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IAETSD JOURNAL FOR ADVANCED RESEARCH IN APPLIED SCIENCES ISSN NO: 2394-8442

Influence of Strontium as a dopant in Hydroxyapatite for Potential


Biomedical Applications

V. Kalaiselvi. *1,, Anitha. P2, Mathammal. R3.


KalaiselviV*1
*1 Research scholar, Department of Physics, Sri Sarada College for women, Salem, Tamil Nadu, India.
*1 Research *1Department
scholar, DepartmentofofPhysics,
Physics, Navarasam Arts&Science
Navarasam arts & Science college
College forfor women.
Women, Erode, Tamil
Arachalur, Erode,Nadu,
Tamil India.
Nadu
2Department of Physics, Vellalar College for women, Erode, Tamil Nadu, India.

3Department of Physics, Sri Sarada College for women, Salem, Tamil Nadu, India.

Corresponding Author: nk.arthikalai@gmail.com,mathammals_shanmugam@yahoo.com

Abstract: Chemically Modified Strontium doped Nano hydroxyapatite with various concentration have been prepared
by Sol Gel method maintaining the Ca, P and Sr ratio as 1.67. The crystallite size, lattice parameter and unit cell volume
were calculated by X ray diffraction, functional groups were analyzed by Fourier Transform Infrared Spectroscopy (FTIR),
Surface morphology by Scanning Electron Microscopy (SEM) and elemental analysis by Energy Dispersive X ray Spectra
(EDS). In vitro behavior was investigated by Antimicrobial Activity.

Keywords: Hydroxyapatite, Strontium, Sol Gel, XRD, FTIR, SEM, EDS, Antimicrobial Activity.

1. INTRODUCTION
Bio ceramics are biocompatible ceramic materials, commonly include bio glass and calcium phosphates such as HAP and β-
TCP and biphasic calcium phosphate. Of the calcium phosphate bio ceramics, HAP is the most widely used for Orthopedic
and dental reconstruction because it is the predominant component of human bone mineral and teeth enamel(1). To date,
HAP implants have been used clinically in the form of powders, granules, cements, dense and porous blocks, biphasic,
coatings, and as composites. Some of the favorable properties of HAP include biocompatibility, lack of an immunogenic
response, and slow resorption. There are many natural sources for HAP which include human bone, bovine bone, coral,
chitosan, fish bone, egg shell(2) and mussel shell(3) among others. However a concern with natural HAP, is transmission of
diseases when proper preparation is not followed to remove all protein. Synthetic HAP is more commonly used, since it is
more easily available, and free of disease transmission.

Synthetic HAP is often stoichiometric with a chemical formula of Ca10 (PO4)6(OH)2, and a specific atomic Ca/P molar ratio
of 1.67(4). Despite its biocompatibility, the inherent mechanical properties of HAP specifically brittleness, low tensile
strength, and poor impact resistance have restricted its use in load bearing applications. HAP use is therefore typically limited
to non-critical load-bearing applications, such as the ossicles of the middle ear, orthopedic bone grafting and dentistry. The
research trends in the field over the past 4 decades includes the application of HAP coatings on metallic implants to improve
the bioactivity of the latter, development of biphasic with varying ratios of HAP and adding dopants(5).

Properties of Nanoparticles depends largely in the synthetic procedure adopted. There exists number of methods to synthesis
of Hydroxyapatite such as Co precipitation method, sol gel method, Mechano chemical method, ultrasonic assisted method,
microwave irradiation method etc. Of all the above method, sol gel method has been adopted for the present work. The
reason for choosing the above method was homogeneous product, high purity, low processing temperature,(6) etc.,
Strontium (Sr), a group 2, period 4, stable metal with chemical similarity of calcium replaces and mimics Calcium in the
human body(7). Strontium appears in bone and teeth are prominently used in dentistry and Orthopedic application. The
reason for doping Sr in hydroxyapatite is that Calcium and Strontium are group 24 elements, so that Strontium can easily
replace Calcium without much difficulty(8).

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IAETSD JOURNAL FOR ADVANCED RESEARCH IN APPLIED SCIENCES ISSN NO: 2394-8442

2 EXPERIMENTAL PROCEDURE
Calcium hydroxide, Orthophosphoric acid, Ammonia and Strontium Oxide were used as the starting precursors. Sr doped
Nano hydroxyapatite prepared at four different concentrations (0.1, 0.5, 1.0 & 1.5wt %) maintaining the ratio [Ca+Sr]/P =
1.67 were prepared by sol gel method. pH of the solution is maintained at 11 using Ammonia. The desired amount of
Calcium hydroxide and Strontium Oxide [Ca+Sr] Solution and Orthophosphoric acid were prepared. Then
Orthophosphoric acid solution was added drop wise to the [Ca+Sr] solution. The prepared solution was fixed at 1.67 ratio.
The pH of the solution was maintained at 11 using aqueous ammonia. The final product was made to stir for one hour and
the resulting precipitate was aged under ice for 22 hours. After ageing, the solution was washed several times with double
distilled water to remove impurities if any. Final solution was centrifuged and dried at 1000C using hot air oven.The prepared
samples were characterized by X-ray Diffraction (XRD), Fourier transform Infrared spectroscopy (FTIR), Scanning Electron
Microscopy (SEM), Energy Dispersive X Ray spectra (EDS) and Antimicrobial Activity.

