Comparative studies of hydroxyapatite (HAp)

nanoparticles synthesized by using different

green templates
Cite as: AIP Conference Proceedings 2240, 080002 (2020); https://doi.org/10.1063/5.0011048
Published Online: 22 May 2020

Vijayalakshmi Varadarajan, Mayya Varsha, Keerthiga Vijayasekaran, and Shinde Vaibhav Shankar

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AIP Conference Proceedings 2240, 080002 (2020); https://doi.org/10.1063/5.0011048 2240, 080002

© 2020 Author(s).
 Comparative Studies of Hydroxyapatite (HAp)
Nanoparticles Synthesized by using Different Green
Templates
Vijayalakshmi Varadarajan1,a) , Mayya Varsha2,b), Keerthiga Vijayasekaran2,c) and
Shinde Vaibhav Shankar2,d)
1
Assistant Professor, Department of Biotechnology, Faculty of Engineering, Karpagam Academy of Higher
Education, Coimbatore, Tamil Nadu, India – 641021
2
UG student, Department of Biotechnology, Faculty of Engineering, Karpagam Academy of Higher Education,
Coimbatore, Tamil Nadu, India – 641021
a)
Corresponding author: vijayalakshminanobio@gmail.com
b)
mvarsharao@gmail.com
c)
vijaykeerthiga96@gmail.com
d)
vaibhavshindeiti65@gmail.com

Abstract. Hydroxyapatite (HAp) nanoparticles have been widely used as a biocompatible ceramic in many areas of medicine,
mainly for orthopedic and dentistry applications due to its resemblance to mineral bone and enamel. In this study, HAp
nanoparticles were synthesized using tartaric acid rich different green templates such as banana peel, tamarind leaves, prickly
pear fruits and grapes. The synthesized HAp nanoparticles from different green templates were characterized with FTIR, DLS,
XRD, SEM analysis and their results were compared. FTIR spectrum with sharp peaks confirmed the presence of functional
groups such as OH and PO43- groups in the synthesized HAp nanoparticles. Particle size analysis showed the acceptable size
range and average particle size for all the synthesized HAp samples, grapes sources exhibited the better result of size range 246.9
nm to 356.20 nm and average particle size 291.3 nm. Zeta potential confirmed that the synthesized HAp nanoparticles had
negative charges on its surface and the higher stability was showed for HAp nanoparticles from grapes with -29mV. XRD
spectrum confirmed that the synthesized HAp nanoparticles matched with the standard HAp peaks and it was found that the
crystallite size was low for HAp nanoparticles from grapes in the range of 129nm. SEM images showed the morphological
characteristics of synthesized HAp nanoparticles and the uniform distribution of HAp nanoparticles with spherical flower like
structure was observed in grapes template. Therefore HAp nanoparticles synthesized using grapes extract showed better results
when compared with other green templates.

INTRODUCTION
Hydroxyapatite (HAp) nanoparticle is used as substitute material for bone and teeth because of its chemical
similarity to the natural calcium phosphate mineral which is present in biological systems [1]. Hydroxyapatite
(Ca10(PO4)6(OH)2) is a biomaterial and comes under bioceramics, used in biomedical applications in the field of
drug delivery, tissue engineering, implants in bone and dentistry because of its properties like osteoconductivity,
biocompatibility and bioactivity [2]. The morphological, chemical and mechanical properties of HAp are modified
by using varying conditions and different synthesis techniques such as wet chemical method, sol gel method,
precipitation method, hydrothermal method, multiple emulsion method, electro deposition technique, bio mimetic
deposition, Solvent or solution casting method, Thermally induced phase separation (freeze drying method), electro-
spinning techniques etc., [3, 4]. Nowadays, green synthesis of nanoparticles has received more attention because it is
easily available, biocompatible and not involving any toxic and redundant chemicals [5]. In the recent years, natural
green sources have become a popular alternative method for the synthesis of different nanoparticles [6]. Green
synthesis of nanoparticles using different parts of natural plant sources has opened a new research era and finds its

3rd National Conference on Current and Emerging Process Technologies – CONCEPT 2020
AIP Conf. Proc. 2240, 080002-1–080002-11; https://doi.org/10.1063/5.0011048
Published by AIP Publishing. 978-0-7354-1999-5/$30.00

