Organic/Inorganic hybrid materials have been attracting much attention since they combine the advantages of inorganic materials with the properties of organic polymers. Titanium dioxide nanoparticles (TiO2) present good thermal stability, accessibility and catalytic properties. Polycaprolactone (PCL) is a bi-ocompatible and bioresorbable material, which is being examined as biode-gradable packaging materials, controlled drug release carriers and other medical applications. Hybrids based on PCL containing different amounts of titanium dioxide nanoparticles, ranging from 0.05% to 0.35% w/w, were prepared using the solution cast method. These systems were characterized by X-ray diffraction (XRD), infrared spectroscopy (FTIR), low-field nuclear magnetic resonance (NMR), thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). The FTIR analysis confirmed that there was an interaction between the PCL chains and the TiO2 nanoparticles. The XRD and DSC analysis showed that the PCL crystallization was affected by TiO2 incorporation, modifying its semi-crystalline structure to a less ordered structure. When TiO2 nanoparticles were added the values of T1H and T1ρH increased for all hybrids, therefore, their addition produced a new material with less molecular mobility. In the TG analysis, it was observed that the introduction of TiO2 nanoparticles decreased the thermal resistance of PCL. In DSC analysis, the PCL/TiO2 hybrids presented a reduction in the crystallization temperature and degree of crystallinity, except for PCL hybrids containing 0.15% w/w of TiO2 nanoparticles.
References
[1]
Arslan, M., Tasdelen, M.A., Uyar, T. and Yagci, Y. (2015) Poly(epsilon caprolactone)/clay Nanocomposites via Host-Guest Chemistry. European Polymer Journal, 71, 259-267. https://doi.org/10.1016/j.eurpolymj.2015.08.006
[2]
Monteiro, M.S.S.B., Neto, R.C., Souza, I.C.S., Silva, E.O. and Tavares, M.I.B. (2012) Inorganic-Organic Hybrids Based on Poly(ε-Caprolactone) and Sílica Oxide and Characterization by Relaxometry Applying Low-Field NMR. Materials Research, 15, 825-832. https://doi.org/10.1590/S1516-14392012005000121
[3]
Muñoz-Bonilla, A., Cerrada, M.L., Fernández-García. M., Kubacka, A., Ferrer, M. and Fernández-García, M. (2013) Biodegradable Polycaprolactone-Titania Nanocomposites: Preparation, Characterization and Antimicrobial Properties. International Journal of Molecular Science, 14, 9249-9266.
https://doi.org/10.3390/ijms14059249
[4]
Brito, L.M., Sebastião, P.J.O. and Tavares, M.I.B. (2015) NMR Relaxometry Evaluation of Nanostructured Starch-PLA Blends. Polymer Testing, 45, 161-167.
https://doi.org/10.1016/j.polymertesting.2015.06.011
[5]
Silva, P.S.R.C., Menezes, L.R. and Tavares, M.I.B. (2016) The Influence of Organo-Clay Ratio in the HIPS-OMMT Nanocomposites Analyzed by Proton Spin-Lattice and Spin-Spin Relaxation Times. Materials Science and Applications, 7, 150-158.
https://doi.org/10.4236/msa.2016.73015
[6]
Monteiro, M.S.S.B., Chávez, F.V., Sebastião, P.J. and Tavares, M.I.B. (2013) 1H NMR Relaxometry and X-Ray Study of PCL/Nevirapine Hybrids. Polymer Testing, 32, 553-566. https://doi.org/10.1016/j.polymertesting.2013.01.016
[7]
Sebastião, P.J., Monteiro, M.S.S.B., Brito, L.M., Rodrigues, E., Chávez, F. and Tavares, M.I.B. (2016) Conventional and Fast Field Cycling Relaxometry Study on the Molecular Dynamics in Polymer Nanocomposites for Use as Drug Delivery System. Journal of Nanoscience and Nanotechnology, 16, 7539-7545.
https://doi.org/10.1166/jnn.2016.12476
[8]
Almeida, A.S., Tavares, M.I.B., Silva, E.O., Neto, R.P.C. and Moreira, L.A. (2012) Development of Hybrid Nanocomposites Based on PLLA and Low-Field NMR Characterization. Polymer Testing, 31, 267-275.
https://doi.org/10.1016/j.polymertesting.2011.11.005
[9]
Mofokeng, J. and Luyt, A.S. (2015) Dynamic Mechanical Properties of PLA/PHBV, PLA/PCL, PHBV/PCL Blends and Their Nanocomposites with TiO2 Nanofiller. Thermochimica Acta, 613, 41-53. https://doi.org/10.1016/j.tca.2015.05.019
[10]
Shi, R., Magaye, R., Castranova, V. and Zhao, J. (2013) Titanium Dioxide Nanoparticles: A Review of Current Toxicological Data. Particle and Fiber Toxicology, 10, 2-33. https://doi.org/10.1186/1743-8977-10-15
[11]
Mofokeng, J.P. and Luyt, A.S. (2015) Morphology and Thermal Degradation Studies of Melt-Mixed Poly(Lactic Acid) (PLA)/Poly(ε-Caprolactone) (PCL) Biodegradable Polymer Blend Nanocomposite with TiO2 as Filler. Polymer Testing, 45, 93-100.
https://doi.org/10.1016/j.polymertesting.2015.05.007
[12]
Pena, J.A., Gutiérrez, S.J., Villamil, J.C., Agudelo, N.A. and Pérez, L.D. (2016) Policaprolactone/Polivinylpyrrolidone/Siloxane Hybrids Materials: Synthesis and in vitro Delivery of Diclofenac and Biocompatibility with Periodontal Ligament Fibroblasts. Materials Science and Engineering C, 58, 60-69.
