Authors: Hsin Nam Ernest Yong, Kim Yeow Tshai, Siew Shee Lim
Abstract: Poly (N-isopropylacrylamide) (PNIPAm) has been one of the most widely studied thermal responsive polymer in tissue engineering owing to its reversible hydrophilic-hydrophobic phase transition across its lower critical solution temperature (~32°C) that is close to human physiological temperatures. Among tissue engineering constructs, nanofibrous scaffolds offer an added advantage in mimicking the morphology of the native extracellular matrix (ECM). Electrospinning has been reported as one of the most facile method to produce PNIPAm nanofibres and neat electrospun nanofibres scaffold is known to possess poor aqueous stability, limiting its use in tissue engineering applications. In contrast, numerous studies on PNIPAm hydrogels have shown relatively good aqueous stability owing to the hydrophilic 3D crosslinked structure of the hydrogel which resist instant dissolution but rather swell to a greater or lesser extent. However, the presence of crosslinkages in PNIPAm hydrogels causes it to be hardly electrospinnable into nanofibres. In the present work, crosslinker free PNIPAm was radical polymerized to a high molecular weight of 385 kDa. To produce nanofibers, electrospinning was carried out on a dedicated %wt of PNIPAm solution containing octaglycidyl polyhedral oligomeric silsesquioxane (OpePOSS) and 2-ethyl-4-methylimidazole (EMI). Resulting PNIPAm nanofibrous network was found to strongly resemble the ECM morphology with fiber diameter of 436.35 ± 187.04 nm, pore size 1.24 ± 1.27 μm and 63.6% total porosity. Aqueous stability was studied in cell culture media over the course of 28 days. The current result shows significant improvement with a gradual mass loss up to a maximum of 35% instead of the near immediate dissolution observed in the case of electrospun neat PNIPAm scaffold without crosslinks.
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Authors: Hsin Nam Ernest Yong, Kim Yeow Tshai, Siew Shee Lim, Ing Kong
Abstract: Smart polymers have been one of the most popularly studied materials owing to their capability to alter physio-chemical behaviour upon exposure to specific external stimuli. The biocompatible thermally responsive poly (N-isopropylacrylamide), PNIPAm shows reversible transition between hydrophilic-hydrophobic characteristics at the vicinity of human physiological temperature has great potential to propel the development of smart tissue engineering scaffold and drug delivery. However, the limited availability and its high cost have dampened the extent of research on this polymer. To address these challenges, the current work demonstrates an economical lab-scale polymerization of crosslinked PNIPAm and the optimised parameters to produce mono-dispersed polymer hydrogel particles were investigated. Characterisation of the synthesized PNIPAm polymer revealed particle size polydispersity index of 0.215, indicative of distribution within the mono-dispersed range, with average hydrodynamic diameter of 346.3 nm. Zeta-potential of the synthesized PNIPAm was found to be -20.6 mV, suggesting an incipient instability in terms of colloidal coagulation. Viscosity of the synthesized PNIPAm (4 wt% concentration in methanol) was 28.6 cP. Thermal gravimetric analysis (TGA) indicated the thermal degradation of main chain PNIPAm fell in the range of 340 to 480°C.
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Authors: Mei Ling Zhou, Dan Mei Hu, Yu Jie Shao, Jing Hong Ma, Jing Hua Gong
Abstract: Temperature-responsive hydrogel fibers with bilayer structure were prepared by a microfluidic spinning device with a Y-shaped connector. The bilayer hydrogel fibers include two layer with different chemical composition. One layer is the ionic crosslinking hydrogel of calcium alginate (CA) and the other layer is temperature-responsive hydrogel which is semi-interpenetrating polymer networks (semi-IPN) of linear poly (N-isopropylacrylamide) (PNIPAM) and CA. The bilayer hydrogel fibers were evaluated by morphology observation, tensile stress measurement, temperature-responsive actuation test and equilibrium swelling ratio test. The results show that the prepared hydrogel fibers have obvious double layer structure with different porous structures. The bilayer hydrogel fibers can bend in water at 50 °C and the bending rate is influenced by the diameter of the fiber. Moreover, the diameter of the hydrogel fibers can be controlled by changing the flow rates of spinning fluids.
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Authors: Ping Zhang, Shan Shan Wu
Abstract: This paper reports a surface functional polymer- poly(N-isopropylacrylamide) (PNIPAM) was grafted on the surface of zinc oxide (ZnO) nanoparticles. It has been demonstrated that Reversible addition fragmentation chain-transfer (RAFT) agent was successfully grafted onto the surface of ZnO. PNIPAM chains were successfully grafted from the surface of ZnO via RAFT process by using RAFT agent immobilized on ZnO. The effect of surface modification on the size, structure, morphology, and properties of ZnO nanoparticles was investigated. The thickness of a PNIPAM monolayer bound to the ZnO core is somewhat larger than the size of the random coil of the corresponding free PNIPAM in aqueous solution, which suggests that the conformation of a PNIPAM chain bound to the ZnO core is extended.
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Authors: Jun Chao Wei, Yan Feng Dai, Yi Wang Chen
Abstract: Cross-linked poly(N-isopropylacrylamide) tethered Hydroxyapatite hybrid materials (HA- PNIPAM) were prepared by the ATRP reaction. The hybrid materials were characterized by FT-IR、TGA、SEM and UV spectra. The TGA results demonstrated that there was 122 g PNIPAM grafted on the surface of per 100g of HA. The UV results showed that the HA-PNIPAM have thermal responsive property around 33°C.
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