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PAPER www.rsc.org/materials | Journal of Materials Chemistry

Hydroxy double salts as versatile storage and delivery matrices†

Richard M. R. Bull, Charles Markland, Gareth R. Williams and Dermot O’Hare*
Received 9th September 2010, Accepted 1st November 2010
DOI: 10.1039/c0jm03020a

The utility of hydroxy double salts (HDSs) for the uptake and delivery of a range of functional anions
via ion exchange is demonstrated. Three novel HDS nanocomposites containing medicinal (ibuprofen
and diclofenac) and agrochemical (2,4,5-trichlorophenoxyacetic acid) species have been synthesised
through ion exchange intercalation. The release of the guest ions from the host has subsequently been
explored. A range of models have been applied to the release kinetics. Release of 2,4,5-
Published on 25 November 2010 on http://pubs.rsc.org | doi:10.1039/C0JM03020A

trichlorophenoxyacetic acid took place over ca. 200 minutes and release of ibuprofen over around
250 minutes. Coating the crystallites of the intercalates with a sodium alginate layer led to release times
being extended to approximately 10 hours, which is an appropriate timescale for an effective release
system.
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Introduction In this article, the ion-exchange intercalation of three func-

Layered double hydroxides (LDHs) comprise positively charged
layers, requiring charge balancing anions to be located between
the layers to ensure electroneutrality. These anions can be easily
replaced through an anion exchange process. A wide range of
functional molecules easily form anions, and as a result LDHs
have been widely explored as hosts for the storage and controlled
release of a broad spectrum of functional anions,1–3 including
drugs,4–6 agrochemicals,7–9 DNA,2,10 and vitamins.11 A related
family of materials known as hydroxy double salts (HDSs)
possesses the same key structural features of positively charged
layers and interlayer anions, but the intercalation chemistry of
HDSs has received little attention. Literature searches reveal far
fewer papers concerned with HDSs than with LDHs. It is clear
therefore that the HDS materials are dramatically underex-
plored.
Choy et al. have undertaken pioneering work in synthesising
hybrids of a Zn-containing hydroxy double salt with vita-
mins,12,13 an antioxidant,14 and indole-3-acetic acid.15 These
authors have often synthesised their nanohybrids through
a coprecipitation route. They and others have also used an ion
exchange route to intercalate guests including simple inorganic
anions (e.g. NO3, ClO4, Cl, MnO4 and SO42),16,17 a drug
(indole-3-acetic acid),15 metal complexes,18–20 alkyl sulfates,21,22
organic carboxylates,23–27 dyes,28 and thiophene monomers.29
Therefore, it has been established that HDSs can undergo facile
ion exchange.30 However, the possibility of using this anion
exchange process to intercalate and then subsequently release
functional guest ions from an HDS has not been extensively
explored to date; we can find only one such report in the litera-
ture.15
tional anions into the HDS [Zn5(OH)8](NO3)2$yH2O (Zn5–NO3)
is reported. The structure of this compound comprises layers of
edge-sharing Zn(OH)6 octahedra. There are Zn vacancies in the
layer, and above and below each vacancy are coordinatively
unsaturated Zn(OH)3 units. The Zn atoms in these units interact
strongly with the anions and water molecules present in the
interlamellar region (see Fig. 1(a)) The Zn5–NO3 material is
particularly well suited for use in biomedical and agricultural
settings because of its high degree of biocompatibility. Two drug
anions were chosen for investigation (ibuprofen and diclofenac,
commonly used non-steroidal anti-inflammatory drugs). In
addition, 2,4,5-trichlorophenoxyacetic acid, a widely used
herbicide, was selected as an exemplar agrochemical. The func-
tional anion intercalates were thoroughly characterised, and the
release of the functional anion studied in vitro in representative
conditions. Mathematical models were applied to the release
kinetics, and post-synthesis modification undertaken to optimise
release times for industrial application. The use of an HDS as
a controlled release matrix is depicted schematically in Fig. 1.

Chemistry Research Laboratory, University of Oxford, Mansfield Road,

Oxford, OX1 3TA, UK. E-mail: dermot.ohare@chem.ox.ac.uk; Tel: +44
(0)1865 272686
† Electronic supplementary information (ESI) available: Parameters
extracted from the kinetic modelling of functional anion release;
additional plots depicting fits of the various models to the experimental
data; photograph of the Zn5–ibu beads. See DOI: 10.1039/c0jm03020a
Fig. 1 Use of an HDS as a controlled release matrix. [Zn5(OH)8](-
NO3)2$yH2O (Zn5–NO3), (a), is reacted with a functional anion (e.g.
ibuprofen, shown) to form an intercalate (b). In (c), the functional anion
is released through exchange with anions present in the release media (e.g.
carbonate or phosphate in the intestinal fluid).

