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Increased risk of neurodegenerative diseases has been envisaged for air pollution exposure. On the other hand, environmental risk factors, including air pollution, have been suggested for Amyotrophic Lateral Sclerosis (ALS) pathomechanism. Therefore, the neurotoxicity of ultrafine particulate matter (PM0.1) (PM < 0.1 μm size) and its sub-20 nm nanoparticle fraction (NP20) has been investigated in motor neuronal-like cells and primary cortical neurons, mainly affected in ALS. The present data showed that PM0.1 and NP20 exposure induced endoplasmic reticulum (ER) stress, as occurred in cortex and spinal cord of ALS mice carrying G93A mutation in SOD1 gene. Furthermore, NSC-34 motor neuronal-like cells exposed to PM0.1 and NP20 shared the same proteomic profile on some apoptotic factors with motor neurons treated with the L-BMAA, a neurotoxin inducing Amyotrophic Lateral Sclerosis/Parkinson-Dementia Complex (ALS/PDC). Of note ER stress induced by PM0.1 and NP20 in motor neurons was associated to pathological changes in ER morphology and dramatic reduction of organellar Ca 2+ level through the dysregulation of the Ca 2+ -pumps SERCA2 and SERCA3, the Ca 2+ -sensor STIM1, and the Ca 2+ -release channels RyR3 and IP3R3. Furthermore, the mechanism deputed to ER Ca 2+ refilling (e.g. the so called store operated calcium entry-SOCE) and the relative currents ICRAC were also altered by PM0.1 and NP20 exposure. Additionally, these carbonaceous particles caused the exacerbation of L-BMAA-induced ER stress and Caspase-9 activation. In conclusion, this study shows that PM0.1 and NP20 induced the aberrant expression of ER proteins leading to dysmorphic ER, organellar Ca 2+ dysfunction, ER stress and neurotoxicity, providing putative correlations with the neurodegenerative process occurring in ALS., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Up to 50 % of total PM 2.5 emissions are due to particles derived from the automotive sector, and both exhaust and non-exhaust emissions contribute to the pollution of urban areas. Fuel incomplete combustion, or lubricant degradation due to high temperatures during the combustion process, are responsible for exhaust emissions. The non-exhaust ones concern brakes, tires and road surface-wear emissions and road resuspension contribution. The present study aims to provide a methodological approach for a detailed chemical characterization of wear friction products by means of a large array of techniques including spectroscopic tools, thermogravimetric analysis (TGA), chromatography, morphological and elemental analysis. The dust sample derived from the wear of a brake pad material was collected after a Noise & Vibration Harshness (NVH) test under loads similar to a Worldwide Light vehicle Test Procedure (WLTP) braking cycle. The TGA shows that only a small fraction is burned during the test in an oxidizing environment, testifying that the sample consists mostly of metals (more than 90 %). Fe exhibits the highest concentrations (50-80 %, even in the form of oxides). Also other kinds of metals, such as Zn, Al, Mg, Si, S, Sn, Mn, occur in small quantities (about 1-2% each). This finding is confirmed by X-ray diffraction (XRD) analysis. The organic fraction of the debris, investigated by means of Raman spectroscopy, has an evident aromatic character, probably due to oxidative phenomena occurring during the braking cycle test. Noteworthy, the extraction of the dust sample with organic solvents, revealed for the first time the presence of ultrafine particles (UFPs), even in the range of few nanometers (nanoparticles), and polycyclic aromatic hydrocarbons (PAHs), recognized as highly toxic compounds. The simultaneous presence of toxic organic carbon and metals makes of concern the non-exhaust emissions and mandatory a deep insight on their structure and detailed composition., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Background: An emerging body of evidence indicates an association between anthropogenic particulate matter (PM) and neurodegeneration. Although the historical focus of PM toxicity has been on the cardiopulmonary system, ultrafine PM particles can also exert detrimental effects in the brain. However, only a few studies are available on the harmful interaction between PM and CNS and on the putative pathomechanisms. Methods: Ultrafine PM particles with a diameter < 0.1 μm (PM0.1) and nanoparticles < 20 nm (NP20) were sampled in a lab-scale combustion system. Their effect on cell tracking in the space was studied by time-lapse and high-content microscopy in NSC-34 motor neurons while pHrodo™ Green conjugates were used to detect PM endocytosis. Western blotting analysis was used to quantify protein expression of lysosomal channels (i.e., TRPML1 and TPC2) and autophagy markers. Current-clamp electrophysiology and Fura2-video imaging techniques were used to measure membrane potential, intracellular Ca2+ homeostasis and TRPML1 activity in NSC-34 cells exposed to PM0.1 and NP20. Results: NP20, but not PM0.1, reduced NSC-34 motor neuron movement in the space. Furthermore, NP20 was able to shift membrane potential of motor neurons toward more depolarizing values. PM0.1 and NP20 were able to enter into the cells by endocytosis and exerted mitochondrial toxicity with the consequent stimulation of ROS production. This latter event was sufficient to determine the hyperactivation of the lysosomal channel TRPML1. Consequently, both LC3-II and p62 protein expression increased after 48 h of exposure together with AMPK activation, suggesting an engulfment of autophagy. The antioxidant molecule Trolox restored TRPML1 function and autophagy. Conclusions: Restoring TRPML1 function by an antioxidant agent may be considered a protective mechanism able to reestablish autophagy flux in motor neurons exposed to nanoparticles.

