Search

The adrenal gland of the lizard Podarcis sicula is formed by a dorsal ribbon of chromaffin cells, generally defined as medullary tissue, arranged along a central part of steroidogenic cells considered as cortical tissue. These two tissues produce catecholamines and steroids as part of the hypothalamo-hypophyseal-adrenal gland axis. Recent studies have demonstrated that Podarcis sicula adrenal gland is not only under hypothalamo-hypophyseal axis control but that several peptides may influence the physiological activity of the gland; among these, vasoactive intestinal peptide is able to enhance strongly both catecholamine and steroid hormone production. The aim of the present study was to verify whether vasoactive intestinal peptide administration could become deleterious. For this reason, we monitored the pattern of expression of two members of the Bcl-2 family, Bcl-2 and Bax, in control and vasoactive intestinal peptide treated specimens. Furthermore, we also tested if peptide treatment induces apoptosis by TUNEL assay.

In this work, an experimental investigation of the nanomechanical properties of flame-formed carbonaceous particle layers has been performed for the first time by means of Atomic Force Microscopy (AFM). To this aim, carbon nanoparticles with different properties and nanostructures were produced in ethylene/air laminar premixed flames at different residence times. Particles were collected on mica substrates by means of a thermophoretic sampling system and then analyzed by AFM. An experimental procedure based on the combination between semi-contact AFM topography imaging, contact AFM topography imaging and AFM force spectroscopy has been implemented. More specifically, a preliminary topological characterization of the samples was first performed operating AFM in semi-contact mode and then tip-sample interaction forces were measured in contact spectroscopy mode. Finally, semi-contact mode was used to image the indented surface of the samples and to retrieve the projected area of indents. The hardness of investigated samples was obtained from the force–distance curves measured in spectroscopy mode and the images of intends acquired in semi-contact mode. Moreover, the Young’s modulus was measured by fitting the linear part of the retraction force curves using a model based on the Hertz theory. The extreme force sensitivity of this technique (down to nNewton) in addition to the small size of the probe makes it extremely suitable for performing investigation of mechanical properties of materials at the nanoscale. The experimental procedure was successfully tested on reference materials characterized by different plastic behavior, e.g., polyethylene naphthalate and highly oriented pyrolytic graphite. Both hardness and Young’s modulus values obtained from AFM measurements for different soot particle films were discussed.

Nanostructured films of carbon and TiO2 nanoparticles have been produced by means of a simple two-step procedure based on flame synthesis and thermophoretic deposition. At first, a granular carbon film is produced on silicon substrates by the self-assembling of thermophoretically sampled carbon nanoparticles (CNPs) with diameters of the order of 15 nm. Then, the composite film is obtained by the subsequent thermophoretic deposition of smaller TiO2 nanoparticles (diameters of the order of 2.5 nm), which deposit on the surface and intercalate between the carbon grains by diffusion within the pores. A bipolar resistive switching behavior is observed in the composite film of CNP-TiO2. A pinched hysteresis loop is measured with SET and RESET between low resistance and high resistance states occurring for the electric field of 1.35 × 104 V/cm and 1.5 × 104 V/cm, respectively. CNP-TiO2 film produced by flame synthesis is initially in the low resistive state and it does not require an electroforming step. The resistance switching phenomenon is attributed to the formation/rupture of conductive filaments through space charge mechanism in the TiO2 nanoparticles, which facilitate/hinder the electrical conduction between carbon grains. Our findings demonstrate that films made of flame-formed CNP-TiO2 nanoparticles are promising candidates for resistive switching components.

