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The success of dental implant placement and prosthetic reconstruction relies on sufficient bone volume at the implant site. Contemporary implantology integrates prosthetic planning with implant placement, emphasizing the importance of pre-established prosthetic goals. Guided Bone Regeneration (GBR) techniques have become crucial for bone reconstruction. This study explores the use of custom-made GBR membranes, designed through CAD-CAM technology, in 10 patients with severe bone defects. Patients underwent meticulous preoperative planning, in which digital diagnostic wax-ups and RealGUIDE™ software for implant positioning were used. The custom-made membranes, which were designed based on the individual defects, exhibited successful adaptation. Surgical phases involved membrane placement, bone grafting, and subsequent implant placement. Clinical–radiographic follow-ups demonstrated favorable bone gain outcomes, which enabled prosthetic rehabilitation. Despite membrane exposure occurring in 30% of cases, it did not compromise overall success. The study underscores the potential of custom-made GBR membranes in achieving prosthetic goals, though challenges like exposure and the need for a second surgery require further investigations. The results indicate a promising alternative for predictable bone regeneration in complex cases, shedding light on the prosthetically guided approach for optimal functional and aesthetic outcomes.

Abstract Messenger RNA (mRNA) therapy is the intracellular delivery of mRNA to produce desired therapeutic proteins. Developing strategies for local mRNA delivery is still required where direct intra‐articular injections are inappropriate for targeting a specific tissue. The mRNA delivery efficiency depends on protecting nucleic acids against nuclease‐mediated degradation and safe site‐specific intracellular delivery. Herein, novel mRNA‐releasing matrices based on RGD‐moiety‐rich gelatin methacryloyl (GelMA) microporous annealed particle (MAP) scaffolds are reported. GelMA concentration in aerogel‐based microgels (µgels) produced through a microfluidic process, MAP stiffnesses, and microporosity are crucial parameters for cell adhesion, spreading, and proliferation. After being loaded with mRNA complexes, MAP scaffolds composed of 10% GelMA µgels display excellent cell viability with increasing cell infiltration, adhesion, proliferation, and gene transfer. The intracellular delivery is achieved by the sustained release of mRNA complexes from MAP scaffolds and cell adhesion on mRNA‐releasing scaffolds. These findings highlight that hybrid systems can achieve efficient protein expression by delivering mRNA complexes, making them promising mRNA‐releasing biomaterials for tissue engineering.

Since May 2018 till the end of 2021, Mayotte island has been the locus of a major submarine volcanic eruption characterized by the offshore emission of more than 6.5 km$^{3}$ of basanitic magma. The eruption occurred along a WNW–ESE trending submarine ridge on the east flank of the island where, in addition, several seemingly recent phonolitic bodies were also identified close to the island. To define realistic scenarios of magma ascent and potentially predict the style of an upcoming event, it is crucial to have a precise understanding on the plumbing system operating below volcanoes. The putative relationships between basanites emitted by the new volcano and these recent phonolites have been experimentally explored by performing crystallization experiments on a representative basanite over a large range of pressures (up to 400 MPa). The results show that the crystallization of basanite at crustal levels (${\le }$12–15 km) yields a phonolitic residual liquid containing up to 3–4 wt% $\mathrm{H}_{2}\mathrm{O}$ after ${\ge }$65 wt% of an assemblage of olivine$+$plagioclase$+$amphibole$+$clinopyroxene$+$biotite$+$magnetite$+$ilmenite$+$apatite. The final iron content of the residual phonolitic liquids is strongly controlled by the depth/pressure of fractionation. Fe-rich phonolites from the submarine ridge are produced at 6–8 km depth, while a shallower differentiation (${\le }$4–5 km) results in the production of liquids with trachyte–benmoreite affinities. If the fractionation process occurs at depths higher than 8 km, the resulting phonolitic melts are progressively enriched in $\mathrm{SiO}_{2}$–$\mathrm{Al}_{2}\mathrm{O}_{3}$ but depleted in FeO*, ie unlike those erupted. We therefore conclude that phonolitic magma production and storage at Mayotte is a rather shallow process.

Bone density at the implant site is correlated to the success of osseointegration. The objective of this in vitro study was to evaluate the efficacy of osseodensification burs in increasing bone density using a solid polyurethane foam block model. The osseodensification burs kit was used to perform 48 osteotomies on a rigid polyurethane foam test ground. Burs were utilized on a TMM2 implant motor for data collection. The osteotomies were divided into two study groups (A and C) in which implant sites, extended 12 and 14 mm deep, respectively, were prepared using the drills to a compaction rotation; two control groups, B and D, represented the osteotomies for which the drills were used in cutting direction. A 3.8 × 12 mm conical implant was inserted into each site; for each implant, data were collected on the peak torque (Cp), mean torque (Cm), and integral depth curve (I). The implants underwent resonance frequency analysis (RFA) to assess the implant stability quotient (ISQ). Correlation analysis was performed between I, Cm, Cp and ISQ. One-way analysis of variance (ANOVA) was used to identify statistically significant differences between groups. Group C, representing osteotomies prepared at 14 mm with osseodensification burs, showed a significantly higher value for each parameter. Implants at sites obtained with osteocondensation drills and prepared at greater depth for autologous particle grafting showed significant increases in each implant stability parameter.

(1) Background: The aim of the study was to assess the potential effectiveness of clinical diagnostic examinations, such as muscle palpation, and instrumental examinations, such as electromyography, in the early detection of TMJ involvement in patients with juvenile idiopathic arthritis (JIA), as early diagnosis of these disorders can reduce the risk of developing facial growth anomalies and dento-skeletal malocclusions. (2) Methods: Evaluations were conducted on a cohort of 15 people with juvenile idiopathic arthritis (JIA) and a comparison group of 15 healthy participants at the start of the trial (T0) and after 18 ± 6 months (T1). Data were obtained through clinical examination, involving muscle palpation of the anterior temporalis, masseters, and sternocleidomastoids, and by instrumental analysis using electromyography. The parametric student’s t-test was used to evaluate group comparisons for data that were normally distributed, whereas the nonparametric Mann–Whitney U test was employed for parameters that did not follow a normal distribution. (3) Results: In the JIA group, higher levels of pain were recorded in the sternocleidomastoid muscles on both sides as compared to the control group (p < 0.05) at both T0 and T1. Electromyography revealed no statistically significant variances both in the JIA group and in the control group, except for the IMP index, characterized by a significant improvement over time for the JIA group. (4) Conclusions: According to the methodology employed in this study, all JIA patients had TMD symptoms, mainly muscle disorders. The existence of statistically significant parameters suggests the potential to regard muscle palpation and electromyography as predictive indicators of TMJ involvement in JIA subjects. Additional research is required to validate their reliability.

