The adverse effects of radiotherapy on the structure of dental hard tissues and longevity of dental restoration.

Purpose: The main goal of this study was to evaluate the impact of different ionizing radiation doses on the mineral (carbonate/phosphate ratio, crystallinity index [CI]) and organic (amide III/phosphate, amide I sub-band ratios) structures, as well as the microhardness, of enamel and dentin, along with their influence on the bonding strength stability of the etch-and-rinse (ER) and self-etch (SE) dental adhesive strategies.Materials and methods: Enamel and dentin human tissue specimens were irradiated (with 0, 20, 40, and 70 Gy radiation doses, respectively) and sectioned to perform an attenuated total reflection-Fourier transform IR spectroscopy assay (ATR-FTIR) and the Vickers microhardness (VHN) test to conduct a biochemical and biomechanical evaluation of the tissues. Regarding the adhesive properties, restored enamel and dentin specimens exposed to the same radiation doses were submitted to microshear bond strength (µSBS) tests for enamel in immediate time (IM) and to microtensile bond strength (µTBS) tests after for IM and 12-month (12 M) period of time, Mann-Whitney U tests were implemented, using the ATR-FTIR data for significant differences (α < 0.05), and three- and two-way analyses of variance, along with post-testing, were performed on the µTBS and µSBS data (MPa), respectively (Tukey post hoc test at α = 0.05).Results: The ATR-FTIR results showed a significant decrease (p < .05) in the amide III/phosphate ratio after 20 Gy for the enamel and after 40 Gy for the dentin. The CI was significantly reduced for both tissues after a dose of 70 Gy (p < .05). All radiation doses significantly decreased microhardness values, relative to the respective enamel and dentin controls (p < .05). In both tissues and adhesive strategies, the decrease in bond strength was influenced by ionizing radiation starting from 40 Gy. The ER strategy showed high percentages of enamel cohesive failure. In general, ER in both tissues showed greater and more stable bond strength than SE against increased radiation doses and long term.Conclusions: It is possible to conclude that structural alterations of enamel and dentin are generated by all radiation doses, decreasing the microhardness of dental hard tissues and influencing bond strength over time, starting at 40 Gy radiation dose. The etch-and-rinse strategy demonstrates better adhesive performance but generates cohesive fractures in the enamel.

Unoccupied Interface and Molecular States in Thiol and Dithiol Monolayers.

The electronic structure of self-assembled monolayers (SAMs) formed by thiols of different lengths and dithiol molecules bound to Au(111) has been characterized. Inverse photoemission spectroscopy (IPES) and density functional theory have been used to describe the molecule/Au substrate system. All molecular layers display a clear signal in the IPES data at the edge of the lowest unoccupied system orbital (LUSO), roughly 3 eV above the Fermi level. There is also evidence, in both the experimental data and the calculation, of a finite density of states just below the LUSO edge, which has been recognized as localized at the Au-substrate interface. Regardless of the molecular lengths and in addition to this induced density of interface states, an apparent antibonding Au-S state has been identified in the IPES data for both molecular systems. The main difference between the electronic structures of thiol and dithiol SAMs is a shift in the energy of the antibonding state.

The Many Faces of Graphene as Protection Barrier. Performance under Microbial Corrosion and Ni Allergy Conditions.

In this work we present a study on the performance of CVD (chemical vapor deposition) graphene coatings grown and transferred on Ni as protection barriers under two scenarios that lead to unwanted metal ion release, microbial corrosion and allergy test conditions. These phenomena have a strong impact in different fields considering nickel (or its alloys) is one of the most widely used metals in industrial and consumer products. Microbial corrosion costs represent fractions of national gross product in different developed countries, whereas Ni allergy is one of the most prevalent allergic conditions in the western world, affecting around 10% of the population. We found that grown graphene coatings act as a protective membrane in biological environments that decreases microbial corrosion of Ni and reduces release of Ni2+ ions (source of Ni allergic contact hypersensitivity) when in contact with sweat. This performance seems not to be connected to the strong orbital hybridization that Ni and graphene interface present, indicating electron transfer might not be playing a main role in the robust response of this nanostructured system. The observed protection from biological environment can be understood in terms of graphene impermeability to transfer Ni2+ ions, which is enhanced for few layers of graphene grown on Ni. We expect our work will provide a new route for application of graphene as a protection coating for metals in biological environments, where current strategies have shown short-term efficiency and have raised health concerns.

Suppressing bacterial interaction with copper surfaces through graphene and hexagonal-boron nitride coatings.

Understanding biological interaction with graphene and hexagonal-boron nitride (h-BN) membranes has become essential for the incorporation of these unique materials in contact with living organisms. Previous reports show contradictions regarding the bacterial interaction with graphene sheets on metals. Here, we present a comprehensive study of the interaction of bacteria with copper substrates coated with single-layer graphene and h-BN. Our results demonstrate that such graphitic coatings substantially suppress interaction between bacteria and underlying Cu substrates, acting as an effective barrier to prevent physical contact. Bacteria do not "feel" the strong antibacterial effect of Cu, and the substrate does not suffer biocorrosion due to bacteria contact. Effectiveness of these systems as barriers can be understood in terms of graphene and h-BN impermeability to transfer Cu(2+) ions, even when graphene and h-BN domain boundary defects are present. Our results seem to indicate that as-grown graphene and h-BN films could successfully protect metals, preventing their corrosion in biological and medical applications.

