Thermoresponsive copolymer-grafted SBA-15 porous silica particles for temperature-triggered topical delivery systems

. A series of poly( N- isopropylacrylamide -co- acrylamide) thermoresponsive random copolymers with different molecular weights and composition were synthesized and characterized by attenuated total reflectance Fourier-transform infrared (ATR-FTIR), differential scanning calorimetry (DSC), size exclusion chromatography (SEC) and proton nuclear magnetic resonance (NMR) spectroscopy. The lower critical solution temperatures (LCST) of the copolymers were tuned by changing the mole ratios of monomers. Copolymer with highest molecular weight and LCST (41.2°C) was grafted on SBA-15 type mesoporous silica particles by a two-step polymer grafting procedure. Bare SBA-15 and the thermoresponsive copolymer-grafted (hybrid) SBA-15 particles were fully characterized by scanning electron microscope (SEM), ATR-FTIR, thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller (BET) analyses. The hybrid particles were tested for their efficiency as temperature-sensitive systems for dermal delivery of the antioxidant rutin (quercetin-3-O-rutinoside). Improved control over rutin release by hybrid particles was obtained which makes them attractive hybrid materials for drug delivery.

[1]  V. Brunella,et al.  Thermoresponsive mesoporous silica nanoparticles as a carrier for skin delivery of quercetin. , 2016, International journal of pharmaceutics.

[2]  H. Kim,et al.  Triple Hit with Drug Carriers: pH- and Temperature-Responsive Theranostics for Multimodal Chemo- and Photothermal Therapy and Diagnostic Applications. , 2016, ACS applied materials & interfaces.

[3]  S. Arpicco,et al.  Delivery of Gemcitabine Prodrugs Employing Mesoporous Silica Nanoparticles , 2016, Molecules.

[4]  W. Pan,et al.  Mutual interaction between guest drug molecules and host nanoporous silica xerogel studied using central composite design. , 2016, International journal of pharmaceutics.

[5]  V. Brunella,et al.  Hybrid drug carriers with temperature-controlled on–off release: A simple and reliable synthesis of PNIPAM-functionalized mesoporous silica nanoparticles , 2016 .

[6]  R. Vedarajan,et al.  Tunable LCST behavior of poly(N-isopropylacrylamide/ionic liquid) copolymers , 2015 .

[7]  Valentina Giovanna Brunella,et al.  Controlled post‐synthesis grafting of thermoresponsive poly(N‐isopropylacrylamide) on mesoporous silica nanoparticles , 2015 .

[8]  H. A. Therese,et al.  Dual responsive PNIPAM-chitosan targeted magnetic nanopolymers for targeted drug delivery , 2015 .

[9]  K. Sen,et al.  Studies on thermoresponsive polymers: Phase behaviour, drug delivery and biomedical applications , 2015 .

[10]  V. Brunella,et al.  Polymerizable Ligands as Stabilizers for Nanoparticles , 2015 .

[11]  Weihua Zhou,et al.  A novel thermal and pH responsive drug delivery system based on ZnO@PNIPAM hybrid nanoparticles. , 2014, Materials science & engineering. C, Materials for biological applications.

[12]  Hossein Hosseinzadeh,et al.  Review of the protective effects of rutin on the metabolic function as an important dietary flavonoid , 2014, Journal of Endocrinological Investigation.

[13]  L. S. Chua.  A review on plant-based rutin extraction methods and its pharmacological activities. , 2013, Journal of ethnopharmacology.

[14]  H. Kim,et al.  Silica-based mesoporous nanoparticles for controlled drug delivery , 2013, Journal of tissue engineering.

[15]  Dan Zhang,et al.  Ordered SBA-15 mesoporous silica with high amino-functionalization for adsorption of heavy metal ions , 2013 .

[16]  Wei Zhang,et al.  Effect of structural constraint on dynamic self-assembly behavior of PNIPAM-based nonlinear multihydrophilic block copolymers , 2013 .

[17]  B. Klösgen,et al.  Mapping the location of grafted PNIPAAM in mesoporous SBA-15 silica using gas adsorption analysis. , 2012, Physical chemistry chemical physics : PCCP.

[18]  H. Yang,et al.  Synthesis and properties of thermo-responsive macroporous PAM-co-PNIPAM microspheres , 2012 .

[19]  Jiucun Chen,et al.  Synthesis and characterization of silica nanoparticles with well-defined thermoresponsive PNIPAM via a combination of RAFT and click chemistry. , 2011, ACS applied materials & interfaces.

[20]  M. Ward,et al.  Thermoresponsive Polymers for Biomedical Applications , 2011 .

[21]  Yongjun Zhang,et al.  PNIPAM microgels for biomedical applications: from dispersed particles to 3D assemblies , 2011 .

[22]  D. Brühwiler,et al.  Influence of the Structural Properties of Mesoporous Silica on the Adsorption of Guest Molecules , 2010, Materials.

[23]  J. Chang,et al.  Thermosensitive Block Copolymers Consisting of Poly(N-isopropylacrylamide) and Star Shape Oligo(ethylene oxide) , 2009 .

[24]  D. Shipp,et al.  Synthesis of poly(methyl methacrylate)–silica nanocomposites using methacrylate-functionalized silica nanoparticles and RAFT polymerization , 2008 .

[25]  J. Fei,et al.  Preparation of polymer-coated mesoporous silica nanoparticles used for cellular imaging by a “graft-from” method , 2008 .

[26]  C. Pan,et al.  Smart Core-Shell Nanostructure with a Mesoporous Core and a Stimuli-Responsive Nanoshell Synthesized via Surface Reversible Addition-Fragmentation Chain Transfer Polymerization , 2008 .

[27]  Chunhua Yan,et al.  Optical sensors based on functionalized mesoporous silica SBA-15 for the detection of multianalytes (H+ and Cu2+) in water , 2007 .

[28]  김영호,et al.  실리카를 함유한 Poly(N-isopropylacrylamide)수화젤의 특성분석 , 2006 .

[29]  P. Cremer,et al.  Effects of end group polarity and molecular weight on the lower critical solution temperature of poly(N‐isopropylacrylamide) , 2006 .

[30]  G. Somorjai,et al.  Structure sensitivity of vibrational spectra of mesoporous silica SBA-15 and Pt/SBA-15. , 2005, The journal of physical chemistry. B.

[31]  Karim Amighi,et al.  Synthesis and characterization of thermosensitive copolymers for oral controlled drug delivery , 2004 .

[32]  M. Schönhoff,et al.  Thermoreversible polymers adsorbed to colloidal silica : a 1H NMR and DSC study of the phase transition in confined geometry , 2002 .

[33]  M. Friedman,et al.  Effect of pH on the stability of plant phenolic compounds. , 2000, Journal of agricultural and food chemistry.

[34]  H. G. Schild.  Poly(N-isopropylacrylamide): experiment, theory and application , 1992 .

[35]  M. Heskins,et al.  Solution Properties of Poly(N-isopropylacrylamide) , 1968 .