Langmuir 2005, 21, 10735-10742 10735

Structure of a Cyclodextrin Functionalized Anionic Clay:

XRD Analysis, Spectroscopy, and Computer Simulations
L. Mohanambe and S. Vasudevan*
Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Bangalore-560012, India

Received March 8, 2005. In Final Form: August 8, 2005

Carboxy-methyl β-cyclodextrin (CMCD) cavities have been intercalated within the galleries of anionic
clay, Mg-Al layered double hydroxide (LDH). The cyclodextrin functionalized LDH has been reported to
adsorb neutral and nonpolar guest molecules. X-ray diffraction, IR, and Raman vibrational spectroscopy
and 13C CPMAS NMR have been used to characterize the confined CMCD molecules, whereas molecular
dynamics simulations have been used to probe the interlayer arrangement and orientation of the intercalated
species. Spectroscopic measurements as well as MD simulations show that there is no significant change
in the geometry of the CMCD cavity on intercalation. Within the galleries of the anionic clay, the CMCD
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anions are arranged as bilayers with the carboxy methyl substituents, located at the narrower opening
of the bucket-like cyclodextrin toroid, anchored to the LDH sheet. This arrangement leaves the wider
opening of the CMCD anion facing away from the layers allowing the interior of the cyclodextrin cavity
to be accessible to guest molecules. Finally, the hydrophobicity of the anchored cyclodextrin cavity has been
Downloaded via BIBCNRS INC on September 2, 2019 at 08:48:41 (UTC).

characterized using fluorescence from pyrene included within it.

Introduction phates,8 and layered double hydroxides9 to create a new

Lamellar inorganic solids in which guest molecules and
ions access interlamellar sites via the intercalaltion
reaction have been widely recognized as offering a unique
route for the design of hybrid materials. Examples of such
solids are widespread; they include the phyllosilicate clays,
the layered double hydroxides, the divalent metal thio-
phosphates, and metal (IV) phosphates and phospho-
nates,1,2 all of which have the ability to act as hosts for
a variety of organic and inorganic guest species. In a
majority of these solids the interaction between host and
guest is Coulombic, with the guest species compensating
for the charge deficit, either positive or negative, of the
inorganic layer. The subsequent host-guest chemistry of
these intercalated solids is restricted to exchange of the
interlamellar charged species for other ions and, to a
limited extent, adsorption of polar molecules, e.g., crown
ethers3 and poly(ethylene oxide),4,5 through ion-dipole
interactions.
Host structures are, of course, not limited to inorganic
solids, a variety of organic hosts are known, the most well-
known of which are the crown ethers, cyclodextrins,
calixarenes, and spherands.6 In principle if the two host
structures, the layered inorganic solid and the organic
host, can be integrated, a new family of host structures
can be envisaged. Indeed such structures have been
realized; modified cyclodextrins have been successfully
intercalated in montmorillonite clays,7 zirconium phos-
* To whom correspondence should be addressed. E-mail:
svipc@ipc.iisc.ernet.in.
(1) Intercalation Chemistry; Whittingham, M. S., Ed.; Academic
Press: New York, 1982.
(2) Alberti, G.; Costantino, U. In Comprehensive Supramolecular
Chemistry Alberti, G., Bein, T., Atwood, J. L., Eds.; Wiley: Chichester,
U.K., 1996; Vol. 7, p 1.
(3) Gluech, D. S.; Brough, A. R.; Mountford, P.; Green, M. L. H. Inorg.
Chem. 1993, 32, 1893.
(4) Aranda, P.; Hitzky, R. Adv. Mater. 1990, 2, 545.
(5) Jeevanandam, P.; Vasudevan, S. Chem. Mater. 1998, 10, 1276.
(6) (a) Vogtle, F. Supramolecular Chemistry; Wiley: Chichester, U.K.,
1991. (b) Steed, J. W.; Atwood, J. L. Supramolecular Chemistry; Wiley:
Chichester, U.K., 2000.
(7) Kijima, T.; Tanaka, J.; Goto, M.; Matsui,Y. Nature 1984, 310, 45.
generation of host structures. Cyclodextrins, herein
abbreviated as CD, are cyclic oligomers of d-gluco-
pyranose (C6H10O) with cylindrical hydrophobic cavities
into which a variety of small molecules may be intro-
duced.
Layered double hydroxides (LDH), the so-called anionic
clays, consist of positively charged brucite-like layers and
interlamellar exchangeable anions.10 Hydrotalcites are
LDH with the chemical composition [Mg1-xAlx(OH)2]x+-
[An-]x/n‚mH2O (Mg-Al-LDH) that consists of positively
charged layers constructed from edge sharing Mg(OH)6
and Al(OH)6 octahedra.11-14 The positive charge of the
layers is compensated for by interlayer anions that are
usually hydrated. The interlayer anion can be exchanged
for other inorganic or organic anions thus imparting new
functionality to the Mg-Al LDH. It is this anion-exchange
capability of the LDHs that has been investigated for many
years. They have been used as catalysts and catalyst
precursors, sorbents and scavengers for halogens and weak
acids15-19 and more recently for storing and delivering
biologically active materials.20,21 The guest species, how-
ever, have, of necessity, to be anions for charge neutrality
to be preserved and as a consequence the host-guest
(8) Kijima, T.; Matsui, Y. Nature 1986, 322, 533.
(9) (a) Zhao, H.; Vance, G. F. J. Chem. Soc., Dalton Trans. 1997, 11,
1961. (b) Zhao, H.; Vance, G. F. J. Inclusion Phenom. 1998, 316, 305-
317. (c) Zhao, H.; Vance, G. F. Clays Clay Miner. 1998, 46, 712.
(10) Khan, I. K.; Hare,D. O. J. Mater. Chem. 2002, 12, 3191.
(11) Constantino, V. R. L.; Pinnavaia, T. J. Inorg. Chem. 1995, 34,
883.
(12) Miyata, S. Clays Clay Miner. 1977, 25, 14.
(13) Miyata, S. Clays Clay Miner. 1983, 31, 305.
(14) Miyata, S. Clays Clay Miner. 1975, 23, 369.
(15) De Roy, A.; Forano, C.; El Malki, K.; Bessi, J. P. In Expanded
Clays and Other Microporous Solids; Occelli, M. L., Robson, H. E., Eds.;
Van Nostrand Reinhold: New York, 1992; Vol. 2, p 108.
(16) Cavani, F.; Trifiró, F.; Vaccari, A. Catal. Today 1991, 11, 173.
(17) Newman, S.; Jones, W. New J. Chem. 1998, 22, 105.
(18) Vaccari, A. Appl. Clay Sci. 1999, 14, 161.
(19) Rives, V.; Ulibarri, M. Coord. Chem. Rev. 1999, 181, 61.
(20) Choy, J. H.; Kwak, S. Y.; Park, J. S.; Jeong, Y. J.; Portier, J. J.
Am. Chem. Soc. 1999, 121, 1399.
(21) Choy, J. H.; Kwak, S. Y.; Jeong, Y. J.; Park, J. S. Angew. Chem.,
Int. Ed. 2000, 39, 4042.