1822 | J. Mater. Chem., 2011, 21, 1822–1828 This journal is ª The Royal Society of Chemistry 2011

Experimental
Analytical techniques
Elemental analysis. Elemental analysis was performed by the
School of Human Sciences, London Metropolitan University,
using the quantitative combustion technique.
Powder X-ray diffraction. Data were collected on a PAN-
Analytical X’Pert Pro diffractometer in reflection mode at 40 kV
and 40 mA using Cu Ka radiation (a1 ¼ 1.54057 Å, a2 ¼
1.54433 Å, weighted average ¼ 1.54178 Å). The samples were
loaded on stainless steel sample holders whose reflections did not
Published on 25 November 2010 on http://pubs.rsc.org | doi:10.1039/C0JM03020A
interfere with characterisation.
Infrared spectroscopy. IR spectra were recorded on a Bio-rad
FTS 6000 FTIR Spectrometer equipped with a high performance
DuraSamp1IR II diamond accessory. Spectra were taken in
attenuated total reflection mode over the range of 400–
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4000 cm1, with 50 scans at 4 cm1 resolution. The strong
absorptions in the range 2500–1667 cm1 are from the Dura-
Samp1IR II diamond surface.
Ultraviolet spectroscopy. UV absorption spectroscopy was
carried out on a T60U PG Instruments UV/VIS Spectrometer
using wavelength scan mode and quartz cuvettes. The wave-
length range used was from 190 to 400 nm.
Thermogravimetric analysis. Measurements were collected
using a Netzsch STA 409 PC instrument. Approximately 70 mg
of sample was heated in a corundum crucible between 25  C and
500  C at a heating rate of 5  C min1 under a flowing stream of
argon.
NMR. 1H NMR spectra were collected on a 300 MHz Varian
Mercury VX-Works spectrometer. D2O was used as the solvent.
Synthesis
All reagents were procured from Sigma-Aldrich or Fluka and
used as supplied. [Zn5(OH)8](NO3)2$2H2O (Zn5–NO3) was syn-
thesised following the method reported by St€ahlin and Oswald,31
with some modifications. 1.0 g of ZnO was added to an aqueous
zinc(II) nitrate solution (5.61 g of Zn(NO3)2 dissolved in 12 mL of
water). The mixture was subsequently stirred vigorously at room
temperature for 4 days.
The functional anions were intercalated by suspending
0.3 mmol Zn5–NO3 in 10 mL of deionised water containing
a three-fold excess of the sodium salt of the guest. Reaction times
and temperatures were optimised to ensure complete reaction of
the Zn5–NO3 host and to maximise the crystallinity of the
product. For 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) inter-
calation, the reaction was stirred at 60  C for 7 days; ibuprofen
(ibu) intercalation was achieved by reaction for 24 h at 40  C,
diclofenac (dic) intercalation was accomplished by undertaking
the reaction for 72 h at 60  C. Solid products were recovered by
filtration, washed with deionised water and acetone, and dried
under vacuum.
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Controlled release
2,4,5-T. Soil was collected locally in Oxford and dried in an
oven at 150  C overnight. A column measuring 2.5 cm in
diameter and 60 cm in height was then half filled with soil and
saturated with tap water. Once the excess water had drained
through, 0.2 g of the 2,4,5-T intercalate (Zn5–2,4,5-T) was placed
on the top of the soil with 5 mL of tap water. 5 mL aliquots were
collected from the bottom of the column at regular intervals, and
5 mL tap water added to the top of the column after each aliquot
was taken. The concentration of 2,4,5-T in the aliquots was
measured by UV analysis. The Zn5–2,4,5-T powder could not be
salvaged.
Enteric coated beads. The enteric coated beads were formed
following a modified version of the method reported by Zhang
et al.32 Other authors have successfully adopted similar
approaches to prepare enteric coated LDH particles.33–35 0.2 g of
the Zn5–X (X ¼ ibu, dic) intercalation compound was dispersed
in 7 mL deionised water and stirred vigorously for 30 min. An
aqueous solution of sodium alginate (SA; 0.4 g in 25 mL
deionised water, stirred for 30 minutes) was added dropwise to
the Zn5–X suspension and stirred at 40  C for 1 h. The SA/Zn5–X
suspension was dropped into a calcium chloride solution (0.5 g
CaCl2 in 50 mL deionised water) through a 1.2 mm inner
diameter needle at a rate of 45.5 mL h1 using a syringe pump.
The gel beads formed instantly and were stirred at room
temperature for 1 h. The beads were recovered by filtration,
washed with deionised water, and left to dry in air for 48 h.
Drug anions. 0.2 g of the enteric coated beads were immersed in
50 mL of a pH 2.1 buffer (representative of the pH of the
stomach) and stirred slowly (50 rpm) at 37  C for 2 hours.
Subsequently, they were transferred to a pH 7.3 buffer (simulated
intestinal fluid) and stirred at the same temperature and rate.
3.5 mL aliquots were taken at regular intervals and analysed by
UV spectroscopy. For every aliquot removed, 3.5 mL fresh