Molecules constituting nascent soot particles have been analyzed by two-step laser desorption laser ionization mass spectrometry. Three samples have been collected from a slightly sooting ethylene/air premixed flame with the aim to investigate soot composition in the transition from nucleated to just-grown soot particles. Sampling locations have been selected based on the evolution of the particle size distribution along the flame axis. The mass spectrometric results point to a strong evolution of the molecular composition. Just-nucleated soot is rich in polycyclic aromatic hydrocarbons (PAHs) dominated by medium sizes from 18 to 40 carbon atoms but containing sizes as large as 90 carbon atoms. Most abundant PAHs are in the form of peri-condensed structures. The presence of a large fraction of odd numbered carbon species shows that pentagonal cycles are a common feature of the detected population. Increasing the distance from the burner outlet, i.e., the particle residence time in flame, leads to an evolution of the chemical composition of this population with a major contribution of carbon clusters including also fullerenes up to about 160 carbon atoms. Our data support a scenario in which large PAHs containing pentagonal rings evolve very efficiently upon thermal processing by a series of dehydrogenation and isomerization processes to form fullerenes. This chemistry happens in the early steps of soot growth showing that carbonization is already active at this stage. © 2020 The Authors. Published by Elsevier Inc. on behalf of The Combustion Institute. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)

In this work, we present particle size distribution (PSD), electron paramagnetic resonance (EPR) and Raman spectroscopy measurements of soot particles, collected across the inception region, in two ethylene-air premixed laminar flames and two flames obtained by substituting 30% of the ethylene carbon with benzene. The experimental results are used to investigate the effect of aromatic fuel on the nature and role of radicals in particle nucleation and growth. For all the particles sampled, both in pure ethylene flames and in the ethylene/benzene ones, an EPR signal typical of persistent carbon-centered aromatic radicals is measured. The results point out an involvement of π-radicals during particle nucleation and initial growth process. Under the conditions investigated, our results show that the electron spin density of particles produced by different fuels is mainly related to the amount of H-atoms available in the particles. Moreover, for all the investigated flames, the spin density presents an inverse dependence with the particle size suggesting that particle surface plays an important role in the early steps of the soot formation process.

TiO2 in the form of nanoparticles is characterized by high photocatalytic activity and high resistance to oxidation, making it an excellent candidate to realize coatings for improving the corrosion resistance of aluminium surfaces. Different coating technologies have been proposed over the years, which often involve the use of toxic compounds and very high temperatures. In this work, an alternative and novel one-step method for the coating of aluminium alloy surfaces with titania nanoparticles is presented. The method is based on the combination of aerosol flame synthesis and direct thermophoretic deposition and allows to produce nanostructured thin coating layers of titania with different features. Specifically, 3.5 nm anatase nanoparticles were synthesized and deposited onto aluminium alloy AA2024 samples. The thickness of the coating was changed by modifying the total deposition time. A thermal annealing treatment was developed to improve the adhesion of nano-titania on the substrates, and the morphology and structures of the coatings were characterized using (ultra violet) UV-vis absorption, scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. The corrosion resistance behavior of the coatings was evaluated by means of electrochemical polarization measurements, coupled with a numerical analysis using COMSOL software. Both the experimental and numerical electrochemical polarization curves showed a significant increase in the corrosion potential of coated substrates with respect to the bare aluminium and a decrease in the current density. The coatings obtained with higher deposition time and greater thickness showed the best performances in terms of the resistance of the aluminium surfaces to corrosion.

The electronic band gap of flame-formed carbon nanoparticles (CNPs) is determined for the first time using scanning tunneling spectroscopy (STS). Flame-formed CNPs are sampled from a laminar, burner-stabilized stagnation ethylene-air flame through in-situ insertion of gold-coated mica substrates, on which CNPs are collected as thin films. Optical band gap measurements using UV-vis absorption spectroscopy are also performed to compare with the STS measurements. The suitability of STS in measuring electronic band gaps is first demonstrated through measurements using reference materials: the electronic band gaps of naphthalene, pyrene, and coronene are found to be slightly larger than the respective optical band gaps, as expected, because of the over potential in the presence of a current. Flame-formed CNPs of three different particle size distributions were sampled and tested. The electronic band gap of each CNP shows a clear size-dependency that supports the earlier conclusion (Liu et al. Proc. Natl. Acad. Sci. U.S.A. 116 (2019) 12692-12697) that flame-formed CNPs exhibit apparent quantum confinement or quantum-dot behaviors. Furthermore, the measured electronic band gaps matches the respective optical results within the experimental uncertainty of 0.1-0.2 eV. The over potential observed in PAH samples is not present in CNP sampls, which may indicate stronger intermolecular interactions between the PAHs constituting the CNPs than those of crystalline PAHs.