Gold nanoparticles grown inside carbon nanotubes: synthesis and electrical transport measurements.

The hybrid structures composed of gold nanoparticles and carbon nanotubes were prepared using porous alumina membranes as templates. Carbon nanotubes were synthesized inside the pores of these templates by the non-catalytic decomposition of acetylene. The inner cavity of the supported tubes was used as nanoreactors to grow gold particles by impregnation with a gold salt, followed by a calcination-reduction process. The samples were characterized by transmission electron microscopy and X-ray energy dispersion spectroscopy techniques. The resulting hybrid products are mainly encapsulated gold nanoparticles with different shapes and dimensions depending on the concentration of the gold precursor and the impregnation procedure. In order to understand the electronic transport mechanisms in these nanostructures, their conductance was measured as a function of temperature. The samples exhibit a 'non-metallic' temperature dependence where the dominant electron transport mechanism is 1D hopping. Depending on the impregnation procedure, the inclusion of gold nanoparticles inside the CNTs can introduce significant changes in the structure of the tubes and the mechanisms for electronic transport. The electrical resistance of these hybrid structures was monitored under different gas atmospheres at ambient pressure. Using this hybrid nanostructures, small amounts of acetylene and hydrogen were detected with an increased sensibility compared with pristine carbon nanotubes. Although the sensitivity of these hybrid nanostructures is rather low compared to alternative sensing elements, their response is remarkably fast under changing gas atmospheres.

Humidity sensing by carbon nanocones.

Carbon nano-structures, mainly nanotubes, have been explored in the past as sensing devices. In this report we have considered cones and discs (CNCs) subjected to acid treatment, dry oxidation and high temperature annealing, to study the modifications induced as they are used as sensing elements of varying relative humidity (RH). The relative humidity was varied in cycles of 30 min between 36% and 75%. Not strangely, the acid treated films displayed a much larger variation in resistance for the same difference in RH (16%). In the as-grown material, very small variations were detected among cycles under similar conditions. The changes induced in the sensors structures by the different preparation procedures were characterized by transmission electron microscopy (TEM) and Raman reflexion. These results were used to model their behaviour as RH sensors.

Growth of carbon nanostructures using a Pd-based catalyst.

Carbon nanostructures were synthesized by decomposition of different carbon sources over an alumina supported palladium catalyst via Chemical Vapor Deposition (CVD). Several experimental conditions were varied to verify their influence in the synthesis products: temperature ramping rate, pre-annealing conditions, hydrogen pre-treatment, synthesis temperature and time, together with the use of different carbon sources. Depending on the experimental conditions carbon nanotubes and nanofibers with different shapes and structural characteristics were obtained. Straight, coiled and branched morphologies are the most common. Among our findings, the addition of hydrogen plays a significant role in the structure of the carbonaceous products. For example, the decomposition of acetylene on palladium catalysts at 800 degrees C in the absence of hydrogen produces only carbon micro- spheres as synthesis products. The incorporation of increasing amounts of hydrogen modifies the outcome, from thick fibers to carbon nanotubes. To verify the level of graphitization of the synthesis products we have used high resolution transmission electron microscopy (HRTEM) in addition to Raman spectroscopy. Our results, based on these complementary techniques, indicate the decomposition of acetylene on a palladium based catalyst, produces the best degree of graphitization in carbon nanotubes for a temperature of 800 degrees C and 100 cc/min of hydrogen flow. Similar hydrogen flows on the same catalyst, produced highly graphitized nanofibers by the decomposition of methane at 850 degrees C.

Growth morphology and spectroscopy of multiwall carbon nanotubes synthesized by pyrolysis of iron phthalocyanine.

Carbon nanotubes (CNTs) were synthesized by Chemical Vapor Deposition (CVD) from the pyrolytic decomposition of Iron Phthalocyanine (FePc) molecules, on SiO2/Si(111) substrates in the presence of a hydrogen flow. FePc molecules contribute simultaneously both to the formation of the precursor Fe nanoparticles and also as a Carbon source. Different experimental conditions were examined. Samples were characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and inverse photoemission. The resulting samples are highly oriented multiwall carbon nanotubes films, with heights in the range between: 4 and 20 microm. The tubes diameter is strongly dependent on growth temperature. Our experimental results show evidence of a transition in the growth mechanism, from a tip growth to a base growth mode, as the decomposition temperature is increased. Preliminary spectroscopic measurements performed on these MWCNTs, show the unoccupied density of states has several resonances close to Fermi level, related both to the graphene electronic structure and the formation of the tube.