Nanotechnol Rev 2014; 3(6): 579589

Research highlight
Kamkanam M. Supun Samindra and Nilwala Kottegoda*

Encapsulation of curcumin into layered double

hydroxides
Abstract: This study focuses on the encapsulation of natu
ral curcumin present in turmeric (Curcuma longa L.) into
a layered double hydroxide (LDH), which demonstrates
slow release properties with future potential in therapeu
tic applications such as slow release wound dressings.
Turmeric has been used in traditional medicinal appli
cations since ancient times. The main active substances
in turmeric are curcumin together with two related com
pounds, demethoxycurcumin (DMC) and bisdemethoxy
curcumin (BDMC), which have been extensively studied as
antibacterial compounds. However, these molecules are
unstable and, therefore, demonstrate limited biological
activity and practical applications. In this study, attempts
were made to synthesize curcumin in-situ encapsulated
layered LDHs in order to stabilize the curcumin mole
cules within the nanolayers of the LDHs. The curcumin
intercalated LDHs were synthesized by a simple in-situ
co-precipitation method. The release characteristics of
curcumin from the nanocomposites were quantitatively
monitored under different pH conditions using UV-Visible
spectroscopic methods, and the results indicate that the
nanocomposite has the future potential in slow release
therapeutic applications.
Keywords: curcumin; layered double hydroxides; nano
composites; slow release; turmeric.
DOI 10.1515/ntrev-2014-0018
Received July 19, 2014; accepted August 25, 2014; previously published
online October 10, 2014

*Corresponding author: Nilwala Kottegoda, Department of

Chemistry, University of Sri Jayewardenepura, Gangodawila,
Nugegoda 10250, Sri Lanka; and Sri Lanka Institute of
Nanotechnology, Nanotechnology and Science Park, Mahenawatta,
Pitipana, Homagama 10206, Sri Lanka, e-mail: nilwalak@sjp.ac.lk
Kamkanam M. Supun Samindra: College of Chemical Sciences,
Institute of Chemistry Ceylon, Rajagiriya 10100, Sri Lanka

1 Introduction
Layered double hydroxide (LDH) is a class of anionic clay
minerals, which is represented by the general formula
[MII1-xMIIIx(OH)2]x+(An-)x/nyH2O. Here, MII is a divalent metal
ion, MIII is a trivalent metal ion, and An- is an anion [1].
LDHs have attracted immense industrial and scientific
significance due to the diversity of potential composi
tions and wide range of physical and chemical proper
ties, which include features such as anion exchange
and ease of reconstruction following mild experimental
conditions. Structural properties known for their appli
cations are as catalysts, adsorbent materials, and anion
exchangers, while recent studies have emphasized other
applications including the controlled release of pharma
ceutically active drug components [2]. The most decisive
properties that make LDH useful in these industries are
their low toxicity, biocompatibility, high specific surface
area, and buffering effect [3]. One of the major challenges
in the pharmacology is to formulate active and more
stable drugs that can be released at a controlled rate in
the human body. In this context, LDHs have proven to be
beneficial as a matrix for encapsulation of a wide spec
trum of pharmaceutical and biologically active agents for
these purposes [4].
Turmeric (Curcuma longa L.) is a well-known medici
nal plant found in South Asian countries such as Sri Lanka
and extensively used in Ayurveda, Unani, and Siddha
medicinal treatments as remedy for various diseases [5].
Current Indian traditional medicine uses it for biliary dis
orders, anorexia, cough, diabetic wounds, hepatic disor
ders, rheumatism, and sinusitis [6]. Curcumin is the main
coloring substance, which is responsible for the charac
teristic yellow color in turmeric and finds many applica
tions in food and dye industries and agriculture [7]. More
importantly, it demonstrates antibacterial properties.
The wound healing ability of curcumin involving
the mechanisms of reduced inflammation, granulation,
and remodeling of the tissue has been intensively exam
ined in rats and guinea pigs. The recent studies have
highlighted that punch wounds in curcumin-treated

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580K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides
animals heal much faster than curcumin-untreated
animals [6]. However, the instability of curcumin under
normal environmental conditions has limited its practical
applications.
In this study, attempts were made to stabilize the
unstable curcumin molecules within the nanolayers
present in LDHs. The high aspect ratio in LDHs enables to
take the advantage of more for less as expected in nano
technology applications [8, 9].