3. CHARACTERIZATION TECHNIQUE
Powder X Ray diffraction pattern was recorded with the 2θ range of 0 to 700 using Cu Kα at X ray source (1.54Å). The mean
crystallite size (D) of the particle was calculated from the XRD line broadening measurement from the Debye Scherer
formula
D = 0.91λ/βcosθ

Where λ is the wavelength of the X ray in Ǻ, β is the full width at half maxima value and θ is the diffraction angle. The lattice
parameter a and c value are determined through the hkl peaks positions of apatite from XRD patterns according to the
formula
1/d2 = 4/3(h2+hk+k2)/a2 + l2/c2

Where d is the lattice distance obtained from XRD results. Whereas the Unit Cell parameter was determined by the formula

V= 2.589a2c

The functional groups were analyzed by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy
(SEM) studies reveals the surface morphology of the prepared samples also with elemental analysis attachment (EDS). The
in vitro behavior was done with Antimicrobial Susceptibility test against S.aureus and E coli bacteria using Agar well diffusion
method with DMSO as the solvent.

4. RESULTS AND DISCUSSION


4.1 X- Ray Diffraction (XRD)

Figure 1: XRD Spectra of Sr Doped HAP

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IAETSD JOURNAL FOR ADVANCED RESEARCH IN APPLIED SCIENCES ISSN NO: 2394-8442

XRD pattern for Sr doped HAP for four different concentration that is 0.1, 0.5, 1.0 and 1.5wt% were denoted as SrHAP1,
SrHAP2, SrHAP3, SrHAP4 and shown in figure 1. The result were in well agreement with the standard value with small
increase in the intensity which is mainly due to the addition of dopant which justifies that Sr is incorporated in HAP whereas
it does not modify its structure. The crystallite size, lattice parameter and unit cell volume were tabulated in the table 1. From
the table it was clearly understood that the crystallite size decreased with the increase in the concentration where us the
lattice parameter and unit cell volume increases with the increase in the concentration.

Sample Crystallite Lattice Unit Cell Volume


Size nm Parameter
SrHAP1 74 9.4509 6.8589 1586.108
SrHAP2 68 9.6248 6.8773 1649.428
SrHAP3 63 9.6288 6.8713 1649.386
SrHAP4 61 9.7748 6.9774 1726.044
Table 1: Parameter Values of Sr Doped HAP

4.2 Fourier transform Infrared Spectroscopy (FTIR)


FTIR spectrum for Sr doped HAP was shown in the figure 2. All the functional groups obtained from the FTIR spectrum
matches with the standard values. The band at 601cm-1 reveals the

Figure 2: FTIR Spectra for Sr Doped HAP

Characteristic peak for Hydroxyapatite form. The band at 960 cm-1 , 1030 cm-1 and 1095 cm-1 corresponds to PO43- ions
were assigned respectively to the antisymmetric stretching, the antisymmetric bending modes. The appearance at 3570 cm-1
corresponds to OH groups (9).

4.3 Scanning Electron Microscopy (SEM)


Surface morphological analysis were done for all the prepared samples using SEM. SEM structure reveals the presence of
Nano rod like structure at the 0.1wt% whereas the rod like structure disappears as the concentration gets increased. This is
due to Vander Waals Force of attraction (10).

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IAETSD JOURNAL FOR ADVANCED RESEARCH IN APPLIED SCIENCES ISSN NO: 2394-8442

Figure 3: SEM image of Sr doped HAP

4.4 Energy Dispersive X-ray Spectroscopy (EDS)


Elemental composition analysis was done by EDS. EDS spectrum shows that calcium ions were well replaced by Strontium
ions and increase in the Strontium were recorded in the figure 4.

EDS Spectra for Sr Doped HAP


70

60

50

40

30

20

10

0
SrHAP1 SrHAP2 SrHAP3 SrHAP4

OK PK CaK SrK

Figure 4: EDS spectra for Sr Doped HAP

4.5 Antimicrobial Activity


The Agar Well Diffusion test was performed at Muller Hinton Agar. The technique was carried out by pouring the agar
solution into the petri dish of about 10mm thickness. Then the petri dish was left for 10 minutes to dry at air. Above the
Agar the bacteria was spread over it. A well was created and the sample were poured in the diluted form. The petri plates
were then incubated at 370C for 24 hours. Then the dish was carried out by measuring the width of Zone of Inhibition.

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IAETSD JOURNAL FOR ADVANCED RESEARCH IN APPLIED SCIENCES ISSN NO: 2394-8442

e
Figure 5: Antimicrobial image for Sr doped HAP against S.aureus and E coli bacteria

Sample Zone of Inhibition


S.aureus E coli
SrHAP1 15 -
SrHAP2 15 -
SrHAP3 17 -
SrHAP4 19 -
Table 2: Antimicrobial Activity of Sr Doped HAP

The Zone of Inhibition of Sr doped HAP was in the range of 15 to 19mm for S.aureus bacteria and there is no Zone of
Inhibition for E coli bacteria.

5. CONCLUSION
Thus Strontium doped Hydroxyapatite is synthesized by Solgel method under four different concentrations. XRD pattern
reveals that the Crystallite size decreases with increase in the concentration where us the lattice parameter and unit cell
volume increases with the increase in the concentration. FTIR analysis reveals that all the functional groups were present as
that of the standard characterization peaks. SEM reveals the presence of Nano rod structure which is in similar to that of
the human teeth morphology. EDS confirms all the elemental groups of the prepared samples. Antimicrobial activity shows
very good zone of inhibition against S.aureus bacteria and no inhibition rate for E coli bacteria. From all the above studies,
it was came into conclusion that Sr doped Nano HAP can be used for biomedical applications such as Orthopedic and
Dentistry.

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