Abstract
Carrageenan-based magnetic composites were prepared via in situ synthesis of iron oxides in a gelatinous network of the polysaccharide. The repeatable synthesis process involved three steps: immersion into ferrous salt (FeCl2) solution, alkali treatment in sodium hydroxide solution and oxidation with hydrogen peroxide, successively performed with τ- or κ-carrageenan hydrogels as the starting material. Field emission scanning electron microscope observations, X-ray diffractometry and superconducting quantum interference device (SQUID) magnetometry were carried out for the freeze-dried composites. Feroxyhite and magnetite and/or maghemite particles were produced after one cycle and multicycles of the in situ process, respectively, with a size less than several tens of nanometers, and were distributed throughout the inside as well as on the surface of numerous fibrillar entities constituting the carrageenan matrix. Nearly all the composite products explored displayed a superparamagnetic (SPM) property at 298 K; the estimated saturation magnetization (Ms) increased with increasing concentrations of FeCl2 in the gel immersion step and with repetition of the standardized process of iron oxide synthesis. By repeating the synthesis cycle 3–4 times, a composite of practically high Ms reaching ∼25 emu (g sample)−1 was easily obtained without impairing the SPM character. Insight was provided into the evolution mechanism of the oxidation state and dimensional distribution of the cyclically loaded iron oxide nanoparticles through comparison with another composite series obtained by a co-precipitation method with a 1:2 mixture of ferrous/ferric salts.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Marchessault, R. H., Ricard, S. & Rioux, P. In situ synthesis of ferrites in lignocellulosics. Carbohydr. Res. 224, 133–139 (1992).
Raymond, L., Revol, J.-F., Ryan, D. H. & Marchessault, R. H. In situ synthesis of ferrites in cellulosics. Chem. Mater. 6, 249–255 (1994).
Sourty, E., Ryan, D. H. & Marchessault, R. H. Characterization of magnetic membranes based on bacterial and man-made cellulose. Cellulose 5, 5–17 (1998).
Suber, L., Foglia, S., Ingo, G. M. & Boukos, N. Synthesis, and structural and morphological characterization of iron oxide-ion-exchange resin and -cellulose nanocomposites. Appl. Organometal. Chem. 15, 414–420 (2001).
Chatterjee, J., Haik, Y. & Chen, C. J. Biodegradable magnetic gel: synthesis and characterization. Colloid Polym. Sci. 281, 892–896 (2003).
Nishio, Y. Material functionalization of cellulose and related polysaccharides via diverse microcompositions. Adv. Polym. Sci. 205, 97–151 (2006).
Matsumoto, Y., Teramoto, Y. & Nishio, Y. Preparation of thermoplastic magnetic wood via etherification and in-situ synthesis of iron oxide. J. Wood Chem. Tech. 30, 373–381 (2010).
Liu, S., Zhou, J. & Zhang, L. In situ synthesis of plate-like Fe2O3 nanoparticles in porous cellulose films with obvious magnetic anisotropy. Cellulose 18, 663–673 (2011).
Kroll, E., Winnik, F. M. & Ziolo, R. F. In situ preparation of nanocrystalline γ-Fe2O3 in Iron(II) cross-linked alginate gels. Chem. Mater. 8, 1594–1596 (1996).
Veiga, V., Ryan, D. H., Sourty, E., Llanes, F. & Marchessault, R. H. Formation and characterization of superparamagnetic cross-linked high amylose starch. Carbohydr. Polymers 42, 353–357 (2000).
Jones, F., Cölfen, H. & Antonietti, M. Interaction of κ-carrageenan with nickel, cobalt, and iron hydroxides. Biomacromolecules 1, 556–563 (2000).
Pardoe, H., Chua-anusorn, W., Pierre, T. G. & Dobson, J. Structural and magnetic properties of nanoscale iron oxide particles synthesized in the presence of dextran or polyvinyl alcohol. J. Magn. Magn. Mater. 225, 41–46 (2001).
Kim, D. K., Mikhaylova, M., Zhang, Y. & Muhammed, M. Protective coating of superparamagnetic iron oxide nanoparticles. Chem. Mater. 15, 1617–1627 (2003).
Nishio, Y., Yamada, A., Ezaki, K., Miyashita, Y., Furukawa, H. & Horie, K. Preparation and magnetometric characterization of iron oxide-containing alginate/poly(vinyl alcohol) networks. Polymer 45, 7129–7136 (2004).
