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Journal of Physics and Chemistry of Solids 107 (2017) 62–67

Contents lists available at ScienceDirect

Journal of Physics and Chemistry of Solids


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

Synthesis and characterization of Zn-Ti layered double hydroxide MARK


intercalated with cinnamic acid for cosmetic application

Yong Li, Liping Tang, Xinxu Ma, Xinrui Wang , Wei Zhou, Dongsheng Bai
Beijing Key Lab of Plant Resource Research and Development, School of Science, Beijing Technology and Business University, Beijing 100048, PR China

A R T I C L E I N F O A BS T RAC T

Keywords: The use of sunscreen is recently growing and their efficacy and safety must be taken into account since they are
Layered double hydroxides applied on the skin frequently. In this work, an organic ultraviolet (UV) ray absorbent, cinnamic acid (CA) was
Cinnamic acid intercalated into Zn-Ti layered double hydroxide (LDH) by anion-exchange reaction. ZnTi-CA-LDH, a new type
UV blocking of host-guest UV-blocking material has been synthesized. Detailed structural and surface morphology of ZnTi-
Sunscreen cream
CA-LDH were characterized by XRD, FT-IR, SEM and TEM. ZnTi-CA-LDH exhibits a superior UV blocking
ability compared to pure CA and ZnTi-CO3-LDH. The thermal stability of the intercalated ZnTi-CA-LDH was
investigated by TG-DTA, which showed that the thermostability of CA was markedly enhanced after
intercalation into ZnTi-CO3-LDH. The EPR data showed greatly decreased photocatalytic activity compared
to common inorganic UV blocking agents TiO2 and ZnO. Furthermore, the sample was formulated in a
sunscreen cream to study the matrix protective effect towards UV rays.

1. Introduction of the material and anion exchange properties of LDH materials make
them receive much attention in the fields of catalysis, separation,
UV radiation from the sun is conventionally divided into three biology, adsorbents and functional additives [7–11]. Therefore, it can
categories depending on its wavelength, UVC (100–280 nm), UVB be anticipated that the incorporation of the organic UV absorbent into
(280–320 nm) and UVA (320–400 nm). Short wavelength UVC radia- an LDH matrix will give rise to one kind of fine sunscreens with the
tion is completely absorbed in the ozone layer, the remaining UVB following advantages. Firstly, the supramolecular layered host-guest
together with UVA reach the earth surface and cause damage to our structure of LDH enables both physical shielding (by LDH host layers)
skin (such as sunburn, suntan, acceleration of aging, skin cancer, etc.) and chemical absorption (by interlayer guest) of UV light. Secondly, the
[1]. Therefore, protection of human health from solar ultraviolet presence of the inorganic LDH host matrix may improve the thermal
radiation has been a complex problem and thus advanced materials and optical stability of the intercalated organic UV absorber. Finally,
are in demand for the effective treatment and protection of human the absence of a close contact between skin and organic UV absorber
health. could increase the safety of the cosmetic formulations [12,13].
Sunscreens are widely used to protect human skin against the In this paper, we describe the intercalation of cinnamic acid (CA) in
harmful effects of UV radiation. A wider variety of organic compounds ZnTi-LDH. Cinnamic acid (CA) is an organic compound with the
including camphors, benzophenones, cinnamates, and triazines have formula (C6H5CHCHCO2H) and it is widely spread in the plants, such
been frequently used as sunscreen material because of their excellent as cinnamon, balsams and shea buffer. It is used as flavors and
UV ray absorption ability. However, some disadvantages restrict their pharmaceutical ingredients. In addition, CA and its derivatives are
wide application, such as instability and toxicity at high concentration also used as a UV-absorber in cosmetic preparations, because they
[2,3]. It is an interesting alternation to incorporate organic UV absorb a broad range of UV light, their molar extinction coefficient is
absorber in an inorganic host matrix to avoid direct contact of organic high. Unfortunately, it may show a loss of its specific function when
molecules to the human skin. penetrating the skin surface and may pose safety problems when used
Layered double hydroxides (LDHs) are a class of anionic clays, at a high concentration [14]. To avoid a direct contact with skin and
consist of stacked brucite-type [Mg(OH)2] octahedral layers with water optimize the UV blocking properties, ZnTi-LDH was chosen as lamellar
molecules and anions occupying the space between the layers [4–6]. host. Zn and Ti are metals largely used both in pharmaceutical and
The tunable metal ions in a wide range without changing the structure cosmetic formulations, they both used as oxide (ZnO and TiO2) for sun


