–guest inclusion complex formation, but
the different inclusion interactions on the ECP support can mainly attributed to the sorption of dyes by the polymer
be used to advantage for their chromatographic separation network, independently of its degree of cross-linking.
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Crini [61,125] explained the mechanisms for the sorp- pollutant molecules depending on their chemical affinities,
tion of pollutants on ECP materials by the presence provided that the accessibility is not limited by excessive
of both physical sorption in the polymer network and cross-linking. Crini [125], Vélaz et al. [129], and García-
the formation of a host–guest inclusion complex, in Zubiri et al. [262] pointed out that both the inclusion within
accordance with the results of Szejtli et al. [186–189]. the CD cavities and the interaction with the network must
However, Crini [61,125] demonstrated that other interac- be considered, although, again, the low BET surface area
tions such as hydrogen bonding, hydrophobic interactions of polymers implies a negligible effect of physical sorp-
(pollutant–pollutant and polymer–pollutant interactions), tion onto the surface, as expected for gel-like sorbents.
aggregation mechanisms (in the presence of large dye The main role can be attributed to the presence of CD
molecules), and ion-exchange cannot be ignored, in partic- cavities. García-Zubiri et al. [263] recently showed that
ular when the ECP polymer is modified by reactive groups. the host–guest interaction of the adsorbate within the
Similar interpretations were recently reported by García- CD cavities corresponded to the hole-filling mechanisms
Zubiri et al. [262–264], Bonenfant et al. [243], and Pratt et al. considered in the dual-mode approach, while the poly-
[246]. For example, Bonenfant et al. [243] showed that the mer cross-linking networks are capable of entrapping more
sorption of nonylphenol ethoxylate in an ECP polymer can adsorbate molecules via partition. They demonstrated that,
be mainly associated with the formation of a very stable when the sorption was governed by the inclusion within
inclusion complex, but this complex was favored by the the CD moieties, a simple Langmuir isotherm fitted the
polymer network. The performance can be also explained data properly. The classic Freundlich equation was also
by the presence of hydrophobic van der Waals interactions appropriate when phenol was the adsorbate because its
formed between polymer and pollutant. Moreover, EPI can interaction with ␤-CD was less specific than that of 1-
enhance the sorption through the generation of chains at naphthol. Similar conclusions were reported by Fenyvesi
the surface of the polymer [124] that can contribute to et al. [194]. Pratt et al. [246] showed that the systematic
increasing the interaction between the gel and the pollu- variation of the experimental conditions, in particular the
tant molecules. Recently, Pratt et al. [246] concluded that CD and EPI composition, used in the synthesis of the mate-
the sorption of p-nitrophenol onto ECP polymers cannot rials provided an interesting detailed understanding of the
be unequivocally attributed to the formation of inclusion ECP polymer sorption mechanism with p-nitrophenol in
complexes with CD sites as there appears to be a synergis- solutions. A similar study was proposed by Liu et al. [248]
tic role of the network composed of glyceryl bridges and in the case of the removal of pesticides (bromacil, simazine,
dihydroxypropyl moieties formed from EPI in regard to the atrazine) by CD polymers.
material structure properties. These authors showed that
the content of the cross-linkages and side chains increases 4.5. Personal remarks
the sorption capacity and the material swellability, as well
as changes to the hydrophile–lipophile balance of the poly- A survey of the literature shows that large-scale appli-
mer. cation of CDs and their derivatives has been made possible
Recently, Liu et al. [248], studying sorption of pesti- by their ease of manufacture and their lack of toxicity.
cides onto CD-based polymers by multivariate regression Cyclodextrins have found applications in the pharma-
analysis, pointed out the main role of CD units. Li et al. ceutical, agrochemical, and food industries as well as in
[166,249–251] also suggested that the sorption of phenolic cosmetics, toiletries, and chemistry. Except for commercial
compounds onto ECP particles was mainly due to the for- applications in analytical chemistry and chromatography,
mation of inclusion complexes between the hydrophobic CDs and CD-based polymers have failed, however, to find
cavities of CD molecules and organic solutes in water. Based practical application in wastewater treatment at the indus-
on kinetic measurements, they suggested that the rate- trial scale.
limiting step may be chemisorption. However, the polymer Nevertheless, the increasing number of publications
structure was also important in the data interpretation. on pollutant removal using cyclodextrin-based materials
Moon et al. [259–261] pointed out the role of both molecu- shows that there is a growing interest in the develop-
lar inclusion and chemical interactions (hydrogen bonding, ment of new materials used in wastewater treatment.
etc.). Although their higher cost compared to that activated car-
It is now accepted that sorption of organic solutes in bon is a drawback, the usefulness of ECP resins in water
