Colloids and Surfaces B: Biointerfaces 73 (2009) 103–109

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Colloids and Surfaces B: Biointerfaces

journal homepage:www.elsevier.com/locate/colsurfb

Inorganic layered double hydroxides as ascorbic acid (vitamin C) delivery system—

Intercalation and their controlled release properties
M.S. Gasser
Hot Labs Centre, Atomic Energy Authority, P.Code 13759, Cairo, Egypt

article info abstract

Article history: ZnFe– and MgFe–LDHs were prepared by the anion exchange method, with the aim of adsorption of the ascorbic acid from
Received 4 December 2008 the aqueous solutions by ion exchange process between anionic derivatives in LDH (Cl) and the anionic vitamin. This leads to
Received in revised form 1 May 2009 successful intercalation of the vitamin into gallery space of LDH that offers a new route to safe preservation of bioactivity as
Accepted 5 May 2009 Available online 14
well as controlled release. The prepared LDHs were characterized by XRD, TG–DTA and FT-IR spectroscopy. Adsorption of
May 2009
the ascorbic acid by the LDH under investigation was studied in terms of pH value, amount of LDH, contact time, VC
(ascorbate) concentration and chemical composition of the host materials. The results indicate the relatively fast adsorption of
Keywords:
the anionic vitamin by ZnFe–LDH–Cl and MgFe–Cl–LDH; reaches the equilibrium in 60 min. The shapes of the adsorption
Layered double hydroxide (LDH)
Adsorption isotherms suggest specific interaction and high affinity. The batch kinetics of ascorbic acid adsorption onto ZnFe–Cl and
Ascorbic acid MgFe–Cl–LDHs were studied. Furthermore, their release behaviors are also examined by spontaneous deintercalation with
Intercalation carbonate anion.
Controlled release
Vitamin C (VC) © 2009 Elsevier B.V. All rights reserved.

1. Introduction
LDH consists of positively charged hydrotalcite-like layer of metal
hydroxide and the interlayer region typically occupied by anionic species and
water molecules. Layer structure is stabi-lized by hydrogen bonding among
water molecule, anionic species and hydroxide layer. Various kinds of
inorganic or organic anions could be readily introduced and stabilized into the
hydroxide interlayer by simple ion exchange reaction or coprecipitation [1–3].
Recently, LDHs are employed as the host material to synthesize a new
organic–inorganic nanohybrid material and have received considerable
attentions. The organic/LDHs nanohy-brid materials have been investigated
because the resulting intercalation compounds are expected to possess a novel
nanos-tructure and new function [4–10]. A synthesis of biomolecule/LDH
nanohybrid materials in particular is of great interest. In fact, the intercalation
of the biomolecule such as nucleotide [11,12], deoxyribonucleic acid [13],
amino acid [14–17] and polypep-tide [18] into LDHs was described in order
to prepare the biomolecule/LDH nanohybrid materials. Hydrotalcite is known
to be biocompatible material and has found pharmaceutical appli-cations as
antacid. In addition, anionic drug molecules have
been intercalated into various LDHs, with an aim to study and assess the use
of these intercalation compounds as materials for storage, transport and
ultimately controlled release of drug [19–21].
Vitamin C is very sensitive to oxidation in the presence of oxygen. A
small amount of metal ions assists this reaction under neutral and alkaline
conditions. Many enzymes also easily decompose vitamins within biosystem.
On the other hand, human body requires only a very small amount of vitamins
for physiological functions. Both insufficient and excessive supplies of
vitamins cause harmful effects on human body. For reliable supply, it is
necessary to develop a con-trolled delivery system for vitamins. In this regard,
LDH could be an excellent candidate matrix due to high anion exchange
capacity and biocompatibility [22,23]. Not only LDH could protect vitamins
against decompositions, but also intercalated vitamins could be intentionally
taken out from the LDH lattice in an ambient con-dition. Their releases in
carbonated aqueous solution seem to take place mainly by ion exchange and
diffusion reactions that could be readily controlled by the manipulation of
reaction conditions and structural properties of LDH.

In this work, two layered double hydroxide materials, namely ZnFe–Cl

and MgFe–Cl–LDHs, are prepared and characterized. Adsorption of ascorbic
acid by the LDH under investigation was studied in terms of pH value,
amount of LDH, contact time, VC (ascorbate) concentration and chemical
composition of the host materials. An XRD investigation was also carried out
E-mail address: mona gasser@yahoo.com. to learn about

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doi:10.1016/j.colsurfb.2009.05.005
104 M.S. Gasser / Colloids and Surfaces B: Biointerfaces 73 (2009) 103–109

the type of adsorption reaction. Further, the kinetics of ascorbic acid release
from the host materials was investigated.

