Device-Compatible Chiroptical Surfaces through Self-Assembly of Enantiopure Allenes.

Chiroptical methods have been proven to be superior compared to their achiral counterparts for the structural elucidation of many compounds. To expand the use of chiroptical systems to everyday applications, the development of functional materials exhibiting intense chiroptical responses is essential. Particularly, tailored and robust interfaces compatible with standard device operation conditions are required. Herein, we present the design and synthesis of chiral allenes and their use for the functionalization of gold surfaces. The self-assembly results in a monolayer-thin room-temperature-stable upstanding chiral architecture as ascertained by ellipsometry, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure. Moreover, these nanostructures anchored to device-compatible substrates feature intense chiroptical second harmonic generation. Both straightforward preparation of the device-compatible interfaces along with their chiroptical nature provide major prospects for everyday applications.

Calibration of Raman spectroscopy at 1064 nm for beeswax quantification.

In the early sixties, coating with molten beeswax was considered a valuable method for preventing the erosive action of weather and/or salinity on the surface of granite sculptures and monuments. This technique had been traditionally employed by the Galician stoneworkers for partial repair of historical monuments. For this purpose, beeswax was applied to the Renaissance Frieze in the Cloister of the Cathedral of Santiago de Compostela in Galicia (Northwest Spain). The beeswax treatment was counterproductive. An intense grain disaggregation of the granite can be observed in the Frieze, owing to the crystallization of salts. As a consequence, the restoration of the Cloister presents many problems. This fact imposes the need for an exhaustive study of the wax-stone system and the demand for a nondestructive method to measure the beeswax thickness at the stone surface. The aim of this contribution is the evaluation of a laser-based method, namely Fourier transform Raman spectroscopy, for analyzing the wax presence in specific rocky material of the Frieze to be restored. To obtain a reliable quantitative calibration, we prepared beeswax films of five different thicknesses on aluminum plates (26.6-97.2 microm). Nylon was selected as external reference to obtain the Raman emission independently from the laser beam power. The ratios of the relative intensities of the Raman bands corresponding to beeswax and nylon were used for the construction of a calibration curve used for the quantitative analysis. The intensities at 2879 cm(-1), I(c2879), and 2880 cm(-1), I(n2880), for beeswax and nylon, respectively, in the Raman spectra of each material were used. A linear dependence was found for the ratio I(c2879)/I(n2880) with the beeswax thickness. The validation of this calibration curve was tested with a second validation set of samples that spans beeswax film thicknesses both inside and outside the calibration range (12.1 to 180 mum), in order to evaluate in addition the accuracy of the model at extrapolation. Without complex sample preparation, near-infrared Raman spectroscopy resulted in an effective technique for localizing the wax with lateral resolution of tens of micrometers, and for determining wax layer thickness in the stone with an uncertainty of a few micrometers.

Physicochemical properties of calcium phosphate coatings produced by pulsed laser deposition at different water vapour pressures.

Calcium phosphate coatings were produced by pulsed laser deposition from targets of non-stoichiometric hydroxyapatite (Ca/P = 1.70) at a substrate temperature of 485 degrees C and different processing pressures of water vapour: 0.15, 0.30, 0.45, 0.60 and 0.80 mbar. The physicochemical properties of these coatings were studied using Fourier-transform IR spectroscopy (FT-IR) and energy dispersive X-ray analysis (EDX). A minimum pressure of water vapour was necessary in order to obtain a crystalline coating, as deduced from the FT-IR spectroscopy of these coatings. This analysis also revealed that when the deposition pressure of water vapour was further increased, the coatings were less crystalline and the content of hydroxyl groups, the carbonate substitution for phosphate, and the Ca/P ratio, as measured by EDX, were lower. These effects can be explained by a combined substitution of carbonate and HPO4(2-) for phosphate, being predominant the carbonate substitution at low pressures and the HPO4(2-) substitution at high pressures.

New biomorphic SiC ceramics coated with bioactive glass for biomedical applications.

A new generation of light, tough and high-strength material for medical implants for bone substitutions with a good biological response is presented. The innovative product that fulfills all these requirements is based on biomorphic silicon carbide ceramics coated with a bioactive glass layer. The combination of the excellent mechanical properties and low density of the biomorphic SiC ceramics, used as a base material for implants, with the osteoconducting properties of the bioactive glass materials opens new possibilities for the development of alternative dental and orthopedic implants with enhanced mechanical and biochemical properties that ensures optimum fixation to living tissue. Biomorphic SiC is fabricated by molten-Si infiltration of carbon templates obtained by controlled pyrolysis of wood. Through this process, the microstructure of the final SiC product mimics that of the starting wood, which has been perfected by natural evolution. The basic features of such microstructure are its porosity (ranging from 30% to 70%) and its anisotropy, which resembles the cellular microstructure and the mechanical characteristics of the bone. The SiC ceramics have been successfully coated with a uniform and adherent bioactive glass film by pulsed laser ablation using an excimer ArF laser. The excellent coverage of the SiC rough surface without film spallation or detachment is demonstrated. In order to assess the coating bioactivity, in vitro tests by soaking the samples in simulated body fluid have been carried out. After 72 h, the formation of a dense apatite layer has been observed even in interconnecting pores by SEM and energy dispersive X-ray spectroscopy analysis demonstrating the bioactive response of this product.

