Polycarboxy/Sulfo Betaine-Calcium Phosphate Hybrid Materials with a Remineralization Potential.

Biomacromolecules control mineral formation during the biomineralization process, but the effects of the organic components' functionality on the type of mineral phase is still unclear. The biomimetic precipitation of calcium phosphates in a physiological medium containing either polycarboxybetaine (PCB) or polysulfobetaine (PSB) was investigated in this study. Amorphous calcium phosphate (ACP) or a mixture of octacalcium phosphate (OCP) and dicalcium phosphate dihydrate (DCPD) in different ratios were identified depending on the sequence of initial solution mixing and on the type of the negative functional group of the polymer used. The more acidic character of the sulfo group in PSB than the carboxy one in PCB determines the dominance of the acidic solid phases, namely, an acidic amorphous phase or DCPD. In the presence of PCB, the formation of ACP with acicular particles arranged in bundles with the same orientation was observed. A preliminary study on the remineralization potential of the hybrid material with the participation of PSB and a mixture of OCP and DCPD did not show an increase in enamel density, contrary to the materials based on PCB and ACP. Moreover, the latter showed the creation of a newly formed crystal layer similar to that of the underlying enamel. This defines PCB/ACP as a promising material for enamel remineralization.

The effect of experimental conditions in root dentin microcracks detection by micro-computed tomography.

The aim of the study was to assess the effect of different experimental conditions on registration of microcracks by means of micro-computed tomography. Twenty roots of permanent lower incisors were instrumented with SAF system, filled with a single-cone technique and retreated with the Pro Taper Universal Retreatment system. Each sample was measured in dry, water, and moist conditions. The dry scanning was done after drying of the roots for a period of 4 h in ambient conditions followed by a second observation in wet environment after 48 h of rehydrating in distilled water. A time scan was performed to measure the dentin shrinkage while drying the samples in the tomograph's device compartment. All roots underwent complex inhomogeneous shrinkage and deformation due to the internal stress upon dehydration. This deformation opened the existing cracks to an extent above the current resolution of today's laboratory computed tomography scanners. Contrary, rehydration of the dentin reversed the deformation thus closing some of the cracks below the computed tomography resolution making them undetectable. The first dehydration of dentin may be a source of cracks initiation itself.

Ultra-Short Laser Surface Properties Optimization of Biocompatibility Characteristics of 3D Poly-ε-Caprolactone and Hydroxyapatite Composite Scaffolds.

The use of laser processing for the creation of diverse morphological patterns onto the surface of polymer scaffolds represents a method for overcoming bacterial biofilm formation and inducing enhanced cellular dynamics. We have investigated the influence of ultra-short laser parameters on 3D-printed poly-ε-caprolactone (PCL) and poly-ε-caprolactone/hydroxyapatite (PCL/HA) scaffolds with the aim of creating submicron geometrical features to improve the matrix biocompatibility properties. Specifically, the present research was focused on monitoring the effect of the laser fluence (F) and the number of applied pulses (N) on the morphological, chemical and mechanical properties of the scaffolds. SEM analysis revealed that the femtosecond laser treatment of the scaffolds led to the formation of two distinct surface geometrical patterns, microchannels and single microprotrusions, without triggering collateral damage to the surrounding zones. We found that the microchannel structures favor the hydrophilicity properties. As demonstrated by the computer tomography results, surface roughness of the modified zones increases compared to the non-modified surface, without influencing the mechanical stability of the 3D matrices. The X-ray diffraction analysis confirmed that the laser structuring of the matrices did not lead to a change in the semi-crystalline phase of the PCL. The combinations of two types of geometrical designs-wood pile and snowflake-with laser-induced morphologies in the form of channels and columns are considered for optimizing the conditions for establishing an ideal scaffold, namely, precise dimensional form, mechanical stability, improved cytocompatibility and antibacterial behavior.

New Approach toward Laser-Assisted Modification of Biocompatible Polymers Relevant to Neural Interfacing Technologies.

We report on a new approach toward a laser-assisted modification of biocompatible polydimethylsiloxane (PDMS) elastomers relevant to the fabrication of stretchable multielectrode arrays (MEAs) devices for neural interfacing technologies. These applications require high-density electrode packaging to provide a high-resolution integrating system for neural stimulation and/or recording. Medical grade PDMS elastomers are highly flexible with low Young's modulus < 1 MPa, which are similar to soft tissue (nerve, brain, muscles) among the other known biopolymers, and can easily adjust to the soft tissue curvatures. This property ensures tight contact between the electrodes and tissue and promotes intensive development of PDMS-based MEAs interfacing devices in the basic neuroscience, neural prosthetics, and hybrid bionic systems, connecting the human nervous system with electronic or robotic prostheses for restoring and treating neurological diseases. By using the UV harmonics 266 and 355 nm of Nd:YAG laser medical grade PDMS elastomer is modified by ns-laser ablation in water. A new approach of processing is proposed to (i) activate the surface and to obtain tracks with (ii) symmetric U-shaped profiles and (iii) homogeneous microstructure This technology provides miniaturization of the device and successful functionalization by electroless metallization of the tracks with platinum (Pt) without preliminary sensitization by tin (Sn) and chemical activation by palladium (Pd). As a result, platinum black layers with a cauliflower-like structure with low values of sheet resistance between 1 and 8 Ω/sq are obtained.