10.1021/la050628t CCC: $30.25 © 2005 American Chemical Society

Published on Web 09/24/2005
10736 Langmuir, Vol. 21, No. 23, 2005
chemistry of the LDHs is limited to ion exchange reactions.
Insertion of neutral, nonpolar, or poorly water-soluble
guest molecules is not possible. However, when the
internal surface of an Mg-Al LDH is functionalized by
intercalating the anionic carboxy-methyl derivative of
β-cyclodextrin it was found that the Mg-Al LDH could
retain a variety of aromatic molecules22 and organometallic
molecules23 as well as adsorb iodine from vapor as well
as from polar and nonpolar solutions.24 Functionalization
has resulted in the extension of the host-guest chemistry
of the anionic clay, from simple ion-exchange reactions to
the inclusion of nonpolar inorganic and organic molecules.
The cyclodextrin-LDH hybrid provides a combination of
the best of both worlds; the host-guest chemistry of the
organic cyclodextrin cavity with the mechanical and
thermal robustness of the lamellar inorganic host.
Understanding the properties as well as exploiting the
chemistry of the functionalized Mg-Al LDH requires a
detailed knowledge of the arrangement and orientation
of the intercalated β-cyclodextrin cavities within the
galleries of the layered host. Traditionally powder X-ray
diffraction has been the technique of choice for probing
the interlayer arrangement of guest molecules in inter-
calation compounds. The arrangement is inferred from
the interlayer separation and geometrical considerations
assuming that the guest molecule is rigid and has the
same geometry as that outside the layers. The use of
computer simulations has greatly augmented our present
understanding of the orientation and organization of
interlamellar guest molecules. Molecular dynamics pro-
vides a powerful technique to probe the structural and
dynamic properties at a molecular level and offers a direct
connection between local structural details and experi-
mental measurements. In particular, simulations are well
suited for the study of intercalated guest molecules.25 MD
simulations and energy minimization have been used to
study the Mg-Al LDH crystal structure26 and to predict
the interlayer arrangement of intercalated halide ions27
as well as the influence of layer charge and hydration on
the orientation of organic guest molecules.28,29 In the
present study, we have used experimental measurements
and computer simulations to probe the interlayer ar-
rangement of carboxy-methyl derivatized β-cyclodextrin
cavities intercalated in hydrotalcite. Vibration (IR and
Raman) and 13C NMR spectroscopy have been used to
establish the extent of change in structure and geometry
of the β-cyclodextrin cavities on intercalation, whereas
MD simulations have been used to understand the
orientation and arrangement of the intercalated β-cyclo-
dextrin cavities that account for the observed X-ray
interlayer spacing. The combination of experimental
measurements with MD simulations has allowed us to
obtain a molecular level description of the organization
of β-cyclodextrin cavities in the galleries of the Mg-Al
LDH. Finally, we characterize the hydrophobicity of the
(22) Mohanambe, L.; Vasudevan, S. J. Phys. Chem. B 2005, 109,
11865.
(23) Mohanambe, L.; Vasudevan, S. Inorg. Chem. 2005, 44, 2128.
(24) Mohanambe, L.; Vasudevan, S. Inorg. Chem. 2004, 43, 6421.
(25) (a) Zeng, Q. H.; Yu, A. B.; Lu, G. Q.; Standish R. K. J. Phys.
Chem. B 2004, 108, 10025-10033. (b) Miroslav, P.; Pavla, C.; Dagmar,
M.; Zdenek M.; Josef, S. J. Colloid Interface Sci. 2001, 236, 127-131.
(26) Jianwei, W.; Andrey, G. K.; Kirkpatrick, R. J.; Xiaoqiang, H.
Chem. Mater. 2001, 13, 145-150
(27) Andrey, G. K.; Kirkpatrick, R. J.; Randall, T. C. Am. Mineral.
2000, 85, 1046-1052.
(28) Newman, S. P.; Samuel, J. W.; Coveney, P, V.; Jones, W. J. Phys.
Chem. B 1998, 102, 6710-6719.
(29) Newman, S. P.; Cristina, T. D.; Coveney, P, V.; Jones, W.
Langmuir 2002, 18, 2933-2939.
Mohanambe and Vasudevan
intercalated β-cyclodextrin cavity using the fluorescence
of pyrene molecules included in the intercalated cavity.
Experimental Section
Preparation and Characterization. Mg1-xAlx(OH)2(NO3)x
[LDH-NO3] was prepared by coprecipitation by dropwise ad-
dition of known volumes of aqueous Mg(NO3)2 (0.04 M) and Al-
(NO3)3 (0.02 M) into NaOH at a constant pH of 8, under N2
atmosphere, following the procedure reported by Meyn et al.30
The resulting white precipitate was aged for 24 h prior to washing
with de-carbonated water. The intercalation of β-cyclodextrin
cavities within the Mg-Al LDH was achieved by ion-exchanging
the NO3- ions in Mg1-xAlx(OH)2(NO3)x with methyl-carboxylate
derivatized β-cyclodextrin ions. The sodium salt of carboxy-methyl
β-cyclodextrin, C42H70-nO35(CH2COONa)n (CMCD) was obtained
from Cerestar Company (Hammond, IN). The average number
of carboxylate groups per β-CMCD molecule, as established by
pH titrations, is 3.8. The ion-exchange intercalation of β-CMCD
in the Mg-Al LDH was effected following the procedure of ref
9. A total of 100 mg of Mg-Al LDH-NO3 was added to 10 mL
of 10 mM of aqueous β-CMCD solution at 65 °C and stirred for
24 h. Completion of the intercalation of the β-CMCD was