buffer was added. For the release of ibu from the uncoated
intercalate, the same procedure was undertaken but 0.2 g of the
uncoated intercalate was used and the entire reaction undertaken
in a pH 7.3 buffer.
Results
Intercalation
Anion exchange intercalation of the functional guests into Zn5–
NO3 was found to be a facile process. The XRD pattern of the
ibuprofen intercalate (Zn5–ibu) is shown in Fig. 2.
As can be seen from Fig. 2, a significant increase in the basal
spacing of the HDS occurs upon intercalation (from 9.1 Å to
25.7 Å). This is to be expected given that all the guest molecules
are larger than the precursor nitrate anion. No basal reflections
corresponding to the Zn5–NO3 material could be observed in the
patterns of the reaction products, confirming that intercalation
had occurred successfully. The HDS has a layer thickness of
around 5 Å, and for ibu and dic the interlayer spacings (z d200
5 Å) are a little under twice the length of the guests (e.g. ibu has
a length of ca. 12.6 Å, and the interlayer spacing is 20.7 Å). This
suggests that the guest molecules are arranged in intertwined
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Published on 25 November 2010 on http://pubs.rsc.org | doi:10.1039/C0JM03020A
Fig. 2 XRD patterns of (a) Zn5–NO3 and (b) Zn5–ibu.
bilayers with the carboxylic acid groups pointing towards the
metal hydroxide layers. However, the interlayer spacing for Zn5–
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2,4,5-T is much smaller and implies that the anions adopt
a monolayer arrangement between the layers. Previous reports
have studied the intercalation of the same guests into LDHs.
These investigations suggested that ibuprofen, diclofenac and
2,4,5-T adopt bilayer arrangements in the interlayer space. The
orientations suggested for the Zn5–NO3 intercalates therefore
agree well with the literature precedent for the drug anions, but
suggest a different arrangement for 2,4,5-T (a monolayer in Zn5–
2,4,5-T as compared to a bilayer in its LDH intercalates).1,36
The success of the reaction was also confirmed using IR
spectroscopy. The IR spectra of the intercalates show clear
vibrations corresponding to the functional anion guests: the
spectrum for Zn5–ibu is given in Fig. 3.
The broad absorption at around 3400 cm1 arises from the nOH
absorptions of the hydroxide layers and co-intercalated water,
and the absorptions below 1000 cm1 from the Zn–O vibrational
modes.
The spectrum of Zn5–ibu is clearly very similar to that of pure
ibuprofen. The key peaks that distinguish Zn5–ibu from Zn5–
NO3 are those found at 1380 cm1 and 1580 cm1. These corre-
spond to the C–H aliphatic bend and the C–C aromatic stretch of
the guest respectively, and are only seen for Zn5–ibu. The N–O
stretch seen at 1360 cm1 in Zn5–NO3 disappears upon
Fig. 3 IR spectra of (a) Zn5–NO3; (b) Zn5–ibu; and (c) ibuprofen. The
strong absorptions in the range 2500–1667 cm1 are from the Dura-
Samp1IR II diamond surface.
1824 | J. Mater. Chem., 2011, 21, 1822–1828
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intercalation of ibuprofen, confirming that the precursor NO3
ion has been replaced with the desired guest.
Elemental and thermogravimetric analyses (TGA) were
undertaken to determine the formulae and water content of the
intercalates. While the elemental analysis confirms there is no
nitrate remaining in the reaction products, the carbon percent-
ages observed are significantly lower than would be expected for
complete replacement. This can be explained by incorporation of
carbonate present in the air (and in small amounts in the
deionised water used for reaction), which is common in the
intercalation reactions of LDHs. Carbonate contamination can
usually be confirmed using IR spectroscopy; in this case, the
guests have vibrations at the same wavenumber as carbonate
(1380 cm1), and so IR does not provide any further information.
However, the amount of the guests recovered in release studies is
consistent with carbonate incorporation.
The TGA trace (Fig. 4) reveals mass loss in four main steps.
The first corresponds to the loss of two interlayer water mole-
cules (calculated mass after decomposition 95% of initial mass).
This is followed by dehydration of the layers (86%) and subse-
quently decomposition of carbonate anions and degradation of
the ibuprofen ions to give a final mass of 52%. This pattern is
typical of organic guests intercalated into layered metal
hydroxides.
The TGA data agree well with the formulae calculated from
elemental analysis. Key data on the intercalates are summarised
in Table 1. The Zn5–X materials were inspected by scanning
electron microscopy before and after intercalation. The materials
were found to consist of irregularly shaped platelets of a few
hundred nanometres in size. There was no appreciable change in
particle size or shape upon intercalation.
Guest recovery