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application in many fields [7]. The intense demand and need of HAp in various biomedical applications especially in
bone implants paved the way to explore different ways to synthesize this biomaterial, one such method is green
template assisted HAp synthesis [8]. Nowadays more attention required towards the replacement of chemical
methods with green assisted methods for the benefit of human health and environment [9]. Various natural materials
have been used as template agents for the synthesis of HAp nanoparticles because of their properties such as
renewable, non toxic, environmental friendly and cost effective [10]. In recent study, Horta et al., synthesized green
nanohydroxyapatite (nHAp) from hen eggshell by the precipitation method was proved with high phase purity
monoclinic hydroxyapatite, with an average crystallite size around 18 nm [11]. Gopi, D et al., discussed the green
synthesis of biocompatible nanostructured hydroxyapatite from Cirrhinus mrigala fish scale and TEM analysis
shows that Cirrhinus mrigala nHAp are in the agglomerated rod-like nanostructured shapes particles with average
size of 30-50 nm [12] . Different green sources were explored by researchers in order to synthesize HAp with better
properties. It was found that, tartaric acid has the ability to influence the characteristics of crystalline phase,
morphology and size of the HAp nanoparticles [13]. Therefore in this study, HAp nanoparticles were synthesized by
using tartaric acid rich green templates such as banana peel, tamarind leaves, grapes and prickly pear fruit and the
results were compared. The proposed green synthesis method is advantageous because of its characteristics such as
cost effective and eco-friendly.

MATERIALS AND METHODS

Chemicals used
Calcium nitrate (Ca(NO3)2.4H2O) purchased from LOBA Chemie and Ammoniun dihydrogen phosphate
(NH4)H2PO4 purchased from SDFCL were used as precursors for Calcium and Phosphate respectively. Ethanol
(C2H5OH) from Changshu Yangyuan chemical (China) was used as solvent and sodium hydroxide (NaOH) from
Chemspure was used to adjust pH in the synthesis process of HAp nanoparticles.
Green sources such as banana peel, grapes, prickly pear fruits and tamarind leaves were collected from different
places. Banana (Musa paradisiaca) and Grapes (Vitis vinifera) were purchased from the local market in Coimbatore.
Tamarind (Tamarindus indicus) leaves and Prickly pear (Opuntia ficus indica) fruits were collected from the local
area of Dharapuram, Tamilnadu.

Sample preparation
Green templates were prepared by grinding the air dried green sources such as banana peel, tamarind leaves,
grapes and prickly pear fruits into powder. Banana collected from local market from which peel was chopped and air
dried into powder. Tamarind leaves were air dried and grinded into powder form. Prickly pear fruits were washed
with distilled water and peeled off. The fleshes after removal of peels were air dried and crushed into powder. The
collected grapes were rinsed with distilled water. Then the pulp was crushed and added with distilled water in the
ratio of 10:1 g/mL. The extract was collected from the mixture and heated at 40°C. After heating, the extract was
used for the synthesis process.

Methodology
In this study, Calcium nitrate and Ammonium dihydrogen phosphate were taken as precursors for Calcium and
Phosphate respectively, flow chart was given in the Fig. 1. An equimolar concentration 0.6M of Ca(NO 3)2.4H2O
and (NH4)H2 PO4 were prepared and maintained its pH 10 and pH 12 respectively by using 2M Sodium hydroxide
solution. Calcium nitrate dissolved in ethanol was stirred vigorously at room temperature and Ammonium
dihydrogen phosphate dissolved in distilled water was added slowly into stirred Calcium nitrate. After sometime,
milky white solution was formed.
After stirring, green sources used as template were added. Different green sources such as banana peel powder,
tamarind leaves, prickly pear and grapes were used for the synthesis. After addition of green templates, stirring was
allowed for 24 hrs at room temperature. Further, the synthesized nanoparticles were kept undisturbed for aging at
overnight. After aging, the synthesized nanoparticles were dried in hot air oven at 40°C. Further it was calcinated at
800°C to form the crystalline HAp powder. The calcinated samples were characterized by FTIR, DLS, XRD and
SEM analysis.

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 FIGURE. 1 Synthesis of HAp nanoparticles by green synthesis method

Characterization techniques
The synthesized HAp nanoparticles by using different green templates such as banana peel, tamarind leaves,
grapes and prickly pear fruits were characterized by FTIR to study its functional group nature. Further, it was
analysed with DLS to determine its size range, average particle size and zeta potential. Then the crystal structure
was analysed by XRD analysis and morphological properties by SEM analysis.