Although the majority of existing combustion devices operate at high pressure conditions, most of our understanding of the soot formation process and soot physicochemical properties rely on studies performed at atmospheric pressure. Pressure is known to have nonlinear effects on combustion processes and a significant influence on soot formation; soot loading increases with increasing combustion pressure. Soot characteristics directly affect soot oxidation and optical/radiative properties, and it is desirable to have a better insight into them under high-pressure conditions. Due to scarcity of information on soot primary particles, aggregate morphology, and soot nanostructure relevant to high-pressure combustion, there are challenges in predicting soot oxidation and radiation, particularly at engine-relevant conditions. In this study, we perform Raman spectroscopy measurements on soot sampled from a set of laminar diffusion flames of ethylene at various pressures, ranging from atmospheric pressure to 12 bar. Our results show an increase in soot maturity as the pressure increases within the range of investigated pressures. In the examined co-flow flames, pressure seems to have an indirect influence on soot nanostructure through an earlier inception of soot, resulting in longer residence times of the carbon soot particles in the hot and reactive flame environment. It is found that soot maturity, tracked through the size of graphitic domains, La, increases linearly with residence times. The longer residence time of soot in high-pressure flames could be the main cause of the higher degree of graphitization observed, which suggests a greater resistance to oxidation with increasing pressure.

Reactive adsorption of hydrogen sulphide (H2S) from gaseous streams at room temperature with mixed Zn and Cu active phase supported onto γ-alumina is dealt in this manuscript. Sorbents with a fixed total metal content and variable Cu:Zn ratios were prepared by impregnation of commercial γ-alumina spheres in order to investigate the role of the support and the possible synergic effect between the two metals on the adsorption mechanism and performance. H2S (500–3000 ppmv in N2) removal tests were run under dynamic conditions at 30 °C. Experimental techniques such as BET and pore size distribution by N2-adsorption, SEM-EDX, XRD and DRIFT analysis were coupled for the characterization of fresh and spent sorbents. TPD/TPO experiments on saturated sorbents were performed to assess their regenerability and allowed the speciation of adsorbed sulphur species, testifying the complexity of the surface reactions and the effect of the support.

TiO2 in the form of nanocrystals possesses photocatalyst properties leading to excellent capability of degrading a number of environmental contaminants such as organics, bacteria, and viruses. However, the antimicrobial activity of nano-TiO2 coatings against different microorganisms is not yet well established. Candida albicans, Aspergillus niger, Staphylococcus aureus and Streptococcus mutans are common nosocomial and environmental pathogens responsible for biofilm-associated infections especially in indoor environments. In this study, we produced thin coatings of TiO2 nanoparticles on aluminum substrates and assessed whether they may prevent fungi and bacteria biofilm formation and whether this may be a synergistic effect of TiO2 nanoparticles with UV irradiation, which is more representative of the natural conditions for passive devices. Coatings of flame-synthesized nanoparticles were produced by direct thermophoretic deposition on aluminum substrates through a rotating disk inserted in the flame. Particle and coating characterization was performed by means of differential mobility analysis, Raman and X-ray diffraction spectroscopy. Microbial biofilm formation on substrates with different TiO2 thicknesses were evaluated by the colorimetric crystal violet method and quantified by spectrophotometry in four different fungi and bacteria strains; the results were corroborated by scanning electron microscopy analysis. Substrates with minimal TiO2 nanoparticle layers demonstrated a strong anti-biofilm effect against both fungi and bacteria, due to the well-known cellular component photo-oxidation and to the enhanced nanomaterial surface area. Interestingly, UV irradiation of the substrates at a low intensity for a short time demonstrated a significant enhancement of the titania antimicrobial activity. TiO2 nanoparticle coatings may be proposed as self-cleaning and self-disinfecting materials able to reduce microbial infections, especially in indoor environments where hygiene is needed.