2. Experimental

2.1. Preparation of ZnFe–Cl–LDH

The ZnFe–Cl–LDH was prepared under N2 atmosphere. A mixed aqueous

solution containing Zn(II) and Fe(III) (the ratio is 2:1) was titrated in a
dropwise manner with NaOH (0.1 M) solution. The resulting white precipitate
was isolated by centrifugation, washed with decarbonated water to remove the
excess chloride ion, and then freeze-dried. MgFe–Cl–LDH was prepared with
the same method.

2.2. Characterization

X-ray diffraction (XRD) patterns were obtained at 20 mA, 40 kV with

Philips PW 3710 powder diffractometer equipped with Ni-filtered Cu K Fig. 1. Powder X-ray diffraction patterns for: (a) ZnFeCl–LDH and (b) ZnFe–VC.

radiation ( = 1.5405 Å). Infrared spectra were obtained with a Bruker IFS-88
FT-IR spectrometer by a standard KBr disk method. The stoichiometry of
each VC–LDHs nanohybrid was determined by thermogravimetry (TG–
DTA).
2.3. Adsorption experiments
The adsorption experiments of ascorbic acid (VC) on Zn–Fe–Cl and
MgFe–Cl–LDHs were carried out by suspending duplicate sam-ples of 0.1 g
of Zn–Fe–Cl and Mg–Fe–LDH in 10 mL of aqueous solution of 200 mg/L.
The optimum initial pH, contact time and amount of LDHs were then
determined. The suspensions were agitated at 75 rpm at room temperature.
The filtrate was ana-lyzed spectrophotometrically [24] by measuring its
maximum absorbance at 265 nm, using a Shimadzu double beam recording
spectrophotometer model 160 A, to determine ascorbic acid con-tent adsorbed
by Zn–Fe–Cl. This amount was determined from the difference between
initial and final concentration of the metal ion in the supernatant solutions.
The optimum conditions of ascor-bic acid onto ZnFe–Cl–LDH were applied
to study the adsorption onto MgFe–Cl. The adsorption isotherms were
measured by batch equilibration technique.
2.4. Kinetic studies
ent time mixing intervals, the solutions were separated and the VC content
determined by UV absorption at 265 nm.
3. Results and discussion
3.1. LDHs characterization
The XRD patterns for ZnFe–Cl and MgFe–Cl–LDHs, before and after
intercalation exhibit the well developed (0 0 l) reflections such as (0 0 3) and
(0 0 6), as shown in Figs. 1 and 2. The intercalation of vitamins into the
lamellar host structure is clearly observed by the increase in the basal spacing
upon replacing Cl− ions with vitamin molecules. The diffraction peak at 8.5 Å
for the ZnFe–Cl–LDH cor-responds to the basal spacing of LDH with Cl− in
the interlayer. The (0 0 l) reflection peaks shift to lower angles upon the
interca-lation of the vitamins. XRD patterns (Figs. 1 and 2) indicate that the
intercalation of VC in ZnFe–Cl and MgFe–Cl gives rise to an increase in basal
spacing (from d = 8.5 and 7.9 Å) to (10.8 and 11.5 Å), for ZnFe–Cl and
MgFe–Cl, respectively. The subtraction of 4.8 Å as the hydrotalcite-layer
thickness [25] from the d = 10.8 and 11.5 Å gives 6 and 6.7 Å as interlayer
space occupied by VC, that could be attributed to intercalation for VC species
between brucite sheets of ZnFe–Cl or MgFe–LDH. We propose that ascorbate
species are located between brucite sheets of LDH, as shown in Fig. 3a and b.
In addition, the well ordered (0 0 l) peaks imply that the anion

Kinetic studies were investigated in beakers, 25 mL, by taking 0.06 g of

prepared LDHs in 10 mL of aqueous solution containing known concentration
of ascorbic acid (200 mg/L) at pH 7 at con-stant temperature. The solution in
the beakers was kept stirred in a thermostat shaker adjusted at the desired
temperature. One beaker was withdrawn as a function of time while the
solution in the other beakers was being continuously stirred. Thus, the ratio of
the vol-ume of solution to the weight of adsorbent in the beaker does not
change from the original ratio. The solution from the withdrawn beaker was
filtrated to separate the adsorbent and a fixed volume of the solution was
pipetted out for the determination of the amount of unabsorbed ascorbate
(VC) still present in solution.