Corresponding author.
E-mail address: wangxinrui@th.btbu.edu.cn (X. Wang).

http://dx.doi.org/10.1016/j.jpcs.2017.02.018
Received 18 October 2016; Received in revised form 21 December 2016; Accepted 3 February 2017
Available online 29 March 2017
0022-3697/ © 2017 Elsevier Ltd. All rights reserved.
Y. Li et al. Journal of Physics and Chemistry of Solids 107 (2017) 62–67

photoprotection and dermatologic treatments, as zinc ions are also Table 1


known to have a critical and important role in overall skin health [15]. Composition of the emulsion.
We have successfully prepared the ZnTi-CO3-LDH precursor at first,
Ingredients Percent by
and intercalated CA into ZnTi-LDH by anion-exchange reaction. UV weight
ray resistance ability, thermal stability and photocatalytic capability
were investigated. The anti-ultraviolet performance of the intercalation Phase A Purified water 85.06
Ethylenediamine tetraacetic acid disodium salt 0.10
products in sunscreen cream has also been evaluated compared with
Stabileze QM ( PVM/MA Decadiene crosspolymeer) 0.30
those of the same formulations have not added the intercalation Phase B Prolipid 141 ( Glyceryl stearate/behenyl alcohol/ 5.00
products. The studies suggest that ZnTi-CA-LDH composites have palmitic acid/stearic acid,etc)
potential applications as safe sunscreen materials. X-Tend 226 (Phenethyl Benzoate) 1.00
Ceraphyl 368 (Ethylhexyl palmitate) 5.00
Ceraphyl SLK (Isodecyl pivalate) 2.00
2. Experimental
Phase C NaOH(10%) 1.04
Phase D Liquid Germall Plus (Diazolidinylurea/ 0.50
2.1. Materials Iodopropynyl butylcarbamate/Methylparaben)
Phase E ZnTi-CA-LDH 10.00
Analytical grade Zn(NO3)2·6H2O, TiCl4, urea, CA, disodium EDTA
and anhydrous alcohol were purchased from Sinopharm Chemical
elemental analysis instrument. The generation of radical species was
Reagent Co., Ltd and used without further purification. Stabileze QM
monitored by electron spin resonance (EPR) spectroscopy (Bruker
(PVM/MA Decadiene crosspolymeer), Prolipid 141 (Glyceryl stearate/
E500 EPR spectrometer) with dimethylpyridine N-oxide (DMPO) as a
behenyl alcohol/palmitic acid/stearic acid, etc), X-Tend 226
spin-trapping reagent, The sample are irradiated with a lamp simulat-
(Phenethyl Benzoate), Ceraphyl 368 (Ethylhexyl palmitate), Ceraphyl
ing solar light for 1 min. The cream were investigated by a Agilent Cary
SLK (Isodecyl pivalate) and Liquid Germall Plus (Diazolidinylurea/
60 UV spectrophotometer.
Iodopropynyl butylcarbamate/Methylparaben) were kindly provided
by Ashland (Beijing, China). The deionized and decarbonated water
was used in all the preparation processes. 2.5. Preparation of sunscreen creams