2 Materials and methods

2.1 Chemicals
All the chemicals and reagents used were of analytical
grade purchased from Sigma Aldrich (St. Louis, MO, USA)
and used without further purification. Curcumin was
extracted from locally available turmeric, and the crude
extract was used without further purification.

2.2 E
 xtraction of crude curcumin from
turmeric
2.2.1 Sample preparation
Turmeric extract was prepared by using 20 g of ground
turmeric rhizome dissolved in 100.00 cm3 acetone and
left for 7days at room temperature. After 7 days, turmeric
extract was filtered, evaporated, and concentrated.

2.2.2 Column chromatography

The acetone extract was filtered and concentrated in a
rotary evaporator, then re-precipitated with petroleum
ether and vacuum dried. The crude curcuminoid mixture
contained curcumin, DMC, and BDMC. This mixture was
passed through a silica gel (60120 mesh) glass column.
Approximately 4 g of crude curcuminoids were mixed
with 8 g of silica gel by using dry column packing method.
Then, the sample was injected on top of the column and
eluted with chloroform followed by chloroform:methanol
ratio with increasing polarity. The collected fractions were
subjected to TLC test using chloroform:methanol (95:5) as
a solvent system, and spots were detected by its character
istic yellow color. Fractions with similar retention time, Rf
value, were pooled [10].

2.3 S
 ynthesis of layered double hydroxide
(LDH)
Mg-Al-LDH with nitrate anions within the layers was
used for comparison purposes. LDH was prepared by a
pH controlled co-precipitation method by adding a solu
tion containing Mg2+ and Al3+ ions (300.00 cm3 of Mg2+
and Al3+ solution was prepared by dissolving 1 mol dm-3
Mg(NO3)2.6H2O and 1 mol dm-3 Al(NO3)3.6H2O in 2:1 ratio)
dropwise to a solution containing 300.00 cm3 of 1 mol
dm-3 NaNO3 under vigorous stirring conditions at 60C.
During the addition period, the pH of the solution was
maintained at 9 by adding 1 mol dm-3 NaOH. Nitrogen
gas was purged in order to avoid any contamination by
atmospheric CO2. The slurry was then stirred overnight
in a closed container at 60C. Finally, it was filtered and
washed thoroughly with distilled water to remove impu
rities and was dried at 90C resulting in a white solid
[11, 12].

2.4 Synthesis of curcumin-encapsulated

LDH: in-situ method
Curcumin-encapsulated Mg-Al-LDH was prepared by an
in-situ co-precipitation method. A solution containing
Mg2+ and Al3+ (Mg2+:Al3+ ratio 2:1) was added dropwise
to a solution containing 200.00 cm3 of curcumin under
vigorous stirring conditions at 60C. During the addi
tion period, the pH of the solution was maintained at 9
by adding 1 mol dm-3 NaOH. Nitrogen gas was purged in
order to avoid any contamination by atmospheric CO2.
The slurry was then stirred overnight in a closed con
tainer at 60C. Finally, it was filtered and washed thor
oughly with distilled water to remove impurities and was
dried at 90C [11, 12].

2.5 Characterization techniques

Functional group identification was done using Bruker
Vertex 80 FT-IR (Fourier transform-infrared spectroscopy)
with OPUS 6.5 software. The desiccated sample was added
to standard KBr in 1:100 ratio and mixed thoroughly. The
portion of the mixed sample was pelletized, and the trans
mission spectra of the resulting pellet were obtained in
10004000 cm-1. The composition and purity of LDH
and LDH-curcumin were determined by Bruker D8 focus
Powder X-ray diffractometer (PXRD) fitted with a copper
tube (CuK radiation, 1.541 source), an incident beam
monochromator, and a scintillation detector. Diffraction

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K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides581

patterns were collected over the range 170 2 and a

step size of 0.020. Thermogravimetric analysis was done
at the temperature range of 25900C on a Thermo SDT
Q600 TG-DTA analyzer under N2 atmosphere at a heating
rate of 10C/min. TGA results may be used to determine
the water content and properties such as thermal stability,
decomposition, and the composition of the material. UVVisible spectroscopy was done using Shimadzu UV-3600
(using the solid state attachment, a thin layer of sample
pressed onto a substrate of analytical-grade BaSO4) to
evaluate the structural and bonding stability of LDH
and LDH-curcumin nanocomposites. The release studies
were carried out using the same spectrophotometer but
with the solution state attachment. Surface morphologi
cal analysis was carried out using a Hitachi SU 6600 SEM
(scanning electron microscope), which has an accelerat
ing voltage of 20.0 kV.