The anthropogenic particulate matter (PM), suspended air dust that can be inhaled by humans and deposited in the lungs, is one of the main pollutants in the industrialized cities atmosphere. Recent studies have shown that PM has adverse effects on respiratory diseases. These effects are mainly due to the ultrafine particles (PM0.1, PM < 100 nm), which, thanks to their PM size, are efficiently deposited in nasal, tracheobronchial, and alveolar regions. Pulmonary macrophages are a heterogeneous cell population distributed in different lung compartments, whose role in inflammatory response to injury is of particular relevance. In this study, we investigated the effect of PM0.1 on Human Lung Macrophages (HLMs) activation evaluated as proinflammatory cytokines and chemokine release, Reactive Oxygen Species (ROS) production and intracellular Ca 2+ concentration ([Ca 2+ ] i ). Furthermore, PM0.1, after removal of organic fraction, was fractionated in nanoparticles both smaller (NP20) and bigger (NP100) than 20 nm by a properlydeveloped analytical protocol, allowed isolating their individual contribution. Interestingly, while PM0.1 and NP20 induced stimulatory effects on HLM cytokines release, NP100 had not effect. In particular, PM0.1 induced IL-6, IL-1β, TNF-α, but not CXCL8, release from HLMs. Moreover, PM0.1, NP20 and NP100 did not induce β-glucuronidase release, a preformed mediator contained in HLMs. The long time necessary for cytokines release (18 h) suggested that PM0.1 and NP20 could induce ex-novo production of the tested mediators. Accordingly, after 6 h of incubation, PM0.1 and NP20 induced mRNA expression of IL-6, TNF-α and IL-1β. Moreover, NP20 induced ROS production and [Ca 2+ ] i increase in a time-dependent manner, without producing cytotoxicity. Collectively, the present data highlight the main proinflammatory role of NP20 among PM fractions. This is particularly of concern because this fraction is not currently covered by legal limits as it is not easily measured at the exhausts by the available technical methodologies, suggesting that it is mandatory to search for new monitoring techniques and strategies for limiting NP20 formation., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Volatile organic compounds (VOC) and polycyclic aromatic hydrocarbons (PAH), emitted in the environment from a wide range of combustion sources, are hazardous to human health and considered important precursors of both primary and secondary particulate pollutants. In the present work, light hydrocarbons up to C 9 , as main components of combustion-derived VOC, and PAH produced in fuel-rich conditions of premixed ethylene flames were analyzed by implementing a molecular-beam time of flight mass spectrometer (MB-TOFMS), purposely built for on-line fast monitoring of the environmental impact of combustion systems. The reliability of the MB-TOFMS was preliminarily verified on a slightly-sooting flame, comparing the results with those obtained by batch sampling and gas chromatographic techniques. Electron ionization (EI) and multi-photon ionization (MPI) were used as MB-TOFMS sources and tested on combustion gases of a no-sooting premixed ethylene flame where VOC and PAH are present in traces not detectable with batch sampling and conventional analytical techniques. The mass identification accuracy was improved and guaranteed by systematically performing internal mass calibration, exploiting the formation of "in situ" clusters from combustion water in the molecular beam apparatus. Selective and sensitive monitoring of light hydrocarbons and PAH, derived from oxidation and pyrolysis reactions featuring combustion, was shown to be especially effective when using the MB-TOFMS equipped with MPI source. This technique showed to be effective also for the detection of radical species that are important for the risk assessment of aerosol and fundamental understanding of aerosol chemistry at a molecular level., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The continuous synthesis in controlled gas flame reactors is here demonstrated as a very effective approach for the direct and easy production of structurally reproducible carbon nanodots. In this work, the design of a simple deposition system, inserted into the reactor, is introduced. A controlled flame reactor is employed in the present investigation. The system was optimized for the production of carbon nanoparticles including fluorescent nanocarbons. Blue and green fluorescent carbon could be easily separated from the carbon nanoparticles by extraction with organic solvents and characterized by advanced chemical (size exclusion chromatography and mass spectrometry) and spectroscopic analysis. The blue fluorescent carbon comprised a mixture of molecular fluorophores and aromatic domains; the green fluorescent carbon was composed of aromatic domains (10-20 aromatic condensed rings), bonded and/or turbostratically stacked together. The green-fluorescent carbon nanodots produced in the flame reactor were insoluble in water but soluble in N-methylpyrrolidinone and showed excitation-independent luminescence. These results provide insights for a simple and controlled synthesis of carbon nanodots with specific and versatile features, which is a promising pathway for their use in quite different applicative sectors of bioimaging.