In order to demonstrate the potential utility of these nano-
composites, experiments were performed to probe whether the
guest ions could be recovered intact from the HDS host. The
intercalates were reacted with a small excess of sodium carbonate
in D2O for 24 h. After 24 h, the solid product was removed by
filtration. 1H NMR of the filtrate showed that the guests had
been recovered intact, and no other signals due to decomposition
were observed.
Fig. 4 TGA plot for Zn5–ibu.
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Table 1 Summary of data on the intercalation compounds of Zn5–NO3
Guest Structure Intercalate formula
2,4,5-T [Zn5(OH)8](C8H4Cl3O3)1.9(CO3)0.05$2H2O
Ibu [Zn5(OH)8](C13H17O2)1.25(CO3)0.375$2H2O
Published on 25 November 2010 on http://pubs.rsc.org | doi:10.1039/C0JM03020A
Dic [Zn5(OH)8](C14H10Cl2NO2)1.4(CO3)0.3$H2O
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Controlled release
Experiments were then performed to study the release of the
functional guests from the Zn5–X intercalates. The Zn5–2,4,5-T
intercalate was investigated as a potential delivery agent for
2,4,5-T using a soil column. The results of the experiment are
given in Fig. 5.
90% of the 2,4,5-T guest is released from the HDS host over
a period of around 120 min. The observed release kinetics are less
rapid than has been observed previously from LDH hosts under
the same conditions, but post-synthesis modification is required
to extend release times such that they are commercially useful.
Next, the release of ibuprofen from the as-synthesised Zn5–ibu
material was studied in a pH 7.3 buffer (representative of the pH
in the intestinal tract, Fig. 6(a)). 90% release was seen in around
200 min. Release over this time period may be of use in drug
delivery, but it is likely that the nanocomposite would be
destroyed by the low pH (ca. 2.1) of the stomach before reaching
the small intestine. This would prevent the active agent getting to
the intestinal tract where it is absorbed into the body.
Given the promise of this initial result, Zn5–ibu and the
diclofenac intercalate (Zn5–dic) were coated with sodium algi-
nate (an ‘enteric coating’). The coating is stable in the stomach,
allowing the intact nanocomposite to pass through into the small
Fig. 5 The release of 2,4,5-T as a function of time.
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Elemental percentages observed
(calculated) d200/Å
C 18.34 (18.58); H 1.55 (2.00); N 0 (0) 13.8
C 25.96 (25.66); H 3.90 (4.31); N 0 (0) 25.7
C 26.28 (26.20); H 2.29 (2.65); N 2.23
21.6
(2.15)
intestine. However, the higher pH of the latter (7.3) will dissolve
the enteric coating, exposing the Zn5–X intercalate to the intes-
tinal fluids and allowing the active agent to be released. The
results of the experiments with coated Zn5–ibu and Zn5–dic are
detailed in Fig. 6(b) and (c).
For the first 120 minutes, the coated nanocomposites were
stirred in a pH 2.1 buffer (representative of stomach pH). No
release occurs (see Fig. 6(b) and (c)). The coated materials were
then transferred to a pH 7.3 buffer (representative of the small
intestine). Following transfer, 90% release is seen from coated
Zn5–ibu in 560 min, and from coated Zn5–dic in 500 min. These
timescales are suitable for use as drug delivery agents, allowing
release of a drug to occur over ca. 8–9 h. A system based on these
materials could ensure a safe but effective level of drug is
maintained in the body through the day or overnight.
Kinetic analysis
In order to gain more insight into the kinetics of the release
processes, we applied five commonly used models to the release
curves. Models used were the first-order rate model, a parabolic
diffusion model, the modified Freundlich equation, the Elovich
model, and the Avrami–Erofe’ev equation.37–42 In each model, C0
is the amount of guest in the HDS at t ¼ 0, Ct is the amount of
guest in the HDS at time t, and kd is the rate of release. a, b, and
n are constants. The functional forms of the equations are given
in Table 2. Fits of the models to the experimental release data are
shown in Fig. 7.
It is clear that, in the majority of cases, the models do not
adequately describe the experimental data; if the model provides
a good fit to the data, one would expect to observe a linear graph
in each case, which is not seen. The exception to this is the
uncoated Zn5–ibu, where the Avrami–Erofe’ev, Freundlich, and
first-order kinetic models give a good fit to the experimental data
(R2 > 0.99), and the Elovich equation provides a reasonable fit
(R2 z 0.93). The parabolic model provides a very poor fit even to
the uncoated Zn5–ibu release curve (R2 z 0.28). This is illus-
trated in Fig. S1 in the ESI†, and parameters extracted for Zn5–
ibu are listed in Table S1†.
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Fig. 6 Release of the active agent from (a) uncoated Zn5–ibu; (b) coated
Zn5–ibu; and (c) coated Zn5–dic.