confirmed by the absence of 00l reflections with basal spacing
8.9 Å, characteristic of Mg-Al LDH NO3, in the powder X-ray
diffraction and the appearance of a new set of 00l reflections
with a basal spacing of 24.5 Å. Completion of the ion exchange
was also verified by the absence of the bands due to the NO3-
ion in the infrared and Raman spectra and the presence of bands
due to the carboxylate (COO-) anion of the intercalated β-CMCD.
The β-CMCD stoichiometry in the Mg-Al LDH was established
from C, H, and N elemental analysis (C%)18.9, H%)5.06) and
also by estimation of the un-exchanged β-CMCD in the reactant
solution. The composition of the starting Mg-Al LDH-NO3 was
Mg0.7Al0.3(OH)2(NO3)0.3 and of Mg-Al LDH-CMCD was Mg0.7-
Al0.3(OH)2(CMCD)0.073.
The themogravimetric analysis (TGA) showed a two-step
weight loss (see the Supporting Information). There is a ∼8%,
weight loss at ∼ 80°C that probably corresponds to water sticking
on the exterior of the crystallites. The second weight loss at ∼
300°C is due to the decomposition of the intercalated carboxy-
methyl β-cyclodextrin. The Na salt of CMCD decomposes at 270°C.
Between 80°C and 250°C there is a gradual weight loss (∼7%),
which may be due to interlamellar water. The intercalated Mg-
Al LDH-CMCD is stable on exposure to the atmosphere as well
as moisture and the intercalated β-CMCDs are no longer
exchangeable e.g. with carbonate ions. The strong affinity of
carbonate for LDH is well-known and the absence of exchange
is evidence for the anchoring of the β-CMCD cavities.
Measurement Techniques. Powder X-ray diffraction pattern
of Mg-Al LDH-NO3 and Mg-Al LDH-CMCD was recorded on
a Shimadzu XD-D1 X-ray diffractometer using Cu KR radiation
of λ 1.54 Å. The samples were mounted by pressing the powders
on a glass plate, and the data was collected at a scan speed of
2° 2θ/min. FT-IR spectra were recorded as KBr pellets on a Bruker
IFS55 spectrometer operating at 4 cm-1 resolution. FT-Raman
spectra were recorded on a Bruker IFS FT-Raman spectrometer
using an Nd:YAG (λ ) 1064 nm) laser for excitation. Spectra
were recorded at a resolution of 4 cm-1 with an unpolarized beam
using an Al sample holder. Laser power was kept at 150 mw. 13C
cross-polarization magic angle spinning (CP-MAS) NMR was
recorded on a Bruker DSX-300 solid-state spectrometer at a
Larmor frequency of 75.46 MHz with a contact time of 1 ms. The
spectra were externally referenced to tetramethylsilane (TMS).
Mg/Al ratios in the LDH were determined by inductively coupled
plasma spectroscopy (Jobin Yvon JY24). CHN analysis was
performed on a CHNS (CARLO ERBA) elemental analyzer.
Fluorescence spectra were recorded on a Perkin-Elmer LS50B
model, with excitation and emission slit-widths of 5-10 nm and
a scan speed of 60 nm/min. TGA were recorded on a Perkin-
Elmer-Pyris-Diamond thermo gravimetric/differential thermal
analyzer (TG/DTA) system in flowing air.
(30) Meyn, M.; Beneke K.; Lagaly, G. Inorg. Chem. 1990, 29, 5201.
Structure of an Anionic Clay
Simulation Methods
Simulations were performed using either the Cerius2
or Materials Studio software packages31 running on SGI
machines. The first step in the simulation was the
preparation of the positively charged Mg-Al LDH layers.
The hydroxide layers were constructed using atomic
coordinates from the previously reported crystal structure
of hydrotalcite,32 [Mg4Al2(OH)12](CO3)‚3H2O, whose X-ray
crystal structure had been refined in a rhombohedral unit
cell with space group R3m and lattice parameters a ) b
) 3.05 Å and c ) 22.81 Å. The interlayer carbonate ions
and water were removed from the hydrotalcite structure,
and a super cell was constructed containing 50 hydrotalcite
crystallographic unit cells. The super cell parameters were
a ) 15.275, b ) 15.275, c ) 60.00 Å; R ) 90.0, β ) 90.0,
γ ) 120.0°, (equivalent to 5 × 5 hydrotalcite unit cells in
the ab plane and a two layer repeat with an initial
interlayer spacing of 30 Å). Unit cell parameters were
chosen considering the fact that the area of a unit cell of
hydrotalcite is 8 Å2 and the area of the β-cyclodextrin
around 200 Å2. The Mg/Al ratio was adjusted to 2.12 so
that each hydroxide layer contains 17Mg2+ and 8Al3+
atoms with the constraint that Al3+ ions did not occupy
adjacent octahedra. The composition of the Mg-Al LDH
supercell was thus [Mg68Al32(OH)128]32+. Instead of placing
full formal charges on the Mg and Al ions, charges were
averaged over the atoms of the Mg-Al LDH layer using
the charge equilibration method.33 The partial charges
are +0.64 for Mg, +1.3 for Al, -0.605 or -0.59 for O, and
+0.19 or +0.17 for H depending on the environment of
the atom. Although there is no X-ray crystallographic
evidence for long range ordering of Al3+ ions in the
hydrotalcite structure, we were forced to assume complete
ordering because of the periodic boundary condition
imposed on the simulation super cell and the fact that
partial occupancy was disallowed. Except for periodic
boundary conditions, no symmetry constraints were
imposed. The structure was treated as triclinic (P1), and
all lattice parameters were treated as independent
variables in the simulation.
The CMCD guest anions were constructed starting from