2.5. Deintercalation kinetics

The dissolution test was performed at constant temperature (25 ◦ C) by

suspending VC–LDH (1.2 g to ca. 0.2 g of VC) in aqueous solution (200 mL)
at pH 9 in a double-jacket conical flask connected to a thermostated water
bath. The concentration of the carbonate solution was 0.5 mol/L. The
mass/volume ratio of 1.2 g/200 mL was chosen according to the solubility of
VC at this pH value. At differ- Fig. 2. Powder X-ray diffraction patterns for: (a) MgFeCl–LDH and (b) MgFe–VC.
 M.S. Gasser / Colloids and Surfaces B: Biointerfaces 73 (2009) 103–109
Fig. 3. Schematic illustrations of: (a) ZnFe–VC–LDH and (b) MgFe–VC.
exchange reaction occurs without any deterioration of the main layered
structure of LDH.
Figs. 4 and 5 show the infrared spectra for the ZnFe–LDH and MgFe–
LDH hybrids and ascorbate LDH. The absorption band at 1387 cm − , is
1
assigned to the stretching vibration of Cl− . This band completely disappeared
in the LDH spectrum after the ion exchange reaction, which indicates that the
interlayer Cl− anion is completely replaced by the ascorbic acid molecules.
The absorp-tion bands at 2930–3100 cm− correspond to the asym and sym (C
1 The VC–LDH is well known to exhibit a distinctive reduction in mass
H) modes of CH2 group in the vitamin molecules. The other
Fig. 4. Infrared spectra for: (a) Zn3 Fe(Cl)–LDH and (b) Zn2 Fe–ascorbate (VC)–LDH.
105
Fig. 5. Infrared spectra for: (a) Mg3 Fe(Cl)–LDH and (b) Mg2 Fe–ascorbate (VC)–LDH.
vitamin bands originated from various functional groups are also found at
1740–1700 cm− (C O), 1300–1000 cm− (C O), and 1600–1475 cm−
1 1 1
(conjugate C C). The band broadening by inter-calation results from the
electrostatic interaction between vitamin molecules and hydroxide sheets to
suggest their safe stabilization in the interlayer space of LDH [26].
between 80 and 200 ◦ C owing to the loss of surface-adsorbed and interlayer
water. The other major mass loss occurs in the temperature range from 280 to
500 ◦ C due to the concomi-tant dehydroxylation of inorganic layer and the
decomposition of intercalated chloride anion [27]. As shown in Fig. 6, VC–
ZnFe–LDH shows a mass loss (ca. 15% mass) between 80 and 150 ◦ C due to
the evaporation of surface-adsorbed and interlayer waters. Decomposi-tion of
intercalated vitamin was observed around 350 ◦ C along with dehydroxylation
of the hydroxide layer.
Fig. 6. TG profiles for: (a) Zn2 Fe–VC–LDH and (b) Mg2 Fe–VC–LDH.
106 M.S. Gasser / Colloids and Surfaces B: Biointerfaces 73 (2009) 103–109
Fig. 7. Effect of pH on the amount adsorbed of ascorbate from aqueous solution onto ZnFe–Cl
and MgFe–Cl. The concentration of ascorbate = 200 mg/L, T = 25 ◦ C ± 1, amount of LDHs =
0.06 g/10 mL, Std. error = 0.90.
3.2. VC intercalation studies
3.2.1. Equilibrium investigation
Unless otherwise stated, the concentration of VC in solution was 200
mg/L. The equilibrium parameters of ZnFe–Cl and MgFeLDHs for adsorption
of VC from aqueous solution were studied. The main factors affecting the
adsorption are pH, amount of LDHs, contact time and the VC concentration.
The adsorption of VC increases with the increase of pH from 5.5 to 11.0
as shown in Fig. 7. Therefore, ZnFe–Cl and MgFeLDHs are effective for
adsorption of VC over the pH range 5.5–11.0.
The amount of LDHs was varied from 0.02 to 0.30 g/10 mL and
equilibrated for 1 h, Fig. 8. The experimental results revealed that VC
adsorption efficiency increases to reach a value of 98% using 0.2 and 0.14
g/10 mL weight of ZnFe–Cl and MgFeLDHs for VC, respectively. Further
increase in the weight of the adsorbent has no effect on adsorption percentage.
Fig. 8. Effect of LDHs weight on the amount adsorbed of ascorbate from aqueous
solution onto ZnFe–Cl and MgFe–Cl. The concentration of ascorbate = 200 mg/L, pH
7.5, T = 25 ◦ C ± 1, contact time = 1 h, Std. error = 0.88.
Fig. 9. Effect of contact time on the amount adsorbed of ascorbate from aqueous solution onto
ZnFe–Cl and MgFe–Cl. The concentration of ascorbate = 200 mg/L, pH 7.5, T = 25 ◦ C ± 1,
amount of LDHs = 0.06 g/10 mL, Std. error = 1.4.
The effect of contact time of adsorption of VC from aqueous solution by
ZnFe–Cl and MgFeLDHs was studied. The adsorp-tion efficiency increases
with time and attains equilibrium within 60 min for ZnFe–Cl and MgFeLDHs,
Fig. 9.
The role of VC concentration on the adsorption was studied using ZnFe–
Cl and MgFeLDHs within the range 50–500 mg/L. The results obtained are
represented in Fig. 10, as a relation between the con-centrations of VC in the
solution and in LDHs. From this figure, it is clear that the concentration of VC
in the LDHs increases with increasing their initial concentration in solution up
to a concentra-tion of 500 mg/L.
3.2.2. Adsorption isotherm
The investigated equilibrium adsorption of VC can be math-ematically
expressed in terms of the adsorption isotherms. The adsorption data are
commonly fitted to the Langmuir model at 25 ◦ C. The Langmuir equation
was applied to the adsorption
Fig. 10. Effect of initial VC concentration on its concentration in the LDHs. pH 7.5,
contact time = 1 h, T = 25 ◦ C ± 1, amount of LDHs = 0.06 g/10 mL, Std. error = 0.99.
 M.S. Gasser / Colloids and Surfaces B: Biointerfaces 73 (2009) 103–109 107