This study focuses on the dissolution process and surface characterization of amosite fibres following interaction with a mimicked Gamble’s solution at a pH of 4.5 and T = 37 °C, up to 720 h. To achieve this, a multi-analytical approach was adopted, and the results were compared to those previously obtained on a sample of asbestos tremolite and UICC crocidolite, which were investigated under the same experimental conditions. Combining surface chemical data obtained by XPS with cation release quantified by ICP-OES, an incongruent behaviour of the fibre dissolution was highlighted for amosite fibres, similarly to asbestos tremolite and UICC crocidolite. In particular, a preferential release of Mg and Ca from the amphibole structure was observed, in agreement with their Madelung site energies. Notably, no Fe release from amosite fibres was detected in our experimental conditions (pH of 4.5 and atmospheric pO2), despite the occurrence of Fe(II) at the M(4) site of the amphibole structure, where cations are expected to be rapidly leached out during mineral dissolution. Moreover, the oxidation of both the Fe centres initially present on the fibre surface and those promoted from the bulk, because of the erosion of the outmost layers, was observed. Since biodurability (i.e., the resistance to dissolution) is one of the most important toxicity parameters, the knowledge of the surface alteration of asbestos possibly occurring in vivo may help to understand the mechanisms at the basis of its long-term toxicity.

Carbonatites host Earth’s main REE deposits, with bastnaesite (LREE)CO$_3$F being the main economic REE-bearing mineral. However, bastnaesite mineralisation processes are debated between hydrothermal or magmatic origin. This study aims to assess if bastnaesite can be magmatic, and to characterise the REE behaviour during carbonatite crystallisation. Crystallisation experiments have been performed from 900 to 600 °C at 1 kbar, on a REE-rich calciocarbonatitic composition. REE-bearing calcite is the dominant crystallising mineral, driving the residual melt towards natrocarbonatitic compositions. Both halogens (i.e., Cl and F) and water decrease the temperature of calcite saturation. REE are slightly incompatible with calcite: for all REE, partition coefficients between carbonate melt and calcite are comprised between 1 and 11, and increase with temperature decrease. Britholite (REE, Ca)$_{5}$((Si,P)O$_{4}$)$_3$(F,OH) crystallises at high temperatures (700–900 °C), while pyrochlore (Ca,Na,REE)$_{2}$Nb$_{2}$O$_{6}$(OH,F) crystallises at low temperatures (600–700 °C), as well as REE-rich apatite (600–650 °C). No bastnaesite is found in crystallisation experiments. We thus performed a bastnaesite saturation experiment at 600 °C. The bastnaesite-saturated melt contains 20 wt% of REE: such magmatic saturation is unlikely to happen in nature. Textural evidences imply a Na, Cl, REE-rich fluid at high temperatures and hydrous conditions. We propose that fluids are the main mineralising agent for bastnaesite at hydrothermal stage ($

The correction of malocclusions with severe skeletal deformity generally requires surgery combined with orthodontic or prosthodontic treatment; partially or totally edentulous patients, and patients with a prosthetic fixed crown, represent treatment restrictions and, therefore, challenges. The purpose of this study is to show a complete multidisciplinary approach and the planning involved (pre-, intra-, and post-operative) for a patient with a class-II or -III dento-skeletal malformation, who presents a total or partial edentulism or a fixed-type rehabilitation and, therefore, requires a combined orthognathic surgical treatment with prosthetic rehabilitation. Orthognathic surgery can be performed on an edentulous or prosthodontic patient to correct discrepancies between the jaws, followed by the placement of implants or a mobile prosthesis to rehabilitate the maxillary bones maxillary Different surgical approaches and technical variations have been proposed; however, the key to the success of such treatments lies in the multidisciplinary nature of the entire diagnostic, programmatic, and therapeutic path, which, therefore, necessitates close collaboration between different specialists—in particular, the maxillofacial surgeon, the orthodontist, and the prosthetist.

Mesoporous silica nanoparticles (MSNPs) are currently used in different fields like catalysis, nanomedicine, and conservation science, taking advantage of their high surface area. Here, we synthesized and functionalized mesoporous dendritic fibrous nanoparticles to realize a smart delivery system of protective agents for metals. Different MSNPs were obtained via the microemulsion method followed by a hydrothermal or refluxing treatment at different w/o ratios, times, and temperatures. Dendritic spherical silica nanoparticles with specific features such as an appropriate size (450 nm), a very large surface area (600 m2 g−1), and a high yield synthesis (86%) were selected for surface modification. The fiber surface of the selected MSNPs was functionalized with 3-aminopropyl triethoxysilane (3-APTES). 3-APTES works as a pH-driven “nanogate”, suppressing the immediate leakage of the total guest molecule load and modulating the release as a function of pH conditions. Surface-modified MSNPs were tested as a reservoir of the most diffused corrosion inhibitors: Mercaptobenzothiazole (MBT) and 1H-Benzotriazole (BTA); their release properties were studied in solutions with pH = 4 and 7. Functionalized and non-functionalized MSNPs showed a good loading efficiency of guest molecules (34–64%) and a pH-dependent release of the corrosion inhibitors on a timescale of several hours.

Solubility experiments were performed on a trachyte and a pantellerite from Pantelleria. The trachyte has $\mathrm{SiO}_{2}=65.2$ wt%, $\mathrm{Al}_{2}\mathrm{O}_{3}=15.2$ wt% and a peralkaline index $(\mathrm{P.I.} = \mathrm{molar}[(\mathrm{Na}_{2}\mathrm{O}+ \mathrm{K}_{2}\mathrm{O})/\mathrm{Al}_{2}\mathrm{O}_{3}]) \sim 1$ while the pantellerite has $\mathrm{SiO}_{2}=72.2$ wt%, $\mathrm{Al}_{2}\mathrm{O}_{3}=11$ wt% and a $\mathrm{P.I.}=1.3$. Solubility experiments were performed in the pressure range of 50–300 MPa at ${T}=950~\text{°C}$ for the trachyte and 50–200 MPa at ${T}=850~\text{°C}$ for the pantellerite. The water content of experimental glasses was determined by Karl Fischer titration, elemental analyser and FT–IR spectroscopy. Water content appears similar in both compositions for analogous pressure conditions, varying from ${\sim }2.5$ wt% at 50 MPa to ${\sim }5.8$ at 200 MPa. Comparison of the experimental data with the thermodynamic models shows that the empirical model of Moore et al. [1998] better matches the experimental data for both compositions, while the thermodynamic models of Papale et al. [2006] and Ghiorso and Gualda [2015] tend to overestimate melt water content, probably due to the paucity of peralkaline melt compositions used for calibration. One inference of these new solubility data is on MI-derived depth of felsic reservoirs at Pantelleria which deepens from 2.4 to 3.5 km.

