Oxidation and degradation of polypropylene transvaginal mesh

<p>Polypropylene (PP) transvaginal mesh (TVM) repair for stress urinary incontinence (SUI) has shown promising short-term objective cure rates. However, life-altering complications have been associated with the placement of PP mesh for SUI repair. PP degradation as a result of the foreign body reaction (FBR) has been proposed as a contributing factor to mesh complications. We hypothesized that PP oxidizes under <i>in vitro</i> conditions simulating the FBR, resulting in degradation of the PP. Three PP mid-urethral slings from two commercial manufacturers were evaluated. Test specimens (<i>n</i> = 6) were incubated in oxidative medium for up to 5 weeks. Oxidation was assessed by Fourier Transform Infrared Spectroscopy (FTIR), and degradation was evaluated by scanning electron microscopy (SEM). FTIR spectra of the slings revealed evidence of carbonyl and hydroxyl peaks after 5 weeks of incubation time, providing evidence of oxidation of PP. SEM images at 5 weeks showed evidence of surface degradation, including pitting and flaking. Thus, oxidation and degradation of PP pelvic mesh were evidenced by chemical and physical changes under simulated <i>in vivo</i> conditions. To assess changes in PP surface chemistry <i>in vivo</i>, fibers were recovered from PP mesh explanted from a single patient without formalin fixation, untreated (<i>n</i> = 5) or scraped (<i>n</i> = 5) to remove tissue, and analyzed by X-ray photoelectron spectroscopy. Mechanical scraping removed adherent tissue, revealing an underlying layer of oxidized PP. These findings underscore the need for further research into the relative contribution of oxidative degradation to complications associated with PP-based TVM devices in larger cohorts of patients.</p

Surface-Initiated Polymerization of Superhydrophobic Polymethylene

We report a new surface-initiated polymerization strategy that yields superhydrophobic polymethylene (PM) films from initially smooth substrates of gold and silicon. The films are prepared by assembling a vinyl-terminated self-assembled monolayer, followed by exposure of the surface to a 0.1 M solution of borane, and polymerizing from the borane sites upon exposure to a solution of diazomethane at −17 °C. Surface-initiated polymethylenation (SIPM) presents rapid growth in relation to other surface-initiated reactions, producing PM films thicker than 500 nm after 2 min of reaction and 3 μm after 24 h of reaction. AFM and SEM images show the presence of micro- and nanoscale features that enable the entrapment of air when exposed to water. Consistent with this result, these films exhibit advancing water contact angles greater than 160°, dramatically different than 103° measured for smooth PM films, and hysteresis values ranging from 2° to 40°, depending on the substrate and polymerization time. The superhydrophobic character of the films results in the entrapment of air at the polymer/solution interface to provide remarkable resistances greater than 1010 Ω·cm2 against the transport of aqueous redox probes and cause the film to behave as a “perfect” capacitor

Amplification of Surface-Initiated Ring-Opening Metathesis Polymerization of 5‑(Perfluoro‑<i>n</i>‑alkyl)norbornenes by Macroinitiation

This article reports the enhanced rate of the surface-initiated polymerization (SIP) of 5-(perfluoro-<i>n</i>-alkyl)­norbornenes (NBFn) by combining two SIP techniques, namely surface-initiated atom-transfer polymerization (SI-ATRP) to grow a macroinitiator and surface-initiated ring-opening metathesis polymerization (SI-ROMP) to produce the final coating. This polymerization approach promotes the rapid growth of dense partially fluorinated coatings that are highly hydrophobic and oleophobic and yield thicknesses from 4–12 μm. Specifically, the growth rate and the limiting thickness of pNBFn with different side chain lengths (<i>n</i> = 4, 6, 8, and 10) at various monomer concentrations and temperatures are evaluated through two approaches: growing the polymer from an initiator-terminated monolayer (control) or from a modified poly­(2-hydroxyethyl methacrylate) (PHEMA) macroinitiator. X-ray photoelectron spectroscopy (XPS) analysis shows that 38% of the hydroxyl termini in the macroinitiator react with a norbornenyl diacid chloride (NBDAC) molecule, and 7% of such anchored norbornenyl groups react with a catalyst molecule. The kinetic data have been modeled to determine the propagation velocity and the termination rate constant. The PHEMA macroinitiator provides thicker films and faster growth as compared to the monolayer, achieving a 12 μm thick coating of pNBF8 in 15 min. Increasing the monomer side chain length, <i>n</i>, from 4 to 10 improves the growth rate and the limiting polymer thickness. Performing the polymerization process at higher temperature increases the growth rate and the limiting thickness as evidenced by an increase in the film growth rate constant. Arrhenius plots show that the reactions involved in the macroinitiation process exhibit lower activation energies than those formed from a monolayer. Electrochemical impedance spectroscopy reveals that the films exhibit resistance against ion transport in excess of 1 × 10¹⁰ Ω·cm²