2.2. Preparation of ZnTi-CO3-LDH The cream used for the sunscreen formulations had the following
composition, see Table 1.
ZnTi-CO3-LDH precursor was prepared by the co-precipitation of Hydrophilic-phase A and oil-phase B were heated separately to
zinc and titanium salts from a homogeneous solution. TiCl4 (0.44 mL), 80 ℃, until the components of each part were solubilized. The oily
Zn(NO3)2·6H2O (4.76g) and urea (6.0g) were dissolved in deionized preparation was added slowly to the hydrophilic preparation with
water (200 mL) under vigorous stirring. The resulting reactant was constant stirring. Next, phase C was added into the above mixture with
aged in an autoclave at 130 ℃ for 48 h. The precipitate was centrifuged, constant stirring. Cooled down to 45 ℃, then phase D was added. It was
washed thoroughly with deionized water, and finally dried at 60 ℃ for necessary to continue stirring until the emulsion formed was cooled to
12 h. room temperature. Finally, the intercalated product (10%) were added.
In addition, the cream without any intercalated product were prepared
2.3. Preparation of ZnTi-CA-LDH as a blank.

CA anion intercalated LDH (ZnTi-CA-LDH) was prepared by anion- 3. Results and discussion
exchange using ZnTi-CO3-LDH precursor. CA (0.2 M) was dissolved in
a mixed solution of water and ethanol with 1:1 vol ration. ZnTi-CO3- 3.1. Structural and morphological characterization of LDH
LDH precursor (0.12 M) was mixed with the solution of CA followed by
aging under N2 atmosphere at 50 ℃ overnight. The resulting precipi- The XRD patterns of ZnTi-CO3-LDH precursor and ZnTi-CA-LDH
tate was centrifuged, thoroughly washed, and dried under vacuum at are shown in Fig. 1. The XRD pattern of the ZnTi-CO3-LDH precursor
60 ℃ overnight. (Fig. 1a) exhibits typical characteristics of the LDH phase. The strong
(003) peak reflection at 13.22° and the reflections of (006), (009) at
2.4. Characterization
003
X-ray diffraction (XRD) measurements were carried out by a 009
Bruker D2 X-ray powder diffraction with Cu Kα radiation(
λ=1.5406 Å) at 30 kV, 10 mA, and the recorded range of 2θ is from
5° to 70° with a scan rate of 5° min−1. The FT-IR spectra were recorded
Intensity

on a Thermo Scientific Nicolet IS 10 instrument equipped in attenuated 006


total reflectance (ATR) mode. Thermogravimetric (TG) analysis was
performed on TGA Q5000IR instrument in the temperature range 20–
012 110 113
650 ℃ with a heating rate of 10 ℃ min−1 in air. Scanning electron b
microscopy (SEM) images were obtained using a Hitachi S-4700
003
scanning electron microscope operating at 20 kV. High resolution
TEM (HRTEM) observations were carried out on a JEOL JEM-2100 012 009
006 110 113 a
transmission electron microscope. Diffuse reflectance spectra were
performed on a UV–vis–NIR spectrophotometer (UV-3700,
Shimadzu), BaSO4 served as a reference standard. Content analysis 10 20 30 40 50 60 70
of metals was performed by ICP atomic emission spectroscopy on a
Shimadzu ICPE-9000 instrument using the solutions prepared by
2 Theta (degree)
dissolving the samples in hot concentrated H2SO4. Carbon, hydrogen, Fig. 1. X-ray powder diffraction patterns of (a) ZnTi-CO3-LDH precursor and (b) ZnTi-
and nitrogen analyses were carried out using a vario EL CUBE CA-LDH.

63
Y. Li et al. Journal of Physics and Chemistry of Solids 107 (2017) 62–67

24.42°, 35.02°, which correspond to the basal and higher-order


c
reflections. The basal spacing value (d003) of the ZnTi-CO3-LDH is
0.669 nm, which is close to the value reported in the literature [16]. It