Table 2 The kinetic models employed for analysis

Model Equation

First-order ln (Ct/C0) ¼ kdt Fig. 7 Kinetic models fitted to the experimental release data for Zn5–
Parabolic diffusion (1  Ct/C0)/t ¼ kdt0.5 + a 2,4,5-T (-); Zn5–ibu (C); coated Zn5–ibu (:); and coated Zn5–dic (;).
Freundlich ln (1  Ct/C0) ¼ ln (kd) + a ln (t) (a) Elovich model, (b) first-order release, (c) Freundlich equation, (d)
Elovich 1  Ct/C0 ¼ a ln (t) + b parabolic model, and (e) Avrami–Erofe’ev model.
Avrami–Erofe’ev ln (ln(1  Ct/C0)) ¼ n ln kd + n ln t

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For release from coated Zn5–ibu, Zn5–dic, and Zn5–2,4,5-T,
a marked discontinuity can be observed in all kinetic models.
This occurs at approximately the same timepoint for each model,
after ca. 100 min for Zn5–2,4,5-T (corresponding to approxi-
mately 90% release), and 240 min (60–65% release) for coated
Zn5–ibu and Zn5–dic. Detailed analysis revealed that, generally
speaking, the Avrami–Erofe’ev and Freundlich models provide
a good fit to the data in the first section of release, but that the
Elovich and first order equations give a better fit in the latter
stage. This is illustrated for coated Zn5–ibu in Fig. S2 in the ESI†.
The parameters extracted for Zn5–2,4,5-T, Zn5–ibu (coated),
and Zn5–dic using the models are given in Table S2†. Looking at
Published on 25 November 2010 on http://pubs.rsc.org | doi:10.1039/C0JM03020A
the data as a whole, the first-order, Freundlich, and Avrami–
Erofe’ev models give a reasonably consistent value of the rate
constant for release from Zn5–ibu (uncoated) of around 6–9 
103 min1. The values calculated from Avrami–Erofe’ev and
first-order equations agree particularly well. For the other
intercalates, there is less agreement between the models, but
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taking the values from Avrami–Erofe’ev and first-order models,
it appears that release initially occurs rapidly, and then slows
markedly in the second stage of the process. This is entirely
consistent with what can be seen from visual inspection of the
release curves. Broadly speaking, the rates of release are: Zn5–ibu
(uncoated) > Zn5–2,4,5-T > Zn5–ibu (coated) z Zn5–dic
(coated). This correlates with the contact the intercalate has with
the medium into which it is releasing its guest. The uncoated
Zn5–ibu is stirred around as individual particles, maximising
contact. The Zn5–2,4,5-T lies on a soil surface while water is
added from above, reducing the amount of contact possible, and
the coated drug intercalates are stirred in pellet form, resulting in
still less contact with the release medium.
It is interesting that the change in release rate occurs at almost
the same time for the coated Zn5–ibu and Zn5–dic materials,
suggesting that this timepoint is determined in the main by the
inclusion of the nanocomposite into a pellet rather than by the
inherent properties of the intercalates. The fact that the change in
rate happens earlier for Zn5–2,4,5-T than for the coated drug
intercalates suggests that the mechanistic change is also corre-
lated with the extent to which the intercalation compounds can
come into contact with the release medium.
Duan et al. have recently proposed a mechanism to explain
such two-stage release behaviour.43 In this mechanism, surface
adsorbed guest molecules are released first in a rapid phase,
followed by slower release of intercalated guest ions. This exact
mechanism cannot be responsible for the observations reported
here, for a number of reasons. First, the uncoated Zn5–ibu
material displays only one release phase: therefore the surface
adsorbed and intercalated guests must be released at approxi-
mately the same rate. Second, where discontinuities in release
rate are seen, they are seen only after a significant proportion of
the guest (>65%) has been released, and it is unlikely that such