the β-cyclodextrin molecule (built using crystal data from
PDB entries).34 The primary hydroxyl groups present on
the narrow side of the β-cyclodextrin molecule are more
reactive than the secondary hydroxyl groups present on
the wider rim.35 Hence, four of the seven primary hydroxyl
groups of the β-cyclodextrin were substituted randomly
by carboxy-methyl groups. The as-built β-CMCD anion
with formal charge of -4 was energy minimized using a
modified version of the Dreiding force field36 with partial
atomic charges calculated using the charge equilibration
method.33 The energy minimized β-CMCD structure was
found to be slightly distorted from that of β-cyclodextrin.
The bond lengths are identical, but the bond angles show
small deviations from those for β-cyclodextrin (see the
Supporting Information) leaving the openings of the
cyclodextrin cavity noncircular. This deviation is a con-
sequence of the fact that the placement of the carboxy-
(31) Cerius2, version 4.2; Accelrys: San Diego, CA, 2001. Materials
Studio Modeling, version 3.1.0.0; Accelrys Software Inc: San Diego,
CA, 2004.
(32) Bellotto, M.; Rebours, B.; Clause, O.; Lynch, J.; Bazin, D.; Elkaim,
E. J. Phys. Chem. 1996, 100, 8527-8534.
(33) Rappe, A. K.; Goddard, W. A., III. J. Phys. Chem. 1991, 95, 3358.
(34) Lindner, K.; Saenger, W. Carbohydr. Res. 1982, 99, 103.
(35) Szejtli, J. Cyclodextrins and Their Inclusion Complexes; Aka-
demiai Kiado: Budapest, 1982.
(36) Mayo, S. L.; Olafson, B. D.; Goddard, W. A., III. J. Phys. Chem.
1990, 94, 8897-8909.
Langmuir, Vol. 21, No. 23, 2005 10737
methyl substituents on the narrower opening of the
β-CMCD cavity is not symmetric.
An integral number of the appropriate β-CMCD anions
were then introduced between the Mg-Al LDH layers
such that overall charge neutrality was maintained. In
each case, the β-CMCD molecules were placed in the
galleries with their longest axis (passing through the
center of the β-cyclodextrin cavity) oriented approximately
parallel to the interlayer normal in a bilayerlike arrange-
ment. Thermogravimetric measurements of the Mg-Al
LDH CMCD hybrids did not indicate any significant
change in weight between 100 and 150 °C due to loss of
water. Consequently, interlamellar water molecules were
not introduced in the simulation of the Mg-Al LDH-
CMCD hybrid. Simulations were also initiated with the
CMCD anions oriented with their axis perpendicular to
the interlayer normal and displaced to different degrees
from the center of the gallery (see the Supporting
Information). These models are unable to reproduce the
experimentally determined interlayer spacing and hence
were discarded.
The total nonbonded potential interaction energy of the
simulated system consisted of long-range Coulombic
interactions between partial atomic charges and van der
Waals interactions, computed using the Ewald summation
technique. Short-range repulsive van der Waals interac-
tions were treated with a direct cutoff radius of ap-
proximately 8 Å. The potential energy due to bonded
interactions was computed using a modified version of
the Dreiding force field. The modification due to Newman
et al.37 includes additional parameters for Mg and has
been shown to reproduce the experimental structure of
the Mg-Al LDH layer during simulations well as being
applicable to the organic moiety.
Molecular dynamics simulations were performed on a
constant composition, isothermal-isobaric (NPT) en-
semble at 300 K.38 A time-step of 0.001 ps was used.
Temperature was maintained using the Hoover thermo-
stat39 implemented with a relaxation time of 0.1 ps and
a cell-mass pre-factor of unity.40 The equivalent hydrostatic
pressure was set to 0.0001GPa (approximately 1 atm).
Periodic boundary conditions were applied in three
dimensions so that the simulation cell is effectively
repeated infinitely in each direction.41 Total simulation
time ranged was 100 ps. The results showed that equi-
librium values for the crystallographic parameters and
thermodynamic quantities such as the potential energy
were generally reached within the first 15-20 ps. Equi-
librium values of the lattice parameters were judged to
have been reached when these quantities fluctuate around
their average values, which remain constant over time.
Equilibrium values of the lattice parameters and ther-
modynamic quantities were also checked by repeating the
simulations with a different starting orientations of the
inter-lamellar CMCD anions as well as interlayer spacing.
Convergence to similar conformations and properties from
different initial values is a good indicator that equilibrium
has occurred.
(37) Newman, S. P.; Greenwell, H. C.; Coveney, P. V.; Jones, W. In
Computer simulation of layered double hydroxides - Layered Double
Hydroxides: Present and Future; Rives, V., Ed; Nova Science: New
York, 2001.
(38) Haile, J. M. Molecular Dynamic Simulation: Elementary
Methods; Wiley-Interscience: New York, 1992.
(39) Hoover, W. H. Phy. Rev. A 1985, 31.
(40) User guide, Cerius2, version 4.2; Accelrys: San Diego, CA, 2001.
(41) Allen, M. P.; Tildesley, D. J. In Computer simulation of Liquids;
Oxford University Press: New York, 1987; p 385.
10738 Langmuir, Vol. 21, No. 23, 2005 Mohanambe and Vasudevan

