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Embolic beads for transarterial chemoembolization (TACE) should possess radiopacity and biodegradability at the same time, to be visualized in a body under fluoroscopy and CT scanning to avoid complicating disease. In this study, we fabricated radiopaque and biodegradable beads composed of Lipiodol (LPD) (ethiodized oil) and polycaprolactone (PCL), a biocompatible and biodegradable polymer. LPD/PCL beads were first fabricated with a home-made microfluidic device. By changing the flow-rate ratio in the microfluidic device, the mean diameter of LPD/PCL beads could be well controlled. The radiopacity was evaluated by the fluoroscopic imaging and the CT number measurements. Furthermore, the biodegradability was evaluated by collecting the weight loss data of LPD/PCL immersed in lipase/PBS solution and PBS. The results showed that LPD/PCL beads obtained in this study had sufficient radiopacity and biodegradability, which would be an alternative embolic agent for TACE.
Poly(ε-caprolactone) (PCL) is one of the leading biocompatible and biodegradable polymers. However, the mechanical property of PCL is relatively poor as compared with that of polyolefins, which has limited the active applications of PCL as an industrial material. In this study, to enhance the mechanical property of PCL, cellulose nanofibers (C-NF) with high mechanical property, were employed as reinforcement materials for PCL. The C-NF were fabricated via the electrospinning of cellulose acetate (CA) followed by the subsequent saponification of the CA nanofibers. For the enhancement of the mechanical property of the PCL composite, the compatibility of C-NF and PCL was investigated: the surface modification of the C-NF was introduced by the ring-opening polymerization of the ε-caprolactone on the C-NF surface (C-NF-g-PCL). The polymerization was confirmed by the Fourier transform infrared (FTIR) spectroscopy. Tensile testing was performed to examine the mechanical properties of the C-NF/PCL and the C-NF-g-PCL/PCL. At the fiber concentration of 10 wt%, the Young’s modulus of PCL compounded with neat C-NF increased by 85% as compared with that of pure PCL, while, compounded with C-NF-g-PCL, the increase was 114%. The fracture surface of the composites was analyzed by scanning electron microscopy (SEM). From the SEM images, it was confirmed that the interfacial compatibility between PCL and C-NF was improved by the surface modification. The results demonstrated that the effective surface modification of C-NF contributed to the enhancement of the mechanical property of PCL.
A new peptide amphiphile (PA) called C16-W3K has hierarchical structures, presenting unique solution states, micelle structures, and secondary structures. In this work, the effects of salt (sodium dihydrogenorthophosphate) concentration on the hierarchical structural transitions of the C16-W3K solution due to its active hydrogen bonding in the peptide were discussed. In order to analyze the effects of salt on the structural transitions, the mechanical and structural analyses were conducted by viscosity measurements, transmission electron microscopy (TEM), and circular dichroic (CD) spectroscopy. It was found that the C16-W3K solutions with different salt concentrations presented different multi-scale structural transitions from spherical micelles with α-helix molecular conformations in the sol state to wormlike micelles with β-sheet conformations in the gel state. Additionally, we found that the speed of transition increased as the salt concentration increased and the conformational ratio of β-sheet to α-helix in the solutions increased with the increase in the salt concentration.
Cellulose nanofibers (Cel-F) were extracted by a simple and harmless Star Burst (SB) method, which produced aqueous cellulose-nanofiber solution just by running original cellulose beads under a high pressure of water in the synthetic SB chamber. By optimizing the SB process conditions, the cellulose nanofibers with high aspect ratios and the small diameter of ∼23 nm were obtained, which was confirmed by transmission electron microscopy (TEM). From the structural analysis of the Cel-F/PVA composite by the scanning electron microscopy (SEM), it was found that the Cel-F were homogeneously dispersed in the PVA matrix. Considering the high molecular compatibility of the cellulose and PVA due to the hydrogen bonding, a good adhesive interface could be expected for the Cel-F and the PVA matrix. The influences of the morphological change in Cel-F on the mechanical properties of the composites were analysed. The Young’s modulus rapidly increased from 2.2 GPa to 2.9 GPa up to 40 SB treatments (represented by the unit Pass), whereas the Young’s modulus remained virtually constant above 40 Pass. Due to the uniform dispersibility of the Cel-F, the Young’s modulus of the 100 Pass composite at the concentration of 5 wt% increased up to 3.2 GPa. The experimental results corresponded well with the general theory of the composites with dispersed short-fiber fillers, which clearly indicated that the potential of the cellulose nanofibers as reinforcement materials for hydrophilic polymers was sufficiently confirmed.