In July 2017 three research flights circumnavigating the megacity of London were conducted as a part of the STANCO training school for students and early career researchers organised by EUFAR (European Facility for Airborne Research). Measurements were made from the UK's Facility for Airborne Atmospheric Measurements (FAAM) BAe-146-301 atmospheric research aircraft with the aim to sample, characterise and quantify the impact of megacity outflow pollution on air quality in the surrounding region. Conditions were extremely favourable for airborne measurements, and all three flights were able to observe clear pollution events along the flight path. A small change in wind direction provided sufficiently different air mass origins over the 2 d such that a distinct pollution plume from London, attributable marine emissions and a double-peaked dispersed area of pollution resulting from a combination of local and transported emissions were measured. We were able to analyse the effect of London emissions on air quality in the wider region and the extent to which local sources contribute to pollution events. The background air upwind of London was relatively clean during both days; concentrations of CO were 88–95 ppbv, total (measured) volatile organic compounds (VOCs) were 1.6–1.8 ppbv and NOx was 0.7–0.8 ppbv. Downwind of London, we encountered elevations in all species with CO>100 ppbv, VOCs 2.8–3.8 ppbv, CH4>2080 ppbv and NOx>4 ppbv, and peak concentrations in individual pollution events were higher still. Levels of O3 were inversely correlated with NOx during the first flight, with O3 concentrations of 37 ppbv upwind falling to ∼26 ppbv in the well-defined London plume. Total pollutant fluxes from London were estimated through a vertical plane downwind of the city. Our calculated CO2 fluxes are within the combined uncertainty of those estimated previously, but there was a greater disparity in our estimates of CH4 and CO. On the second day, winds were lighter and downwind O3 concentrations were elevated to ∼39–43 ppbv (from ∼32 to 35 ppbv upwind), reflecting the contribution of more aged pollution to the regional background. Elevations in pollutant concentrations were dispersed over a wider area than the first day, although we also encountered a number of clear transient enhancements from local sources. This series of flights demonstrated that even in a region of megacity outflow, such as the south-east of the UK, local fresh emissions and more distant UK sources of pollution can all contribute substantially to pollution events. In the highly complex atmosphere around a megacity where a high background level of pollution mixes with a variety of local sources at a range of spatial and temporal scales and atmospheric dynamics are further complicated by the urban heat island, the use of pollutant ratios to track and determine the ageing of air masses may not be valid. The individual sources must therefore all be well-characterised and constrained to understand air quality around megacities such as London. Research aircraft offer that capability through targeted sampling of specific sources and longitudinal studies monitoring trends in emission strength and profiles over time.

Background: Recently, intraoral scanning (IOS) has been proposed as a new tool to evaluate the accuracy of static computer-assisted implant surgery (s-CAIS); however, further research is needed to improve the precision of IOS for full-arch impressions. The purpose of the study was to assess the accuracy of s-CAIS in an edentulous patient either in vivo or in vitro with two different evaluation techniques and to investigate if their results are comparable. Methods: A patient with terminal dentition was selected and four implants were placed using s-CAIS with a bone-supported stackable template. Segmentation used for designing a template was 3D printed, and then four implants were placed in the model following the same protocol as for s-CAIS. The model then underwent cone beam computed tomography (CBCT) and laboratory scanning to evaluate its accuracy. Data were uploaded to specific software, and accuracy values were automatically generated. Results: A statistical analysis was not attempted since all measurements were performed on the same patient and model. When descriptively comparing the accuracy of the two methods of treatment evaluation in the in vitro scenario, comparable results were obtained between IOS and CBCT, except for the angle. Conclusions: As the intraoral scanning procedure in fully edentulous patients is not yet clinically validated, utilizing CBCT can still be recommended for the accurate evaluation of computer-assisted implant placement.

Perovskite solar cells (PSCs) and modules are driving the energy revolution in the coming photovoltaic field. In the last 10 years, PSCs reached efficiency close to the silicon photovoltaic technology by adopting low-cost solution processes. Despite this, the noble metal (such as gold and silver) used in PSCs as a counter electrode made these devices costly in terms of energy, CO2 footprint, and materials. Carbon-based perovskite solar cells (C-PSCs) and modules use graphite/carbon-black-based material as the counter electrode. The formulation of low-cost carbon-based inks and pastes makes them suitable for large area coating techniques and hence a solid technology for imminent industrialization. Here, we want to present the upscaling routes of carbon-counter-electrode-based module devices in terms of materials formulation, architectures, and manufacturing processes in order to give a clear vision of the scaling route and encourage the research in this green and sustainable direction.

Introduction: The number of people with migrant status living in Europe is proliferating. Most of the refugees in Italy come from war zones, and many of them denounce having been victims of persecutory acts in their country of origin. Highly cultured migrant populations have shown better results and oral health behaviour than those who were poorly cultured. The PROTECT project aimed to build a network for the early management of head and neck pathologies among refugees and migrants, promoting the dissemination of correct information about the prevention and treatment of these pathologies. Materials and methods: A national cross-sectional study among the refugees and migrant population in the Lazio region, Italy, from February 2018 to September 2021 was performed. The oral health of 3023 participants was investigated within a network of 56 reception centres and cultural associations. Data collected via an oral health survey questionnaire gathered information on participants’ demographic factors, migration status and dental behaviours and clinical examinations of the participants with the help of mouth mirrors, periodontal probes and artificial light. Results: The mean age was 31.6 ± 13.1, and among all the subjects, 2058 were male (68.1%) and 965 were women (41.9%). Most participants were born in Nigeria, followed by Bangladesh, Pakistan, Somalia, Mali and Senegal. The overall oral pain prevalence was 48.2%. The prevalence of patients claiming poor oral hygiene was 32.4%; 36.2% of the subjects consumed high amounts of sugar; and 26.7% saw their dentist for a check-up in the last year. At the clinical examination, 68.9% of patients had caries experience (considering decay of deciduous teeth, and caries of permanent teeth and teeth with fillings), with 32.2% showing pulpal involvement. Low levels of oral hygiene were also found at the clinical examination, with 46.5% of patients presenting plaque and calculus. The trend of the DMFT index was found to be 5.41. Good periodontal health (CPI = 0) was present in approximately 33.5% of patients. The CPI = 1 index reported bleeding from gingivitis in 37% of patients; tartar was found in 27% of patients (CPI = 2). The percentage of patients with CPI = 3 was 3.6%. Just over half (52.2%) of the migrants examined had malocclusion, and only 0.7% had a malocclusion in treatment. Conclusions: The goal to be achieved is to develop education and prevention programs for head–neck diseases, and perhaps even more. The first step towards this goal can be removing the obstacles migrants encounter in accessing health care.

