Proceedings of the “International Conference on Advanced Nanomaterials & Emerging Engineering Technologies” (ICANMEET-2013) organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, India, 24th -26th, July, 2013
Synthesis and Characterization of Chitosan-Coated Iron Oxide Nanoparticles A. M. Rabel#1, V. Jayanthi#2, N. Nixon Raj#3, D. Ramachandran#4 and J. Brijitta#5 #
Centre for Nanoscience and Nanotechnology, Sathyabama University, Chennai-600 119, Tamilnadu, India. 1
[email protected]
Abstract— Iron oxide nanoparticles were synthesized and its surface was modified by chitosan. Their surface morphology, crystallite size, crystalline phase were characterized using FESEM and XRD respectively.
mixture until pH 11 was reached. The final black precipitate was then collected and washed several times with water.
C. Synthesis of Chitosan – coated iron oxide nanoparticles The as synthesized iron oxide nanoparticles were dried and Over the past few decades nanoparticles are widely made into a powder.200 mg of Chitosan 85 % deacetylated employed in biomedical/pharmaceutical field for applications was made into a gel using 2-5mL of formaldehyde. The iron such as contrast agents, tumor targeting/therapy, drug delivery, oxide powders 200 mg were added with the chitosan solution etc [1]. Biodegradable nanoparticles as effective drug delivery which is in the form of gel and make to mix under magnetic carriers have attracted the scientific community due to their stirrer for 1 hr. Finally after obtaining a homogenous mixture therapeutic benefits without any side effects. Biocompatible the chitosan coated iron oxide particles were filtered and dried magnetic nanoparticles comprises of a magnetic (e.g. iron for further analysis. oxide/magnetite) core and a biocompatible polymeric shell (e.g. dextran, starch) [2]. D. Characterization Magnetic nanoparticles (MNP’s) can be used as effective Surface morphology, Crystallite size and phase were MRI contrast agents by harvesting the super paramagnetic characterized using FESEM SUPRA 55, Carl Zeiss and properties of these particles [3]. By selective incorporation of powder X-ray Diffractometer, Rigaku Smartlab. And the MNP’s into the tumour cells, it is possible to detect the presence of chitosan [9] was confirmed by FTIR analysis. growth of the tumours at the primitive stages itself. In vivo applications of these nanoparticles demand for stable and III. RESULTS AND DISCUSSION aggregation free MNP’s with sizes so small that it can be A. Surface Morphology circulated in the blood stream for a longer time with invicinity to the immune system [4, 5]. One such MNP which can be Fig. 1 shows the FESEM image of spherical shaped used as MRI contrast agent is Iron Oxide (Fe3O4). uncoated iron oxide nanoparticles finely distributed. Size In this paper we report a two pot method to synthesize ranging from 10nm to 25nm. Fig. 2 shows the EDS spectra Fe3O4 nanoparticles coated with Chitosan [6]. The Fe3O4taken using Oxford Instruments attached with Carl Zeiss Chitosan particles have been characterized for its size and SUPRA 55 FESEM, the spectra confirms the presence of iron elemental composition and crystal structure. Super and oxygen and its stoichiometry ratio confirms it is present paramagnetic iron oxide nanoparticles of narrow size range as iron oxide. can be easily produced and coated with various polymers providing convenient readily targetable MRI agents [7, 8]. I. INTRODUCTION
II. EXPERIMENTAL A. Chemicals Ferrous Sulphate extra pure, 99.5% (FeSO4.7H2O) (SRL Pvt.Ltd), Ferric chloride hexahydrate, 98% (FeCl3.6H2O) (Himedia), Ammonia 25 %( v/v), 25-29 %( Merck), Chitosan 85 % deacetylated (Alfa Aesar). B. Synthesis of iron oxide nanoparticles Co-precipitation process was carried using the following protocol. 0.95g of FeCl3.6H2O and 0.55g FeSO4.7H2O were taken and mixed with 15mL of Millipore water (double distilled). The mixture was stirred in a magnetic stirrer for 10 mins. Ammonia 7% solution was prepared and added the
978-1-4799-1379-4/13/$31.00©2013 IEEE
569
Fig.1. FESEM image of uncoated iron oxide nanoparticles
Proceedings of the “International Conference on Advanced Nanomaterials & Emerging Engineering Technologies” (ICANMEET-2013) organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, India, 24th -26th, July, 2013
The diameter, d of the Fe3O4 nanoparticles before and after coating with chitosan is calculated using Debye-Scherrer formula given by, (Eq. 1) d = K ×λ B × Cos θ B where K is 0.89 (Scherrer’s constant), λ is the wavelength of X-rays, θB is the Bragg diffraction angle, and B is the full width at half-maximum (FWHM) of the highly intense diffraction peak. Using the Debye-Scherrer formula, the average crystallite size of Fe3O4 before coating with chitosan is found to be 16.8 nm and after coating is 18.1 nm. Fig.2. EDS Spectra of uncoated iron oxide nanoparticles
20
30
40
50
(440)
Fe3O4 Chitosan
(440)
(333) (333)
(400)
(220)
(400)
(311)
(220)
Intensity (a.u)
(311)
Fig 3 shows the FESEM images of Chitosan-coated iron oxide nanoparticles. The heterogeneous surface morphology with different contrast in the image shows presence of other moiety which was confirmed to be chitosan using FTIR analysis (not shown).