RESULTS AND DISCUSSIONS

Synthesis of HAp nanoparticles using different green templates

HAp nanoparticles were synthesized by using Calcium nitrate and Ammonium dihydrogen phosphate as
precursors for calcium and phosphate respectively. Since tartaric acid influence the nanoparticles properties such as
average size, surface morphology and crystal structure. Tartaric acid rich green sources such as banana peel,
tamarind leaves, prickly pear and grapes were chosen to enhance the characteristics of HAp nanoparticles. The green
templates were used in the form of powder and extract for the synthesis which was shown in the Fig. 2.

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 FIGURE. 2 Green templates from different sources- Banana peel, Tamarind leaves, Prickly pear fruit, Grapes

FIGURE. 3 Synthesis of HAp nanoparticles using different green templates

HAp nanoparticles were synthesized by using Calcium nitrate and Ammonium dihydrogen phosphate as
precursors with equimolar concentration of 0.6M at pH 10 and pH 12 respectively. Further, green templates (banana
peel powder, tamarind leaves powder, prickly pear fruits powder and grapes extract) were added with a
concentration of 1wt %. After addition of green templates, stirring was allowed for 24 hrs at room temperature.

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Then, the synthesized nanoparticles were kept undisturbed for aging at overnight. After aging, the synthesized
nanoparticles were dried in hot air oven at 40°C. Further it was calcinated at 800°C to form the crystalline HAp
powder. The synthesis process was shown in the Fig. 3.

Characterization of synthesized HAp nanoparticles using different green templates

The synthesized HAp nanoparticles from different green templates with rich tartaric acid content such as banana
peel, tamarind leaves, grapes and prickly pear fruits were characterized by FTIR to study its functional group nature.
Further, it was analysed with DLS to determine its size range, average particle size and zeta potential. Then the
crystal structure was studied by XRD analysis and surface morphological properties by SEM analysis.

FTIR analysis
The synthesized HAp samples were analyzed by FTIR to study its functional groups and summarized in the
Table 1. From the spectrum, Fig. 4a it was found that Hydroxyapatite (HAp) nanoparticles synthesized from banana
peel showed peak at 3725 cm-1 which represented the Stretching mode of OH group. Peaks at 2326 cm-1, 1429 cm-1
and 860 cm-1 indicated the presence of CO32- group. According to other researchers, dissolving of atmospheric CO 2
resulted in CO32- as the crystallization was carried out in alkaline range. A sharp peak at 1019 cm-1 indicated the P-O
stretching mode of PO43- group. From the Fig. 4b, HAp nanoparticles synthesized from tamarind leaves showed the
presence of OH group, Stretching mode at 3599 cm-1. CO32- groups were presented in the range of 2300 and 1396
cm-1 range due to the atmospheric carbon. Peaks in the range of 1086 cm -1 indicated the P-O stretching mode of
PO43- group.

FIGURE. 4 FT-IR Spectra of HAp Nanoparticles Synthesized from Various green templates a) Banana Peel, b) Tamarind leaves,
c) prickly pear fruits and d) grapes.
Fig. 4c indicated the spectrum of HAp nanoparticles synthesized from Prickly pear fruits. Peaks at 3733 cm -1 and
2309 cm-1 represented the presence of OH group in stretching and bending mode respectively. CO 32- groups are
indicated by the peaks at the 1480 and 893 cm-1. A sharp peak at 1069 cm-1 indicated the presence of PO43- group in
stretching mode. From the Fig. 4d, HAp nanoparticles synthesized from grapes showed the presence of OH group in

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stretching and bending mode at 3590 cm-1 and 2317 cm-1 respectively. Peak at 1429 cm-1 indicated the presence of
CO32- group. Peaks at 1136 cm-1, 1061 cm-1 and 690 cm-1 represented the presence of PO43- group in stretching
asymmetric and stretching mode respectively.