Transmittance (%)
should be noted that several weak reflections appear at 2θ=22, 31 and 3220
36° for ZnTi-CO3-LDH, which can be assigned to a small amount of 1532 1396
zinc hydroxide impurity (PDF card No. 20–1437). After CA anion was
intercalated into the interlayer galleries of ZnTi-LDH, the main
b
characteristic reflections of the product appear at 6.34° (003), 12.51°
(006), 18.71° (009) and the d003 (1.362 nm), d006 (0.681 nm) and d009 3070
(0.463 nm) spacings present a good multiple relationship for the basal, 1418
second and third-order reflections (Fig. 1b). The results suggested that a 1670 1627 1285
CA was successfully intercalated into the interlayer galleries of the
LDH. This is confirmed by the shift of the (003), (006) and (009)
3225 1502 1384
diffraction peaks to low angle. It should be noted that the 009 reflection
is stronger than 006, implying that the accumulation of aromatic ring
4000 3500 3000 2500 2000 1500 1000
brings about the increase of charge density in the third-way plane
within the interlayer region. According to bond-length and bond-angle wavenumber (cm-1)
data, the length of the CA anion calculated is 1.07 nm. The XRD data
Fig. 3. FT-IR spectra of (a) ZnTi-CO3-LDH precursor, (b) CA and (c) ZnTi-CA-LDH.
indicate that the interlayer distance of ZnTi-CA-LDH is 1.36 nm.
Subtracting the thickness of the LDH layer (0.48 nm), the gallery
height of ZnTi-CA-LDH is 0.88 nm. The gallery height of ZnTi-CA-LDH
is lower than the length of CA anion. So the CA anion intercalated
cannot locate in the form of perpendicular to the layer. It is suspected Table 2
that CA anions arrange in a monolayer and in a inclining orientation Chemical Compositions of ZnTi-CO3-LDH and ZnTi-CA-LDH.
toward the hydroxide layers, and the carboxyl groups of CA anions link
Samples Zn/Ti ratio Chemical composition
to the up and down layers, respectively, as shown in Fig. 2.
The FT-IR spectra of ZnTi-CO3-LDH precursor, CA and ZnTi-CA- ZnTi-CO3-LDH 0.91 Zn0.476Ti0.524 (OH)2 (CO3)0.524·H2O
LDH are shown in Fig. 3. The spectrum of ZnTi-CO3-LDH precursor ZnTi-CA-LDH 0.98 Zn0.495Ti0.505(OH)2(C9H7O2)1.009·0.43H2O
(Fig. 3a) shows a strong broad absorption band between 3500 and
3100 cm−1 due to the OH stretching mode of layer hydroxyl groups and
of interlayer water molecules. The band at 1502 cm−1 together with its
accompanying band at 1384 cm−1 is attributed to mode υ3 of interlayer
carbonate species [17,a]. Fig. 3b shows the FT-IR spectrum of CA, ZnTi-CA-LDH (0.98) is almost the same as that in ZnTi-CO3-LDH
cinnamic acid exhibits the strong characteristic vibrations at the (0.91), indicating that no destruction of the layers occurred during the
frequencies of 1670 cm−1 due to C˭O stretching vibration of the intercalation process. We note the molar ratios of metal cations in the
carboxylic acid group, 1627 cm−1 to C˭C stretching, 1285 cm−1 to C- layers are lower than the values in the nominal ratio, possibly as a
O stretching, and 1418 cm−1 to OH in-plane bending, respectively. The result of the emergency of zinc hydroxide impurity in the synthesis
spectrum of the ZnTi-CA-LDH (Fig. 3c) showed a broad band in the process and TiCl4 is easy to decompose during operation. Nevertheless,
range of 2700–3400 cm−1, due to the stretches of hydrogen-bonded the changes do not matter for our study.
hydroxyl group of both hydroxide layers and interlayer water. The The surface morphology and particle size of ZnTi-CO3-LDH pre-
strong vibrations due to COO− characteristic antisymmetric and cursor and ZnTi-CA-LDH were investigated by SEM and TEM. The
symmetric stretching of the intercalated cinnamate appear at 1532 synthesized Zn-Ti-LDH (Fig. 4A) shows the presence of hierarchical
and 1396 cm−1, the characteristic peak of the carbonate anion was also structure consisting of two-dimensional thin nanoflakes, with a dia-
absent. These results clearly confirms that cinnamic acid is stably meter of ca. 300 nm −1 µm. From the SEM micrograph (Fig. 4B), it can
intercalated in its anion form to electrostatically interact with positively be seen that the ZnTi-CA-LDH particles are aggregated and clearly
charged LDH layers. exhibited the presence of hierarchical structure with the sizes range
Elemental analysis data for ZnTi-CO3-LDH and ZnTi-CA-LDH are between 3 and 8 µm, aggregation result is related to the interaction
listed in Table 2. The results confirm that carbonate anions in the among the flake-like crystals. The HRTEM micrographs of ZnTi-CO3-
precursor were replaced by CA anions. The molar ratios of metal ions in LDH (Fig. 4C) and ZnTi-CA-LDH (Fig. 4D) indicate the single-crystal-