This paper is the second of a series dealing with clusters formation mechanism. In part 1, water clusters with the addition of an electrophilic molecule such as ethanol were studied by Time Of Flight Mass Spectrometry (TOFMS). Mass distributions of molecular clusters of ethanol, water and ethanol-water mixed clusters, were obtained by means of two different ionization methods: Electron Ionization (EI) and picosecond laser Photo-Ionization (PI) at a wavelength of 355 nm. In part 2, the same experimental approach was employed to obtain mass spectra of clusters generated by acetone-water binary mixtures with a different composition. Strong dependence of the mass spectra of clusters with EI and PI on the acetone-water mixing ratio was observed. It was shown that the spectral pattern changes gradually and water-rich cluster signals become fainter while acetone-rich cluster signals become more intensive with increasing acetone concentrations from 0.3% to 40%. Owing to the hydrogen bond acceptor character of acetone, its self-association is discouraged with respect to ethanol. The autocorrelation function (AF) was used to analyze the variation of the water clusters composition with the increase of the acetone concentration in terms of fundamental periodicities. However, although acetone and ethanol present a very different hydrogen-bonding ability, similarly to ethanol-water system, in acetone-water system the formation of water-rich clusters and subsequent metastable fragmentation are the dominant process that determine the clusters distribution, irrespective of the ionization process, while the ionization process significantly affects the acetone-rich clusters distribution. Graphical Abstract ᅟ.

Rationale: Time-of-Flight (TOF) Mass Spectrometry is a powerful analytical technique, provided that an accurate calibration by standard molecules in the same m/z range of the analytes is performed. Calibration in a very large m/z range is a difficult task, particularly in studies focusing on the detection of high molecular weight clusters of different molecules or high molecular weight species., Methods: External calibration is the most common procedure used for TOF mass spectrometric analysis in the gas phase and, generally, the only available standards are made up of mixtures of noble gases, covering a small mass range for calibration, up to m/z 136 (higher mass isotope of xenon). In this work, an accurate calibration of a Molecular Beam Time-of Flight Mass Spectrometer (MB-TOFMS) is presented, based on the use of water clusters up to m/z 3000., Results: The advantages of calibrating a MB-TOFMS with water clusters for the detection of analytes with masses above those of the traditional calibrants such as noble gases were quantitatively shown by statistical calculations. A comparison of the water cluster and noble gases calibration procedures in attributing the masses to a test mixture extending up to m/z 800 is also reported. In the case of the analysis of combustion products, another important feature of water cluster calibration was shown, that is the possibility of using them as "internal standard" directly formed from the combustion water, under suitable experimental conditions., Conclusions: The water clusters calibration of a MB-TOFMS gives rise to a ten-fold reduction in error compared to the traditional calibration with noble gases. The consequent improvement in mass accuracy in the calibration of a MB-TOFMS has important implications in various fields where detection of high molecular mass species is required. In combustion products analysis, it is also possible to obtain a new calibration spectrum before the acquisition of each spectrum, only modifying some operative conditions. Copyright © 2016 John Wiley & Sons, Ltd., (Copyright © 2016 John Wiley & Sons, Ltd.)

