Abstract
In this article, we report a novel method for synthesizing temperature-sensitive polymer-modified cellulose nanofibril (CNF) cryogel microspheres. The pristine cryogel microspheres were first prepared using a spray-freeze dry method in the presence of a chemical crosslinker. Afterwards, NIPAm (N-isopropylacrylamide), a temperature-sensitive monomer, was polymerized and grafted to the cellulose cryogel microspheres through in situ free radical polymerization in the cryogel microreactor. The morphology, chemical structure, thermal sensitivity, bulk density and water uptake capacity of the hybrid microspheres were characterized. The CNF–PNIPAm hybrid microspheres exhibited a good temperature response at around 32 °C in water. The swelling behavior and drug release capability of CNF–PNIPAm hybrid microspheres were also investigated. The microspheres with PNIPAm exhibited a controllable drug release rate. The temperature effect on the drug release rate was also observed. These results indicated that porous CNF–PNIPAm hybrid microspheres could serve as a new type of material for controlled drug release.
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Agnihotri SA, Aminabhavi TM (2006) Novel interpenetrating network chitosan-poly(ethylene oxide-g-acrylamide) hydrogel microspheres for the controlled release of capecitabine. Int J Pharm 324:103–115
Ayers MR, Hunt AJ (2001) Synthesis and properties of chitosan–silica hybrid aerogels. J Non-Cryst Solids 285:123–127
Bae YH, Okano T, Hsu R (1987) Thermo-sensitive polymers as on-off switches for drug release. Die Makromol Chem Rapid Commun 8:481–485
Cai H, Sharma S, Liu W, Mu W, Liu W, Zhang X, Deng Y (2014) Aerogel microspheres from natural cellulose nanofibrils and their application as cell culture scaffold. Biomacromolecules 15:2540–2547
Costa P, Lobo JMS (2001) Modeling and comparison of dissolution profiles. Eur J Pharm Sci 13:123–133
García-González CA, Alnaief M, Smirnova I (2011) Polysaccharide-based aerogels-promising biodegradable carriers for drug delivery systems. Carbohydr Polym 86:1425–1438
Gavillon R, Budtova T (2007) Aerocellulose: new highly porous cellulose prepared from cellulose-NaOH aqueous solutions. Biomacromolecules 9:269–277
Guenther U, Smirnova I, Neubert RHH (2008) Hydrophilic silica aerogels as dermal drug delivery systems–Dithranol as a model drug. Eur J Pharm Biopharm 69:935–942
Hebeish A, Farag S, Sharaf S, Shaheen TI (2014) Thermal responsive hydrogels based on semi interpenetrating network of poly (NIPAm) and cellulose nanowhiskers. Carbohydr Polym 102:159–166
Innerlohinger J, Weber HK, Kraft G (2006) Aerocellulose: aerogels and aerogel-like materials made from cellulose. Macromol Symp 244:126–135
Kadib AE, Molvinger K, Guimon C, Quignard F, Brunel D (2008) Design of stable nanoporous hybrid chitosan/titania as cooperative bifunctional catalysts. Chem Mater 20:2198–2204
Litschauer M, Neouze MA, Haimer E, Henniges U, Potthast A, Rosenau T, Liebner F (2011) Silica modified cellulosic aerogels. Cellulose 18:143–149
Lo CL, Lin KM, Hsiue GH (2005) Preparation and characterization of intelligent core-shell nanoparticles based on poly(D, L-laclitde)-g-gpoly(N-isopropyl acrylamide-co-methacrylic acid). J Controlled Release 104:477–488
Mehling T, Smirnova I, Guenther U, Neubert RHH (2009) Polysaccharide-based aerogels as drug carriers. J Non-Cryst Solids 355:2472–2479
Mikkonen KS, Parikka K, Ghafar A, Tenkanen M (2013) Prospects of polysaccharide aerogels as modern advanced food materials. Trends Food Sci Tech 34:124–136
Molvinger K, Quignard F, Brunel D, Boissiere M, Devoisselle J (2004) Porous chitosan-silica hybrid microspheres as a potential catalyst. Chem Mater 16:3367–3372
Novotna K, Havelka P, Sopuch T, Kolarova K, Vosmanska V, Lisa V, Svorcik V, Bacakova L (2013) Cellulose-based materials as scaffolds for tissue engineering. Cellulose 20:2263–2278
Risk S, Duru D, Gaudy D, Jacob M (1994) Natural polymer hydrophilic matrix: influencing drug release factors. Drug Dev Ind Pharm 16:2563–2574
Ritschel WA, Thompson GA, Lucker PW, Wetzelsberger K (1980) Biopharmaceutic evaluation of etofylline clofibrate and its drug formulation. Arzneim Forsch Drug Res 30:2020–2023
Sai H, Fu R, Xing L, Xiang J, Li Z, Li F, Zhang T (2015) Surface modification of bacterial cellulose aerogels’ web-like skeleton for oil/water separation. ACS Appl Mater Interface 7:7373–7381
Smirnova I, Mamic J, Arlt W (2003) Adsorption of drugs on silica aerogels. Langmuir 19:8521–8525
Song W, Lima AC, Mano JF (2010) Bioinspired methodology to fabricate hydrogel spheres for multi-applications using superhydrophobic substrates. Soft Matter 6:5868–5871
Taşdelen B, Kayaman-Apohan N, Güven O, Baysal BM (2005) Preparation of poly (N-isopropylacrylamide/itaconic acid) copolymeric hydrogels and their drug release behavior. Radia Phys Chem 73:340–345
Ulker Z, Erkey C (2014) An emerging platform for drug delivery: aerogel based systems. J Control Release 177:51–63
Vilac N, Amorim R, Machado AF, Parpot P, Pereira MFR, Sardo M, Rocha J, Fonseca AM, Neves IC, Baltazar F (2013) Potentiation of 5-fluorouracil encapsulated in zeolites as drug delivery systems for in vitro models of colorectal carcinoma. Colloids Surf B 112:237–244
You YZ, Kalebaila KK, Brock SL (2008) Temperature-controlled uptake and release in PNIPAM-modified porous silica nanoparticles. Chem Mater 20:3354–3359
Zhang JT, Huang SW, Cheng SX, Zhuo RX (2004) Preparation and properties of poly (N-isopropylacrylamide)/poly (N-isopropylacrylamide) interpenetrating polymer networks for drug delivery. J Polym Sci Pol Chem 42:1249–1254
Zhang W, Zhang Y, Lu C, Deng Y (2012) Aerogels from crosslinked cellulose nano/micro-fibrils and their fast shape recovery property in water. J Mater Chem 22:11642–11650
Zhang X, Lin Z, Chen B, Zhang W, Sharma S, Gu W, Deng Y (2014) Solid-state flexible polyaniline/silver cellulose nanofibrils aerogel supercapacitors. J Power Sources 246:283–289
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Zhang, F., Wu, W., Zhang, X. et al. Temperature-sensitive poly-NIPAm modified cellulose nanofibril cryogel microspheres for controlled drug release. Cellulose 23, 415–425 (2016). https://doi.org/10.1007/s10570-015-0799-4
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DOI: https://doi.org/10.1007/s10570-015-0799-4