The therapeutic use of ozone has been suggested for a long time in general dentistry and paediatric dentistry for its antimicrobial, virucidal, disinfectant, and biocompatible properties. Ozone has also anti-inflammatory, analgesic, and immunostimulant properties, and it promotes tissue regeneration. Dental treatment in children is often complex and ozone could support the clinician to enhance the approach and prognosis with young patients, non-cooperant children, or special needs patients. The efficiency of ozone will certainly increase if studies continue to show positive outcomes in a growing number of dental paediatric conditions. This review explores the recent literature of ozone therapy in paediatric dentistry and suggests fields of application for future randomized controlled trials (RCTs).

The aim of this study was to develop smart materials with stimuli-responsive properties for the long-term protection of steel. The idea was to obtain a tailored and controlled release of protective agents in response to the environment stimuli. First, the protective efficacy of three inhibitors containing a carboxylic moiety, such as p-aminobenzoic (pAB), succinic (SA), and caffeic (CA) acids, was investigated in alkaline chloride solutions. The results revealed that pAB is the most effective protective agent, significantly better than SA and CA. It is surprising that the steel surface in the pAB solution remains unchanged even after 5 months of corrosion treatment, whereas the formation of degradation products in the SA and CA solutions was observed after only 6 days. Based on these findings, pAB was selected and used for the functionalization of silica nanoparticles and layered double hydroxides (LDHs) that can act as delivery vehicles and as an inhibitor reservoir. Specifically, pAB was chemisorbed on silica amino groups via an amide bond, and this makes possible a gradual inhibitor release induced by an alkaline environment. The intercalation of pAB in its anionic form into the LDHs structure is responsible for a completely different behavior since the release is induced by chloride ions and occurs by an anionic exchange reaction. Thus, these materials play a dual role by acting as an inhibitor reservoir and by capturing chlorides. These findings reveal that it is possible to create a reservoir of corrosion inhibitors gradually released on demand based on the chemical environment. The stimuli-responsive properties and the complementary protective action of inhibitor-loaded silica and LDHs make them attractive for the long-term protection of steel and open the way for innovative solutions in the preservation of concrete cultural heritage.

When investigating gilded artifacts or works of art, the determination of the gilding thickness plays a significant role in establishing restoration protocols or conservation strategies. Unfortunately, this is done by cross-sectioning the object, a destructive approach not always feasible. A non-destructive alternative, based on the differential attenuation of fluorescence radiation from the sample, has been developed in the past years, but due to the intrinsic random nature of X-rays, the study of single or few spots of an objects surface may yield biased information. Furthermore, considering the effects of both porosity and sample inhomogeneities is a practice commonly overlooked, which may introduce systematic errors. In order to overcome these matters, here we propose the extrapolation of the differential-attenuation method from single-spot X-ray fluorescence (XRF) measurements to macro-XRF (MA-XRF) scanning. In this work, an innovative algorithm was developed for evaluating the large amount of data coming from MA-XRF datasets and evaluate the thickness of a given overlapping layer over an area. This approach was adopted to study a gilded copper-based buckle from the sixteenth to seventeenth century found in Rome. The gilded object under investigation was also studied by other analytical techniques including scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). Previous results obtained from SEM-EDS were used to confront the data obtained with the proposed methodology and validate it. MA-XRF elemental distribution maps were fundamental in identifying and choosing sampling areas to calculate the thickness of the gilding layer, avoiding lead islands present in the sample that could negatively influence the results. Albeit the large relative standard deviation, the mean thickness values fell within those found in literature and those obtained from previous studies with SEM-EDS. Surface fissure has been found to deeply affect the results obtained, an aspect that is often disregarded.

Background: In recent years, the incidence of neoplastic diseases in children has increased significantly. Immunodepression triggers undesirable effects in the oral cavity such as mucositis, opportunistic infections, oral bleeding, xerostomia, dysgeusia, decay, dental malformations and pain. Objective: We aim to assess, through salivary tests, the quality of saliva in pediatric patients affected by oncohematological diseases and treated with chemo/radiotherapy compared to non-treated subjects. Methods: A total of 20 subjects aged between 5 and 18 years, with oncological pathologies undergoing radio and/or chemotherapy, were evaluated. The control group consisted of 20 healthy children of the same age. The two groups of subjects were asked to undergo salivary tests. Descriptive statistics were computed for each item. Fisher’s exact test was conducted to compare case and control groups. Results: Subjects treated with chemo/radiotherapy had a lower pH and therefore a higher salivary acidity that predisposes to caries and the oral hygiene of children with oncohematological diseases was more deficient than that of the control group. Conclusions: The early detection of these indicators, and the prevention carried out to limit their severity, is an important aspect of the comprehensive care of oncohematological subjects. Pediatric dentists can play a crucial a role enabling good quality of life during cancer therapy.

Cell separation and sorting are essential steps in cell biology research and in many diagnostic and therapeutic methods. Recently, there has been interest in methods which avoid the use of biochemical labels; numerous intrinsic biomarkers have been explored to identify cells including size, electrical polarizability, and hydrodynamic properties. This review highlights microfluidic techniques used for label-free discrimination and fractionation of cell populations. Microfluidic systems have been adopted to precisely handle single cells and interface with other tools for biochemical analysis. We analyzed many of these techniques, detailing their mode of separation, while concentrating on recent developments and evaluating their prospects for application. Furthermore, this was done from a perspective where inertial effects are considered important and general performance metrics were proposed which would ease comparison of reported technologies. Lastly, we assess the current state of these technologies and suggest directions which may make them more accessible. Figure A wide range of microfluidic technologies have been developed to separate and sort cells by taking advantage of differences in their intrinsic biophysical properties

An optimization work on dye-sensitized solar cells (DSSCs) based on both artificial and natural dyes was carried out by a fine synthesis work embedding gold nanoparticles in a TiO2 semiconductor and perfecting the TiO2 particle sizes of the scattering layer. Noble metal nanostructures are known for the surface plasmon resonance peculiarity that reveals unique properties and has been implemented in several fields such as sensing, photocatalysis, optical antennas and PV devices. By embedding gold nanoparticles in the mesoporous TiO2 layer and adding a scattering layer, we were able to boost the power conversion efficiency (PCE) to 10.8%, using an organic ruthenium complex. The same implementation was carried out using a natural dye, betalains, extracted from Sicilian prickly pear. In this case, the conversion efficiency doubled from 1 to 2% (measured at 1 SUN illumination, 100 mW/cm2 under solar simulation irradiation). Moreover, we obtained (measured at 0.1 SUN, 10 mW/cm2 under blue light LED irradiation) a record efficiency of 15% with the betalain-based dye, paving the way for indoor applications in organic natural devices. Finally, an attempt to scale up the system is shown, and a betalain-based- dye-sensitized solar module (DSSM), with an active area of 43.2 cm2 and a PCE of 1.02%, was fabricated for the first time.