Identifying the location of Cu ions in nanostructured SAPO-5 molecular sieves and its impact on the redox properties.

Combining X-ray Absorption Fine Spectroscopy (XAFS) with Anomalous Small-Angle X-ray Scattering (ASAXS) determines the location of Cu2+ ions in silicoaluminophosphate (SAPO-5) frameworks prepared by hydrothermal crystallization or impregnation. As expected, for the hydrothermally prepared sample, incorporation in the SAPO-5 framework was observed. For the first time preferential location of Cu2+ ions at the inner and outer surfaces of the framework is determined. Temperature-Programmed Reduction (TPR) and X-ray Photoelectron Spectroscopy (XPS) investigations demonstrated that such Cu2+ is stable in an argon (Ar) atmosphere up to 550 °C and can only be reduced under a hydrogen atmosphere. In contrast, Cu2+ deposited by impregnation on the pure SAPO-5 framework can be easily reduced to Cu+ in an Ar atmosphere. At lower Cu amounts, mononuclear tetrahedrally coordinated Cu species were formed which are relatively stable in the monovalent form. In contrast, at higher Cu amounts, CuO particles were found which change easily between the mono- and bivalent species.

Yttria-zirconia coatings studied by grazing-incidence small-angle X-ray scattering during in situ heating.

The morphology of sol-gel derived dip-coated yttria-doped zirconia films containing variable amounts of yttria has been studied using in situ grazing-incidence small-angle X-ray scattering (GISAXS) whilst heated incrementally to 1000 °C. A procedure to analyse in situ GISAXS data has been devised which allows a quantitative analysis of time-dependent GISAXS data tracing processes such as chemical reactions or manufacturing procedures. To achieve this, the relative positions of the Yoneda peak and the through beam are used to fix the vertical q scale when the sample thickness is subject to fluctuations due to chemical reactions or deposition processes. A version of Beaucage's unified model with a structure factor from Hosemann's model for paracrystals describes the yttria-zirconia film data best. It is interpreted in terms of particles forming from a polymeric gel network and subsequently agglomerating into larger units subject to Ostwald ripening as both size and average separation distance of the scattering objects increase. The sample with the highest yttria content shows progressive surface roughening from 850 °C which may indicate the onset of chemical segregation.

Silver ion incorporation and nanoparticle formation inside the cavity of Pyrococcus furiosus ferritin: structural and size-distribution analyses.

Highly symmetrical protein cage architectures from three different iron storage proteins, heavy and light human ferritin chains (HuHFt and HuLFt) and ferritin from the hyperthemophilic bacterium Pyrococcus furiosus (PfFt), have been used as models for understanding the molecular basis of silver ion deposition and metal core formation inside the protein cavity. Biomineralization using protein cavities is an important issue for the fabrication of biometamaterials under mild synthetic conditions. Silver nanoparticles (AgNPs) were produced with high yields within PfFt but not within HuHFt and HuLFt. To explain the molecular basis of silver incorporation, the X-ray crystal structure of Ag-containing PfFt has been solved. This is the first structure of a silver containing ferritin reported to date, and it revealed the presence of specific binding and nucleation sites of Ag(I) that are not conserved in other ferritin templates. The AgNP encapsulated by PfFt were further characterized by the combined use of different physical-chemical techniques. These showed that the AgNPs are endowed with a narrow size distribution (2.1 +/- 0.4 nm), high stability in water solution at millimolar concentration, and high thermal stability. These properties make the AgNP obtained within PftFt exploitable for a range of applications, in fields as diverse as catalysis in water, preparation of metamaterials, and in vivo diagnosis and antibacterial or tumor therapy.

Photoluminescence of atomic gold and silver particles in soda-lime silicate glasses.

We report the chemistry and photophysics of atomic gold and silver particles in inorganic glasses. By synchrotron irradiation of gold-doped soda-lime silicate glasses we could create and identify unambiguously the gold dimer as a stable and bright luminescing particle embedded in the glassy matrix. The gold dimer spectra coincide perfectly with rare gas matrix spectra of Au(2). The glass matrix is, however, stable for years, and is hence perfectly suited for various applications. If the irradiated gold-doped sample is annealed at 550 degrees C a bright green luminescence can be recognized. Intense 337 nm excitation induces a decrease of the green luminescence and the reappearance of the 753 nm Au(2) emission, indicating a strong interrelationship between both luminescence centers. Time-dependent density functional theory (TD-DFT) calculations indicate that the green luminescence can be assigned to noble metal dimers bound to silanolate centers. These complexes are recognized as the first stages in the further cluster growth process, which has been investigated with small-angle x-ray scattering (SAXS). In silver-doped glasses, Ag(0) atoms can be identified with electron paramagnetic resonance (EPR) spectroscopy after synchrotron activation. Annealing at 300 degrees C decreases the concentration of Ag(1), but induces an intense white light emission with 337 nm excitation. The white luminescence can be decomposed into bands that are attributed to small silver clusters such as Ag(2), Ag(3) and Ag(4), and an additional band matching the green emission of gold-doped glasses.