In the present work, water clusters with the addition of an electrophilic molecule such as ethanol have been studied by time of flight mass spectrometry (TOFMS). Mass distributions of molecular clusters of ethanol, water, and ethanol-water mixed clusters were obtained by two different ionization methods: electron ionization (EI) and picosecond laser photo-ionization (PI) at a wavelength of 355 nm. It was shown that short pulse laser ionization increases the signal intensity and promotes the extension of the detected mass range of the clusters in comparison with EI. Much larger clusters were detected in our experiments with respect to the current literature. The autocorrelation function (AF) was introduced in the analysis of the composition of the water clusters in terms of fundamental periodicities for obtaining information on clusters formation mechanisms. Besides, it was found that ethanol molecules are capable of substitutional interaction with hydrogen-bonded water clusters in ethanol-water binary mixtures but the self-association of ethanol was the dominant process. Moreover, the increase of ethanol concentration promotes both the formation of hydrated ethanol clusters and the self-association of ethanol clusters in ethanol-water binary mixtures. The formation of water-rich clusters and subsequent metastable fragmentation were found to be the dominant processes determining the water-rich cluster distribution, irrespective of the ionization process, while the ionization process significantly affects the ethanol-rich cluster distribution.

We performed a combined experimental and theoretical study of the C1s Near-Edge X-ray Absorption Fine-Structure (NEXAFS) spectroscopy and X-ray Photoelectron Spectroscopy in the gas phase of two polycyclic aromatic hydrocarbons (phenanthrene and coronene), typically formed in combustion reactions. In the NEXAFS of both molecules, a double-peak structure appears in the C1s → LUMO region, which differ by less than 1 eV in transition energies. The vibronic coupling is found to play an important role in such systems. It leads to weakening of the lower-energy peak and strengthening of the higher-energy one because the 0 - n (n > 0) vibrational progressions of the lower-energy peak appear in nearly the same region of the higher-energy peak. Vibrationally resolved theoretical spectra computed within the Frank-Condon (FC) approximation and linear coupling model agree well with the high-resolution experimental results. We find that FC-active normal modes all correspond to in-plane vibrations.

Water clusters are multimers of water molecules held together by hydrogen bonds. In the present work, multiphoton ionization in the UV range coupled with time of flight mass spectrometry has been applied to water clusters with up to 160 molecules in order to obtain information on the electronic states of clusters of different sizes up to dimensions that can approximate the bulk phase. The dependence of ion intensities of water clusters and their metastable fragments produced by laser ionization at 355 nm on laser power density indicates a (3+1)-photon resonance-enhanced multiphoton ionization process. It also explains the large increase of ionization efficiency at 355 nm compared to that at 266 nm. Indeed, it was found, by applying both nanosecond and picosecond laser ionization with the two different UV wavelengths, that no water cluster sequences after n = 9 could be observed at 266 nm, whereas water clusters up to m/z 2000 Th in reflectron mode and m/z 3000 Th in linear mode were detected at 355 nm. The agreement between our findings on clusters of water, especially true in the range with n > 10, and reported data for liquid water supports the hypothesis that clusters above a critical dimension can approximate the liquid phase. It should thus be possible to study clusters just above 10 water molecules, for getting information on the bulk phase structure.