2.8 Release studies of LDH-curcumin

nanocomposite
Approximately 50 g of LDH-curcumin nanocomposite was
placed uniformly in the bottom of a 100-cm3 glass beaker,
and 100.00cm3 of pH-adjusted buffer solution was added
carefully along the wall of the beaker to avoid agitation.
Under different pH conditions (pH: 2, 5, 8), the release of
curcumin was quantitatively monitored over 2h of fixed
time period, withdrawing 5.00ml of solution every 15-min
time interval, and the UV-Visible absorption spectra was
recorded to quantify the concentration of de-intercalated
curcumin in the aqueous phase (during the period of
study, the total volume was kept constant).

3 Results and discussion

3.1 Thin-layer chromatography (TLC)

2.6 UV degradation of curcumin

Approximately 20 g of crude curcumin was placed uni
formly in the bottom of a 1-l glass beaker, and 1000.00cm3
of pH-adjusted buffer solution was carefully added along
the wall of the beaker to avoid agitation. The degradation
of curcumin was quantitatively monitored in the pres
ence of a UV source over 2h of fixed time period. The total
volume of the beaker was kept constant, and 5.00 ml of
solution was withdrawn every 30-min time interval. UVVisible absorption spectroscopy was used to quantify the
concentration of de-intercalated curcumin in the aqueous
phase (total volume of the solution was kept constant by
adding the removed solutions back).

2.7 UV degradation of LDH-curcumin

Approximately 50 g of well-dried LDH-curcumin nano
composite was placed uniformly in the bottom of a
100-cm3 glass beaker, and 100.00 cm3 pH-adjusted
buffer solution was carefully added along the wall of
the beaker to avoid agitation. Degradation of curcumin
being released from the LDH-curcumin nanocomposite
was quantitatively monitored in the presence of a UV
source over 2 h of fixed time period in acidic medium.
The total volume of the beaker was kept constant, and
5.00 ml of solution was withdrawn every 30-min time
interval. UV-Visible absorption spectroscopy was used to
quantify the concentration of de-intercalated curcumin
in the aqueous phase.

All the eluted sample fractions in silica gel column chroma

tography were collected quantitatively in test tubes (approx
imately 20 cm3) and were subjected to TLC technique using
chloroform:methanol (95:5) as the developing solvent
system. Curcumin can be easily detected as yellow spots,
and fractions were pooled according to their Rf values [7].
According to Figure 1, the curcumin component was
comparatively nonpolar compared to demethoxycur
cumin (DMC) and bisdemethoxycurcumin (BDMC). Hence,
after the sample introduction, curcumin eluted during the
mobile phase, which was having a lower affinity during
the stationary phase. The component, therefore, moved
along the glass column at a faster rate compared to the
other components. Then, the pure curcumin fractions
(Figure 2) were collected at fractions 16 (Rf value of cur
cumin is around 0.75).
In Figure 3, the three main components in turmeric are
listed according to their Rf values. Therefore, the seventh
and eighth fractions were contaminated with demethoxy
curcumin (DMC), which has an Rf value of approximately
0.57. Then, the pure demethoxycurcumin (DMC) compo
nent was collected using fractions 911 (Figure 4). But
further extraction can be ignored as the study was com
pletely focused on curcumin.

3.2 C
 haracterization of curcumin-LDH
nanocomposites
The nature of the changes in the bonding environment of
curcumin after encapsulation into LDH was studied using

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582K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides
HO

CH3

H3C
O

OH

HO
Curcumin

[A]
[B]
[C]

HO

CH3

Rf [A]: 7.5/10 = 0.75

Rf [B]: 5.7/10 = 0.57
Rf [C]: 4.2/10 = 0.42

OH

HO
Demethoxycurcumin

Figure 3TLC plate for turmeric extracts using chloroform:methanol

(95:5) as a solvent system.
HO

OH

HO
Bisdemethoxycurcumin

Figure 1Structures of curcumin, demethoxycurcumin, and

bismethoxycurcumin.

