JEAS  Vol.6 No.4 , December 2016
Fabrication and Characterisation of Novel Natural Lycopodium clavatum Sporopollenin Microcapsules Loaded In-Situ with Nano-Magnetic Humic Acid-Metal Complexes
Abstract: Sporopollenin exines microcapsules, derived from the naturally occurring spores of Lycopodium clavatum, have been loaded in-situ with humic acid sodium salt-Zinc (HA-Zn) complex. The chemical treatment method utilised to prepare the sporopollenin microcapsules from raw spores was discussed and the resulted sporopollenin microcapsules were characterised using SEM, TGA and FTIR. Metal complexes of the sodium salt of humic acid and zinc ion were prepared using different protocols and in-situ loaded into the pre-treated sporopollenin microcapsules. The resulted complex was characterised before and after the encapsulation process using FTIR, TGA and XRD techniques. The morphology of the empty and loaded sporopollenin was not altered. Infrared spectroscopy revealed an increase in the absorption for COO vibrations at 1583 and 1384 cm1 in the FTIR spectra of HA-Zn complex compared to that of the original sodium salt of humic acid, indicative of bonding of the metal ions in hydrated form to the carboxyl or phenolic hydroxyl groups or both of the sodium humate molecules. TGA results of the HA-Zn complex loaded sporopollenin showed that around %15 of residual HA-Zn was successfully encapsulated indicative of the efficiency of the protocol used. We showed also that biodegradable magnetite nanoparticles can be surface modified with HA and encapsulated into sporopollenin. The resulted biosorbents microcapsules can be used for enhanced magnetic removal of either heavy metals or HA from different aqueous media.
Cite this paper: Dyab, A. , Abdallah, E. , Ahmed, S. and Rabee, M. (2016) Fabrication and Characterisation of Novel Natural Lycopodium clavatum Sporopollenin Microcapsules Loaded In-Situ with Nano-Magnetic Humic Acid-Metal Complexes. Journal of Encapsulation and Adsorption Sciences, 6, 109-131. doi: 10.4236/jeas.2016.64009.

[1]   Lorch, M., Thomasson, M.J., Diego-Taboada, A., Barrier, S., Atkin, S.L., Mackenzie, G. and Archibald, S.J. (2009) MRI Contrast Agent Delivery Using Spore Capsules: Controlled Release in Blood Plasma. Chemical Communications, 2009, 6442-6444.

[2]   Hall, S. R., Bolger, H. and Mann, S. (2003) Morphosynthesis of Complex Inorganic Forms Using Pollen Grain Templates. Chemical Communications, 2003, 2784-2785.

[3]   Barrier, S., Rigby, A.S., Diego-Taboada, A., Thomasson, M.J., Mackenzie, G. and Atkin, S.L. (2010) Sporopollenin Exines: A Novel Natural Taste Masking Material. LWT—Food Science and Technology, 43, 73-76.

[4]   Gezici, O. and Ayar, A. (2009) Stepwise Frontal Analysis to Derive Equilibrium Sorption Data for Copper and Aniline on Functionalized Sporopollenin. Clean—Soil, Air, Water, 37, 349-354.

[5]   Ucan, M., Gurten, A. and Ayar, A. (2003) Determination of the Rate Control Step of Chlorinated Anilines in Ligand Exchange Reactions on Solid Phase by Using Breakthrough Technique. Colloids and Surfaces A, 219, 193-199.

[6]   Pehlivan, E., Ersoz, M., Yildiz, S. and Duncan, H.J. (1994) Sorption of Heavy Metal Ions on New Metal-Ligand Complexes Chemically Derived from Lycopodium clavatum. Separation Science and Technology, 29, 1757-1768.

[7]   Virginia, J., Franziska, S., Heidemarie, R., Ines. F., Ilona, D., Werner, Ö., Ulrich, P. and Janina, K. (2011) Surface-Enhanced Raman Scattering with Silver Nanostructures Generated in Situ in a Sporopollenin Biopolymer Matrix. Chemical Communications, 47, 3236-3238.

[8]   Pehlivan, E. and Yildiz, S. (1988) Modified Sporopollenin as a Novel Anion, Cation and Ligand Exchange Medium. Analytical Letters, 21, 297-309.