Fig. 12. First-order plots for the adsorption of VC by ZnFe–Cl–LDH in aqueous solu-tion at
different temperatures. R2 = 0.95.
Fig. 11. The Langmiur adsorption isotherm for VC on the LDHs. R2 = 0.98.

mechanism to shift to intraparticle diffusion of the solute adsorbed from the

equilibrium for LDH, using the expression, Ce = solution into the LDHs pores could be a limiting step. In this study, two
models namely those of Weber and Morris model
1 + Ce (1) and that suggested by Helfferich [29] were also used. The amount of VC at
1/2
time t is plotted against t in Figs. 14 and 15 according to the Weber and
Morris [30] equation:
where Ce is the equilibrium concentration (mg/L), qe is the amount
adsorbed at equilibrium (mg/g), and Qo is the Langmuir constant related to
monolayer adsorption capacity. The linear plots of Ce/qe vs Ce show that the
adsorption obeys the Langmuir model, Fig. 11. Qo determined from the
Langmuir plot, was 18.87 and 28.41 mg/g for ZnFe–Cl and MgFe–Cl,
respectively, Fig. 11.
3.2.3. Kinetics investigation
To describe the changes in the adsorption of studied ions with time, several
kinetic models were tested. Our hypothesis was that the uptake of VC
adsorption from the solution by the ZnFe–Cl and MgFe–Cl–LDHs followed a
pseudo-first-order mechanism. The order for the adsorption process of VC on
LDHs surfaces has been examined by Lagergren first-order rate expression
[28] by plotting log (qe − qt) against time,