Rebars corrosion phenomena can modify the structural behaviour of reinforced concrete (RC) members and consequently the seismic performance of RC structures. Since many existing RC structures are affected by this phenomenon, the influence of the reinforcement corrosion on the seismic performance is still under examination, especially when the corrosive attack is localized in the dissipative areas of the plastic hinges. In this work, the effect of localized corrosion is numerically investigated, through the adoption of a suitable finite element model, object of validation with the outcomes of an experimental campaign carried out in the Laboratory of the University of Rome “Tor Vergata”, on un-corroded and corroded RC columns subjected to axial load and cyclic horizontal actions. Particular attention has been paid to the definition of the three-dimensional model and to the modelling of the corroded rebars and their corrosion morphology. Indeed, different modelling strategies are proposed with the aim to properly simulate the cyclic behaviour of the corroded columns. The main results show how more refined strategies taking into account the morphological aspects of the corrosion phenomenon produce a better fit with the experimental results for both Damage Control and Life Safety limit states performance.

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-A2BC push–pull ZnII porphyrins, characterized by a strong and directional electron excitation process along the push–pull system, have been extensively investigated. On the other hand, A4 β-pyrrolic substituted tetraaryl ZnII 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 A4 β-substituted ZnII 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.

To investigate temporomandibular joint (TMJ) involvement signs such as muscle pain, the ratio of masseter and temporal muscle activity, mouth opening width and jaw deviation during mouth opening in children and adolescents with juvenile idiopathic arthritis (JIA), a group of 32 subjects with JIA and a control group of 32 healthy subjects were evaluated. Data were collected clinically by muscle palpation (masseters, anterior temporalis and sternocleidomastoids) and instrumental analysis (electromyography and kinesiography). Higher pain was registered in the masseter and sternocleidomastoid muscles on both sides and in the right anterior temporalis in the JIA group compared to the control group (p < 0.05). Electromyography showed no statistically significant difference in the frequency of the pathological ratio of masseter and temporal muscle activity (MM/TA < 1) both in the JIA group and in the control group. Kinesiography showed a statistically significant difference in mouth opening width and jaw deviation during mouth opening between the groups (p < 0.05): JIA subjects showed lower mouth opening values and wider deviation on mouth opening; 29 out of 32 JIA subjects showed jaw deviation towards the right side. JIA affects the TMJ, causing myalgia in the head and neck muscles, a reduction in mouth opening width and an increase in jaw deviation during mouth opening.

Measurement of NO2 at low concentrations (tens of ppts) is non-trivial. A variety of techniques exist, with the conversion of NO2 into NO followed by chemiluminescent detection of NO being prevalent. Historically this conversion has used a catalytic approach (molybdenum); however, this has been plagued with interferences. More recently, photolytic conversion based on UV-LED irradiation of a reaction cell has been used. Although this appears to be robust there have been a range of observations in low-NOx environments which have measured higher NO2 concentrations than might be expected from steady-state analysis of simultaneously measured NO, O3, jNO2, etc. A range of explanations exist in the literature, most of which focus on an unknown and unmeasured “compound X” that is able to convert NO to NO2 selectively. Here we explore in the laboratory the interference on the photolytic NO2 measurements from the thermal decomposition of peroxyacetyl nitrate (PAN) within the photolysis cell. We find that approximately 5 % of the PAN decomposes within the instrument, providing a potentially significant interference. We parameterize the decomposition in terms of the temperature of the light source, the ambient temperature, and a mixing timescale ( ∼ 0.4 s for our instrument) and expand the parametric analysis to other atmospheric compounds that decompose readily to NO2 (HO2NO2, N2O5, CH3O2NO2, IONO2, BrONO2, higher PANs). We apply these parameters to the output of a global atmospheric model (GEOS-Chem) to investigate the global impact of this interference on (1) the NO2 measurements and (2) the NO2 : NO ratio, i.e. the Leighton relationship. We find that there are significant interferences in cold regions with low NOx concentrations such as the Antarctic, the remote Southern Hemisphere, and the upper troposphere. Although this interference is likely instrument-specific, the thermal decomposition to NO2 within the instrument's photolysis cell could give an at least partial explanation for the anomalously high NO2 that has been reported in remote regions. The interference can be minimized by better instrument characterization, coupled to instrumental designs which reduce the heating within the cell, thus simplifying interpretation of data from remote locations.

The observations collected during the BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS) campaign in summer 2011 over Canada are analysed to study the impact of forest fire emissions on the formation of ozone (O3) and total peroxy nitrates ∑PNs, ∑ROONO2). The suite of measurements on board the BAe-146 aircraft, deployed in this campaign, allows us to calculate the production of O3 and of ∑PNs, a long-lived NOx reservoir whose concentration is supposed to be impacted by biomass burning emissions. In fire plumes, profiles of carbon monoxide (CO), which is a well-established tracer of pyrogenic emission, show concentration enhancements that are in strong correspondence with a significant increase of concentrations of ∑PNs, whereas minimal increase of the concentrations of O3 and NO2 is observed. The ∑PN and O3 productions have been calculated using the rate constants of the first- and second-order reactions of volatile organic compound (VOC) oxidation. The ∑PN and O3 productions have also been quantified by 0-D model simulation based on the Master Chemical Mechanism. Both methods show that in fire plumes the average production of ∑PNs and O3 are greater than in the background plumes, but the increase of ∑PN production is more pronounced than the O3 production. The average ∑PN production in fire plumes is from 7 to 12 times greater than in the background, whereas the average O3 production in fire plumes is from 2 to 5 times greater than in the background. These results suggest that, at least for boreal forest fires and for the measurements recorded during the BORTAS campaign, fire emissions impact both the oxidized NOy and O3, but (1 ∑PN production is amplified significantly more than O3 production and (2) in the forest fire plumes the ratio between the O3 production and the ∑PN production is lower than the ratio evaluated in the background air masses, thus confirming that the role played by the ∑PNs produced during biomass burning is significant in the O3 budget. The implication of these observations is that fire emissions in some cases, for example boreal forest fires and in the conditions reported here, may influence more long-lived precursors of O3 than short-lived pollutants, which in turn can be transported and eventually diluted in a wide area.

