Intraoral low-temperature degradation of monolithic zirconia dental prostheses: 5-year results of a prospective clinical study with ex vivo monitoring.

OBJECTIVES: To investigate the 5-year intraoral evolution and kinetics of low-temperature degradation (LTD) of second-generation monolithic prostheses made of 3% molar yttrium-doped tetragonal zirconia polycrystal (3Y-TZP) and the influence of masticatory mechanical stresses and glaze layer on this evolution. METHODS: A total of 101 posterior tooth elements were included in this prospective clinical study, which comprised ex vivo LTD monitoring (at baseline, 6 months, 1 year, 2 years, 3 years, and 5 years) using Raman spectroscopy (n = 2640 monoclinic phase measurement points per evaluation time) and scanning electron microscopy (SEM). Four types of areas (1-2 mm2 surface, six on molars, and four on premolars) were analysed on each element surface: occlusal, axial, glazed, or unglazed. Raman mapping, high-resolution SEM, and focused ion beam-SEM were performed on selected samples. RESULTS: The dental prostheses developed a tetragonal-to-monoclinic transformation at the extreme surface of the material after six months in a buccal environment, and this process increased significantly over time. Over the five years of monitoring, the transformation developed nonuniformly with the presence of localised clusters of monoclinic grains. Tribological stresses generate grain pull-out from these clusters, which may raise questions regarding the release of 3Y-TZP nanoparticles into the body. The prosthesis fracture rate was 4.5% after 5 years. SIGNIFICANCE: LTD developed in vivo on the surfaces of 3Y-TZP dental prostheses and progressed slowly but significantly over time, up to 5 years investigation. However, the effects of aging on the failure rate recorded and of zirconia nanoparticles released into the body require further investigation.

Intraoral low-temperature degradation of monolithic zirconia dental prostheses: Results of a prospective clinical study with ex vivo monitoring.

OBJECTIVE: To investigate the intraoral development and kinetics of low-temperature degradation (LTD) in second-generation 3 mol.% yttria-doped tetragonal zirconia polycrystal (3Y-TZP) monolithic prostheses, as well as the influence of masticatory mechanical stress and glaze layer on it. METHODS: A total of 101 posterior tooth elements were included in a prospective clinical study, which included ex vivo LTD monitoring (at baseline, 6 months, 1 year, and 2 years) using Raman spectroscopy (n = 2640 monoclinic phase measurement points per evaluation time) and SEM. Four types of areas (1-2 mm2 surface, 6 on molars, and 4 on premolars) were analyzed on each element surface: occlusal, axial, glazed, or unglazed. Raman depth mapping and high-resolution SEM were performed on the selected samples. RESULTS: LTD developed in 3Y-TZP monolithic restorations 6 months after intraoral placement and progressed with time. After two years, the tetragonal-to-monoclinic transformation was non-uniform, with the presence of localized clusters of transformed grains. In axial areas, the grain aspect was typical of the classical nucleation-growth process reported for LTD, which progresses from the surface to a depth of several tens of microns. However, in occlusal areas, tribological stress generated surface crushing and grain pull-out from the clusters, which induced an underestimation of the aging process when the evaluation was limited to monoclinic phase quantification. Glazing cannot be considered a protection against LTD. SIGNIFICANCE: If LTD occurs in dental prostheses in the same way as in orthopedic prostheses, its clinical impact is unknown and needs to be further studied.

Nanoplasmonics tuned "click chemistry".

Nanoplasmonics is a growing field of optical condensed matter science dedicated to optical phenomena at the nanoscale level in metal systems. Extensive research on noble metallic nanoparticles (NPs) has emerged within the last two decades due to their ability to keep the optical energy concentrated in the vicinity of NPs, in particular, the ability to create optical near-field enhancement followed by heat generation. We have exploited these properties in order to induce a localised "click" reaction in the vicinity of gold nanostructures under unfavourable experimental conditions. We demonstrate that this reaction can be controlled by the plasmonic properties of the nanostructures and we propose two physical mechanisms to interpret the observed plasmonic tuning of the "click" chemistry.