Figure 1. X-ray diffraction patterns of (a) Mg-Al LDH-NO3 (I) and Mg-Al LDH-CMCD (II). (b) Plot of 1/00l reflection vs d
spacing. The dashed line is the least-squares fit to a straight line.

Figure 2. (a) Structure of β-CMCD molecule and (b) possible orientations of CMCD molecules within the Mg-Al LDH galleries.

Results and Discussion of the truncated cone41 (Figure 2). This would increase
the effective torus thickness depending on the orientation
X-ray Diffraction. The X-ray diffraction patterns of
of the carboxy-methyl groups. (Choy et al.,42 however, have
Mg-Al LDH NO3 and Mg-Al LDH-CMCD are as shown
considered substitution of the secondary hydroxyl groups
in Figure 1a. Because of the layered nature of the
located on the wider rim of the β-CD cavity.) It is, in
intercalated Mg-Al LDH compounds the crystallites
principle, possible to deduce the arrangement of the
exhibit a pronounced preferred orientation, consequently
intercalated β-cyclodextrin cavities from the observed
only 00l reflections are seen in the XRD patterns. The 00l
interlayer spacing and the molecular dimensions of the
reflections may be indexed with a interlayer spacing of
CMCD molecule. For CMCD molecules intercalated in
24.5 Å (Figure 1b). The ion-exchange intercalation of
Mg-Al LDH, more than one type of arrangement appears
β-CMCD, with an average degree of carboxy-methyl
to satisfy the X-ray lattice spacing (Figure 2). In the earliest
substitutions of 3.8 per β-cyclodextrin molecule, in Mg0.7-
report, Vance et al.9 had proposed two different arrange-
Al0.3(OH)2(NO3)0.3 occurs with an increase in the interlayer
ments; a monolayer with the β-CD axis perpendicular to
lattice spacing from 8.9 to 24.5 Å (Figure 1a). The thickness
the interlayer normal and a bilayer arrangement with
of brucite-like layer of the Mg-Al LDH is 4.8 Å. The lattice
the axis parallel to the normal. For carboxy-ethyl β-cy-
dilation on intercalation, therefore, corresponds to a
clodextrin cavities intercalated in Zn-Al LDH, too, two
separation of the brucite layers by 19.7 Å. The observed
different arrangements had been proposed.42 The authors,
lattice spacing for the β-cyclodextrin intercalated in Mg-
however, rule out the perpendicular arrangement based
Al LDH is similar to that reported by Vance et al.,9 who
on stoichiometric considerations and the area occupied
had found lattice spacing values ranging from 20.63 to
by each molecule. In these models it has been assumed
26.8 Å, depending on the degree of carboxy-methyl
that the geometry, and hence molecular dimensions, of
substitution. The reported lattice spacing for the carboxy-
the CMCD molecules are unaffected on intercalation.
ethyl substituted β-cyclodextrin intercalated in Zn-Al
Additionally, deduction of the arrangement of the inter-
LDH is 27.2 Å.42
calated CMCD molecules from lattice spacing values would
The β-cyclodextrin molecule may be considered as a also require a reasonable estimation of the increase in
truncated cone with an approximate torus thickness of dimension of the β-CD molecule on substitution of the
7.8 Å.43 The outer diameter of the wider end of the cone hydroxyls by carboxy-methyl groups.
is 15.4 Å, whereas that of the narrower end is 7.8 Å. The
carboxy-methyl groups are attached by substitution of (43) (a) Connors, K. A. In Comprehensive Supramolecular Chemistry;
the primary hydroxyl groups located at the narrower end Szejtli, J., Osa, T., Eds.; Wiley: Chichester, U.K., 1996; Vol. 3, p 234.
(b) Szejtli, J. In Comprehensive Supramolecular Chemistry; Szejtli, J.,
Osa, T., Eds.; Wiley: Chichester, U.K., 1996; Vol. 3, p 17. (c) Szejtli, J.
(42) Choy, J. H.; Jung, E. Y.; Son, Y. H.; Park, M. J. Phys. Chem. In Comprehensive Supramolecular Chemistry; Szejtli, J., Osa, T., Eds.;
Solids 2004, 65, 509. Wiley: Chichester, U.K., 1996; Vol. 3, p 12.
Structure of an Anionic Clay
Figure 3. 13C solid-state CP-MAS NMR spectra of (a) Na salt
of CMCD and (b) Mg-Al LDH-CMCD.
Spectroscopy. 13C NMR. The 13C CP-MAS NMR
spectra of CMCD and Mg-Al LDH-CMCD are as shown
in Figure 3 along with the assignment of the resonances.
The 13C resonance of the carboxylate group appearing at
