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The 2020 lockdown represented a natural experiment to measure the effects of traffic pollution on human health, due to the restrictions during the Covid-19 pandemic. In Rome a reduction of 36% of road traffic and of 40% of airborne benzene were observed. A biological monitoring campaign was carried out on Rome residents, aimed at identifying the biomarkers of exposure for the main urban pollutants, such as benzene and polycyclic aromatic hydrocarbons and biomarkers of oxidative stress to nucleic acids. A targeted analysis by liquid HPLC-MS/MS and an untargeted metabolomic analysis, with nuclear magnetic resonance (NMR) were carried out on urine samples of 47 volunteers collected in 2020 and in 2021. The results show that urinary concentrations of the benzene metabolite (SPMA) and some PAHs are lower on average in 2020 than in 2021. Three oxidative stress analysed, 8- Hydroxyguanine, 8-oxo-7,8-dihydro-guanosine and 8-oxo-7,8-dihydro-2’-deoxyguanosine are affected by the traffic reduction more than the dose biomarkers of the pollutants considered, suggesting an influence of the different lifestyle. The untargeted metabolomic analysis confirms the results of the targeted analysis, also highlighting an increase in succinic acid excretion in 2020 compared to 2021. The increase in urinary succinic acid concentration in 2020 is probably attributable to a different diet and a greater sedentary lifestyle during the lockdown period.

The present paper extrapolates quantitative data for ozone virucidal activity on the basis of the available scientific literature data for a safe and effective use of ozone in the appropriate cases and to explore the safety measures developed under the stimulus of the current emergency situation. Ozone is a powerful oxidant reacting with organic molecules, and therefore has bactericidal, virucidal, and fungicidal actions. At the same time, it is a toxic substance, having adverse effects on health and safety. Its use is being proposed for the disinfection of workplaces’ and public places’ atmosphere, and for disposable masks and personal protective equipment disinfection for reuse, with particular reference to the COVID-19 pandemic outbreak. Ozone can be generated in situ by means of small, compact ozone generators, using dried ambient air as a precursor. It should be injected into the room that is to be disinfected until the desired ozone concentration is reached; after the time needed for the disinfection, its concentrations must be reduced to the levels required for the workers’ safety. The optimal use of ozone is for air and surface disinfection without human presence, using a concentration that is effective for the destruction of viruses, but not high enough to deteriorate materials.

In recent studies, oxidative stress after scuba diving has been explored by measuringurinary biomarkers in volunteers under controlled conditions. Dive depth and duration, watertemperature, and workload are all variables that can elicit metabolic responses. A controlled divingexperiment was performed in an indoor pool at 20, 30, and 40 m depths at a water temperature of32 ºC, on three different days. Samples of urine from five male scuba divers were taken before divingand at four time points after diving, and then tested for their concentration of five different oxidativestress biomarkers by means of liquid chromatography tandem mass spectrometry and by 1H nuclearmagnetic resonance metabolomics analysis. The results showed no variation in the five biomarkers after diving, but a decreasing trend was observed over the three days, with no differences among thethree depths. The lack of effect on oxidative stress biomarkers has been attributed to the comfortablewater temperature and to the absence of exercise in the divers during the experiment. Instead, anincrease in hypoxanthine excretion, which can be considered a biomarker sensitive to hyperbaric exposure, was found after diving. Finally, the results suggest a physiological mechanism of metabolicadaptation to a new condition.

Background: Hyperbaric exposure (HE) is proven to be a stressor to several mechanisms in living cells. Even if after homeostasis restoration, harmful effects are expected, in particular a presence of free radicals. These latter are the stimulus to negative phenomenon as inflammation or cancer. In Italy, with 7500 km of sea shores, a large quantity of workers is exposed to HE during occupational activities. A deep knowledge of HE and bodily effects is not well defined; hence a multidisciplinary assessment of risk is needed. To detect one or more indicators of HE a research group is organised, under the INAIL sponsorship. The research project focused on the oxidative stress (OxS) and this paper details on the possible protocol to estimate, with a large amount of techniques on several human liquids, the relationship between OxS and HE. Specific attention will be paid to identify confounding factors and their influence. Methods: Blood and urine will be sampled. Several lab techniques will be performed on samples, both targeted, to measure the level of well-known biomarkers, and untargeted. Regard the formers: products of oxidation of DNA and RNA in urine; inflammation and temperature cytokines and protein carbonyles in blood. Untargeted evaluation will be performed for a metabolomics analysis in urine. Confounding factors: temperature, body fat, fitness, allergies and dietary habits. These factors will be assessed, directly or indirectly, prior and after HE. The final scope of the project is to determine one or more indicators that relates to HE in hits twofold nature: depth and duration. Conclusion: The relationship between OxS and HE is not deeply investigated and literature proposes diverging results. The project aims to define the time dependence of biomarkers related to OxS, to rise knowledge in risk assessment in workers exposed to HE.