[9]   Shaw, G., Sykes, M., Humble, R.W., Mackenzie, G., Marsdenans D. and Phelivan, E. (1988) The Use of Modified Sporopollenin from Lycopodium clavatum as a Novel Ion- or Lignand-Exchange Medium. Reactive Polymers, 9, 211-217.

[10]   Beckett, S.T., Atkin S.L. and Mackenzie, G. (2003) Dosage Form. WO Patent No. WO2005/ 000280.

[11]   Atkin S.L., Beckett S. and Mackenzie, G. (2005) USA Patent Application 20050002963.

[12]   Hamad, S.A., Dyab, A.K.F., Stoyanov, S.D. and Paunov, V.N. (2011) Encapsulation of Living Cells into Sporopollenin Microcapsules. Journal of Materials Chemistry, 21, 18018-18023.

[13]   Paunov, V.N., Mackenzie, G. and Stoyanov, S.D. (2007) Sporopollenin Micro-Reactors for In-Situ Preparation, Encapsulation and Targeted Delivery of Active Components. Journal of Materials Chemistry, 17, 609-612.

[14]   Yan, K., Li, P., Zhu, H., Zhou, Y.J., Ding, S.J., Li, Z., Xu, Z. and Chu, P.K. (2013) Recent Advances in Multifunctional Magnetic Nanoparticles and Applications to Biomedical Diagnosis and Treatment. RSC Advances, 3, 10598-10618.

[15]   Qu, H., Ma, H., Riviere, A., Zhou, W. and O’Connor, C.J. (2012) One-Pot Synthesis in Polyamines for Preparation of Water-Soluble Magnetite Nanoparticles with Amine Surface Reactivity. Journal of Materials Chemistry, 22, 3311-3313.

[16]   Jiang, J.S., Gan, Z.F., Yang, Y., Du, B., Qian, M. and Zhang, P. (2009) A Novel Magnetic Fluid Based on Starch-Coated Magnetite Nanoparticles Functionalized with Homing Peptide. Journal of Nanoparticle Research, 11, 1321-1330.

[17]   Gupta, A.K. and Gupta, M. (2005) Synthesis and Surface Engineering of Iron Oxide Nanoparticles for Biomedical Applications. Biomaterials, 26, 3995-4021.

[18]   Krizzova, J., Spanova, A., Rittich, B. and Horak, D. (2005) Magnetic Hydrophilic Methacrylate-Based Polymer Microspheres for Genomic DNA Isolation. Journal of Chromatography A, 1064, 247-253.

[19]   Neuberger, T., Schopf, B., Hofmann, H., Hofmann, M. and Rechenberg, B. (2005) Superparamagnetic Nanoparticles for Biomedical Applications: Possibilities and Limitations of a New Drug Delivery System. Journal of Magnetism and Magnetic Materials, 293, 483-496.

[20]   Ruckenstein, E. and Li, Z.F. (2005) Surface Modification and Functionalization through the Self-Assembled Monolayer and Graft Polymerization. Journal of Colloid and Interface Science, 113, 43-63.

[21]   Neouze, M.A. and Schubert, U. (2008) Surface Modification and Functionalization of Metal and Metal Oxide Nanoparticles by Organic Ligands. Monatshefte fur Chemie, 139, 183-195.

[22]   Zhang, X., Zhang, P., Wu, Z., Zhang, L., Zeng, G. and Zhou, C. (2013) Adsorption of Methylene Blue onto Humic Acid-Coated Fe3O4 Nanoparticles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 435, 85-90.

[23]   Yang, K., Zhu, L., Lou, B. and Chen, B. (2005) Correlations of Nonlinear Sorption of Organic Solutes with Soil/Sediment Physicochemical Properties. Chemosphere, 61, 116-128.

[24]   Tipping, E. (2002) Cation Binding by Humic Substances. Cambridge University Press, West Nyack.

[25]   Huang, W.L., Schlautman, M.A. and Weber, W.J. (1996) A Distributed Reactivity Model for Sorption by Soils and Sediments. 5. The Influence of Near-Surface Characteristics in Mineral Domains. Environmental Science & Technology, 30, 2993-3000.