a high percentage of the guest is surface adsorbed given the small
amount of physisorption possible cf. the total ion exchange
capacity. It is proposed that a similar mechanism can account for
the experimental observations, however. Considering first Zn5–
2,4,5-T, the experimental method involves sprinkling the powder
on the top of a soil column. Only a small percentage of the HDS
particles will be in contact with the soil; the rest will be stacked on
top of these particles. When the Zn5–ibu and Zn5–dic intercalates
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Fig. 8 Schematic showing the release mechanism proposed for Zn5–
2,4,5-T and coated Zn5–ibu and Zn5–dic. (a) The fully intercalated
particles packed together such that only some are in direct contact with
the release medium. (b) The particles on the outside of the aggregate
release their guests first; this process is relatively facile. (c) The particles in
the centre of the aggregate then release their guests rather slowly as there
is a significant barrier to diffusion to the outside of the aggregate.
are coated, beads of ca. 1000 mm are produced (see Fig. S3 in the
ESI†). These will contain a large number of HDS particles, some
of which will be at the edges of the bead, and others in the centre.
Hence, a mechanism closely related to that proposed by Duan
can explain the change in release rate observed for Zn5–2,4,5-T,
and coated Zn5–ibu and Zn5–dic. It is proposed that first those
particles in contact with the release media release their guests.
Because there is direct contact, this process is facile and relatively
rapid. In the second stage of release, particles not directly in
contact with the release medium must discharge their guests, and
this process is much slower because to exit the bead (or powder
stack for 2,4,5-T), the guest must not only diffuse out of
a particular HDS particle, but must also pass around other
particles to escape the aggregate. Such a process is shown in
Fig. 8.
A very recent report by Pan et al. details an in-depth study of
the controlled release of ibuprofen from a Mg/Al LDH.44 These
authors found that particle size was an important factor in
determining the release profile, and that different kinetic models
were most appropriate for release from different particle sizes.
Furthermore, they found that the particles tend to dis-aggregate
as release occurs. Although not directly comparable with the
work reported here, Pan’s study does suggest that the particle
shape and arrangement in the release matrix can have a profound
effect on the release profile, as has been observed in our inves-
tigations.
Conclusions
The development of sustained release systems is of profound
importance in medicine to ensure that pharmaceutical agents are
delivered to the correct part of the body at the right time, and in
agriculture to prevent excess quantities of pesticides leaching into
lakes and rivers and causing eutrophication. In this paper, the
facile production of functional anion nanocomposites with
a hydroxy double salt through anion exchange is demonstrated
via the intercalation of three exemplar guests (2,4,5-T, ibuprofen,
and diclofenac). With post-synthesis modification, release can be
extended to around 10 hours. While standard kinetic models can
account well for the release behaviour observed from individual
particles, they cannot explain the release pattern from aggre-
gates. The latter processes occur in two stages, the first of which
is much faster than the second. The HDS nanocomposites
reported herein have excellent potential as delivery systems for
J. Mater. Chem., 2011, 21, 1822–1828 | 1827

functional anions, and are highly suitable for this purpose as they
are cheap, facile and environmentally friendly to prepare, and
biocompatible.
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