[A]
[B]
[C]

[8] [9] [10] [11]

[A]
[B]
[C]

Figure 4TLC plate of corresponding fractions 811. Rf [8]:

0.6/9.9=0.69 and Rf [8]:0.56/9.9=0.56; Rf [9]: 0.55/9.9=0.55;
Rf [10]: 0.58/9.9=0.58; Rf [11]: 0.53/9.9=0.53.

Figure 2TLC plate of corresponding fractions 17. Rf [1]:

7.3/9.9=0.73; Rf [2]: 7/9.9=0.7; Rf [3]: 7.1/9.9=0.71 Rf [4]:
6.9/9.9=0.69; Rf [5]: 7/9.9=0.7; Rf [6]: 7/9.9=0.7; Rf [7]: 7/9.9=0.7,
and Rf [7]: 0.55/9.9=0.55.

and indicate the presence of O-H groups. After the inter

calation, there is a noticeable shift of the O-H stretching
vibrational bands. For pure LDH, pure curcumin and LDHcurcumin the -OH stretching (v-OH) vibrations were observed
at 3385, 3357 and 3380 cm-1 respectively (Table 1). This is
due to the formation of strong hydrogen bonds between
curcumin and -OH groups in LDH. The change in broad
ness of the O-H peak further confirms the organic nature of
the interlayer region compared to the parent nitrate.
For LDH-curcumin, the band position of the stretch
ing vibration of CO groups present in the curcumin has
shifted from 1383cm-1 to 1364cm-1 due to the interaction
with LDH where this shift agrees with a strong van der
Waals bonding network. A band at 1358cm-1 for pure LDH
is due to the stretching vibration of CO, which might

[1] [2]

[3] [4] [5] [6] [7]

Fourier transform infrared spectroscopy (FTIR). Figure 5

compares the FTIR spectra of pure LDH, curcumin, and
curcumin-intercalated LDH. FTIR spectra of pure LDH and
LDH-curcumin show bands in the region of 33003400cm-1

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K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides583

[a]
2934
1383

Transmittance

[b]

1614
3357

942
769

1635

[c]

1358

3385

663

2919
1629
764
1364

3380

4500

4000

3500

3000

2500

2000

1500

1000

500

Wavenumber (cm-1)
Figure 5FT-IR spectra of (a) curcumin, (b) pure LDH, and (c) LDH-curcumin.

Type of bond

Pure
LDH cm-1

Pure
curcumin cm-1

LDHcurcumin cm-1

O-H stretching

CO stretching
H-O-H bending

C-H stretching

Al-O-H stretching
Mg-O-H stretching

3385
1358
1635

942
769

3357
1383
1614
2934

3380
1364
1629
2919
944
764

Lin (counts)

Table 1FT-IR bands frequencies (cm-1) of pure LDH, pure curcumin,

and LDH-curcumin.

[a]

[b]

have formed due to the absorption of atmospheric carbon

dioxide gas.
For pure curcumin and LDH-curcumin, C-H stretching
bands were observed at 2934 and 2919 cm-1, respectively.
In pure LDH, the typical bands were observed at 942cm-1
for Al-O-H stretching and 769cm-1 for Mg-O-H stretching.
For pure LDH, pure curcumin, and LDH-curcumin, peaks
at 1635, 1614, and 1629 cm-1 correspond to the bending
vibration mode of hydrated water molecules and weakly
bonded water molecules [13, 14].
Powder X-ray diffraction analysis (PXRD) was used
to understand the successful encapsulation of curcumin
into the LDH. PXRD pattern of the pure nitrate-LDH and
LDH-curcumin are shown in Figure 6. A typical diffraction
peak at 2=10 was observed for the pure nitrate-LDH cor
responding to the basal reflection. This peak position and
the interlayer spacing of 8.75 agrees with that reported
for nitrate-intercalated LDHs [15]. Surprisingly, for cur
cumin-LDH, the basal reflection has shifted to a higher

10

20

30

40
50
2-Theta-scale

60

70

80

Figure 6PXRD patterns of (a) pure nitrate-LDH and (b) LDHcurcumin nanocomposite.