[26]   Gezici, O., Kara, H., Ersoz, M. and Abali, Y. (2005) The Sorption Behavior of a Nickel-Insolubilized Humic Acid System in a Column Arrangement. Journal of Colloid and Interface Science, 292, 381-391.

[27]   Gezici, O. and Kara, H. (2011) Towards Multimodal HPLC Separations on Humic Acid-Bonded Aminopropyl Silica: RPLC and HILIC Behaviour. Talanta, 85, 1472-1482.

[28]   Heitkamp, D. and Wagner, K. (1982) New Aspects of Uranium Recovery from Seawater. Industrial & Engineering Chemistry Process Design and Development, 21, 781-784.

[29]   Ho, C.H. and Miller, N.H. (1985) Effect of Humic Acid on Uranium Uptake by Hematite Particles. Journal of Colloid and Interface Science, 106, 281-288.

[30]   Seki, H. and Suzuki, A. (1990) Adsorption of Lead Ions on Immobilized Humic Acid. Journal of Colloid and Interface Science, 134, 59-65.

[31]   Okada, A. and Usuki, A. (1995) The Chemistry of Polymer-Clay Hybrids. Materials Science and Engineering C, 3, 109-115.

[32]   Szabo, G., Prosser, S.L. and Bulman, R.A. (1990) Determination of the Adsorption Coefficient (KOC) of Some Aromatics for Soil by RP-HPLC on Two Immobilized Humic Acid Phases. Chemosphere, 21, 777-788.

[33]   Szabo, G., Farkas, G. and Bulman, R.A. (1992) Evaluation of Silica-Humate and Alumina- Humate HPLC Stationary Phases for Estimation of the Adsorption Coefficient, Koc, of Soil for Some Aromatics. Chemosphere, 24, 403-412.

[34]   Koopal, L.K., Yang, Y., Minnaard, A.J., Theunissen, P.L.M. and Van Riemsdijk, W.H. (1998) Chemical Immobilisation of Humic Acid on Silica. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 141, 385-395.

[35]   Klavins, M. and Eglite, L. (2002) Immobilisation of Humic Substances. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 203, 47-54.

[36]   Prado, A.G.S., Miranda, B.S. and Dias, J.A. (2004) Attachment of Two Distinct Humic Acids onto a Silica Gel Surface. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 242, 137-143.

[37]   Hatay, I., Gup, R. and Ersoz, M. (2008) Silica gel Functionalized with 4-Phenylaceto-phynone 4-Aminobenzoylhydrazone: Synthesis of a New Chelating Matrix and Its Application as Metal Ion Collector. Journal of Hazardous Materials, 150, 546-553.

[38]   Wang, J., Zhang, D., Lawson, T.R. and Bartsch, R.A. (2009) Sorption of Heavy Metal Ions by Silica Gel-Immobilized, Proton-Ionizable Calix[4]Arenes. Talanta, 78, 477-483.

[39]   Gubbuk, I.H. (2011) Isotherms and Thermodynamics for the Sorption of Heavy Metal Ions onto Functionalized Sporopollenin. Journal of Hazardous Materials, 186, 416-422.

[40]   Atta, A.M. and Dyab, A.K.F. (2014) Coated Magnetite Nanoparticles, Method for the Preparation Thereof and Their Uses. EP 2804186.

[41]   Brunner U. and Honegger, R. (1985) Chemical and Ultrastructural Studies on the Distribution of Sporopolleninlike Biopolymers in Six Genera of Lichen Phycobionts. Canadian Journal of Botany, 63, 2221-2229.

[42]   Ahlers, F., Thom, I., Lambert, J., Kuckuk, R. and Wiermann, R. (1999) 1H NMR Analysis of Sporopollenin from Typha angustifolia. Phytochemistry, 50, 1095-1098.

[43]   Dominguez, E., Mercado, J.A., Quesada, M.A. and Heredia, A. (1999) Pollen Sporopollenin: Degradation and Structural Elucidation. Sexual Plant Reproduction, 12, 171-178.

[44]   Bohne, G., Richter, E., Woehlecke, H. and Ehwaldi, R. (2003) Diffusion Barriers of Tripartite Sporopollenin Microcapsules Prepared from Pine Pollen. Annals of Botany, 92, 289-297.