In vitro response of pre-osteoblastic cells to laser microgrooved PEEK.

Polyetheretherketone (PEEK) is currently being used in implants as an alternative to titanium, due to its mechanical properties, cytocompatibility and inertness. Several studies have demonstrated that certain patterning on the implants promotes the oriented cell growth of osteoblasts, favouring the formation of bone tissue. This patterning improves the implant's osteointegration in the bone and its mechanical stability. Therefore, the objective of this work is to micro-structure PEEK by laser radiation and to carry out an exhaustive study of the orientation of pre-osteoblast cells that grow on this material. Parallel microgrooves were obtained using an ArF excimer laser coupled with a mask projection unit with distances of 25, 50, 75 and 100 µm between grooves. The cell growth on these PEEK surfaces was studied, in order to compare the effect of different distances between grooves on the biological response of MC3T3-E1 pre-osteoblastic cells. Preferential cell orientation was observed for all studied distances, which was more pronounced in the 25 and 50 µm ones.

Excimer laser chemical ammonia patterning on PET film.

Laser is a promising technique used for biopolymer surface modification with micro and/or nano features. In this work, a 193 nm excimer laser was used for poly (ethylene terephthalate) (PET) surfaces chemical patterning. The ablation threshold of the PET film used in the experiments was 62 mJ/cm(2) measured before surface modification. Surface chemical patterning was performed by irradiating PET film in a vacuum chamber filled with ammonia at the flux of 10, 15, 20, 25 ml/min. Roughness of the surface characterized by profilometry showed that there were no significant observed change after modification comparing original film. But the hydrophilicity of the surface increased after patterning and a minimum water contact angle was obtained at the gas flux of 20 ml/min. FT-IR/ATR results showed the distinct amino absorption bands presented at 3352 cm(-1)and 1613 cm(-1) after modification and XPS binding energies of C(1s) at 285.5 eV and N(1s) at 399.0 eV verified the existence of C-N bond formation on the PET film surface. Tof-SIMS ions mapping used to identify the amine containing fragments corroborates that amino grafting mainly happened inside the laser irradiation area of the PET surface. A hypothesized radical reaction mechanism proposes that the collision between radicals in ammonia and on the PET surface caused by the incident laser provokes the grafting of amino groups.

A new generation of bio-derived ceramic materials for medical applications.

A new generation of bio-derived ceramics can be developed as a base material for medical implants. Specific plant species are used as templates on which innovative transformation processes can modify the chemical composition maintaining the original biostructure. Building on the outstanding mechanical properties of the starting lignocellulosic templates, it is possible to develop lightweight and high-strength scaffolds for bone substitution. In vitro and in vivo experiments demonstrate the excellent biocompatibility of this new silicon carbide material (bioSiC) and how it gets colonized by the hosting bone tissue because of its unique interconnected hierarchic porosity, which opens the door to new biomedical applications.

Influence of the non-bridging oxygen groups on the bioactivity of silicate glasses.

The effect of the composition and bonding configuration of the bioactive silica-based glasses on the initial stage in vitro bioactivity is presented. Information of the IR active Si-O groups of glass in the system SiO(2)-P(2)O(5)-CaO-Na(2)O-K(2)O-MgO-B(2)O(3) was obtained by fourier transform Infrared (FTIR) spectroscopy. Two different bands associated to non-bridging oxygen stretching vibrations (Si-O-1NBO and Si-O-2NBO) and a gradual shifting of the bridging oxygen stretching vibration (Si-O) have been observed and evaluated. Both effects are attributed to a decrease of the local symmetry originating from the incorporation of alkali ions into the vitreous silica network. The Si-O-NBO(s)/Si-O(s) absorbance intensity ratio increases with a gradual incorporation of the alkali ions (diminution of SiO(2) content) following a linear dependence up to values close to 50 wt % of SiO(2). In vitro test analysis by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA) showed a correlation between the amount and type of the non-bridging oxygen functional groups and the growth of the silica-rich and CaP layers. It was found that a minimum concentration of Si-O-NBO bonds in the glass network is required in order to have an efficient ion exchange and dissolution of the silica network. Finally, the bioactivity of the glass is favored by the presence of the Si-O-2NBO groups in the glassy network. The role of these functional groups in the dissolution of the silica network through the formation of silanol groups and the adsorption of water is discussed.