179 ppm in the spectra of the sodium salt of CMCD shifts
to 181 ppm in the Mg-Al LDH-CMCD hybrid. This shift
indicates that the carboxylate groups of the β-CMCD are
now in a different environment (intercalated in the Mg-
Al LDH galleries). The resonance positions of the carbon
atoms of the gluco-pyranose ring of the β-cyclodextrin
molecule are unaffected on intercalation.
Infrared Spectroscopy. The FT-IR spectra of CMCD and
Mg-Al LDH-CMCD are as shown in Figure 4, and the
peak positions and their assignments are given in Table
1. The spectra recorded at 60 K was identical indicating
the absence of any temperature dependence. As may be
seen from Figure 4, the positions of most bands show no
change on intercalation. The positions of the main features
of the spectra, the C-H stretch at 2929 cm-1, the C-O
stretch at 1162 cm -1, and the C-C stretch at 948 cm-1,
are all unaffected on intercalation. The bands that do show
change are the C-O stretch of the carboxylate group and
the bands associated with the -CH2OH group. The C-O
shows a small shift on intercalation; it appears at 1605
cm-1 in the sodium salt of CMCD and 1595 cm-1 in Mg-
Al LDH-CMCD. The bands appearing between 800 and
580 cm-1 that have been assigned to internal rotational
modes of the -CH2OH group also show small shifts in
their position ranging from 5 to 8 cm-1 on intercalation.
Similar shifts are also observed for the bands between
580 and 500 cm-1 that have been assigned to a combination
of the -CH2OH internal rotation modes with the C-C-O
bending modes.44 The layer metal-hydroxyl (M-OH)
stretching modes appear at 444 and 673 cm-1.
Raman Spectra. The FT-Raman spectra of CMCD and
Mg-Al LDH-CMCD are shown in Figure 5, and the peak
positions and their assignments are shown in Table 1. As
in the case of the infrared spectra, the positions of most
Raman bands are unaffected on intercalation and show
(44) Hineno, M. Carbohydr. Res. 1977, 56, 219.
Langmuir, Vol. 21, No. 23, 2005 10739
Figure 4. Infrared spectra of (a) Na salt of CMCD and (b)
Mg-Al LDH-CMCD.
no temperature dependence. The Raman and infrared
spectra allow for the characterization of the linkage
between the gluco-pyranose units but the Raman has the
advantages that the modes associated with these bonds
are fairly intense.45 These modes are the equatorial C-H
deformation (at the R linkage) appearing at 847 cm-1 and
the linkage C-O-C stretch modes at 920 and 950 cm-1
(these modes are indicated in Figure 5). It may be seen
that the positions of these modes do not change on
intercalation. The features below 600 cm-1 due to skeletal
ring vibration modes of the gluco-pyranose units are also
unaffected.
To summarize, the NMR and vibrational spectra
indicate that the structural integrity of the β-cyclodextrin
cavity is preserved on intercalation in the Mg-Al LDH.
The absence of any significant change in the positions of
the vibrational modes of the gluco-pyranose units as well
as in their linkages in the infrared and Raman spectra
suggests that the geometry of the intercalated β-cyclo-
dextrin cavity is essentially the same as that outside the
layers.
Computer Simulations. A snapshot of the simulation
supercell of the carboxy-methyl β-cyclodextrin cavities in
the galleries of Mg-Al LDH following 100 ps of simulation
is shown in Figure 6. Lattice parameters were obtained
by averaging over the last 10 ps of the simulation at which
time thermal equilibration was determined to be reached
by the constancy of the potential energy of the system and
the interlayer spacing.
The in-layer unit cell parameters show little change
from the starting unit cell values. The average interlayer
spacing obtained from simulation studies 24.62 Å is in
reasonable agreement with the experimental value 24.5
Å The snapshots shows that the CMCD anions in the
galleries are arranged as perpendicular bilayers and are
anchored to the Mg-Al LDH layers via the four carboxy-
methyl groups. Adjacent CMCD anions are closely packed
with the wider opening of the β-CD cavity away from the
(45) Tu, A. T.; Lee, J.; Milanovich, F. P. Carbohydr. Res. 1979, 76,
239.
10740 Langmuir, Vol. 21, No. 23, 2005 Mohanambe and Vasudevan