[45]   Liu, J.F., Zhao, Z.S. and Hang, G.B. (2008) Coating Fe3O4 Magnetic Nanoparticles with Humic Acid for High Efficient Removal of Heavy Metals in Water. Environmental Science & Technology, 42, 6949-6954.

[46]   Anirudhan, T. and Ramachandran, M. (2007) Surfactant-Modified Bentonite as Adsorbent for the Removal of Humic Acid from Wastewaters. Applied Clay Science, 35, 276-281.

[47]   Zhiguo, S., Jitao, Y., Li, Z. and Hongyong, X. (2016) Preparation, Characterization and Photocatalytic Activity of Sodium Humate/Nano-TiO2 Coating on Glass Spheres for Flue Gas Denitrification. Nano, 11, Article ID: 1650070.

[48]   Lubal, P., Siroky, D., Fetsch, D. and Havel, J. (1998) The Acidobasic and Complexation Properties of Humic Acids: Study of Complexation of Czech Humic Acids with Metal Ions. Talanta, 47, 401-412.

[49]   Vinkler, P., Lakatos, B. and Meisel, J. (1976) Infrared Spectroscopic Investigations of Humic Substances and Their Metal Complexes. Geoderma, 15, 231-242.

[50]   Erdogan, S., Baysal, A., Akba, O. and Hamamci, C. (2007) Interaction of Metals with Humic Acid Isolated from Oxidized Coal. Polish Journal of Environmental Studies, 16, 671-675.

[51]   Tan, K.H. (1978) Formation of Metal-Humic Acid Complexes by Titration and Their Characterization by Differential Thermal Analysis and Infrared Spectroscopy. Soil Biology & Biochemistry, 10, 123-129.

[52]   Shaw, G. (1970) Sporopollenin. In: Harborne, J.B., Ed., Sporopollenin in Phytochemical Phylogeny, Academic Press, London, Chapter 3, 31-58.

[53]   Shaw, G. (1971) The Chemistry of Sporopollenin. In: Brooks, J. Grant, P.R. and Muir, M., Eds., Sporopollenin, Academic Press, London, 305-350.

[54]   Pehlivan, E. and Yildiz, S. (1988) Modified Sporopollenin as a Novel Anion, Cation and Ligand Exchange Medium. Analytical Letters, 21, 297-309.

[55]   Pehlivan, E., Ersoz, M., Pehlivan, M., Yildiz, S. and Duncan, H.J. (1995) The Effect of pH and Temperature on the Sorption of Zinc(II), Cadmium(II), and Aluminum(III) onto New Metal-Ligand Complexes of Sporopollenin. Journal of Colloid and Interface Science, 170, 320-325.

[56]   Ersoz, M., Pehlivan, M., Duncan, H.J., Yildiz, S. and Pehlivan, M. (1995) Ion Exchange Equilibria of Heavy Metals in Aqueous Solution on New Chelating Resins of Sporopollenin. Reactive Polymers, 24, 195-202.

[57]   Pehlivan, M., Vural, U.S., Okdan, A., Pehlivan, E. and Yildiz, S. (1995) Transport Studies of Amino Acids through a Liquid Membrane System Containing Carboxylated Poly (Styrene) Carrier. Journal of Membrane Science, 104, 263-269.

[58]   Ersoz, M., Vural, U.S., Yigitoglu, M. and Sezgin, M. (1996) Kinetic Study of Ligand Exchange Reaction of Anions as Ligands on DAE-Sporopollenin. Journal of Colloid and Interface Science, 184, 319-324.

[59]   Atta, A.M., Al-Lohedan, H.A. and Al-Hussain, S.A. (2014) Synthesis of Stabilized Myrrh-Capped Hydrocolloidal Magnetite Nanoparticles. Molecules, 19, 11263-11278.

[60]   Khalil, M.I. (2013) Process for Preparing Magnetic (Fe3O4) and Derivatives Thereof. EP 2505558 A1.

[61]   Koesnarpadia, S., Santosab, S., Siswantab, D. and Rusdiarsob, B. (2015) Synthesis and Characterizatation of Magnetite Nanoparticle Coated Humic Acid (Fe3O4/HA). Procedia Environmental Sciences, 30, 103-108.