cross-linked polymers can occur by two main mechanisms: and wastewater treatment applications arises from sev-
hole-filling of the CD cavities and partition in the poly- eral advantages: ease of synthesis (ECP and ECP derivatives
mer network. The first interaction (i.e. inclusion complex) are commercial products), ease of regeneration, the pos-
is clearly influenced by the compatibility between the sibility of tailoring for special applications, and the high
adsorbate and the cavity of the cyclodextrin [1,23,129]. sorption capacity and selectivity with targeted pollutants.
This is a key factor for determining the amount adsorbed For sorption-oriented processes, ECP materials could rep-
by this mechanism, although the influence of the poly- resent an interesting alternative. However, most of these
mer structure should not be disregarded, in particular for publications are not directly practice-oriented and com-
larger pollutants that cannot be totally included within mercial ECP sorbents have not yet been significantly used
the cavities. The importance of the partition mechanism in this domain even though they possess some other advan-
in the sorption process can be tailored by choosing the tages such as easier regeneration over currently available
appropriate cross-linking agent [61,263]. The other cavi- carbon and organic resins for pollutant removal. Perhaps
ties formed by the cross-linking bridges will also entrap one reason why ECP sorbents have not been widely used
ARTICLE IN PRESS
G Model
in industry is the lack of knowledge about the engineer- difficult due to differences in materials and methodolo-
ing of such materials. We think that, for novel sorbents gies. Research into new materials is often focused on their
to be accepted by industry, it will be necessary to adopt technical performance, while economic aspects are usually
a multidisciplinary approach in which chemists, biologists, neglected. ECP for wastewater treatment are basically at
microbiologists, polymerists and engineers work together. the stage of laboratory-scale study and much work is nec-
From the polymer chemist’s point of view, research essary to demonstrate their possibilities on an industrial
needs to look into the precise role of the polymer network. scale.
Though a number of ECP materials with various structures
and properties have been proposed for pollutant removal,
it is still ambiguous how ECP characteristics affect sorption Acknowledgments
affinity toward pollutants, not only in single solution but
also and particularly in multi-pollutant mixtures. Work is The authors thank Bertrand Sancey (University of
also required for a better understanding of sorption mech- Franche-Comté, France), Peter Winterton (University of
anisms. There is no doubt that the formation of an inclusion Toulouse III, Toulouse, France), Giuseppe Trunfio (Univer-
complex due to ˇ-CD molecules through host–guest inter- sity of Messine, Italy), and Corina Bradu (University of
actions plays an important role in the performance of Bucarest, Romania) for their critical reading of this review
the polymer network. However, other interactions such as and their comments on earlier versions of the manuscript,
hydrogen bonding, hydrophobic interactions, electrostatic the three reviewers for their numerous remarks, and grate-
forces and acid–base interactions between the (modified) fully acknowledge the financial support of the Agence de
polymer network and the pollutant as well as physical sorp- l’Eau Rhône-Méditerranée & Corse (Metaldex Project 2009-
tion are also involved. This latter point is a further area 2012).
of debate since ECPs possess low surface areas. Very lim-
ited information is also available on the regeneration of
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ARTICLE IN PRESS

Progress in Polymer Science xxx (2012) xxx–xxx

Contents lists available at SciVerse ScienceDirect

Progress in Polymer Science

Environmental applications of water-insoluble

∗ Corresponding author. Tel.: +33 3 81 66 57 01; fax: +33 3 81 66 57 97.

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4.2. A recent review of the literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction natural molecules derived from starch [11,12]. These sub-

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Sorbent Pollutants References

Activated carbon Phenolic compounds [28]

2. General considerations Cyclodextrins (CDs) or cycloamyloses are cyclic

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Fig. 2. Non-conventional sorbents for the removal of pollutants from wastewater.

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of application of CDs is separation science. As already

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Table 2 conclusions were previously reported by Fenyvesi et al.

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CH2O CH2 CHOH CH2O

Fig. 8. A possible structure of a water-insoluble ␤-cyclodextrin–epichlorohydrin polymer.

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Cross-linking agent Reference(s) Sorbent Surface area (in Reference

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Country Corresponding author Contaminant(s) Reference(s)

Canada Evans CH 2-naphthol [241,242]

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p-Nitrophenol ECP m = 0.2; V = 7; pH 4.6; CT = 1440; 22 ◦ C 387 ␮mol g−1 [246]

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