Table 1. Infrared and Raman Band Assignments of CMCD and Mg-Al LDH-CMCD
IR Raman
CMCD LDH-CMCD CMCD LDH-CMCD
(cm-1) (cm-1) assignments γ (cm-1) (cm-1) assignments γ
3475 ∼3400 O-H stretch 2911 2911 C-H stretch
2929 2927 C-H stretch 2939 2939 C-H stretch
1605 1595 C-O stretch of -COO 1455 1455 C-H bending
1456, 1419, 1326, 1454, 1419, 1326, O-C-H, C-C-H, C-O-H 1411, 1387, 1409-1417, C-C stretch, C-O-H bend,
1245, 1205 1245, 1205 bending (coupled modes) 1337 1387,1339 CH2 deformation
(coupled modes)
1161 1162 C-O stretch 1130, 1106, 1130, 1111, C-O-H stretch, OH deformation,
1089, 1047 1085,1047 C-C skeletal stretch
(coupled vibrations)
947 948 C-C stretch 920, 950 924, 930, 949 C-O-C stretch of
R-D-(1 f 4)-linkages
757, 709, 608, 579 796, 762, 615, 581 internal rotation modes 847 847, 858 C-H bending (equatorial) w
about CH2OH (side) [R linkage]
508, 537w 513w, 531w, 557 internal rotation modes
about CH2OH (side) +
C-C-O bending modes
444, 673 M-OH stretch <600 <600 CD-ring vibrations