The integration of nanoparticles (NPs) into functional materials is a powerful tool for the smart engineering of their physical properties. If properly designed and optimized, NPs possess unique optical, electrical, quantum, and other effects that will improve the efficiency of optoelectronic devices. Here, we propose a novel approach for the enhancement of perovskite light-emitting diodes (PeLEDs) based on electronic band structure deformation by core-shell NPs forming a metal-oxide-semiconductor (MOS) structure with an Au core and SiO2 shell located in the perovskite layer. The presence of the MOS interface enables favorable charge distribution in the active layer through the formation of hole transporting channels. For the PeLED design, we consider integration of the core-shell NPs in the realistic numerical model. Using our verified model, we show that, compared with the bare structure, the incorporation of NPs increases the radiative recombination rate of PeLED by several orders of magnitude. It is intended that this study will open new perspectives for further efficiency enhancement of perovskite-based optoelectronic devices with NPs.

The aim of the study is to observe retrospectively the correlation between Oral Squamous Cell Carcinoma (OSCC) and risk factors; including tobacco, alcohol and Family History of Cancer (FHC). A total of 478 patients were included retrospectively from the database of the Department of Oral Sciences and Maxillofacial Surgery, Sapienza University of Rome. A Test Group (TG) consisted of 239 patients with a confirmed diagnosis of OSCC. A Control Group (CG) consisted of 239 patients without history and/or diagnosis of oral cancer. The logistic regression models were used to calculate the adjusted Odd Ratios (ORs) associated with alcohol, tobacco and FHC; including the General Family History of Cancer (GFHC) and Family History of Head and Neck Cancer (FHHNC) and their 95% Confidence Intervals (CI). The high rate of tobacco consumption was associated with an OR of 1.035 (95% CI 1.001–1.070) and a statistical significance (p = 0.041). Drinker patients showed a significant risk of developing OSCC (p = 0.05) and the OR was 1.035 (95% CI 1.010–1.061). The GFHC was associated with a marginal risk of OSCC with an OR of 1.095 (95% CI 0.953–1.259), without significance (p = 0.199). The FHHNC showed a notable risk increase with an OR of 1.871 (95% CI 0.902–3.882), without significance (p = 0.092). Alcohol and tobacco may be associated with an increase in the risk of OSCC.

Background: Titanium implant surfaces are continuously modified to improve biocompatibility and to promote osteointegration. Graphene oxide (GO) has been successfully used to ameliorate biomaterial performances, in terms of implant integration with host tissue. The aim of this study is to evaluate the Dental Pulp Stem Cells (DPSCs) viability, cytotoxic response, and osteogenic differentiation capability in the presence of GO-coated titanium surfaces. Methods: Two titanium discs types, machined (control, Crtl) and sandblasted and acid-etched (test, Test) discs, were covalently functionalized with GO. The ability of the GO-functionalized substrates to allow the proliferation and differentiation of DPSCs, as well as their cytotoxic potential, were assessed. Results: The functionalization procedures provide a homogeneous coating with GO of the titanium surface in both control and test substrates, with unchanged surface roughness with respect to the untreated surfaces. All samples show the deposition of extracellular matrix, more pronounced in the test and GO-functionalized test discs. GO-functionalized test samples evidenced a significant viability, with no cytotoxic response and a remarkable early stage proliferation of DPSCs cells, followed by their successful differentiation into osteoblasts. Conclusions: The described protocol of GO-functionalization provides a novel not cytotoxic biomaterial that is able to stimulate cell viability and that better and more quickly induces osteogenic differentiation with respect to simple titanium discs. Our findings pave the way to exploit this GO-functionalization protocol for the production of novel dental implant materials that display improved integration with the host tissue.

The gasification of lignite could be a promising sustainable alternative to combustion, because it causes reduced emissions and allows the production of syngas, which is a versatile gaseous fuel that can be used for cogeneration, Fischer-Tropsch synthesis, or the synthesis of other bio-fuels, such as methanol. For the safe and smooth exploitation of syngas, it is fundamental to have a high quality gas, with a high content of H2 and CO and minimum content of pollutants, such as particulate and tars. In this work, experimental tests on lignite gasification are carried out in a bench-scale fluidized-bed reactor with olivine as bed material, chosen for its catalytic properties that can enhance tar reduction. Some operating parameters were changed throughout the tests, in order to study their influence on the quality of the syngas produced, and pressure fluctuation signals were acquired to evaluate the fluidization quality and diagnose correlated sintering or the agglomeration of bed particles. The effect of temperature and small air injections in the freeboard were investigated and evaluated in terms of the conversion efficiencies, gas composition, and tar produced.

Children with autism spectrum disorder (ASD) have significantly higher prevalence and caries severity compared to the average population. Knowledge about the oral health indices of children with this mental disorder is key to designing efficient plans of intervention. This paper reports the results of a study on the oral health status of children with ASD in central Italy. This is the first study of this type in Italy. The sample consists of 229 autistic children aged between 5 and 14 years, attending the Unit of Special Needs Policlinico Umberto I in Rome. Each patient received an intraoral examination to investigate decayed, missing, and filled teeth as well as periodontal status. Information on demographic attributes, dietary habits, medical history, and child’s cooperativeness at the first visit was also recorded. Of the participants, 79.26% presented signs of gingivitis and about 90% of them had plaque. Caries prevalence was 66.38%. The average of the total number of decayed, missing, and filled teeth in the permanent and primary dentition was 2.91. Among the factors considered, only dietary habits and the periodontal indices showed statistically significant association with caries prevalence and caries severity. Despite the selection bias, that prevents us to interpret the results presented as epidemiological evidence, our study suggests that children with ASD in central Italy represent a population at risk.

The Kathmandu Valley in south Asia is considered as one of the global "hot spots" in terms of urban air pollution. It is facing severe air quality problems as a result of rapid urbanization and land use change, socioeconomic transformation, and high population growth. In this paper, we present the first full year (February 2013–January 2014) analysis of simultaneous measurements of two short-lived climate forcers/pollutants (SLCF/P), i.e., ozone (O3) and equivalent black carbon (hereinafter noted as BC) and aerosol number concentration at Paknajol, in the city center of Kathmandu. The diurnal behavior of equivalent BC and aerosol number concentration indicated that local pollution sources represent the major contributions to air pollution in this city. In addition to photochemistry, the planetary boundary layer (PBL) and wind play important roles in determining O3 variability, as suggested by the analysis of seasonal changes of the diurnal cycles and the correlation with meteorological parameters and aerosol properties. Especially during pre-monsoon, high values of O3 were found during the afternoon/evening. This could be related to mixing and entrainment processes between upper residual layers and the PBL. The high O3 concentrations, in particular during pre-monsoon, appeared well related to the impact of major open vegetation fires occurring at the regional scale. On a synoptic-scale perspective, westerly and regional atmospheric circulations appeared to be especially conducive for the occurrence of the high BC and O3 values. The very high values of SLCF/P, detected during the whole measurement period, indicated persisting adverse air quality conditions, dangerous for the health of over 3 million residents of the Kathmandu Valley, and the environment. Consequently, all of this information may be useful for implementing control measures to mitigate the occurrence of acute pollution levels in the Kathmandu Valley and surrounding area.