qe Qo b Qo
K 1/2
log(qe − qt ) = log qe − 2.303 t (2)
where qe and qt are the amounts of VC adsorbed at equilibrium and at time t,
respectively, and K is the overall rate constant.
The effect of temperature on the kinetics of 200 mg/L VC adsorp-tion on
ZnFe–Cl and MgFe–Cl–LDHs from aqueous solution at pH 7.5 has been
examined at different temperatures from 15 to 40 ◦ C. The values of K were
calculated from the slopes of the straight lines shown in Figs. 12 and 13 and
listed in Table 1. The overall rate con-stant slightly increases with the
increase in temperature from 15 to 40 ◦ C for ZnFe–Cl and MgFe–Cl–LDHs.
Other models are also tested because the Lagergren equation cannot give
definite mechanism. It is also known that intensive stirring of the adsorptive
system may cause the rate limiting
12
qt = kd t / (3)
The slope of the straight line of qt vs t yields the value of kd, the rate
constant of intraparticle transport. The plots are linear and pass through the
1/2
origin. The plots of qt vs t shown in Figs. 14 and 15 for all temperatures are
neither linear nor do they pass through the origin. It appears that in no case is
the Weber and Morris equation (Eq. (3)) followed by adsorption system.
3.2.4. VC release properties
Deintercalation of the VC–LDH was carried out in 0.5 M car-bonate
aqueous solution. The VC intercalated in the LDH materials was first ion
exchanged by carbonate at pH 9 and the amount of released VC was
determined from its UV absorption at 265 nm. VC release profiles for ZnFe–
VC–LDH and MgFe–VC–LDH are presented

Table 1
Rate constants for the adsorption of 200 mg/L VC with ZnFe–Cl and MgFe–Cl–LDHs.

Temperatures (◦ C) Overall rate constant, K (×102 min−1 )

ZnFe–Cl MgFe–Cl
15 3.8 0.9
25 4.0 1.4
40 4.4 2.6
Fig. 13. First-order plots for the adsorption of VC by MgFe–Cl–LDH in aqueous solu-tion at
different temperatures. R2 = 0.98.
108 M.S. Gasser / Colloids and Surfaces B: Biointerfaces 73 (2009) 103–109
Fig. 14. Weber–Morris plots for adsorption for the adsorption of CV onto ZnFe–Cl.
R2 = 0.93.
in Fig. 16. The release profile of ZnFe–VC–LDH shows a high initial VC
release rate in the initial 10 min, and reaches an almost con-stant level after
20 min. The maximum amount of VC released is almost 40% of the total. The
release profile of MgFe–VC–LDH shows that the VC release is relatively fast
in the first 15 min, but sig-nificantly slower than that for ZnFe–VC–LDH.
The amount of VC released increases linearly after this initial period and
reaches 53% after 120 min. These data indicate that the MgFe–VC–LDH
release system is more effective than the ZnFe–VC–LDH system, because the
VC release rate of MgFe–VC–LDH is slower and the amount of VC gradually
increases over a long period. Similar to the release of other drugs from
pillared LDH described in the literature [4], the rapid release of the
intercalated material during the first 15 min is followed by a slow release of
some or all of remaining drug. Ambrogi et al. suggested that the rate of drug
diffusion out of the matrix is controlled by the rigidity of the layers and the
diffusion path length. In contrast to the release of other drugs from
intercalated LDH materials reported in the literature [31], the release of VC
from intercalated LDH materials prepared in this work is not complete within
120 min. The cause of the partial release may be attributed
Fig. 15. Weber–Morris plots for adsorption for the adsorption of CV onto MgFe–Cl.
R2 = 0.94.
Fig. 16. Release patterns of intercalated vitamin C from ZnFe–VC–LDH and
MgFe–VC–LDH. Std. error = 1.4.
to the possibility that the drug molecules are deeply embedded in the LDH
host via coprecipitation and complete release is very slow. Another interesting
observation is that the release of VC from ZnFe VC–LDH is very rapid within
first 15 min and then almost ceases. The initial rapid release of VC from
MgFe–VC–LDH is followed by a slower linear increase, this indicates that the
drugs intercalated in the ZnFe–LDH host are more difficult to release than
those in Mg/Al–LDH. This may reflect a stronger interaction between the
drug anions and the ZnFe host layers because of the higher change density on
the layers compared with that in MgFe LDH. It can be con-cluded therefore
that MgFe–VC–LDH materials are more suitable as a controlled-release host.
4. Conclusions
This study clearly shows that the vitamin is stabilized in the interlayer
space of LDH without any changes in its chemical and functional integrity
through hybridization, and that the stabilized vitamin can be intentionally
discharged from the hybrids either through ion exchange reaction or
dissolution of LDH framework in an ambient condition. Therefore, it is
expected that the inorganic LDH can be an excellent host lattice for safe
storage and effective delivery of the biological compounds that are rather
unstable in the ambient environment or during their delivery within the
biosys-tem.
Acknowledgment
My great appreciation and sincere gratitude to Prof. Dr. H.F. Aly, Prof. of
Nuclear Chemistry and Ex-Chairman of Atomic Energy Authority, for his
valuable help and support throughout this work.
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