2 value of 11.5, and the observed interplane spacing for

curcumin-LDH is 7.66 .
The possible encapsulation reaction of curcumin
into LDH can be explained by considering the structure of
the curcumin. The structure of LDH consists of positively
charged cation layers and anions in the interlayer spacing
and water molecules. The keto-enol tautomerism of cur
cumin as given in Figure 7A allows to form a negative charge
on the curcumin structure at basic pH values; hence, as a
result, curcumin can be intercalated or encapsulated into
the interlayer spacing and surface hydroxyl groups during

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584K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides
O

OH

HO
H 3C

H 3C

OH

HO
H 3C

OH

H3C

6.9A
HO

OH
O

CH3

H3C

Figure 8Width of curcumin molecule.

OH

HO
H3C O

Inter plane distance

H3C O

C
Inter plane distance

Figure 7(A) Curcumin exhibits keto-enol tautomerism. (B) Plane

of curcumin perpendicular to the cation layer. (C) Plane of curcumin
parallel to the cation layer.

the co-precipitation reaction. Although curcumin molecules

demonstrate an overall hydrophobic nature, the presence
of hydrophilic hydroxyl groups and the negative charges
originated as a result of keto-enol tautomerism drives the
curcumin groups into the interlayer spacing of LDHs.
As a result of keto-enol tautomerism, curcumin is able
to adapt into a flat conformation allowing the plane of the
curcumin to be placed within the interlayer spacing either
parallel or perpendicular to the cation layer.
The interlayer spacing compared to the smaller nitrate
group reduced when curcumin was intercalated.
According to Figure 8, when comparing the width of
the curcumin (approximately 6.9 ) molecule with the basal
spacing between the cation layer, it is almost impossible
or less feasible to stack in a perpendicular arrangement
to the cation plane, hence, to accommodate the charge
balance and the most stable form of staking between the
interlayer in a parallel conformation. The other reason for
the lower interlayer spacing is attributed to the reduction of
the degree of hydration between the layers, in the presence
of large organic molecules. Additionally, some extra peaks

corresponding to un-intercalated crystalline curcumin

molecules are observed. These peaks do not disappear
upon washing with excessive water or acetone indicating a
strong affinity toward the nanolayers. These molecules are
expected to be encapsulated onto the layers and layer edges.
Typical TGA curve for pure LDH (Appendix Figure 1)
showed weight loss around 100C due to the evolving of
surface water. The second weight loss was at around 200C
corresponding to the removal of the interlayer water in the
layered structure [16].
The structure of LDH consists of positively charged cation
layers and anions in the interlayer spacing. In addition, water
molecules in between the layers are hydrogen bonded to the
interlayer anions and to the -OH groups on the surface of the
brucite-like structure. Hence, the LDH consists of much higher
water content than other respective composites. In TGA anal
ysis of pure LDH, the initial weight loss between room tem
perature and 200C was reported around 59.2% which is due
to the removal of interlayer and physisorbed water (Appendix
Figure 2). The weight loss between 450C to 1000C is attrib
uted to the complete dehydroxylation of the Mg-Al hydroxide
layers and the temperature treatment beyond 600C caused a
collapse of the layered structure (Table 2).
In LDH-curcumin nanocomposites, the interlayer
spacing consists of organic anions, water molecules, and
other anions (hydroxide) that may intercalate during the
synthesis. As a result of the presence of organic mole
cules, which are less prone to be hydrated, LDH-curcumin
consists of much lower water content compared to pure
LDH. In TGA analysis, the weight loss of LDH-curcumin
due to the removal of water was reported around 18%.
This observation further corroborates the PXRD evidences
of reduction in the degree of hydration. After the removal

Table 2Percentage weight loss (%) of pure LDH, curcumin, and LDH-curcumin.
Sample
Pure LDH

Room temperature to 200C weight loss/% 200400C Weight loss/%

Curcumin

LDH-curcumin

4001000C Weight loss/%

55.8 (94C) (removal of surface water)

4.8 (305C) (complete dehydroxylation) 3.6 (482C) (complete decomposition)
3.4 (187C) (removal of interlayer water)

3.3 (174C) (dehydroxylation of OH groups) 45.9 (391C) (complete decomposition)