layer. The cavity openings on opposite sides of the bilayer

are not in registry but are randomly positioned.
The structures of the anchored CMCD cavities, obtained
from simulations, have been compared with the structure
outside the layers in Figure 7. In Figure 7, the structure
on the left is the energy minimized, optimized structure
of the CMCD anion outside the layers. This is the structure
that was placed in the interlamellar space at the start of
the simulation. The structure on the right is that obtained
after 100 ps of simulation. Two views are shown, one
looking down the interlayer normal and the other per-
pendicular to it. The bond lengths of CMCD anion following
100 ps of simulation show no change from the values at
the start. In the optimized structure of β-CMCD, the
C-O-C bond angles of the gluco-pyranose units are 114°
(for one of the gluco-pyranose unit’s the angle is 112°) and
the value of the C-O-C angle of the R-1-4 linkage that
links the gluco-pyranose units also 114°. For the inter-
calated CMCD ion the values for the C-O-C angles of
the gluco-pyranose units, too, have an average value of
114°. The linkage C-O-C angle, however, was found to
vary between 107° and 124°, although the average value
∼114° is still close to the value at the start of the
simulation. It may be seen from Figure 6 that the angle
that the carboxy-methyl substituents make with the CD
ring are different for the intercalated ion. Outside the
layers, these group are splayed, but on intercalation, the Figure 5. Raman spectra of (a) Na salt of CMCD and (b) Mg-
requirement that all four groups anchor to the Mg-Al Al LDH-CMCD.
LDH layer causes a change in angle. For the CMCD
so there is plenty of space, in principle, for guest molecules
molecule outside the layers, the O-C-COO- bond angles
to enter and form adducts with the anchored cavities,
are 110°, 111°, 112°, and 114°, whereas for the intercalated
similar to those found between β-cyclodextrin molecules
ion the values, after 100 ps of simulation, are 113°, 114°,
and nonpolar, hydrophobic guest molecules in aqueous
115°, and 120°. An examination of the structure shows
solutions. This would be true provided that the hydro-
that these changes in the linkage angles allow all four of
phobicity of the intercalated β-cyclodextrin cavities is
the carboxy-methyl groups to anchor onto the Mg-Al LDH
similar to that of the cavity outside the layer.
sheet.
Polarity of the Intercalated Carboxymethyl-β-
The results of the computer simulation are in broad cyclodextrin. To establish the hydrophobicity of the
agreement with the infrared and Raman spectroscopy microenvironment within the intercalated β-cyclodextrin
results, that the positions of the vibrational modes of the cavities, the fluorescence spectra of pyrene included within
gluco-pyranose units as well as the linkages show little the Mg-Al LDH-CMCD was examined. The fluorescence
change on intercalation implying that the geometry of of pyrene has been widely used to establish the polarity
the CMCD ion is preserved within the galleries of the of the medium in which it is present.46 In polar solvents
Mg-Al LDH. The experimental measurements and com- there is an enhancement in the intensity of the symmetry
puter simulations present a consistent picture of the forbidden (0-0) band (Ham effect).47 The relative intensity
β-cyclodextrin functionalized anionic clay. The interca- of the first, II, and third, IIII, vibronic bands of the first
lated β-CMCD cavities are arranged as perpendicular
bilayers with their wider opening facing away from the (46) Kalyanasundaram, K.; Thomas, J. K. J. Am. Chem. Soc. 1977,
layers. The cavities occupy ∼50% of the gallery volume, 99, 2039.
Structure of an Anionic Clay
Figure 6. Snapshot of the simulations of Mg-Al LDH-CMCD.
The simulation unit cell is indicated by dashed lines and also
one of the anchored CMCD cavities. Color codes: red, O; gray,
C; white, H; pink, Al; and green, Mg.
Figure 7. Molecular structure of CMCD molecule. The
structure on the left of the figure is the potential energy
minimized optimized geometry of the CMCD molecule. The
structure on the right is a snapshot of the same molecule in the
Mg-Al LDH-CMCD hybrid following 100 ps of molecular
dynamic simulation. (a) View down the interlayer normal and
(b) perpendicular to the interlayer normal. Color codes: red,
O; gray, C; and white, H.
singlet emission (S1 f S0) correlates reasonably well with
solvent polarity. The intensity ratio of pyrene, II/IIII, varies,
typically, from 0.6 in nonpolar solvents, like hexane, to
1.95 in polar solvents, like dimethyl sulfoxide.48
The fluorescence spectrum of pyrene included within
the Mg-Al LDH-CMCD by sorption from an aqueous
(47) (a) Koyanagi, M. J. Mol. Spectrosc. 1968, 25, 273. (b) Robinson,
G. W. J. Chem. Phys. 1967, 46, 572.
(48) Bernard Valeur, In Molecular Fluorescence; Principles and
Applications; Wiley-VCH: New York, 2001.
Langmuir, Vol. 21, No. 23, 2005 10741
Figure 8. Variation of the intensity ratio of the first, I, and
third, III, vibronic bands in the fluorescence spectra of pyrene
as function of solvent polarity. The bar indicates the range of
I/III ratios observed for pyrene included within Mg-Al LDH-
CMCD. The inset shows the fluorescence spectra of pyrene
included within Mg-Al LDH-CMCD.
solution (∼0.8 µM) of pyrene is shown as an inset in Figure
8. The emission spectra were obtained by excitation within
the pyrene absorption band at 335 nm. The average value
of the intensity ratio of II/IIII (I370 nm/I390 nm) is 0.92. To
place this value on a relative polarity scale the fluorescence
spectra of pyrene in different solvents was recorded and
the values of the intensity ratio of II/IIII plotted as a function
of the dielectric constant of the solvent. It may be seen
from Figure 8 that the polarity within the cavities of the
anchored β-CMCD cavities lies between that of a methanol
and 1:1 methanol-water mixture. The value of the
dielectric constant ∼55 is similar to that reported for
β-cyclodextrin cavities.
Conclusions
The anionic clay, Mg-Al LDH, can be functionalized by
anchoring the carboxy-methyl derivative of β-cyclodextrin
to the gallery walls. Functionalization has the promise of
greatly extending the host-guest chemistry of the anionic
clay, from simple ion-exchange reactions to also include
neutral and nonpolar guest species. A key requirement
for this is a detailed knowledge of the precise arrangement
and geometry of the β-cyclodextrin cavities in the inter-
layer space of the Mg-Al LDH. This paper describes an
analysis of the structure of the β-cyclodextrin intercalated
Mg-Al LDH using X-ray diffraction,13C NMR spectros-
copy, and infrared and Raman spectroscopy augmented
with MD simulations. Spectroscopic measurements in-
dicate that the geometry of the anchored β-cyclodextrin
cavities is essentially unchanged from that outside. This
is also supported by MD simulations which show that the
structure of the gluco-pyranose units of the β-cyclodextrin
cavity are preserved on intercalation but there are minor
changes in the angles of the bonds that link these units.
Snapshots of the MD simulations show how a bilayer
arrangement, with the axis of the β-cyclodextrin cavity
perpendicular to the Mg-Al LDH sheets allows for the
experimentally observed interlayer lattice spacing to be
realized.
The β-cyclodextrin cavities in the intercalated bilayer
are arranged with their wider opening facing away from
10742 Langmuir, Vol. 21, No. 23, 2005
the layer. This, in principle, can allow guest molecules to
access the interior of the β-cyclodextrin cavity. Using the
fluorescence of pyrene as a probe, we have established
that the hydrophobicity of the microenvironment within
the anchored β-cyclodextrin cavities is similar to that
reported for β-cyclodextrin. Since the structure, too, is
similar, our results suggest that the host-guest chemistry
of β-cyclodextrin, too, should be reproduced by the
intercalated β-cyclodextrin cavities. Initial reports of the
inclusion of neutral aromatics,22 ferrocene,23 and iodine24
suggest this to be true. Functionalization of the anionic
clay has, therefore, resulted in the creation of hydrophobic
Mohanambe and Vasudevan
nanopockets within the hydrophilic interlamellar space
of the layered metal hydroxide.
Supporting Information Available: (1) Thermo-
gravimetric data for CMCD and Mg-Al LDH-CMCD. (2) Table
of bond angles of β-CD, β-CMCD molecules before and after 100ps
of MD simulation. (3) Snapshots of the Mg-Al LDH-CMCD
with CMCD anions oriented with their axis perpendicular to the
interlayer normal and displaced to different degrees from the
center of the gallery, before and after 100ps of molecular dynamics
simulation. This material is available free of charge via the
Internet at http://pubs.acs.org.
LA050628T