Green Synthesis of Magnetite (Fe3O4) Nanoparticles Using Seaweed (Kappaphycus alvarezii) Extract
© The Author(s). 2016
Received: 4 February 2016
Accepted: 23 May 2016
Published: 2 June 2016
In this study, a simple, rapid, and eco-friendly green method was introduced to synthesize magnetite nanoparticles (Fe3O4-NPs) successfully. Seaweed Kappaphycus alvarezii (K. alvarezii) was employed as a green reducing and stabilizing agents. The synthesized Fe3O4-NPs were characterized with X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared (FT-IR), and transmission electron microscopy (TEM) techniques. The X-ray diffraction planes at (220), (311), (400), (422), (511), (440), and (533) were corresponding to the standard Fe3O4 patterns, which showed the high purity and crystallinity of Fe3O4-NPs had been synthesized. Based on FT-IR analysis, two characteristic absorption peaks were observed at 556 and 423 cm−1, which proved the existence of Fe3O4 in the prepared nanoparticles. TEM image displayed the synthesized Fe3O4-NPs were mostly in spherical shape with an average size of 14.7 nm.
With the recent rapid development and evolvement of technology, human beings have put their faith in nanotechnology and believe that it can ameliorate their current living standard . As a consequence, the nanoparticle has drawn a huge interest from researchers globally due to specific characteristics such as shape, size, and distribution, which could be utilized in a distinct field of applications . Synthesis of Fe3O4-NPs has been carried out because of its unique properties, such as being superparamagnetic , biocompatible, biodegradable, and expected to be non-toxic to humans [4–6]. These unique properties allow Fe3O4-NPs to be widely used in different areas of applications, such as catalysis [7, 8], magnetic storage media , biosensors , magnetic resonance imaging (MRI) [11, 12], and targeted drug delivery [13–15].
Numerous methods of fabrication of Fe3O4-NPs can be employed, such as sol-gel method , solid state synthesis , and flame spray synthesis . In contrast to the time-consuming chemical and physical methods which involve complicated procedures, green method is much easier and safer to use, and plant-mediated synthesis of nanoparticles is still a new scheme and the outcome is yet to be studied. There are a couple of successful studies in synthesizing Fe3O4-NPs by using plant extract. For instance, fruit extract of Artemisia annua , leaf extract of Perilla frutescens , Tridax procumbens  and caricaya papaya , peel extract of plantain , and also seed extract of grape proanthocyanidin . However, there are only finite studies on the synthesis of Fe3O4-NPs from marine plants.
Kappaphycus alvarezii (K. alvarezii) is a type of red seaweed from the family of Solieriaceae. It is well-known in the food industries for its gelling properties . Carrageenan gives the thickening characteristic, which can be used as a function of green stabilizer in synthesis of nanoparticles without using hazardous chemicals. Based on the literature review, there are still no specific researches done on seaweed K. alvarezii for the Fe3O4-NPs synthesis, and this inspires and motivates us to work on this. Hence, in this research, a novel green method of synthesizing Fe3O4-NPs using seaweed K. alvarezii is proposed.
Iron (II) chloride tetrahydrate (FeCl2.4H2O ≥ 99 %) and iron (III) chloride hexahydrate (FeCl3. 6H2O, 97 %) were purchased from Sigma-Aldrich. Sodium hydroxide (NaOH) was obtained from R&M Chemicals. All the chemicals were used without further purification. The seaweed K. alvarezii is a type of red seaweed which was acquired from Sabah, Malaysia. All the aqueous solutions were prepared by deionized water from ELGA Lab Water Purification System, UK. The sensION+ MM374 GLP 2 channel Benchtop Meter was employed to control the pH of the solution. An Esco Isotherm Forced Convection Laboratory Oven was used to dry the washed sample.
Preparation of Kappaphycus alvarezii Extract
The seaweed was washed under running water to remove dirt, salt, and foreign particles. Then, it was soaked overnight (24 h) in deionized water to bleach the yellowish color so that it became colorless. After that, the seaweed was rinsed and dried under sunlight for 3 days. The dried seaweed was chopped into small pieces before being blended using a hammer mill with a 3-mm filter diameter. Finally, the dried seaweed was stored until further processing. The dried seaweed reduced the storage space required and can be stored for a number of years without appreciable loss of the gelling property. In this study, 0.5 g of dried seaweed was weighed and soaked in 50 ml of deionized water for 24 h. The resulting extract was used as a seaweed extract solution.