Dynamic Color Tuning with Electrochemically Actuated TiO₂ Metasurfaces

Dynamic tuning of metamaterials is a critical step toward advanced functionality and improved bandwidth. In the visible spectrum, full spectral color tuning is inhibited by the large absorption that accompanies index changes, particularly at blue wavelengths. Here, we show that the electrochemical lithiation of anatase TiO2 to Li0.5TiO2 (LTO) results in an index change of 0.65 at 649 nm with absorption coefficient less than 0.1 at blue wavelengths, making this material well-suited for dynamic visible color tuning. Dynamic tunability of TiO2 is leveraged in a Fabry–Perot cavity and a gap plasmon metasurface. In the Fabry–Perot configuration, the device exhibits a shift in reflectance of over 100 nm when subjected to only 2 V bias while the gap plasmon metasurface achieves enhanced switching speed. The dynamic range, speed, and cyclability indicate that the TiO2/LTO system is competitive with established actuators like WO3, with the additional advantage of reduced absorption at high frequencies

Transferable Graphene Oxide Films with Tunable Microstructures

This report describes methods to produce large-area films of graphene oxide from aqueous suspensions using electrophoretic deposition. By selecting the appropriate suspension pH and deposition voltage, films of the negatively charged graphene oxide sheets can be produced with either a smooth “rug” microstructure on the anode or a porous “brick” microstructure on the cathode. Cathodic deposition occurs in the low pH suspension with the application of a relatively high voltage, which facilitates a gradual change in the colloids’ charge from negative to positive as they adsorb protons released by the electrolysis of water. The shift in the colloids’ charge also gives rise to the brick microstructure, as the concurrent decrease in electrostatic repulsion between graphene oxide sheets results in the formation of multilayered aggregates (the “bricks”). Measurements of water contact angle revealed the brick films (79°) to be more hydrophobic than the rug films (41°), a difference we attribute primarily to the distinct microstructures. Finally, we describe a sacrificial layer technique to make these graphene oxide films free-standing, which would enable them to be placed on arbitrary substrates

Influence of Ionizing Radiation and the Role of Thiol Ligands on the Reversible Photodarkening of CdTe/CdS Quantum Dots

We investigate the influence of high energy photons and thiol ligands on the photophysical properties of sub-monolayer CdTe/CdS quantum dots (QDs) immobilized in porous silica (PSiO₂) scaffolds. The highly disperse, uniform distributions of QDs in a three-dimensional PSiO₂ framework ensure uniform interaction of not only radiation but also subsequent surface repassivation solutions to all immobilized QDs. The high optical densities of QDs achieved using PSiO₂ enable straightforward monitoring of the QD photoluminescence intensities and carrier lifetimes. Irradiation of QDs in PSiO₂ by high energy photons, X-rays, and γ-rays leads to dose-dependent QD photodarkening, which is accompanied by accelerated photooxidative effects in ambient environments that give rise to blue-shifts in the peak QD emission wavelength. Irradiation in an oxygen-free environment also leads to QD photodarkening but with no accompanying blue-shift of the QD emission. Significant reversal of QD photodarkening is demonstrated following QD surface repassivation with a solution containing free-thiols, suggesting reformation of a CdS shell, etching of surface oxidized species, and possible reduction of photoionized dark QDs to a neutral, bright state. Permanent lattice displacement damage effects may contribute toward some irreversible γ radiation damage. This work contributes to an improved understanding of the influence of surface ligands on the optical properties of QDs and opens up the possibilities of engineering large area, low-cost, reuseable, and flexible QD-based optical radiation sensors