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Three perfluorinated Zn II porphyrins were evaluated as n-type sensitizers in photoelectrosynthetic cells for HBr and water splitting. All the dyes are featured by the presence of pentafluorophenyl electron-withdrawing groups to increase the ground-state oxidation potential and differ for the nature and position of the π-conjugate linker between the core and anchoring group tasked to bind the metal oxide, in order to assess the best way of coupling with the semiconductor. A phenyl-triazole moiety was used to link the carboxylic anchoring group onto the meso position, while an ethynyl-phenyl linker was chosen to bridge carboxylic and cyanoacrylic groups onto the β-pyrrolic position. A combination of electrochemical, computational, and spectroscopic investigations confirmed the strong electron-withdrawing effect of the perfluorinated porphyrin core, which assures all the investigated dyes of the high oxidation potential required to the coupling with water oxidation catalysts (WOC). Such an electron-poor core, however, affects the charge separation character of the dyes, as demonstrated by the spatial distribution of the excited states, leading to a nonquantitative charge injection, although tilting of the molecules on the semiconductor surface could bring the porphyrin ring closer to the semiconductor, offering additional charge-transfer pathways. Indeed, all the dyes demonstrated successful in the splitting of both aqueous HBr and water, with the best results found for the SnO 2 /TiO 2 photoanode sensitized with the β-substituted porphyrin equipped with a cyanoacrylic terminal group, achieving 0.4 and 0.1 mA/cm 2 photoanodic currents in HBr and water under visible light, respectively. The faradaic yield for oxygen evolution in the presence of an Ir IV catalyst was over 95%, and the photoanode operation was stable for more than 1000 s. Thus, the perfluorinated porphyrins with a cyanoacrylic anchoring group at the β-position should be considered for further development to improve the charge-transfer character.

Dye-Sensitized Solar Cells (DSSCs) are a highly promising alternative to conventional photovoltaic silicon-based devices, due to the potential low cost and the interesting conversion efficiencies. A key-role is played by the dye, and porphyrin sensitizers have drawn great interest because of their excellent light harvesting properties mimicking photosynthesis. Indeed, porphyrins are characterized by strong electronic absorption bands in the visible region up to the near infrared and by long-lived π * singlet excited states. Moreover, the presence of four meso and eight β-pyrrolic positions allows a fine tuning of their photoelectrochemical properties through structural modification. Trans -A 2 BC push-pull Zn II porphyrins, characterized by a strong and directional electron excitation process along the push-pull system, have been extensively investigated. On the other hand, A 4 β-pyrrolic substituted tetraaryl Zn II porphyrins, which incorporate a tetraaryl porphyrinic core as a starting material, have received lower attention, even if they are synthetically more attractive and show several advantages such as a more sterically hindered architecture and enhanced solubility in most common organic solvents. The present contribution intends to review the most prominent A 4 β-substituted Zn II porphyrins reported in the literature so far for application in DSSCs, focusing on the strategies employed to enhance the light harvesting capability of the dye and on a comparison with meso -substituted analogs.

Background: The aim of the present investigation was to evaluate if an orthodontic population of Class III malocclusion patients shows a different prevalence of maxillary canine impaction than Class I subjects., Material and Methods: Fifty-eight subjects were retrospectively selected and assigned to the Class I group (n= 32) or the Class III group (n= 26), depending on the ANB and WITS values. Lateral cephalograms were used to collect angular and linear measurements that described the skeletal and dental maxillary features of the subjects, while orthopantomography was used to assess the impaction or the correct eruption of the maxillary canines. An independent samples T-test or a Mann-Whitney U-test was used to compare the cephalometric values between the two groups, while a chi-squared test was used to evaluate the distribution of maxillary canine impaction between the two groups., Results: No statistically significant difference was found for the cephalometric variables, and the frequency of canine impaction showed no difference between the Class III and Class I subjects., Conclusions: Patients with skeletal Class III malocclusions did not show a different prevalence of canine impaction; therefore, such skeletal features cannot be used as a diagnostic aid for assessment of the risk of maxillary canine impaction. Key words: Skeletal Class III, Angle Class III, maxillary canine impaction, tooth impaction., Competing Interests: Conflict of interest statement:The authors declare that they have no conflict of interest.

Objectives: To develop and validate a new reproducible 3D upper airway analysis based on skeletal structures not involved in the modification, which occur during orthognathic surgery., Methods: From retrospective cohort of orthognathic surgically treated patients, pre- and postsurgical CBCT-scans of 10 post-pubertal patients were randomly selected. Two operators identified the landmarks, calculated the airway volumes, cross sections and linear measurements on the 10 scans twice at two different time intervals. Statistical analysis included test for normal distribution, technical error measurements, and intra- and inter-observers reliability., Results: Intra- and inter-observer reliability was excellent for volumes and cross sections. The entire data sets exhibited normal distribution. Technical error of measurements showed an error in the range of 1.6 to 10.2% for volume, 1.6 to 12.2% for cross-sectional measurements, and 0.3 to 2.5% for linear measurements. No systematic errors were detected., Conclusions: This new proposed definition of upper airway boundaries was shown to be technical feasible and tested to be reliable in measuring upper airway in patients undergoing orthognathic surgery.

Background: Data from epidemiological studies investigating the prevalence and severity of malocclusions in children are of great relevance to public health programs aimed at orthodontic prevention. Previous epidemiological studies focused mainly on the adolescence age group and reported a prevalence of malocclusion with a high variability, going from 32% to 93%. Aim of our study was to assess the need for orthodontic treatment in a paediatric sample from Southern Italy in order to improve awareness among paediatricians about oral health preventive strategies in pediatric dentistry., Material and Methods: The study used the IOTN-DHC index to evaluate the need for orthodontic treatment for several malocclusions (overjet, reverse overjet, overbite, openbite, crossbite) in a sample of 579 children in the 2-9 years age range., Results: The most frequently altered occlusal parameter was the overbite (prevalence: 24.5%), while the occlusal anomaly that most frequently presented a need for orthodontic treatment was the crossbite (8.8%). The overall prevalence of need for orthodontic treatment was of 19.3%, while 49% of the sample showed one or more altered occlusal parameters. No statistically significant difference was found between males and females., Conclusions: Results from this study support the idea that the establishment of a malocclusion is a gradual process starting at an early age. Effective orthodontic prevention programs should therefore include preschool children being aware paediatricians of the importance of early first dental visit. Key words: Orthodontic treatment, malocclusion, oral health, pediatric dentistry., Competing Interests: Conflict of interest statement:The authors declare that they have no conflict of interest.

In this chapter we report on the characterization of linear antigenic sites of human chromogranin A (CgA), a useful tissue and serum marker for neuroendocrine tumours and a precursor of many biologically active peptides. The epitope mapping of CgA has been carried out by peptide microarrays on glass slides coated by a copolymer of N,N-dimethylacrylamide (DMA), N,N-acryloyloxysuccinimide (NAS) and [3-(methacryloyl-oxy) propyl] trimethoxysilyl (MAPS). The microarray support provided sufficient accessibility of the ligand, with no need for a spacer, as the polymer chains prevent interaction of immobilized peptides with substrate. In addition, the polymeric surface constitutes an aqueous micro-environment in which, despite peptide random orientation, linear epitopes are freely exposed. The results reported are in accordance with those obtained in conventional ELISA assays using biotinylated and non-biotinylated peptides.