A time-of-flight mass spectrometer in reflectron configuration has been used for the real-time detection of combustion products. The products of a premixed laminar C2H4/O2 flame at atmospheric pressure were sampled along its axis, diluted with inert gas and carried to the ion source as a molecular beam under minimal perturbation. Electron ionization and different optical ionization sources are compared. Photoionization was achieved with laser radiation from a Nd:YAG nanosecond pulsed laser at two different wavelengths in the UV range (266 and 355 nm). The mass spectra obtained using laser wavelength of 355 nm and electron ionization present a series of ions regularly spaced by 18 m/z units up to m/z 2000. This series allowed precise calibration of the instrument for compounds of high molecular weight. Information on the chemical nature of the analyzed species has been obtained by comparing mass spectra produced with different ionization methods. In order to better understand the growth mechanisms, polycyclic aromatic hydrocarbon sequences have been analyzed by fast Fourier transform of the mass spectra.

The partial contribution of polycyclic aromatic hydrocarbons (PAH), capable of being detected by gas chromatography (GC-PAH), both to the total mass of the extractable organic fraction of flame-formed carbon particulates and to its UV-visible absorption and fluorescence spectra, has been determined by previous work. This contribution indicates the presence of PAH of molecular weight (MW) greater than 400 Da not accessible to conventional analysis. The detection of species in this higher MW range is important for both their potential toxicology and their possible role in soot formation. In the present work extracts of soots have been analyzed by linear mode laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF-MS) to extend the MW range that can be analyzed beyond the GC-PAH. The results have been compared with both analysis by reflector mode LDI-TOF-MS and the MW evaluation obtained by SEC analysis, as the shortcomings and advantages of both techniques appear to be complementary. Matching the results from the two techniques could give interesting insights in the molecular mass range between GC-PAH and the first soot particles (of mass > 2000 Da). Mass spectra in this molecular mass range have been obtained with a main ion sequence spacing of 24 Th and a minor ion sequence also with a spacing of 24 Th but off-set by 12 Th with respect to the main sequence. The two ion progressions have been interpreted by attributing the predominant peaks mainly to PAH with even-carbon numbers and the smaller ones to cyclopenta-fused ring PAH. These distributions indicate the occurrence of two competitive mechanisms in the growth of PAH and soot nucleation, i.e. the addition of acetylene (HACA mechanism) and the incorporation of pentagons by large polycyclic aromatic molecules into their aromatic bonding network., (Copyright (c) 2006 John Wiley & Sons, Ltd.)

The contribution of two- to seven-ring polycyclic aromatic hydrocarbons (PAH) and of larger aromatic structures contained in complex PAH-laden mixtures collected in flames was evaluated by fluorescence spectroscopy. A composition procedure of the fluorescence spectra of individual PAHs, analyzed by gas chromatography/mass spectrometry (GC/MS) was applied for the evaluation of their contribution to the fluorescence spectra of PAH-laden mixtures. In this way, it was possible to put in evidence the contribution to the total fluorescence spectrum of high molecular weight aromatic species present in the PAH-laden mixtures and not detectable by GC/MS. Qualitative and quantitative interpretation of synchronous and conventional fluorescence spectra of PAH-laden mixtures formed in combustion processes was proposed. The composition procedure was showed to be reliable in the UV-visible region for samples dissolved in cyclohexane solutions, but failed in the UV region when the solvent contained heavy atoms, as in the case of dichloromethane. However, the heavy-atom solvent effect was not sufficient to explain the depression of the UV fluorescence signal. Energy transfer interaction between fluorene and other fluorescing PAHs was suggested to be also responsible for this effect on the basis of fluorescence studies performed on single PAHs and their mixtures in cyclohexane, methanol, and dichloromethane.

Oligomeric carbon and siloxane series have been observed by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS), during the analysis of the dichloromethane (DCM)-soluble fractions of condensable material recovered from fuel-rich flames. Laser desorption (LD) spectra showed a pattern of oligomeric dimethyl-siloxane structures with a spacing of 74 u. The siloxane series appears to have originated as contamination of samples by silicone oil used to lubricate connections of polymer tubing. This was confirmed by extracting silicone tubing and silicone grease with DCM followed by MALDI-MS analysis. A series of peaks with a mass spacing of 24 u was also observed, superimposed on the continuum of unresolved organic ions. This oligomeric series appears to correspond to polycyclic aromatics separated by (mainly) ethylene bridges. Thus LD-MS appears to have revealed a series of soot precursors, intermediate between polycyclic aromatics and particulate soot, which was not detected by MALDI-MS. More detailed work is necessary to define these species with precision., (Copyright 2004 John Wiley & Sons, Ltd.)