TABLE 1. FTIR spectral analysis of synthesized HAp nanoparticles from different green sources

Green
Wavenumber (cm-1) Functional Groups Assignment
Templates
3725 OH Stretching mode
2-
Banana Peel 2326 CO3 -
2-
1429 CO3 -
3-
1019 PO4 P-O Stretching mode
2-
860 CO3 -
3599 OH Stretching mode
2-
Tamarind 2300 CO3 -
2-
Leaves 1396 CO3 -
Asymmetric
1086 PO43-
stretching
2-
717 CO3 -
3733 OH Stretching mode
Prickly Pear 2309 OH Bending mode
2-
Fruits 1480 CO3 -
3-
1069 PO4 P-O Stretching mode
2-
893 CO3 -
3590 OH Stretching mode
Grapes 2317 OH Bending mode
2-
1429 CO3 -
3-
1136 PO4 P-O Stretching mode
3-
1061 PO4 Asymmetric Bending
3-
960 PO4 P-O Stretching mode

DLS - Particle size analysis

The calcinated HAp samples were characterized with DLS - particle size analyzer to measure the size range and
average particle size which was shown in the Table 2. From the Fig. 5a, it was observed that the particles
synthesized using banana peel showed the size range from 402.44 nm to 513.71 nm and average particle size was
found to be 422.1 nm. From the Fig. 5b, for the tamarind leaves sourced HAp nanoparticles, the size range was
found to be 279.04 nm to 402.44 nm and average particle size was 319.8 nm. From the Fig. 5c, the HAp
nanoparticles synthesized using prickly pear fruits indicated the size range of 246.9 nm to 356.20 nm and average
particle size was 291.3 nm. From the Fig. 5d, HAp nanoparticles synthesized by grapes sources exhibited the size
range of 246.9 nm to 356.20 nm and average particle size was found to be 292 nm.

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 TABLE 2. Particle size analysis – HAp nanoparticles from different green templates
Green Templates Size Range (nm) Average particle size (nm)
Banana peel 402.44 to 513.71 422.1
Tamarind leaf 279.04 to 402.44 319.8
Prickly pear 246.98 to 356.20 291.3
Grapes 246.98 to 356.20 292

Comparing all the synthesized HAp nanoparticles from different green templates such as Banana peel, Tamarind
leaves, Prickly pear fruits and Grapes, the reduced particle size was obtained for prickly pear fruits and grapes when
compared with banana peel and tamarind leaves. Even it showed reduced particle size for prickly pear fruits and
grapes, other sources such as Banana peel and Tamarind leaves showed the acceptable particle size range and
average particle size.

FIGURE. 5. Particle size analysis of synthesized HAp nanoparticles from a) Banana Peel b) Tamarind leaves c) Prickly Pear
fruits d) Grapes

Zeta Potential
The synthesized HAp nanoparticles were analyzed for zeta potential to study its surface charge and the stability
properties which was shown in the Table 3. From the Fig. 6a, the Zeta potential of HAp nanoparticles from banana
peel was found to be -0.7mV. From Fig. 6b, Zeta potential of HAp nanoparticles from tamarind leaves were
calculated as -16mV. From Fig. 6c, Zeta potential of HAp nanoparticles from Prickly pear fruits were identified as -
0.2mV. From Fig. 6d, Zeta potential of HAp nanoparticles from grapes were found to be -29mV. From the zeta
potential analysis, it was confirmed that the synthesized HAp nanoparticles had negative charges on its surface.
Comparing all four samples, the higher stability was showed for HAp nanoparticles from grapes whereas moderate
stability obtained for HAp nanoparticles from tamarind leaves. HAp nanoparticles from banana peel and prickly
pear fruits showed incipient stability, these particles were more prone to form agglomerates.

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 TABLE 3. Zeta Potential– HAp nanoparticles from different green templates

Green Templates Zeta Potential (mV)

Banana Peel -0.7
Tamarind Leaves -16
Prickly pear Fruits -0.2
Grapes -29

FIGURE. 6 Zeta potential of synthesized HAp nanoparticles from a) Banana Peel b) Tamarind Leaves c) Prickly pear fruits d)
Grapes

XRD analysis
The synthesized HAp nanoparticles from different green templates such as banana peel, tamarind leaves, grapes
and prickly pear fruits were analyzed by XRD to study its crystallite size. Fig. 7 showed the XRD spectrum of
synthesized HAp nanoparticles. The crystallite size (L) was calculated from the scherrer equation which is given by
L= Kλ / β cos θ, K represents broadening constant which was taken as 0.9, λ the wavelength of monochromatic X-
ray beam (λ = 1.5418Å for CuKα radiation), β is the full width half maximum (FWHM) and θ the diffraction angle
(°).