https://doi.org/10.1016/j.msec.2015.08.007
[13]
Wu, C.S. (2004). In situ Polymerization of Titanium Isopropoxide in Polycaprolactone: Properties and Characterization of the Hybrid Nanocomposites. Journal of Applied Polymer Science, 92, 1749-1757.
https://doi.org/10.1002/app.20135
[14]
Enose, A.A., Dasan, P.K., Sivaramakrishnan, H. and Shah, S.M. (2014) Formulation and Characterization of Solid Dispersion Prepared by Hot Melt Mixing: A Fast Screening Approach for Polymer Selection. Journal of Pharmaceutical, 2014, 1-13.
https://doi.org/10.1155/2014/105382
[15]
Monteiro, M.S.S.B., Lunz, J., Sebastião, P.J. and Tavares, M.I.B. (2016) Evaluation of Nevirapine Release Kinetics from Polycaprolactone Hybrids. Materials Science and Applications, 7, 680-701. https://doi.org/10.4236/msa.2016.711055
[16]
Monteiro, M.S.S.B., Rodrigues, C.L., Neto, R.C. and Tavares, M.I.B. (2012) The Structure of Polycaprolactone-Clay Nanocomposites Investigated by 1H NMR Relaxometry. Journal of Nanoscience and Nanotechnology, 12, 7307-7313.
https://doi.org/10.1166/jnn.2012.6431
[17]
Nakamoto, K. (1997) Theory and Applications in Inorganic Chemistry: Infrared and Raman Spectra of Inorganic and Coordination Compound. 5th Edition, John Wiley, Hoboken.
[18]
Li, R., Nie, K., Shen, X. and Wang, S. (2007) Biodegradable Polyester Hybrid Nanocomposites Containing Titanium Dioxide Network and Poly(ε-Caprolactone): Synthesis and Characterization. Materials Letter, 61, 1368-1371.
https://doi.org/10.1016/j.matlet.2006.07.032
[19]
Castillho, A.C. and Alarcón, J.G.O. (2011) Preparation and Characterization of Hybrids Materials of Epoxy Resin Type Bisphenol A with Silicon and Titanium Oxides by Sol Gel Process. Journal of Mexican Chemical Society, 55, 233-238.
[20]
Rodrigues, E.C., Soares, L.A., Júnior Modenes, M.A., Sene, J.J., Bannach, G., Carvalho, C.T. and Ionashiro, M.. (2011) Synthesis and Characterization of Fe(III)-Doped Ceramic Membranes of Titanium Dioxide and Its Application in Photoelectrocatalysis of a Textile Dye. Eclética Quimica, 36, 18-36.
https://doi.org/10.1590/S0100-46702011000100002
[21]
Clemens, P., Wei, X., Wilson, B.L. and Thomas, R.L. (2013) Anatase Titanium Dioxide Coated Single Wall Carbon Nanotubes Manufactured by Sonochemical-Hydrothermal Technique. Open Journal of Composite Materials, 3, 21-32.
https://doi.org/10.4236/ojcm.2013.32A004
[22]
Rashidzadeh, M. (2008) Synthesis of High-Thermal Stable Titanium Dioxide Nanoparticles. International Journal of Photoenergy, 2008, 1-4.
https://doi.org/10.1155/2008/245981
[23]
Bagheri, S., Shameli, K. and Hamid, S.B.A. (2013) Synthesis and Characterization of Anatase Titanium Dioxide Nanoparticles Using Egg White Solution via Sol-Gel Method. Journal of Chemistry, 2013, 1-5. https://doi.org/10.1155/2013/848205
[24]
Narayan, H. and Alemu, H. (2017) A Comparison of Photocatalytic Activity of TiO2 Nanocomposites Doped with Zn2+/Fe3+ and Y3+ Ions. International Journal of Nanoscience Nanotechnology, 13, 315-325.
[25]
Mirzaei, M., Ahadi, H., Shariaty-Niassar, M. and Akbari, M. (2015) Fabrication and Characterization of Visible Light Active Fe-TiO2 Nanocomposites as Nanophotocatalyst. International Journal of Nanoscience Nanotechnology, 11, 289-293.
[26]
Tamjid, E., Bagheri, R., Vossoughi, M. and Simchi, A. (2011) Effect of TiO2 Morphology on in vitro Bioactivity of Polycaprolactone/TiO2 Nanocomposites. Materials Letters, 65, 2530-2533. https://doi.org/10.1016/j.matlet.2011.05.037
[27]
Nandagopal, S., Robin, A., Soney, C.G., Jayachandran, V.P., Nandakumar, K. and Sabu, T. (2016) Gentamicin Loaded Electrospun Poly(ε-Caprolactone)/TiO2 Nanocomposite Membranes with Antibacterial Property against Methicillin Resistant Staphylococcus aureus. Journal Polymer-Plastics Technology and Engineering, 55, 1785-1796. https://doi.org/10.1080/03602559.2016.1171877
[28]
Li, R., Nie, K., Pang, W. and Qingren, Z. (2007) Morphology and Properties of Organic-Inorganic Hybrid Materials Involving TiO2 and Poly(ε-Caprolactone), a Biodegradable Aliphatic Polyester. Journal of Biomedical Research Part A, 83, 114-122.
https://doi.org/10.1002/jbm.a.31224
[29]
Bajsic, E.G., Bulatovic, V.O., Slouf, M. and Situm, A. (2014) Characterization of Biodegradable Polycaprolactone Containing Titanium Dioxide Micro and Nanoparticles. International Journal of Materials and Metallurgical Engineering, 8, 611-615.