Quantitative SERS sensors for environmental analysis of naphthalene.

In the investigation of chemical pollutants, such as PAHs (Polycyclic Aromatic Hydrocarbons) at low concentration in aqueous medium, Surface-Enhanced Raman Scattering (SERS) stands for an alternative to the inherent low cross-section of normal Raman scattering. Indeed, SERS is a very sensitive spectroscopic technique due to the excitation of the surface plasmon modes of the nanostructured metallic film. The surface of quartz substrates was coated with a hydrophobic film obtained by silanization and subsequently reacted with polystyrene (PS) beads coated with gold nanoparticles. The hydrophobic surface of the SERS substrates pre-concentrates non-polar molecules such as naphthalene. Under laser excitation, the SERS-active substrates allow the detection and the identification of the target molecules localized close to the gold nanoparticles. The morphology of the SERS substrates based on polystyrene beads surrounded by gold nanoparticles was characterized by scanning electron microscopy (SEM). Furthermore, the Raman fingerprint of the polystyrene stands for an internal spectral reference. To this extent, an innovative method to detect and to quantify organic molecules, as naphthalene in the range of 1 to 20 ppm, in aqueous media was carried out. Such SERS-active substrates tend towards an application as quantitative SERS sensors for the environmental analysis of naphthalene.

Modelling of the near-field of metallic nanoparticle gratings: localized surface plasmon resonance and SERS applications.

We numerically study the influence of the shape of gold nanostructures on the spectral position of their localized surface plasmon resonance and on Surface Enhanced Raman Scattering efficiency. Calculations are performed using a Finite-Difference Time-Domain (FDTD) method, whose accuracy for dispersive media is enhanced through the use of a Drude-Lorentz model. The relevance of this method is then pointed out by comparing the calculations with experimental data for both the plasmon resonance and the Raman signal enhancement. The influence of a thin layer of water is also investigated.

Detection in near-field domain of biomolecules adsorbed on a single metallic nanoparticle.

In this paper, we study the performances of nanosensors based on Localized Surface Plasmon Resonance in the context of biological sensing. We demonstrate the sensitivity and the selectivity of our designed nanosensors by studying the influence of the concentration of Streptavidin on the shift of Localized Surface Plasmon Resonance wavelength. In addition, to study the detection of biomolecules on a single Au nanoparticle, we used a Scanning Near-field Optical Microscope. These results represent new steps for applications in biological research and medical diagnostics.

Light depolarization induced by metallic tips in apertureless near-field optical microscopy and tip-enhanced Raman spectroscopy.

We have investigated the depolarization effects of light scattered by sharp tips used for apertureless near-field optical microscopy. Dielectric and metal coated tips have been investigated and depolarization factors between 5 and 30% have been measured, changing as a function of the incident light polarization and of the tip shape. The experimental results are in good agreement with theoretical calculations performed by the finite element method, giving a near-field depolarization factor close to 10%. The effect of depolarization has been investigated in polarized tip-enhanced Raman spectroscopy (TERS) experiments; the depolarization gives rise to forbidden Raman modes in Si crystals.

Near-field reflection backscattering apertureless optical microscopy: application to spectroscopy experiments on opaque samples, comparison between lock-in and digital photon counting detection techniques.

An apertureless scanning near-field optical microscope (ASNOM) in reflection backscattering configuration is designed to conduct spectroscopic experiments on opaque samples constituted of latex beads. The ASNOM proposed takes advantage of the depth-discrimination properties of confocal microscopes to efficiently extract the near-field optical signal. Given their importance in a spectroscopic experiment, we systematically compare the lock-in and synchronous photon counting detection methods. Some results of Rayleigh's scattering in the near field of the test samples are used to illustrate the possibilities of this technique for reflection backscattering spectroscopy.