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 FIGURE. 7 XRD Spectrum of HAp nanoparticles from different green templates
XRD patterns of synthesized HAp nanoparticles from different green templates were compared with standard
Hydroxyapatite, JCPDS 00-90-432. From the Fig. 7, the peaks obtained for synthesized HAp nanoparticles were in
concurrence with standard HAp. After calcinations, impurities were removed and there is a high uniformity between
the information of HAp which obtained by green synthesis and that from the standard information, with crystal
system hexagonal in nature. No other impurity was observed in the XRD pattern, representing that the chief
inorganic phase of the sample is hydroxyapatite crystal. The maximum intensity was obtained for the plane (211)
which matched with standard HAp. Then the crystallite size was calculated and summarized in the Table 4.
TABLE 4. Structural Properties of synthesized HAp nanoparticles

Green Sources Plane FWHM (β) Crystallite Size (L) (nm)

Banana Peel 211 7.97 188

Tamarind Leaves 211 7.82 192

Prickly Pear Fruits 211 8.02 187
Grape 211 11.58 129
From the Table 4, it was observed that the crystallite size for synthesized HAp nanoparticles from different green
templates were found to be in the range of 129nm to 192nm. Comparing all four green sources, the crystallite size
was low for HAp nanoparticles from grapes and it was found to be 129nm, HAp nanoparticles from banana peel
showed 188nm, HAp nanoparticles from tamarind leaves indicated 192nm and HAp nanoparticles from prickly pear
fruits calculated as 187nm.

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 SEM analysis
The synthesized HAp nanoparticles were analyzed by FESEM to study its surface morphology and it was
compared. FESEM images of HAp nanoparticles from different sources were shown in the Fig. 8a to Fig. 8d. From
the Fig. 8a, it was shown that the HAp nanoparticles synthesized from Banana peel were spherical in shape with
more aggregates and the average size was approximately found to be in the range of 264 nm to 273.1 nm.

FIGURE. 8 FESEM image of HAp nanoparticles using a) Banana peel b) Grapes c) Prickly pear fruits d) Tamarind leaves
To reduce the agglomeration, capping agents may be used in future. From Fig. 8b, HAp nanoparticles
synthesized from Grapes showed rod like shape with few spherical particles. From Fig. 8c, it was observed that
uniform distribution of flower like spherical particles and its size was found to be in the range of 131nm to 191nm.
From the Fig. 8d, HAp nanoparticles synthesized from Tamarind leaves are in the form of crystals and the
distribution of nanoparticles was non-uniform. The size range was observed to be in the range of 649.6 nm to 749.9
nm. Comparing all four green sources, the uniform distribution of HAp nanoparticles with spherical flower like
structure was observed in grapes template which was better than other sources.

CONCLUSION
HAp nanoparticles were synthesized by using tartaric acid rich green templates such as banana peel, tamarind
leaves, prickly pear fruits and grapes. The synthesized HAp nanoparticles from different green templates were
characterized with FTIR, DLS, XRD and SEM analysis to study its functional group nature, size range, average
particle size, zeta potential, crystallite size and surface morphology respectively. FTIR analysis confirmed the
presence of functional groups such as OH and PO43- groups with sharp peaks in the synthesized HAp nanoparticles.
DLS analysis showed the acceptable size range and average particle size for all the synthesized HAp samples.

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 Comparing all the synthesized HAp nanoparticles, the reduced particle size was obtained for prickly pear fruits
(291.3nm) and grapes (292nm) when compared with banana peel and tamarind leaves. Zeta potential analysis
confirmed that the synthesized HAp nanoparticles had negative charges on its surface. The higher stability was
showed for HAp nanoparticles from grapes (-29mV) whereas moderate stability obtained for HAp nanoparticles
from tamarind leaves (-16mV). HAp nanoparticles from banana peel (-0.7mV) and prickly pear (-0.2mV) fruits
showed incipient stability, these particles were more prone to form agglomerates. XRD spectrum confirmed that the
synthesized HAp nanoparticles matched with the standard HAp JCPDS 00-90-432 and it was found that the
crystallite size was low for HAp nanoparticles from grapes (129nm). SEM images showed the morphological
characteristics of synthesized HAp nanoparticles and the uniform distribution of HAp nanoparticles with spherical
flower like structure was observed in grapes template. Therefore, grapes extract assisted synthesis of HAp
nanoparticles have better result when compared with other templates such as banana peel, tamarind leaves and
pricky pear fruits. The synthesized HAp nanoparticles using tartaric acid rich green template will be a promising
biomaterial for the application of bone and dental implants.

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