17.6 (72C) (removal of water)
8.6 (235C) (complete dehydroxylation) 7.6 (406C) (complete decomposition)

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K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides585

of physisorbed and chemisorbed water, the temperature

between 200C and 450C LDH-curcumin showed com
plete dehydroxylation (8.6% weight loss) and completely
decomposed after 406C [17, 18].
The observations suggest that intercalation of cur
cumin into an LDH thermally stabilizes the curcumin
molecule. It shifts the decomposition temperature from
391C to 406C after encapsulation. This improved stabil
ity allows better processing stability in pharmaceutical
applications during industrial applications.
UV-Visible spectra have been used to evaluate the
change in max value in the pure compounds and the com
posites. As observed by UV-visible spectroscopy pure cur
cumin absorbs at max of 425 nm while the LDH-curcumin
nanocomposite absorbs at 459 nm (Table 3).
Curcumin consists of two chromophores (CO) and
exhibits keto-enol tautomerism, which allows the overall
structure to become more negatively charged and forming
H-bonds with LDH. During these interactions, the level
of conjugation has increased when curcumin curcumin
is encapsulated within the LDH matrix suggesting an
increased stability of curcumin. This observation clearly
concludes that the photo stability of the curcumin has
improved after intercalation into the layered structures.
Scanning electron micrograph of pure Mg-Al-LDH and
LDH-curcumin presented in Figure 9A shows a typical
plate-like morphology for the pure LDH. Interestingly, as
shown in Figure 9B, the same plate-like morphology is pre
served after the synthesis of the nanocomposite, indicating
a topotactic reaction mechanism. However, the crystallin
ity of the composite has reduced once the organic guest
molecules are intercalated. This observation is further sup
ported by the PXRD data. However, any crystalline phases
of other compounds were not observed in SEM imaging.

3.3 UV degradation of curcumin

The main coloring component in turmeric is curcumin,
which is relatively unstable against the constant irradia
tion of UV light at acidic medium.
According to Figure 10, the initial concentration of
curcumin is high, but when it is exposed to UV irradiation,
Table 3max (nm) of pure LDH, pure curcumin, and LDH- curcumin.
Sample

max/nm

Pure LDH

Curcumin

LDH-curcumin

301.00
425.00
459.00

Figure 9SEM images of (A) Pure Mg-Al-LDH, (B) LDH-curcumin

nanocomposite.

it undergoes a rapid loss in curcumin concentration.

The possible degradation products of curcumin at pH2
were determined by HPLC technique and is listed in
Figure 11 [19].
The degradation products of curcumin under various
pH conditions are mainly due to the autoxidation process
where the radical chain reaction leads to the incorporation
of oxygen into curcumin, resulting in the major products
such as dioxygenated bicyclopentadione p
roducts and
ferulic acid, feruloylmethane, vanillin as minor products
[20].

3.4 UV degradation of LDH-curcumin

This evaluation is mainly focusing on the releasing stabil
ity of LDH-curcumin nanocomposite in the presence of UV
light at acidic pH. Figure 12 shows that the LDH-curcumin

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586K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides
ability of LDH-curcumin nanocomposite due to the layered
structure of LDH, which provides stability to curcumin to
remain stable slightly longer under UV irradiation and to
maintain the constant release.
In other words, with time, curcumin molecules are
released to the medium in a sustained manner. In the
process, the released amount of free molecules is higher
than the rate of degradation; therefore, increase in the
concentration is observed.

3.5 Release behavior of LDH-curcumin

Figure 10The graph of absorbance vs. time of UV degradation of

curcumin.

nanocomposite releases curcumin in a consistent level

despite the fact that curcumin, itself, degrades against
the UV light in considerable rate according to Figure 10,
which means the UV irradiation directly affects curcumin
to degrade but showed a minimal effect on the releasing

The releasing ability of LDH-curcumin has been tested

in different pH conditions (pH: 2, 5, 8) under selected
kinetic models. Curcumin has a possibility of exhibiting
keto-enol tautomerism at pH 8. Owing to the presence of a
high concentration of OH- ions in the medium, curcumin
stabilizes between the LDH nanolayers. In other words, at
pH>7, the curcumin molecules exist in keto-enol tauto
merism, and it drives the nanocomposite formation with
the double hydroxide layers. As a result, the curcumin
molecules are well protected within the layers preventing

HO

OH

H3C

H3C

OH
O

OH as
radical
HO
O
CH3

H3C

HO
H 3C

OH

Condensation products

Ferulic acid

Feruloylmethane
OH
O
O
H3C

HO
H 3C

CH3

Vanillin

Acetone

Figure 11Degradation products of curcumin.