The large presence of aromatic compounds in distillate fossil fuels should allow, in line of principle, to follow the fuel consumption and/or the presence of unburned fuel in a high temperature environment like a burner or the exhaust of combustion systems by exploiting the high fluorescence emission of aromatic fuel components. To this aim an UV-excited fluorescence source has to be used since the aromatic fuel components are strongly fluorescing in the UV region of the emission spectrum. In this work UV-excited laser induced fluorescence (LIF) diagnostics was applied to spray flames of kerosene in order to follow the fuel consumption and the formation of aromatic species. A strong UV signal was detected in the spray region of the flame that presented a shape similar to that found in the LIF spectra preliminary measured on the cold spray and in the room-temperature fluorescence of fuel solutions. The decrease of UV signal along the spray flame region was associated to the consumption of the fuel, but more difficult seems to be the attribution of a broad visible emission, that is present downstream of the flame. The visible emission feature could be assigned to flame-formed PAH species contained in the high molecular weight species, hypothesizing that their fluorescence spectra are shifted toward the visible for effect of the high temperature flame environment.

The determination of the structure of carbon materials is an analytical problem that join the research scientific communities involved in the chemical characterization of heavy fuel-derived products (heavy fuel oils, coal-derived fuels, shale oil, etc.) and of carbon materials (polycyclic aromatic compounds, tar, soot) produced in many combustion processes. The knowledge of the structure of these "difficult" fuels and of the carbon materials produced by incomplete combustion is relevant to research for the best low-environmental impact operation of combustion systems; but an array of many analytical and spectroscopic tools are necessary, and often not sufficient, to attempt the characterization of such complex products and in particular to determine the distribution of molecular masses. In this paper the size exclusion chromatography using N-methyl-pyrrolidinone as eluent has been applied for the characterization of different carbon materials starting from typical carbon species, commercially available like polyacenaphthylene, carbon black, naphthalene pitch up to combustion products like soot and soot extract collected in fuel-rich combustion systems. Two main fractions were detected, separated and molecular weights (MWs) determined by comparison with polystyrene standards: a first fraction consisted of particles with very large molecular masses (>100000 u); a second fraction consisted of species in a relatively small MW range (200-600 u). The distribution of these fractions changes in dependence on the carbon sample characteristics. Fluorescence spectroscopy applied on the fractions separated by size-exclusion chromatography has been used and comparatively interpreted giving indications on the differences and similarities in chemical structure of such different materials.

The fluorescence spectra of the condensed species (CS) collected in the soot inception region of a rich premixed laminar ethylene/oxygen flame have been measured by excitation in the UV at 266 and 355 nm excitation wavelength. The contribution of the most abundant polycyclic aromatic hydrocarbons (PAH) to the CS fluorescence has been evaluated in order to attribute the CS fluorescence at different emission wavelengths to specific aromatic structures. The fluorescence peaks detected in the UV region of the CS fluorescence spectrum was found to be mainly due to a typical PAH like fluorene, that is, the most fluorescent one among the PAH analyzed in the CS by chromatographic analysis. The CS exhibited the larger emission in the visible where the PAH contribution has been shown to be negligible and other fluorescing aromatic species, not identified by chromatographic analysis of the CS, have to be considered responsible for the visible fluorescence. Laser induced fluorescence (LIF) flame measurements excited at 266 nm and detected at two selected wavelengths (310 and 410 nm) have been performed along the flame axis and compared with the CS fluorescence intensity. The LIF and CS fluorescence signals show quite similar axial trends demonstrating that the LIF signals are related to CS fluorescence. In particular, the LIF fluorescence signals detected in the UV could be attributed to the PAH fluorescence whereas the unidentified species contained in the CS can be followed by LIF detection in the visible region.