Thermal and magnetic properties of chitosan-iron oxide nanoparticles
Introduction
Chitosan (CS) is a natural polysaccharide obtained by the partial alkaline deacetylation of chitin, a main component of the exoskeleton of crustacean, arthropod and fungi (Liu, Tan, Liu, Chen, & Yu, 2007; Kushwaha Swatantra, Awani, Rai, & Singh, 2010). Chitosan structure is similar to cellulose: composed of β-1,4-linked 2-acetamino-2-deoxy-d-glucopyranose and 2-amino-2-deoxy glucopyranose subunits, this biopolymer has a positive charge, being soluble in various acids, and can interact with poly-anions to form complexes and gels. Chitosan is also non-toxic, hydrophilic, biocompatible, biodegradable and anti-bacterial, and has been used as a biomaterial and a pharmaceutical excipient in drug formulations (Liu et al., 2007).
Biomedical applications of chitosan ranges from drug delivery systems (Soares et al., 2016a; Janes, Fresneau, Marazuela, Fabra, & Alonso, 2001; Rinaudo, 2006; Yuan, Shah, Hein, & Misra, 2010), wound healing (Alemdaroglu et al., 2006; Park, Clark, Lichtensteiger, Jamison, & Johnson, 2009; Takei, Nakahara, Ijima, & Kawakami, 2012), to tissue engineering (Matsuda, Kobayashi, Itoh, Kataoka, & Tanaka, 2005; Qi, Xu, Jiang, Hu, & Zou, 2004; Qin et al., 2009; Yuan, Zhang, Yang, Wang, & Gu, 2004; Zhang, Ni, Zhang, & Ratner, 2003). It is able to encapsulate not only drug molecules, but also other types of nanoparticles (NPs) adding to them further functionalities. For example, magnetic nanoparticles covered with a chitosan network contributes to the enhancement of their magnetic and thermal properties (Shete et al., 2014; Unsoy, Khodadust, Yalcin, Mutlu, & Gunduz, 2014; Zamora-Mora et al., 2014).
Magnetic nanoparticles are widely used for magnetic hyperthermia (Echeverria et al., 2015, Eneko et al., 2015, Guardia et al., 2012, Kobayashi, 2011, Kolosnjaj-Tabi et al., 2014; Obaidat, Issa, & Haik, 2015; Soares, Ferreira, & Borges, 2014; Soares, Ferreira, Igreja, Novo, & Borges, 2012) and magnetic resonance imaging (Atefeh et al., 2015; Jafari, Farjami Shayesteh, Salouti, & Boustani, 2014; Ming et al., 2015, Sun et al., 2008). Iron oxide NPs (Fe3O4 NPs) are the most commonly used magnetic NPs due to their biocompatibility. However, their properties are highly dependent on the synthesis method. Among all synthesis methods chemical precipitation is probably the simplest to produce iron oxide NPs, allowing the use of harmless and biocompatible materials and making the resultant nanoparticles suitable for biomedical applications. By controlling the reaction parameters it is possible to obtain iron oxide NPs as small as 5 nm (Indira & Lakshmi, 2010; McBain, Yiu, & Dobson, 2008; Wu, He, & Jiang, 2008; Wu, Wu, Yu, Jiang, & Kim, 2015). Thermal decomposition technique is also often used to synthetize iron oxide NPs which is based on the decomposition of metal oxysalts (e.g., nitrates, carbonates, and acetates) when heated to the solvent ebullition temperature. Since this technique occurs under controlled environment, it is possible to obtain a better size control, narrow size distribution, and crystallinity of grains (Baptista, Soares, Ferreira, & Borges, 2013; Bigall et al., 2015, Gubin, 2009, Indira and Lakshmi, 2010; Maity & Agrawal, 2007b; Wu et al., 2008).
The low stability in aqueous solutions of iron oxide NPs is a problem when making colloidal solutions envisaging its manipulation and application. This is however solved using appropriate surfactant molecules (e.g. trisodium citrate or oleic acid) or polymers (e.g. chitosan), but an important aspect to know is how they will affect the thermo-magnetic properties of the iron oxide nanoparticles (Soares, Alves et al., 2014; Soares et al., 2015, Soares et al., 2016b).
The main purpose of this work was to produce iron oxide NPs either by chemical precipitation and thermal decomposition techniques in order to study the effect of chitosan on their properties. A chitosan network was used to incorporate these iron oxide NPs to obtain a nano-composite with a magnetic core and a chitosan coating. To access the influence of chitosan its molecular weight was also varied. Finally, viability of the nano-composite as a magnetic hyperthermia agent was also evaluated.
Section snippets
Experimental
All the chemical reagents used in this research work were of analytical grade and used without further purification.
Results and discussion
The magnetic and thermal properties of chitosan-Fe3O4 NPs are closely dependent on the properties of the Fe3O4 NPs. As such, two methods were used to synthesize Fe3O4 NPs: chemical precipitation and thermal decomposition. Although chemical precipitation technique is a facile and rapid method to produce Fe3O4 NPs, the obtained NPs are highly dependent upon the synthesis parameters. Consequently, the low stability of these NPs in aqueous medium generally leads to the need of using adjuvants, such
Conclusions
With the present research work we were able to produce and characterize composite nanoparticles composed by a magnetic core and a polymeric coating suitable for magnetic hyperthermia applications. The effect of chitosan, a biopolymer widely used for biomedical applications, on the magnetic and thermal properties of iron oxide nanoparticles produced by two different synthesis methods was evaluated. The polymeric coating does not affect the magnetic properties of the produced iron oxide NPs since
Acknowledgments
This work is funded by FEDER funds through the COMPETE 2020 Program and National Funds through FCT – Portuguese Foundation for Science and Technology under the project number POCI-01-0145-FEDER-007688, Reference UID/CTM/50025 and by the Associate Laboratory for Green Chemistry LAQV which is financed by national funds from FCT/MEC (UID/QUI/50006/2013) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER - 007265). P.I.P. Soares and J.T. Coutinho acknowledge FCT
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