The early stages of soot formation, namely inception and growth, are highly debated and central to many ongoing studies in combustion research. Here, we provide new insights into these processes from studying different soot samples by atomic force microscopy (AFM). Soot has been extracted from a slightly sooting, premixed ethylene/air flame both at the onset of the nucleation process, where the particle size is of the order of 2–4 nm, and at the initial stage of particle growth, where slightly larger particles are present. Subsequently, the molecular constituents from both stages of soot formation were investigated using high-resolution AFM with CO-functionalized tips. In addition, we studied a model compound to confirm the atomic contrast and AFM-based unambiguous identification of aliphatic pentagonal rings, which were frequently observed on the periphery of the aromatic soot molecules. We show that the removal of hydrogen from such moieties could be a pathway to resonantly stabilized π-radicals, which were detected in both investigated stages of the soot formation process. Such π-radicals could be highly important in particle nucleation, as they provide a rational explanation for the binding forces among aromatic molecules.

Some aspects of soot formation from gas phase molecules at high temperatures are still unclear. Aromatic π-radicals may be key elements for a change in the model of carbon clustering and particle formation. However, experimental investigations are still needed on the radical nature of molecules and particles in flames and on their roles in the transition from molecules to incipient molecular clusters and their further evolution to mature soot. In this paper, we present electron paramagnetic resonance (EPR) and Raman spectroscopy measurements of particles collected in an ethylene-rich premixed flame at various residence times during nucleation. The experimental results, combined with measurement of the particle size distribution by a differential mobility analyzer, are used to investigate the role of radicals in particle nucleation and rearrangement of aromatic molecules in just-nucleated particles. For all the sampled particles, an EPR signal typical of persistent carbon-centered aromatic radicals is measured. An abrupt change in the EPR signal intensity, which is characteristic of stronger supramolecular interactions, is observed when the size distribution changes from monomodal to bimodal, as confirmed by Raman spectroscopy. Our experimental results indicate strong involvement of π-radicals during particle nucleation and growth. The paramagnetic/radical nature of the sampled particles is discussed on the basis of recent studies on the role of resonantly stabilized radicals in soot nucleation. The presence of localized π-electrons on the edge of aromatic soot constituents and their role in carbon clustering are also discussed.

Sorbents for low temperature reactive adsorption of H2S were prepared by dispersing mixed Zn and Cu oxides onto a commercial activated carbon at fixed total metal loading and Cu:Zn atomic ratios from 0:1 to 1:1. Fresh and spent sorbents were characterized by means of ICP-MS, SEM-EDX, XRD, BET and pore size distribution, DRIFT and sulphur elemental analysis. H2S (50-3000 ppmv in N-2) removal tests were run under dynamic conditions at 30 degrees C. Due to the high dispersion of the metal oxide phase and its favorable interaction with the carbonaceous support, the functionalized sorbents showed a strongly enhanced adsorption capacity with respect to the raw activated carbon, under dry conditions. Furthermore, the utilization factor of the active phase (moles of S captured per mole of Cu + Zn) increased along with the Cu content up to 76%, thus demonstrating a clear promoting effect of Cu-insertion on the reactivity of ZnO, already at low Cu concentration. Temperature Programmed Desorption (TPD) of H2S and SO2 from saturated sorbents showed that H2S.adsorption was coupled with oxidation phenomena leading to the formation of metal sulphates apart from metal sulphides and/or elemental sulphur, testifying the complexity of the surface reactions. (C) 2016 Elsevier B.V. All rights reserved.

