In vivo assessment of TiO2 based wear nanoparticles in periprosthetic tissues.

A multimodal approach combining inductively coupled plasma mass spectrometry (ICP-MS), single-particle ICP-MS (spICP-MS), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) and Raman spectroscopy enabled a deeper insight into the balance between total titanium (Ti), the soluble titanium fraction and titanium dioxide based particle fraction levels in periprosthetic tissues collected from patients undergoing revision surgery. Hydrofluoric acid usage in the sample digestion allowed for complete digestion of TiO2 particles, thus enabling accurate estimation of total Ti levels. The TiO2 fraction represents 38-94% of the titanium load in the six samples where particles were detected, and the fraction is present mainly in samples from patients with aseptically loosened total hip arthroplasty. Further attention was given to this fraction determining the elemental composition, particle count, particle size and modification of TiO2. The spICP-MS analysis confirmed the presence of the TiO2-derived (nano)particles (NPs) with a 39- to 187-nm median size and particle count up to 2.3 × 1011 particles per gram of tissue. On top of that, the SEM-EDS confirmed the presence of the TiO2 nanoparticles with 230-nm median size and an anatase crystal phase was determined by Raman spectroscopy. This study presents a novel multimodal approach for TiO2 particle determination and characterization in tissue samples and is the first in vivo study of this character.

Carbon fiber brush electrode as a novel substrate for atmospheric solids analysis probe (ASAP) mass spectrometry: Electrochemical oxidation of brominated phenols.

A carbon fiber brush electrode (CFBE) was newly designed and used as a substrate for both controlled potential electrolysis and atmospheric solids analysis probe (ASAP) mass spectrometry. Electropolymerized and strongly adsorbed products of electrolysis were directly desorbed and ionized from the electrode surface. Electrochemical properties of the electrode investigated by cyclic voltammetry revealed large electroactive surface area (23 ± 3 cm2) at 1.3 cm long array of carbon fibers with diameter 6-9 µm. Some products of electrochemical oxidation of pentabromophenol and 2,4,6-tribromophenol formed a compact layer on the carbon fibers and were analyzed using ASAP. Eleven new oligomeric products were identified including quinones and biphenoquinones. These compounds were not observed previously in electrolyzed solutions by liquid or gas chromatography/mass spectrometry. The thickness around 58 nm and 45 nm of the oxidation products layers deposited on carbon fibers during electrolysis of pentabromophenol and 2,4,6-tribromophenol, respectively, was estimated from atomic force microscopy analysis and confirmed by scanning electron microscopy with energy-dispersive X-ray spectroscopy measurements.