Effect of Various Type of Nanoparticles on Mechanical and Tribological Properties of Wear-Resistant PEEK + PTFE-Based Composites.

The mechanical and tribological properties of polyetheretherketone (PEEK)- and PEEK + PTFE (polytetrafluoroethylene)-based composites loaded with and four types of nanoparticles (carbonaceous, metallic, bimetal oxide, and ceramic) under metal- and ceramic-polymer tribological contact conditions were investigated. It was found that loading with the nanofillers in a small content (0.3 wt.%) enabled improvement of the elastic modulus of the PEEK-based composites by 10-15%. In the metal-polymer tribological contact, wear resistance of all nanocomposites was increased by 1.5-2.3 times. In the ceramic-polymer tribological contact, loading PEEK with metal nanoparticles caused the intensification of oxidation processes, the microabrasive counterpart wear, and a multiple increase in the wear rate of the composites. The three component "PEEK/10PTFE/0.3 nanofillers" composites provided an increase in wear resistance, up to 22 times, for the metal-polymer tribological contact and up to 12 times for the ceramic-polymer one (with a slight decrease in the mechanical properties) compared to that of neat PEEK. In all cases, this was achieved by the polymer transfer film formation and adherence on the counterparts. The various effects of the four types of nanoparticles on wear resistance were determined by their ability to fix the PTFE-containing transfer film on the counterpart surfaces.

Loop and stem dynamics during RNA hairpin folding and unfolding.

2-Aminopurine (2AP) is a fluorescent adenine analog that probes mainly base stacking in nucleic acids. We labeled the loop or the stem of the RNA hairpin gacUACGguc with 2AP to study folding thermodynamics and kinetics at both loci. Thermal melts and fast laser temperature jumps detected by 2AP fluorescence monitored the stability and folding/unfolding kinetics. The observed thermodynamic and kinetic traces of the stem and loop mutants, though strikingly different at a first glance, can be fitted to the same free-energy landscape. The differences between the two probe locations arise because base stacking decreases upon unfolding in the stem, whereas it increases in the loop. We conclude that 2AP is a conservative adenine substitution for mapping out the contributions of different RNA structural elements to the overall folding process. Molecular dynamics (MD) totaling 0.6 µsec were performed to look at the conformations populated by the RNA at different temperatures. The combined experimental data, and MD simulations lead us to propose a minimal four-state free-energy landscape for the RNA hairpin. Analysis of this landscape shows that a sequential folding model is a good approximation for the full folding dynamics. The frayed state formed initially from the native state is a heterogeneous ensemble of structures whose stem is frayed either from the end or from the loop.