Daniel-da-Silva, A. L., Trindade, T., Goodfellow, B. J., Costa, B. F. O., Correia, R. N. & Gil, A. M. In situ synthesis of magnetite nanoparticles in carrageenan gels. Biomacromolecules 8, 2350–2357 (2007).
Ziolo, R. F., Giannelis, E. P., Weinstein, B. A., O'Horo, M. P., Ganguly, B. N., Mehrotra, V., Russell, M. W. & Huffman, D. R. Matrix-mediated synthesis of nanocrystalline γ-Fe2O3: a new optically transparent magnetic material. Science 257, 219–223 (1992).
Van de Velde, F. & De Ruiter, G. A. Carrageenan In: Polysaccharides II. polysaccharides from eukaryotes, Biopolymers Vandamme E. J., De Baets S., Steinbüchel A. (eds) Vol. 6 pp 245–273 (Wiley-VCH, Weinheim, 2002).
Clark, A. H. & Ross-Murphy, S. B. Structural and mechanical properties of biopolymer gels. Adv. Polym. Sci. 83, 57–192 (1987).
Morris, E. R., Rees, D. A. & Robinson, G. Cation-specific aggregation of carrageenan helices: domain model of polymer gel structure. J. Mol. Biol. 138, 349–362 (1980).
Tartaj, P., Morales, M. P., González-Carreño, T., Veintemillas-Vedaguer, S. & Serna, C. J. Advances in magnetic nanoparticles for biotechnology applications. J. Magn. Magn. Mater. 290–291, 28–34 (2005).
Cullity, B. D. & Graham, C. D. (eds) Introduction to Magnetic Materials 2nd edn (John Wiley & Sons, Inc., Hoboken, NJ, 2008).
Gittleman, J. I., Abeles, B. & Bozoeski, S. Superparamagnetism and relaxation effects in granular Ni-SiO2 and Ni-Al2O3 films. Phys. Rev. B 9, 3891–3897 (1974).
Tang, B. Z., Geng, Y., Lam, J. W. Y., Li, B., Jing, X., Wang, X., Wang, F., Pakhomov, A. B. & Zhang, X. X. Processible nanostructured materials with electrical conductivity and magnetic susceptibility: Preparation and properties of maghemite/polyaniline nanocomposite films. Chem. Mater. 11, 1581–1589 (1999).
De Cuyper, M., Müller, P., Lueken, H. & Hodenius, M. Synthesis of magnetic Fe3O4 particles covered with a modifiable phospholipid coat. J. Phys. Condens. Matter 15, S1425–S1436 (2003).
Zhu, H., Yang, D., Zhu, L., Yang, H., Jin, D. & Yao, K. A facile two-step hydrothermal route for the synthesis of γ-Fe2O3 nanocrystals and their magnetic properties. J. Mater. Sci. 42, 9205–9209 (2007).
Rajan, G. S., Stromeyer, S. L., Mauritz, K. A., Miao, G., Mani, P., Shamsuzzoha, M., Nikles, D. E. & Gupta, A. Superparamagnetic nanocomposites based on poly(styrene-b-ethylene/butylene-b-styrene)/cobalt ferrite compositions. J. Magn. Magn. Mater. 299, 211–218 (2006).
Sohn, B. H., Cohen, R. E. & Papaefthymiou, G. C. Magnetic properties of iron oxide nanoclusters within microdomains of block copolymers. J. Magn. Magn. Mater. 182, 216–224 (1998).
Tamura, Y., Ito, K. & Katsura, T. Transformation of γ-FeO(OH) to Fe3O4 by adsorption of iron(II) ion on γ-FeO(OH). J. Chem. Soc. Dalton Trans. 2, 189–194 (1983).
Hao, S., Wang, X., Wei, Y., Wang, Y. & Liu, C. Preparation and properties of nanosize MnZn ferrite from δ-FeOOH. Rare Metals 25, 466–470 (2006).
Acknowledgements
The authors wish to acknowledge Dr A. Otsuka of the Research Center for Low Temperature and Materials Sciences, Kyoto University, for his technical assistance in the SQUID magnetometry measurements. This work was partially financed by a Grant-in-Aid for Scientific Research (A) (no. 23248026 to Y. N.) from the Japan Society for the Promotion of Science.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Oya, K., Tsuru, T., Teramoto, Y. et al. Nanoincorporation of iron oxides into carrageenan gels and magnetometric and morphological characterizations of the composite products. Polym J 45, 824–833 (2013). https://doi.org/10.1038/pj.2012.221
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2012.221