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K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides587

pure curcumin cannot be followed due to the instant dis

solution of curcumin under the low pH values (Figure 13).

4 Conclusions

Figure 12The graph of absorbance vs. time of UV degradation of

LDH-curcumin.

any degradation or release at higher pH values. Therefore,

the LDH-curcumin nanocomposite showed insignificant
release at basic pHs.
One the other hand, the medium of pH 2 consists of
more H+ ions than OH- ions compared to that with pH 5,
which does not allow curcumin to undergo keto-enol tau
tomerism, which enables curcumin to release gradually
due to the destabilization of interaction between LDH and
curcumin. The release pattern demonstrates a slow releas
ing behavior at acidic pHs under zero-order kinetics when
curcumin intercalated to LDH, but the release patterns of

Figure 13(At/A0) vs. time for release of curcumin at pH 2 (zero

order).

Curcumin derived from natural turmeric was successfully

encapsulated into Mg-Al-NO3-LDH by co-precipitation
method. The FT-IR spectra confirmed the presence of cur
cumin in the LDH. The change in the interlayer spacing
in nitrate LDH obtained by PXRD characterization further
suggests the successful encapsulation reactions between
LDH nanolayers and curcumin. Higher thermal stability
was observed from TGA characterization. Comparing the
UV stability of curcumin and LDH-curcumin, a better UV
stability in encapsulated products were observed. Slow
release characteristics were observed at pH 2. The product
therefore, demonstrates future potential as wound
dressings.
Acknowledgments: The authors acknowledge all the aca
demic and non-academic members of SLINTEC for their
valuable guidance and the discussions and for providing
necessary facilities, and Institute of Chemistry, Ceylon, for
the lab facilitation. The authors wish to extend their grati
tude to Prof. B.M.R. Bandara, Department of Chemistry,
University of Peradeniya, Sri Lanka, for the valuable dis
cussions and guidance.

Appendix

Appendix Figure 1TGA thermograms of (a) curcumin, (b) LDHcurcumin, and (c) pure LDH.

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588K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides
120

0.6
391C
[a]

100

0.4

80
0.2
[c]

60

406C

[d]

Deriv. weight (%/C)

Weight (%)

[b]

0.0

40

20

200

400
Temperature (C)

600

-0.2
800

Appendix Figure 2TGA thermograms of (a) curcumin and (b) LDH-curcumin; DTA thermograms of (c) LDH-curcumin and (d) curcumin.

References
[1] Das A, Costa FR, Wagenknecht U, Heinrich G. Nano composites
based on chloroprene rubber: effect of chemical nature and
organic modification of nanoclay on the vulcanizate properties.
Eur. Polym. J. 2008, 44, 34563465.
[2] Mitchell S, Gardner C, Jones W. Terephthalate Intercalated
Layered Double Hydroxides: Use of AFM to Study the Influence
of Temperature on Crystallite Morphology, Resumen SEM/SEA,
Department of Chemistry, Cambridge University, Lensfield Road:
Cambridge (UK), 2008, pp. 161162.
[3] Shafiei S, Birgani ZT, Darvish A, Azimi MS, Solati-Hashjin M.
Layered Double Hydroxides for Diagnostic Applications, International Congress of Evaluation of Medical Diagnosis Modern
Technologies,Tehran, Iran. 2008, pp. 790793.
[4] Nhlapo NS. Intercalation of Fatty Acids into Layered Double
Hydroxide, Department of Chemistry, Faculty of Natural and Agricultural Science, University of Pretoria: Pretoria, 2008.
[5] Chattopadhyay I, Biswas K, Bandyopadhyay U, Banerjee RK.
Turmeric and curcumin: biological actions and medicinal applications. Curr. Sci. (Indian Acad. Sci.), 2004, 87, 4453.
[6] Aggarwal BB, Kumar A, Aggarwal MS, Shishodia S. Curcumin
derived from turmeric (Curcuma longa): a spice for all seasons.
Phytopharmaceuticals in Cancer Chemoprevention 2005, 23,
351387.
[7] Jasim F, Talib T. Some observations on the thermal behaviour
of curcumin under air and argon atmospheres. J. Therm. Anal.
1992, 38, 25492552.
[8] Li B, He J, Evans DG, Duan X. Inorganic layered double
hydroxides as a drug delivery system intercalation
and in vitro release of fenbufen. Appl. Clay Sci. 2004, 27,
199207.
[9] Suzuki N, Nakamura Y, Watanabe Y, Kanzaki Y. Intercalation compounds of layered materials for drug delivery use. II. Diclofenac
sodium. Chem. Pharm. Bull. 2001, 49, 964968.