60
Fe3O4
70
80
2 theta (deg)
Fig.5. X-ray diffraction pattern recorded for the ZnO nanorods
IV. CONCLUSIONS Fig. 3. FESEM image of chitosan-coated iron oxide nanoparticles
We have synthesized Fe3O4 nanoparticles coated with Chitosan. These particles have been characterized for its size using FESEM and elemental composition using EDAX and crystal structure using XRD. Applicability of these particles as MRI contrast agent and anti-microbial activity [10] of these polymer coated nanoparticles is under investigation. ACKNOWLEDGEMENTS Authors acknowledge Dr. Jeppiaar and the management, Sathyabama University for support and Dr. T. Sasipraba for motivation and encouragement. Fig. 4. EDS spectra of chitosan –coated iron oxide nanoparticles.
REFERENCES
B. X-Ray Diffractometer analysis. The X-ray diffraction pattern recorded for Fe3O4 nanoparticles and Fe3O4 coated with Chitosan is shown in Fig. 5. Line broadening of the XRD peaks indicates that the size of the Fe3O4 coated with Chitosan fall in the domain of nano range. The characteristic peaks at 30.29°, 35.63°, 43.35°, 57.26° and 62.85°are indexed using JPCDS and arrived that the Fe3O4 nanoparticles posses cubic magnetite phase with lattice constants a =b=c= 8.35Å respectively.
570
[1] Gupta, Ajay Kumar, and Mona Gupta. "Synthesis and surface engineering of iron oxide nanoparticles for biomedical applications." Biomaterials 26.18 (2005): 3995-4021. [2] Gonzales, Marcela, and Kannan M. Krishnan. "Phase transfer of highly monodisperse iron oxide nanocrystals with Pluronic F127 for biomedical applications." Journal of Magnetism and Magnetic Materials 311.1 (2007): 59-62. [3] AM Rabel, M Vijayalakshmi. “Development Of Surface Modified Super Paramagnetic Iron Oxide. Nanoparticles” International Journal of Applied Bioengineering 5 (2), 52 – 6. [4] Lee, Kyung Sig, and In Su Lee. "Decoration of superparamagnetic iron oxide nanoparticles with Ni2+: agent to bind and separate histidinetagged proteins."Chemical Communications 6 (2008): 709-711.
Proceedings of the “International Conference on Advanced Nanomaterials & Emerging Engineering Technologies” (ICANMEET-2013) organized by Sathyabama University, Chennai, India in association with DRDO, New Delhi, India, 24th -26th, July, 2013 [5] Gupta, Ajay Kumar, and Mona Gupta. "Cytotoxicity suppression and cellular uptake enhancement of surface modified magnetic nanoparticles." Biomaterials26.13 (2005): 1565-1573. [6] Ge, Yuqing, et al. "Fluorescence modified chitosan-coated magnetic nanoparticles for high-efficient cellular imaging." Nanoscale research letters 4.4 (2009): 287-295. [7] Gupta, Ajay Kumar, and Stephen Wells. "Surface-modified superparamagnetic nanoparticles for drug delivery: preparation, characterization, and cytotoxicity studies." NanoBioscience, IEEE Transactions on 3.1 (2004): 66-73. [8] Zhang, Yong, Nathan Kohler, and Miqin Zhang. "Surface modification of superparamagnetic magnetite nanoparticles and their intracellular uptake."Biomaterials 23.7 (2002): 1553-1561. [9] Kaushik, Ajeet, et al. "Iron oxide nanoparticles–chitosan composite based glucose biosensor." Biosensors and Bioelectronics 24.4 (2008): 676-683. [10] Namasivayam, S., Arul Maximus Rabel, and Teena Abhraham. "Antibacterial Activity of Chemogenic Copper Nanoparticles Coated Cotton Fabrics against Pyogenic Bacteria Isolated from Post Operative Patients." Advanced Materials Research 622 (2013): 842-846.
571