Airborne measurements of biomass burning organic aerosol (BBOA) from boreal forest fires reveal highly contrasting properties for plumes of different ages. These measurements, performed using an Aerodyne Research Inc. compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) during the BORTAS (quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment in the summer of 2011, have been used to derive normalised excess organic aerosol (OA) mass concentrations (ΔOA / ΔCO), with higher average ratios observed closer to source (0.190±0.010) than in the far-field (0.097±0.002). The difference in ΔOA / ΔCO between fresh and aged plumes is influenced by a change in dominant combustion conditions throughout the campaign. Measurements at source comprised 3 plume interceptions during a single research flight and sampled largely smouldering fires. Twenty-three interceptions were made across four flights in the far-field, with plumes originating from fires occurring earlier in the campaign when fire activity had been more intense, creating an underlying contrast in emissions prior to any transformations associated with aging. Changing combustion conditions also affect the vertical distribution of biomass burning emissions, as aged plumes from more flaming-dominated fires are injected to higher altitudes of up to 6000 m. Proportional contributions of the mass-to-charge ratio (m/z) 60 and 44 peaks in the AMS mass spectra to the total OA mass (denoted f60 and f44) are used as tracers for primary and oxidised BBOA, respectively. f44 is lower on average in near-field plumes than those sampled in the far-field, in accordance with longer aging times as plumes are transported a greater distance from source. However, high levels of ΔO3 / ΔCO and −log(NOx / NOy) close to source indicate that emissions can be subject to very rapid oxidation over short timescales. Conversely, the lofting of plumes into the upper troposphere can lead to the retention of source profiles after transportation over extensive temporal and spatial scales, with f60 also higher on average in aged plumes. Evolution of OA composition with aging is comparable to observations of BB tracers in previous studies, revealing a consistent progression from f60 to f44. The elevated levels of oxygenation in aged plumes, and their association with lower average ΔOA / ΔCO, are consistent with OA loss through evaporation during aging due to a combination of dilution and chemical processing, while differences in combustion conditions throughout the campaign also have a significant influence on BBOA production and composition.

Chemical modelling studies have been conducted over north-western Europe in summer conditions, showing that night-time dinitrogen pentoxide (N2O5) heterogeneous reactive uptake is important regionally in modulating particulate nitrate and has a~modest influence on oxidative chemistry. Results from Weather Research and Forecasting model with Chemistry (WRF-Chem) model simulations, run with a detailed volatile organic compound (VOC) gas-phase chemistry scheme and the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) sectional aerosol scheme, were compared with a series of airborne gas and particulate measurements made over the UK in July 2010. Modelled mixing ratios of key gas-phase species were reasonably accurate (correlations with measurements of 0.7–0.9 for NO2 and O3). However modelled loadings of particulate species were less accurate (correlation with measurements for particulate sulfate and ammonium were between 0.0 and 0.6). Sulfate mass loadings were particularly low (modelled means of 0.5–0.7 μg kg−1air, compared with measurements of 1.0–1.5 μg kg−1air). Two flights from the campaign were used as test cases – one with low relative humidity (RH) (60–70%), the other with high RH (80–90%). N2O5 heterogeneous chemistry was found to not be important in the low-RH test case; but in the high-RH test case it had a strong effect and significantly improved the agreement between modelled and measured NO3 and N2O5. When the model failed to capture atmospheric RH correctly, the modelled NO3 and N2O5 mixing ratios for these flights differed significantly from the measurements. This demonstrates that, for regional modelling which involves heterogeneous processes, it is essential to capture the ambient temperature and water vapour profiles. The night-time NO3 oxidation of VOCs across the whole region was found to be 100–300 times slower than the daytime OH oxidation of these compounds. The difference in contribution was less for alkenes (× 80) and comparable for dimethylsulfide (DMS). However the suppression of NO3 mixing ratios across the domain by N2O5 heterogeneous chemistry has only a very slight, negative, influence on this oxidative capacity. The influence on regional particulate nitrate mass loadings is stronger. Night-time N2O5 heterogeneous chemistry maintains the production of particulate nitrate within polluted regions: when this process is taken into consideration, the daytime peak (for the 95th percentile) of PM10 nitrate mass loadings remains around 5.6 μg kg−1air, but the night-time minimum increases from 3.5 to 4.6 μg kg−1air. The sustaining of higher particulate mass loadings through the night by this process improves model skill at matching measured aerosol nitrate diurnal cycles and will negatively impact on regional air quality, requiring this process to be included in regional models.

Aerosol chemical composition was found to influence nighttime atmospheric chemistry during a series of airborne measurements in northwestern Europe in summer conditions, which has implications for regional air quality and climate. The uptake of dinitrogen pentoxide, γ (N2O5), to particle surfaces was found to be modulated by the amount of water content and ammonium nitrate present in the aerosol. The conditions prevalent in this study suggest that the net uptake rate of N2O5 to atmospheric aerosols was relatively efficient compared to previous studies, with γ (N2O5) values in the range 0.01–0.03. This is likely a consequence of the elevated relative humidity in the region, which promotes greater aerosol water content. Increased nitrate concentrations relative to particulate water were found to suppress N2O5 uptake. The results presented here contrast with previous ambient studies of N2O5 uptake, which have generally taken place in low-nitrate environments in the USA. Comparison of the N2O5 uptake derived from the measurements with a parameterised scheme that is based on the ratio of particulate water to nitrate yielded reasonably good agreement in terms of the magnitude and variation in uptake, provided the effect of chloride was neglected. An additional suppression of the parameterised uptake is likely required to fully capture the variation in N2O5 uptake, which could be achieved via the known suppression by organic aerosol. However, existing parameterisations representing the suppression by organic aerosol were unable to fully represent the variation in N2O5 uptake. These results provide important ambient measurement constraint on our ability to predict N2O5 uptake in regional and global aerosol models. N2O5 uptake is a potentially important source of nitrate aerosol and a sink of the nitrate radical, which is the main nocturnal oxidant in the atmosphere. The results further highlight the importance of ammonium nitrate in northwestern Europe as a key component of atmospheric composition in the region.

