Graphene oxide increases PMMA's resistance to fatigue and strength degradation.

OBJECTIVES: to characterize the effects of graphene oxide (GO) on polymethyl methacrylate's (PMMA) reliability and lifetime. The hypothesis tested was that GO would increase both Weibull parameters and decreased strength degradation over time. METHODS: PMMA disks containing GO (0.01, 0.05, 0.1, or 0.5 wt%) were subjected to a biaxial flexural test to determine the Weibull parameters (m: modulus of Weibull; σ0: characteristic strength; n = 30 at 1 MPa/s) and slow crack growth (SCG) parameters (n: subcritical crack growth susceptibility coefficient, σf0: scaling parameter; n = 10 at 10-2, 10-1, 101, 100 and 102 MPa/s). Strength-probability-time (SPT) diagrams were plotted by merging SCG and Weibull parameters. RESULTS: There was no significant difference in the m value of all materials. However, 0.5 GO presented the lowest σ0, whereas all other groups were similar. The lowest n value obtained for all GO-modified PMMA groups (27.4 for 0.05 GO) was higher than the Control (15.6). The strength degradation predicted after 15 years for Control was 12%, followed by 0.01 GO (7%), 0.05 GO (9%), 0.1 GO (5%), and 0.5 GO (1%). SIGNIFICANCE: The hypothesis was partially accepted as GO increased PMMA's fatigue resistance and lifetime but did not significantly improve its Weibull parameters. GO added to PMMA did not significantly affect the initial strength and reliability but significantly increased PMMA's predicted lifetime. All the GO-containing groups presented higher resistance to fracture at all times analyzed compared with the Control, with the best overall results observed for 0.1 GO.

Beyond steric selectivity of ions using ångström-scale capillaries.

Ion-selective channels play a key role in physiological processes and are used in many technologies. Although biological channels can efficiently separate same-charge ions with similar hydration shells, it remains a challenge to mimic such exquisite selectivity using artificial solid-state channels. Although there are several nanoporous membranes that show high selectivity with respect to certain ions, the underlying mechanisms are based on the hydrated ion size and/or charge. There is a need to rationalize the design of artificial channels to make them capable of selecting between similar-sized same-charge ions, which, in turn, requires an understanding of why and how such selectivity can occur. Here we study ångström-scale artificial channels made by van der Waals assembly, which are comparable in size with typical ions and carry little residual charge on the channel walls. This allows us to exclude the first-order effects of steric- and Coulomb-based exclusion. We show that the studied two-dimensional ångström-scale capillaries can distinguish between same-charge ions with similar hydrated diameters. The selectivity is attributed to different positions occupied by ions within the layered structure of nanoconfined water, which depend on the ion-core size and differ for anions and cations. The revealed mechanism points at the possibilities of ion separation beyond simple steric sieving.

Electrochemical preparation and characterization of PNIPAM-HAp scaffolds for bone tissue engineering.

In the last decade, a variety of methods for fabrication of three-dimensional biomimetic scaffolds based on hydrogels have been developed for tissue engineering. However, many methods require the use of catalysts which compromises the biocompatibility of the scaffolds. The electrochemical polymerization (ECP) of acrylic monomers has received an increased attention in recent years due to its versatility in the production of highly biocompatible coatings for the electrodes used in medical devices. The main aim of this work was the use of ECP as scaffold fabrication technique to produce highly porous poly(N-isopropylacrylamide) (PNIPAM)/hydroxyapatite (HAp) composite for bone tissue regeneration. The prepared PNIPAM-HAp porous scaffolds were characterized by SEM, FTIR, water swelling, porosity measurements and X-ray diffraction (XRD) techniques. FTIR indicates that ECP promotes a successful conversion of NIPAM to PNIPAM. The water swelling and porosity were shown to be controlled by the HAp content in PNIPAM-HAp scaffolds. The PNIPAM-HAp scaffolds exhibited no cytotoxicity to MG63 cells, showing that ECP are potentially useful for the production of PNIPAM-HAp scaffolds. To address the osteomyelitis, a significant complication in orthopedic surgeries, PNIPAM-HAp scaffolds were loaded with the antibiotic oxacillin. The oxacillin release and the bacterial killing activity of the released oxacillin from PNIPAM-HAp against S. aureus and P. aeruginosa were demonstrated. These observations demonstrate that ECP are promising technique for the production of non-toxic, biocompatible PNIPAM-HAp scaffolds for tissue engineering.