Amorphous carbon (a-C) films have a growing interest in the biological and medical field, as a coating material, due to their biocompatibility and antibacterial property. However, a-C films deposited directly on polymers often show adhesion failure.
In this paper, two types of a-C films, amorphous hydrogenated carbon (a-C:H) film and hydrogen-free a-C (H-free a-C) film were deposited on polytetrafluoroethylene (PTFE) using a plasma deposition method. Prior to a-C film coating, the PTFE substrates were treated with Ar and O2 plasma and an appropriate interlayer was chosen to enhance the adhesion strength. The effect of the plasma pretreatment on the chemical composition of the PTFE was investigated by X-ray photoelectron spectroscopy (XPS). A T-peel test was carried out to evaluate the adhesion strength of the a-C coated PTFE. In the T-peel test, Ar plasma pretreatment improved the adhesion strength more effectively than that of O2 plasma pretreatment, because of the substantial defluorination and oxygen bonding occurred by Ar plasma pretreatment. Moreover, H-free a-C film reduced the numbers of Escherichia coli (E. coli) colonies dramatically, compared with original PTFE and a-C:H coated PTFE. Consequently, H-free a-C film coating can be a promising method to inhibit the increase of bacteria.
Polymethylphenylsilicone (PMPS), a siloxane polymer with a phenyl group, was first successfully electrospun to fabricate different diameters of silicone fibers ranging from 500 nm to 10 μm by considering solubility parameters of 12 different solvents. The resulting PMPS fibers were mixed with polydimethylsiloxane (PDMS) by retaining their original nanofiber structures to produce a polysiloxane-based nanofibrous composite. As for the mechanical properties, the PMPS/PDMS composite presented higher Young’s modulus and higher fracture strain than pure PDMS. The gas permeability test revealed that the PMPS/PDMS composite exhibited higher CO2 permeability than the pure PDMS membrane. Moreover, CO2 permeability gradually increased by raising the compounding ratio of PMPS-fibers in the PMPS/PDMS composite and by decreasing the diameter of PMPS-fibers. The enhancement mechanism observed in both mechanical properties and CO2 permeability was discussed from the viewpoint of the interface between PMPS and PDMS along with the nanofiber network structures.
Poly (cyclohexanedimethanol cyclohexanedicarboxlic acid) (PCC), a fairly newly synthesized polyester, has been studied. Having a good experience of increasing both thermal stability and service temperature when applied to typical polymers, poly (tetramethylene glycol) (PTMG) was selected as a softening agent that was randomly copolymerized into the PCC chains. Another widely-used polyester, poly (ethylene terephthalate) (PET) was also produced in order to investigate the effect of PTMG, which was compared with the properties of the newly developed random PCC-PTMG copolymers (PCCP). In this study, the crystalline structures, the thermal and the mechanical properties of both PCC and PET containing different ratios of the random segment of PTMG were investigated by differential scanning calorimetery (DSC) and tensile tester.
It was found that the crystallization rate of pure PCC was significantly slow, whereas for PCCP, PTMG effectively accelerated the crystallization rate with increasing PTMG, and the sample with 25 wt% of PTMG had the fastest crystallization rate in all PCCP samples. Here, the PTMG acted as an accelerator, simultaneously depressing the movement of PCC molecular chains. The elastic recovery test indicated that the ability of PTMG as a softening agent was highly demonstrated at 20 wt% of PTMG. The results of PCCP were compared with those of PET-PTMG copolymers (PETP) and it was found that there were optimum values of PTMG for the crystallization rate on both samples. Additionally, the results of the elastic recovery test indicated that the softening effects observed in PCCP were more pronounced than those observed in PETP.
A coarse-grained model of peptide amphiphiles (PA) dissolved in aqueous solution was presented, where the effects of PA concentration, temperature and shear stress upon the self-assembly of PA were numerically studied by dissipative particle dynamics (DPD) simulation. We technically investigate the repulsion parameter aHW which indicates the repulsion force between the hydrophilic head of PA and water molecules, hence, at the same time, indicating the change in temperature. It was found that aHW played an important role in the self-assembly dynamics and in the resulting micro-structures of PA. By imposing shear strain on the simulation system, the formation of wormlike PA micelles was accelerated. The simulation results were in good agreement with our previous experimental results and the mechanism of shear-induced transition was proposed.
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