Fig. 2. Chemical structure and schematic representation of CA, ZnTi-CA-LDH and intercalation process.

64
Y. Li et al. Journal of Physics and Chemistry of Solids 107 (2017) 62–67

Fig. 4. SEM images of (A) ZnTi-CO3-LDH precursor and (B) ZnTi-CA-LDH; HRTEM images of (C) ZnTi-CO3-LDH precursor and (D) ZnTi-CA-LDH.

210 nm. The band at 327 nm is primarily ascribed to a π-π* transition


c involving the withdrawal of electronic charge density from the benzene
1.5
ring to the aliphatic chain. The band at 238 nm dues to a mixture of n-
b π* and π-π* transitions, it consists of a charge transfer from the
carboxyl group and aliphatic chain toward the benzene ring. Similarly,
1.0
Absorption

a the bands at 210 nm arise from a mixture of n-π* and π-π* transitions
[18]. After the intercalation process, ZnTi-CA-LDH exhibits more
excellent UV absorption ability between 200 and 400 nm, broader
0.5 and stronger than both pristine CA and ZnTi-CO3-LDH, which is
attributed to supramolecular interactions between guest-guest (hydro-
gen bonding and the van der Waals force) or guest-host (electrostatic
0.0 attraction, hydrogen bonding and the van der Waals force) [19]. The
broadening and enhancing of the absorption bands observed for ZnTi-
CA-LDH leads to an increase of the protection range for the intercala-
200 300 400 500 600 700 800
tion compound compared to the pristine compound. Therefore, the
wavelength (nm) establishment of these specific interactions between the sunscreen and
Fig. 5. UV–visible absorbance spectra of (a) ZnTi-CO3-LDH, (b) CA and (c) ZnTi-CA- the matrix is wanted to extend its protection range.
LDH.
3.3. Thermal and photostability for ZnTi-CA-LDH

line nature of the ZnTi-LDH material. The lattice with interplanar Fig. 6 show the TG-DTA curves of both pristine and intercalated
spacing of 0.38 nm were observed, corresponding to the (006) plane of CA. For CA (Fig. 6A) the endothermic peak at 133 ℃ relative to the
ZnTi-CO3-LDH phase and (012) of ZnTi-CA-LDH. melting point of pure crystalline substance. The other peak at 225 ℃
correspond to the decomposition of CA. In the intercalation compound
3.2. UV absorption properties thermograms, the endothermic peak at 133 ℃ is absent, suggesting
that the UV absorbent has been successfully intercalated into ZnTi-
UV absorbance curves of ZnTi-CO3-LDH, CA, and ZnTi-CA-LDH LDH, which is consistent with the results of XRD and FT-IR. After
are shown in Fig. 5. The curve for ZnTi-CO3-LDH (Fig. 5a) shows intercalation of CA into the LDH host, the thermal decomposition
strong UV absorption between 200 and 400 nm that is attributed to the characteristics of the resulting product are significantly different. For
shielding effect of the LDH layers as well as the incorporation of the ZnTi-CA-LDH, the DTA curve has an endothermic peak around
titanium element in the layers. The UV absorption below ~250 nm 96 ℃ with a corresponding weight loss in the TG curve from ambient
suggests that the LDH layers can strongly absorb short-wavelength UV temperature to 100 ℃, this is caused by the removal of interlayer water.
light. Furthermore, the absorption ranging 250 ~ 400 may be related to With increasing temperature, there are two exothermic band at 403
d-d transition of Ti4+ on the LDH layers [17,c]. The UV absorption and 463 ℃ with a corresponding mass loss in the TG curve, which can
curve of CA (Fig. 5b) suggests that CA presents UV absorption between be assigned to the combustion of the organic guest. The results suggest
200 and 400 nm, the major absorption bands appear at 327, 238 and that the thermal stability of CA has been enhanced after intercalation