[10] Revathy S, Elumalai S, Benny M, Antony B. Isolation, purification and identification of curcuminoids from turmeric (Curcuma
longa L.) by column chromatography. J. Exp. Sci. 2011, 2, 2125.
[11] Yang QZ, Zhang CG, Sun DJ, Jin ZL. Studies on synthesis and
properties of Mg-Al-nitrate layered double hydroxides. Chin.
Chem. Lett. 2003, 14, 7982.
[12] Rajamathi M, Thomas GS, Vishnu Kamath P. The many ways
of making anionic clays. Proc. Indian Acad. Sci. (Chem. Sci.),
2001, 113, 671680.
[13] Kameda T, Saito M, Umetsu Y. Preparation and characterisation
of Mg-Al layered double hydroxides intercalated with 2-naphthalene sulphonate and 2,6-naphthalene disulphonate. Mater.
Trans. 2006, 47, 923930.
[14] Islam M, Patel R. Synthesis and physicochemical characterization of Zn/Al chloride layered double hydroxide and evaluation of its nitrate removal efficiency. Desalination 2010, 256,
120128.
[15] Marappa S, Radha S, Vishnu Kamath P. Nitrate-intercalated layered double hydroxides structure model, order, and disorder.
Eur. J. Inorg. Chem. 2013, 12, 21222128.
[16] Gago S, Pillinger M, Santos TM, Gonalves IS. Zn-Al Layered
Double Hydroxide Pillared by Different Dicarboxylate Anions,
Department of Chemistry, CICECO, University of Aveiro: Aveiro,
Portugal, 2004, pp. 3810193.
[17] Hariharan R, Senthilkumar S, Suganthi A, Rajarajan M.
Photodynamic action of curcumin derived polymer modified
ZnO nanocomposites. Mater. Res. Bull. 2012, 47, 30903099.
[18] Maseka A, Chrzescijanskab E, Zaborskia M. Characteristics of
curcumin using cyclic voltammetry, UVvis, fluorescence and
thermogravimetric analysis. Electrochim. Acta 2013, 107, 441447.
[19] Kumavat SD, Chaudhari YS, Borole P, Mishra P, Shenghani K,
Duvvuri P. Degradation studies of curcumin. Int. J. Pharm. Rev.
Res. 2013, 3, 5055.
[20] Gordon ON, Schneider C. Vanillin and ferulic acid are not the
major degradation products of curcumin. Trends Mol. Med.
2012, 18, 361364.

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K.M. Supun Samindra and N. Kottegoda: Encapsulation of curcumin into layered double hydroxides589

K.M. Supun Samindra is a graduate student at the Institute of

Chemistry Ceylon, Sri Lanka with a Second Class Upper honors
(Special) in the field of Chemistry. His undergraduate research,
supervised by Dr. (Mrs) Nilwala Kottegoda, is focused on
LDH-Curcumin hybrid nano-composites and their therapeutic
potentials and his research interests are in organic and inorganic
nanostructured materials.

Nilwala Kottegoda obtained her BSc Hons in Chemistry, from University of Peradeniya, Sri Lanka, and her Doctor of Philosophy (DPhil)
in materials chemistry from the University of Cambridge, UK. She is
a senior research scientist at Sri Lanka Institute of Nanotechnology
(SLINTEC), and a senior lecturer at the Department of Chemistry,
University of Sri Jayewardenepura, Sri Lanka. Her research interests
are in the areas of nanomaterials, nanocomposites, nanotechnology
for value addition to natural resources in Sri Lanka and nanotechnology for agricultural value addition.

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