CRYSTALLINE STARCH CITRATE BIOPOLYMER NANORODS AS POTENTIAL STABILIZERS IN NANO AND MICRO EMULSIONS

Abstract

The area of green chemistry which involves the synthesis of biodegradable polymers with better stabilizing properties is fast-developing. Starch biopolymer was citrate modified and converted to crystalline nanorods through green methods and was fully characterized using the fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction studies (XRD) and thermogravimetric analysis (TGA). The crystalline starch citrate showed better morphological and thermal stability properties than the ordinary and modified normal starch which has not been converted to nano form. The starch citrate nanoparticle showed characteristic bragg reflection angles at 2θ of 24°, 29° and 33° while the TGA result revealed a single step thermal degradation at 240 to 410 °C and percentage weight loss of about 89%. The SEM and TEM also confirmed the synthesis of rod-like or cylindrical nanoparticles with little or no aggregation. This property coupled with the thermal stability makes starch citrate nanoparticles a good stabilizer for nano and micro emulsions.

Keywords

• Starch citrate,nanoparticles,stabilizer

References

1. 1. Ma, X., Jian, R., Chang, P. R., & Yu, J. (2008). Fabrication and Characterization of Citric Acid-Modified Starch Nanoparticles/Plasticized-Starch Composites. Biomacromolecules, 9(11), 3314–3320. doi:10.1021/bm800987c 2. Yu, J., Wang, N., & Ma, X. (2008). Fabrication and Characterization of Poly(lactic acid)/Acetyl Tributyl Citrate/Carbon Black as Conductive Polymer Composites. Biomacromolecules, 9(3), 1050–1057. doi:10.1021/bm7012857 3. Santander-Ortega, M. J., Csaba, N., Alonso, M. J., Ortega-Vinuesa, J. L., & Bastos-González, D. (2007). Stability and physicochemical characteristics of PLGA, PLGA:poloxamer and PLGA:poloxamine blend nanoparticles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 296(1-3), 132–140. doi:10.1016/j.colsurfa.2006.09.036 4. Santander-Ortega, M. J., Stauner, T., Loretz, B., Ortega-Vinuesa, J. L., Bastos-González, D., Wenz, G., … Lehr, C. M. (2010). Nanoparticles made from novel starch derivatives for transdermal drug delivery. Journal of Controlled Release, 141(1), 85–92. doi:10.1016/j.jconrel.2009.08.012 5. López-León, T., Elaïssari, A., Ortega-Vinuesa, J. L., & Bastos-González, D. (2007). Hofmeister Effects on Poly(NIPAM) Microgel Particles: Macroscopic Evidence of Ion Adsorption and Changes in Water Structure. ChemPhysChem, 8(1), 148–156. doi:10.1002/cphc.200600521 6. Chivrac, F., Pollet, E., Schmutz, M., & Avérous, L. (2008). New Approach to Elaborate Exfoliated Starch-Based Nanobiocomposites. Biomacromolecules, 9(3), 896–900. doi:10.1021/bm7012668 7. Enturi, V., Chowdary, By., & Chowdary, K. P. . (2014). Enhancement of dissolution rate and formulation development of irbesartan tablets by employing starch phosphate: A new modified starch. Asian Journal of Pharmaceutics, 8(3), 171. doi:10.4103/0973-8398.139180 8. Jivraj, M., Martini, L. G., & Thomson, C. M. (2000). An overview of the different excipients useful for the direct compression of tablets. Pharmaceutical Science & Technology Today, 3(2), 58–63. doi:10.1016/s1461-5347(99)00237-0 9. B. Wepner, E. Berghofer, E. Miesenberger, K. Tiefenbacher and P. N. K. Ng, Starch., 51, 354 (1999). 10. Chin, S. F., Pang, S. C., & Tay, S. H. (2011). Size controlled synthesis of starch nanoparticles by a simple nanoprecipitation method. Carbohydrate Polymers, 86(4), 1817–1819. doi:10.1016/j.carbpol.2011.07.012 11. Pang, S. C., Chin, S. F., Tay, S. H., & Tchong, F. M. (2011). Starch–maleate–polyvinyl alcohol hydrogels with controllable swelling behaviors. Carbohydrate Polymers, 84(1), 424–429. doi:10.1016/j.carbpol.2010.12.002 12. Kim, J.-Y., & Lim, S.-T. (2009). Preparation of nano-sized starch particles by complex formation with n-butanol. Carbohydrate Polymers, 76(1), 110–116. doi:10.1016/j.carbpol.2008.09.030 13. Loftsson, T., Másson, M., & Brewster, M. E. (2004). Self-Association of Cyclodextrins and Cyclodextrin Complexes. Journal of Pharmaceutical Sciences, 93(5), 1091–1099. doi:10.1002/jps.20047 14. Rondeau-Mouro, C., Bail, P. L., & Buléon, A. (2004). Structural investigation of amylose complexes with small ligands: inter- or intra-helical associations? International Journal of Biological Macromolecules, 34(5), 251–257. doi:10.1016/j.ijbiomac.2004.09.002 15. Shi, A., Li, D., Wang, L., Li, B., & Adhikari, B. (2011). Preparation of starch-based nanoparticles through high-pressure homogenization and miniemulsion cross-linking: Influence of various process parameters on particle size and stability. Carbohydrate Polymers, 83(4), 1604–1610. doi:10.1016/j.carbpol.2010.10.011 16. Veiseh, O., Gunn, J. W., & Zhang, M. (2010). Design and fabrication of magnetic nanoparticles for targeted drug delivery and imaging. Advanced Drug Delivery Reviews, 62(3), 284–304. doi:10.1016/j.addr.2009.11.002 17. Demitri, C., Del Sole, R., Scalera, F., Sannino, A., Vasapollo, G., Maffezzoli, A., … Nicolais, L. (2008). Novel superabsorbent cellulose-based hydrogels crosslinked with citric acid. Journal of Applied Polymer Science, 110(4), 2453–2460. doi:10.1002/app.28660 18. Fujioka, R., Tanaka, Y., & Yoshimura, T. (2009). Synthesis and properties of superabsorbent hydrogels based on guar gum and succinic anhydride. Journal of Applied Polymer Science, 114(1), 612–616. doi:10.1002/app.30600 19. Salam, A., Pawlak, J. J., Venditti, R. A., & El-tahlawy, K. (2010). Synthesis and Characterization of Starch Citrate−Chitosan Foam with Superior Water and Saline Absorbance Properties. Biomacromolecules, 11(6), 1453–1459. doi:10.1021/bm1000235 20. Chang,P.R.,Yu,J. and Ma,X. (2011), Carbohydrate Polymers. 83, 1016-1019. 21. Abbas,S., Bashari,M., Akhtar,W, Li,W.W. and Zhang,X., (2014), Ultrasonics sonochemistry. 21, 1265-1274. 22. A. Karadag, X. Yang, B. Ozcelik, Q. Huang, Optimization of preparation conditions for quercetin nanoemulsions using response surface methodology, J. Agric. Food Chem. 61 (2013) 2130–2139. 23. Manoi, K., & Rizvi, S. S. H. (2010). Physicochemical characteristics of phosphorylated cross-linked starch produced by reactive supercritical fluid extrusion. Carbohydrate Polymers, 81, 687–694 24. V. Ghosh, A. Mukherjee, N. Chandrasekaran, Ultrasonic emulsification of food grade nanoemulsion formulation and evaluation of its bactericidal activity, Ultrason. Sonochem. 20 (2013) 338–344.