65
Y. Li et al. Journal of Physics and Chemistry of Solids 107 (2017) 62–67

Fig. 6. TG-DTA curves of (A) CA and (B) ZnTi-CA-LDH.

into the galleries of LDH. The TG-DTA data are in accordance with the
FT-IR data, which all suggest that ZnTi-CA-LDH is a complex system of DMPO-OH.
strong supramolecular interactions between host layers and guest and
not a simple mixture of CA and ZnTi-CA-LDH. The interactions
between host layers and guest anions involve electrostatic attraction
c

Intensity (a.u.)
between opposite charges, hydrogen bonding and the van der Waals
force.
As we all know, titanium dioxide (TiO2) and zinc oxide (ZnO)
minerals are frequently employed as inorganic physical sun blockers. b
However, their photocatalytic activity as a side-effect would induce
photodegradation of organic compounds and damage the tissue con-
stituent simultaneously. which are hindering their application for a
practical purposes in sunscreens [20,21]. As a UV-shielding material,
the photocatalytic performance of ZnTi-CA-LDH with solar light
response attracted our research interest. In order to understand the 3460 3480 3500 3520 3540 3560
redox ability of the ZnTi-CA-LDH, the sample is evaluated by measur- Magnetic Field (G)
ing the potential to generate free radicals under UV irradiation. The
free radicals generated can be detected by using the spin-trapping Fig. 8. DMPO spin-trapping EPR spectra recorded for (a) ZnTi-CA-LDH, (b) TiO2 and
(c) ZnO at ambient temperature in aqueous dispersion for DMPO-OH· ( [DMPO]
electron spin resonance (EPR) technique. As a contrast, titanium
=0.20 M, mcat=2.5 mg, Vsolvent=0.5 mL).
dioxide (TiO2) and zinc oxide (ZnO) minerals are also investigated.
Hydroxyl radicals (OH·) and superoxide anion radicals (O2·-) are the
primary reactive oxygen species, which have well-known cytotoxic and
genotoxic characteristics. The generation of active radicals (OH· and UVB UVA
O2·-) from the ZnTi-CA-LDH was detected by EPR with dimethylpyr-
1.5
idine N-oxide (DMPO) as a spin-trapping reagent. The intense EPR
signal observed for the sample corresponds to the adduct of the spin
Absorption

DMPO-O2.- 1.0

c 0.5 b
Intensity (a.u.)

a
0.0
b 300 400 500 600
wavelength (nm)
a
Fig. 9. UV–vis absorption spectra of (a) the blank cream and (b) cream with intercalated
product (10%).

3460 3480 3500 3520 3540 3560 trap molecules with hydroxyl radicals (DMPO-OH·) and superoxide
Magnetic Field (G) anion radicals (DMPO-O2·-) [22].
Fig. 7. DMPO spin-trapping EPR spectra recorded for (a) ZnTi-CA-LDH, (B) TiO2 and
As shown in Fig. 7, the six typical peaks for DMPO-O2·- were
(C) ZnO at ambient temperature in methanol dispersion for DMPO- O2·- ( [DMPO] observed in methanol. Besides, the four characteristic peaks for DMPO-
=0.20 M, mcat=2.5 mg, Vsolvent=0.5 mL). OH· with intensity ratio of 1:2:2:1 were obviously observed in Fig. 8. In
methanol dispersion ZnTi-CA-LDH might formed other radicals.

66
Y. Li et al. Journal of Physics and Chemistry of Solids 107 (2017) 62–67

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