Synthesis of K. alvarezii/Fe3O4-NPs
For the synthesis of K. alvarezii/Fe3O4-NPs, firstly, a solution of Fe3+ and Fe2+ with a 2:1 M ratio was added into the seaweed extract to obtain a yellowish colloidal solution. Then, the freshly prepared 1.0 M of NaOH was added drop-wise to the solution under continuous stirring. The pH of the solution was adjusted to pH 11. The solution was then stirred for 1 h to homogenize the solution and also for the completion of reaction. After that, the as-synthesized Fe3O4-NPs were separated by using a permanent magnet. The Fe3O4-NPs were washed for several times by using deionized water. The nanoparticles were dried in an oven at around 70 °C for 24 h. The dried sample was stored in an air-tight container for further characterization. All the experiments were conducted at ambient temperature.
Characterization of K. alvarezii/Fe3O4-NPs
The presence and phase purity of the synthesized K. alvarezii/Fe3O4-NPs were examined by using a PANalytical X’Pert PRO X-ray diffractometer (XRD). The dried sample was performed at an applied current of 20 mA and accelerating voltage of 45 kV with Cu Kα radiation (λ = 1.54 Å) at 2θ angle configuration scanning from 5° to 80° (scanning rate = 2θ/min). The UV-Vis spectrum of Fe3O4-NPs was determined using Shimadzu UV-Visible Spectrophotometer (UV-1800). Fourier transform infrared (FT-IR) spectroscopy was used to study the presence of the biomolecules which are responsible for the synthesis of Fe3O4-NPs. Dried samples were ground with potassium bromide (KBr) to produce pellet, which was examined in a wavelength range of 400–4000 cm−1. The infrared absorption peaks were obtained from Thermo Scientific Nicolet 6700 Spectrometer. The size and morphology of the synthesized Fe3O4-NPs were observed using FEI TECNAI G2 F20 transmission electron microscope (TEM). The microscope had accelerating voltage from 20 to 200 kV and standard magnification from 22 X to 930 KX. The aqueous dispersion of the nanoparticles was dropped on 300-mesh copper grids and air-dried before viewing under a microscope. TEM images were acquired using a SC1000 ORIUS CCD Camera.
The precipitation occurs because of the Fe3O4-NPs have a high tendency to aggregate into agglomerates as to decrease the energy associated with the large surface area to volume ratio, a phenomenon which is likely deteriorated by the low surface charge .
UV-Vis Spectral Analysis
where d is the crystallite size of synthesized Fe3O4-NPs for (hkl) phase, k is Scherrer constant (0.9), λ is the X-ray wavelength of radiation for Cu Kα (0.154 nm), βhkl is the full-width at half maximum (FWHM) at (hkl) peak in radian, and θ hkl is the diffraction angle for (hkl) phase. Using the equation, the estimated crystallite size of synthesized Fe3O4-NPs was 16.79 nm, which was calculated from the full-width at half maximum of the Fe3O4 (311) diffraction peak  at 2θ = 35.86°. Based on the X-ray diffraction pattern, the synthesized Fe3O4-NPs were figured out to be high purity crystalline, as no impurity peak was observed.
Transmission Electron Microscopy Study
Fourier Transform Infrared Study
In this study, Fe3O4-NPs were synthesized successfully by a simple and green approach using the seaweed K. alvarezii extract without utilizing any chemical-reducing agent and stabilizer. Based on the XRD analysis studied, a high purity crystalline of Fe3O4-NPs was prepared. FT-IR spectroscopy showed the involvement biomolecules present in the extract of seaweed K. alvarezii, which were verified in the synthesizing process of Fe3O4-NPs. The formation of Fe3O4-NPs was confirmed due to the noticeable absorption peaks at 556 and 423 cm−1. TEM result revealed the size and morphology of the synthesized Fe3O4-NPs. Most of the particles possessed spherical shapes with average particle sizes of 14.7 nm. The non-toxic green synthesized Fe3O4-NPs are expected suitable to be employed in various fields of applications, especially in biomedical applications.
NPs nanoparticles, K. alvarezii Kappaphycus alvarezii, XRD X-ray diffraction, UV-Vis ultraviolet-visible spectroscopy, FT-IR Fourier transform infrared, TEM transmission electron microscopy
This research was supported by the grant funded by the Ministry of education (Reference grant number PY/2015/05547 under FRGS grant). Also, the authors would like to express their gratitude to the Research Management Centre (RMC) of UTM for providing a conducive environment to carry out this research.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
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