The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the AtmOsphere) aircraft campaign during July 2010 and January 2011 made observations of OH, HO2, NO3, N2O5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurements of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model constrained by the concentrations of the longer lived species using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with model predictions. The model systematically underpredicts HO2 by ~200% and overpredicts NO3 and N2O5 by around 80 and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3x=NO3+N2O5) family. Production of NO3x is overwhelmingly dominated by the reaction of NO2 with O3, whereas its loss is dominated by aerosol uptake of N2O5, with NO3+VOCs (volatile organic compounds) and NO3+RO2 playing smaller roles. The production of HOx and ROx radicals is mainly due to the reaction of NO3 with VOCs. The loss of these radicals occurs through a combination of HO2+RO2 reactions, heterogeneous processes and production of HNO3 from OH+NO2, with radical propagation primarily achieved through reactions of NO3 with peroxy radicals. Thus NO3 at night plays a similar role to both OH and NO during the day in that it both initiates ROx radical production and acts to propagate the tropospheric oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed and we find that a value of γN2O5=0.05 improves model simulations for NO3 and N2O5, but that these improvements are at the expense of model success for HO2. Improvements to model simulations for HO2, NO3 and N2O5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.

Several studies have provided information on environmental nanoplastic particles/debris, but the in vitro cyto-genotoxicity is still insufficiently characterized. The aim of this study is to analyze the effects of polystyrene nanoparticles (PNPs) in the Hs27 cell line. The viability of Hs27 cells was determined following exposure at different time windows and PNP concentrations. The genotoxic effects of the PNPs were evaluated by the cytokinesis-block micronucleus (CBMN) assay after exposure to PNPs. We performed ROS analysis on HS27 cells to detect reactive oxygen species at different times and treatments in the presence of PNPs alone and PNPs added to the Crocus sativus L. extract. The different parameters of the CBMN test showed DNA damage, resulting in the increased formation of micronuclei and nuclear buds. We noted a greater increase in ROS production in the short treatment times, in contrast, PNPs added to Crocus sativus extract showed the ability to reduce ROS production. Finally, the SEM-EDX analysis showed a three-dimensional structure of the PNPs with an elemental composition given by C and O. This work defines PNP toxicity resulting in DNA damage and underlines the emerging problem of polystyrene nanoparticles, which extends transversely from the environment to humans; further studies are needed to clarify the internalization process.

Two different high potential Zn(II) porphyrin designs carrying either 4 or 5 meso pentafluorophenyl moieties as electron acceptor groups and a further electron withdrawing branch inserted in either the β (1) or meso (2) position were tested in photoelectrosynthetic cells for HBr splitting. Photoaction spectra in the presence of HBr showed that red photons up to 700 nm could be harvested and converted and that 2 performed better than 1, thanks to better electronic properties of the excited state, favored by the insertion of the benzothiadiazole electron withdrawing group. Photoanodic performances in the presence of HBr, however, remained low, due to inefficient regeneration of the oxidized sensitizer as a result of an insufficient driving force for Br− oxidation.

In this work, we studied the manufacturing processes and the conservation state of gilt and painted leather fragments from Palazzo Chigi in Ariccia (Italy) by using different analytical techniques. Leather fragments present a silver leaf superimposed onto leather support. A gold varnish and different painted layers decorate it all. A top-down analytical approach was used to investigate this complex multilayer structure, which adopted techniques with different sampling depths. Organic and inorganic constitutive materials together with related degradation products were studied by time of flight secondary ion mass spectrometry (ToF-SIMS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and macro X-ray fluorescence (MA-XRF). The findings have revealed the presence of different elements and species as calcium and iron in the leather support, which was attributed to the un-hairing process in the leather tanning. Regarding what concerns the silver leaf, where the varnish cracked, silver chlorides, oxides, and sulfides were detected as degradation products of the silver leaf. Proteinaceous compounds were also identified where the silver leaf is unprotected by the varnish. These ion signals reveal a potential use of animal glue on both sides of the silver leaf to promote durable adhesion. In the gold varnish, the surface analysis revealed organic compounds such as resins and oils. In particular, the copresence of linoleic, arachidonic, and lignoceric acid ion signals in the yellow area suggests the use of aloe as a colorant. Lead ions in the same area were detected and attributed to the use of lead as siccative. Blue areas were obtained by using indigo and lead white in addition to an oil binder. This is confirmed by the detection of indigotin, fatty acid, and lead soap ion signals. A copper-based pigment was used to depict the green areas and copper oxalates were identified as its degradation products. Lastly, no significant information about the red colorant was obtained. Colophony is present as a component of the final varnish.

(1) Background: The aim of this study was to optimize, through a cheap and facile protocol, the covalent functionalization of graphene oxide (GO)-decorated cortical membrane (Lamina®) in order to promote the adhesion, the growth and the osteogenic differentiation of DPSCs (Dental Pulp Stem Cells); (2) Methods: GO-coated Laminas were fully characterized by Scannsion Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) analyses. In vitro analyses of viability, membrane integrity and calcium phosphate deposition were performed; (3) Results: The GO-decorated Laminas demonstrated an increase in the roughness of Laminas, a reduction in toxicity and did not affect membrane integrity of DPSCs; and (4) Conclusions: The GO covalent functionalization of Laminas was effective and relatively easy to obtain. The homogeneous GO coating obtained favored the proliferation rate of DPSCs and the deposition of calcium phosphate.

We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

We describe the design and execution of the BORTAS (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment, which has the overarching objective of understanding the chemical aging of air masses that contain the emission products from seasonal boreal wildfires and how these air masses subsequently impact downwind atmospheric composition. The central focus of the experiment was a two-week deployment of the UK BAe-146-301 Atmospheric Research Aircraft (ARA) over eastern Canada, based out of Halifax, Nova Scotia. Atmospheric ground-based and sonde measurements over Canada and the Azores associated with the planned July 2010 deployment of the ARA, which was postponed by 12 months due to UK-based flights related to the dispersal of material emitted by the Eyjafjallajökull volcano, went ahead and constituted phase A of the experiment. Phase B of BORTAS in July 2011 involved the same atmospheric measurements, but included the ARA, special satellite observations and a more comprehensive ground-based measurement suite. The high-frequency aircraft data provided a comprehensive chemical snapshot of pyrogenic plumes from wildfires, corresponding to photochemical (and physical) ages ranging from < 1 day to ~<45 sr 10 days, largely by virtue of widespread fires over Northwestern Ontario. Airborne measurements reported a large number of emitted gases including semi-volatile species, some of which have not been been previously reported in pyrogenic plumes, with the corresponding emission ratios agreeing with previous work for common gases. Analysis of the NOy data shows evidence of net ozone production in pyrogenic plumes, controlled by aerosol abundance, which increases as a function of photochemical age. The coordinated ground-based and sonde data provided detailed but spatially limited information that put the aircraft data into context of the longer burning season in the boundary layer. Ground-based measurements of particulate matter smaller than 2.5 μm (PM2.5) over Halifax show that forest fires can on an episodic basis represent a substantial contribution to total surface PM2.5.