The synthesis of pure titania and carbon-titania nano-powders in a premixed atmospheric fuel-rich flame was studied. The variation of the flame C/O ratio allows to produce both pure titania and carbon-TiO2 nanoparticles. Raman Spectroscopy, X-ray Diffraction, Atomic Force Microscopy, Electrical Low Pressure Impactor and Scanning Electron Microscopy were used to characterize the synthesized nano-powders, in terms of crystallinity, phase content, size and morphology. Produced nano-powders with a dimension of 25-40 nm are composed by both rutile and anatase phases, with rutile being the predominant one. Reactive Oxygen Species analysis performed on the synthesized nano-powders showed that the inclusion of carbon in the nano-powders results in a reduced adverse health effect, in terms of ROS production.

Marine cage aquaculture has the potential to severely impact Posidonia oceanica seagrass meadows and its associated fauna. In order to assess the impact of fish farming in a littoral bay of Corsica, France, physico-chemical (mud and organic matter) and biological (density and compactness of P. oceanica beds and associated macrofauna) variables have been examined in two stations putatively impacted to different degrees (St1 and St2) and in two unimpacted stations (Controls: C1 and C2). Principal Component Analysis of meadow structural variables (shoot density and compactness of matte) and abiotic variables (mud and organic matter percentage into sediment) highlighted differences among stations and, particularly, differences between impacted stations and controls. Results from C1 and C2 totally overlapped. St1 was the station which differed the most from controls. Compared with control stations, St1 and St2 were characterized by higher values of organic matter and mud and by lower values of shoot density and matte compactness. Permutational multivariate analysis of variance (PERMANOVA) did not show significant differences between C1 and C2 in the structure of macrofauna assemblages, whereas significant differences between the two impacted sites and between these and the control conditions emerged. Differences in assemblages were well correlated with the measured abiotic variables. The analysis showed that the species most responsible for difference among stations were typical of muddy sediment with high organic matter content. These species had higher mean abundance values at impacted stations than at controls. This study suggests fish farming determines an increase of organic matter and sedimentation, which resolve in changes in structural properties of the seagrass meadows and, consequently, changes in the associated macrofauna assemblages.

We studied the spatial variability and within-year temporal changes in hydrological features, grain size composition and chemical characteristics of sediments, as well as macrofaunal assemblages, along a heavily modified inlet in the Gulf of Oristano (western Sardinia, Italy). The inlet connects the Cabras lagoon to the gulf through a series of convoluted creeks and man-made structures, including a dam and fish barriers built in the last three decades. Sediments were muddy and mainly composed of the "non-sortable" fraction (i.e., < 8 mu m particle size) in all four areas investigated: Lagoon, Creeks, Channel and Seaward. Along the inlet, however, the ratio between the < 8 mu mn and the 8-64 mu m fractions was highest in Creeks and Channel, between the fish barriers and the dam, suggesting impaired hydrodynamics. Consistently, steep gradients in water salinity, temperature and dissolved oxygen concentrations were found in proximity to the fish barriers. The whole inlet was characterized by a major organic enrichment of sediments, with up to an annual mean of 33.6% of organic matter and 11.7% of total organic carbon in Seaward due to the presence of seagrass leaf litter. Acid-volatile sulphide and chromium-reduced sulphur concentrations were highest throughout the year in Seaward and Lagoon, respectively, with a peak in summer. Consistently, the whole inlet supported low structured macrofaunal assemblages dominated by few opportunist species, with a relatively lower diversity in Lagoon throughout the year and the highest abundances in Seaward in summer. We infer that the presence of artificial structures along the inlet, such as fish barriers and the dam, impair the lagoon-gulf hydrodynamics, sediment exchange and animal recruitment and colonization. We suggest that the removal of these structures would favour water renewal in the Cabras lagoon, but would also increase the outflow of organic C-bonding fine particles into the gulf with serious consequences for Posidonia oceanica and Cymodocea nodosa seagrass meadows. We conclude that all possible consequences of such initiatives should be carefully considered before any action is taken. (C) 2007 Elsevier Ltd. All rights reserved.