Antineoplastic drugs are used to treat cancer, having their therapeutic effect by inhibiting the cell division process. Although cancer cells, due to their rapid growth, are more sensitive to the toxic effects of chemotherapeutic agents, healthy cells and tissues may also be damaged. Many studies show acute and chronic toxicity both in patients treated with chemotherapy and in exposed workers. In fact, exposure to these substances can also be linked to the formation of different types of secondary tumors. The International Agency on Research on Cancer (IARC) included some antineplastic drugs in Group 1 (carcinogenic to humans), in Group 2A (probable carcinogens for In recent years, many studies have evidenced the presence of antineoplastic drug contamination on work surfaces, materials and floors and based on these observations, international and national guidelines have been published to limit occupational exposure, with particular attention to procedures post-preparation of chemotherapy to limit as much as possible the accumulation of contaminated residues. The aim of the following study is to determine the effectiveness of the degradation of four antineoplastic drugs: 5-fluorouracil, azacitidine, cytarabine and irinotecan using a low concentration of sodium hypochlorite solution (0.115%). The analytical platform used to monitor the degradation course of the substances under examination was hydrogen nuclear magnetic spectroscopy (1H NMR). In the same experimental conditions the effectiveness of the degradation of the same antineoplastic drugs with a 99.9% ethanol solution was also evaluated. The study showed that the best degradation efficiency (90% ) is obtained with the hypochlorite solution after 15 minutes.I farmaci antiblastici sono farmaci utilizzati nelle terapie oncologiche che svolgono il loro effetto terapeutico inibendo il processo di divisione cellulare. Sebbene le cellule tumorali, a causa del loro rapido accrescimento, siano maggiormente sensibili agli effetti tossici degli agenti chemioterapici anche le cellule e i tessuti sani possono subire un danno. L’esposizione a tali sostanze, infatti, può essere collegata anche alla formazione di diversi tipi di tumori secondari. L’International Agency on Research on Cancer (IARC) ha inserito alcuni farmaci antiblastici classificandoli come cancerogeni per l’uomo (Gruppo 1), probabili cancerogeni per l’uomo (Gruppo 2A) e possibili cancerogeni per l’uomo (Gruppo 2B). Negli ultimi anni molti studi hanno evidenziato la presenza di contaminazione da farmaci antiblastici su superfici di lavoro, materiali e pavimenti e sulla base di queste osservazioni sono state pubblicate delle linee guida internazionali e nazionali per limitare l’esposizione professionale, ponendo anche particolare attenzione alle procedure di pulizia post preparazione dei farmaci, per limitare quanto più possibile l’accumulo di residui contaminati. Lo scopo del seguente studio è determinare l’efficacia della degradazione di quattro farmaci antiblastici: 5-fluorouracile, azacitidina, citarabina e irinotecano mediante una soluzione di ipoclorito di sodio a bassa concentrazione (0,115%). La piattaforma analitica impiegata per monitorare il decorso della degradazione delle sostanze in esame è stata la spettroscopia magnetica nucleare di idrogeno (1H-NMR). Nelle stesse condizioni sperimentali è stata anche valutata l’efficacia della degradazione degli stessi farmaci antiblastici con una soluzione di etanolo al 99,9%. Lo studio ha evidenziato che la migliore efficienza nella degradazione (90%) si ottiene con la soluzione di ipoclorito dopo soli 15 minuti.

Occupational exposure to hyperbaric atmosphere occurs in workers who carry out their activity in environmentswhere breathing air pressure is at least 10% higher than pressure at sea level, and operations can be divided inDry or Wet activities. The increased air pressure implies the formation of reactive oxygen species (ROS) andreactive nitrogen species (RNS), consumption of antioxidants and reduction of antioxidant enzyme activity,causing lipid peroxidation, DNA and RNA damage. The present study was aimed to establish the relation betweenhyperbaric exposure and metabolic changes due to ROS unbalance, by means of the determination of urinary biomarkers of oxidatively generated damage to DNA and RNA during a controlled diving session. Theinvestigated biomarkers were 8-oxo-7,8-dihydroguanine (8-oxoGua), 8-oxo-7,8-dihydroguanosine (8-oxoGuo),and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo). The experimental session involved six experienced divers subjected to 3 atmospheres absolute for 30 minutesin two different experiments, in both dry and wet conditions. Urine samples were collected at t = 0 (beforeexposure) and 30 (end of exposure),90, 240, 480 and 720 minutes. The concentration of 8-oxoGua, 8-oxoGuo,and 8-oxodGuo was determined by isotopic dilution high performance liquid chromatography (HPLC-MS/MS). In all subjects there is an increase of the urinary excretion of 8oxo-Guo and 8oxo-dGuo, in both conditions, after1.5 - 4 hours from the start of the experiment, and that the values tend to return to the baseline after 12 hours.Besides that, also the nucleic magnetic resonance (NMR)-based untargeted metabolomics was employed for thesame objective on the same samples, confirming a different metabolic response in the subjects exposed to dry orwet conditions. In particular, the observed hypoxanthine urinary level increases during the underwater hyperbaricexposure, in agreement with the trend observed for 8-oxoGuo and 8-oxodGuo levels. Present resultsconfirmed the relationship between exposure and oxidative stress and depicted a clear temporal trend of theinvestigated biomarkers. Due to the possible negative consequences of oxidative stress on workers, presentresearch shows a new line in term of risk prevention.

An easy and effective analytical method was developed for the simultaneous quantification of four tocopherols (Ts) and four tocotrienols (T3s) in three pecan nut cultivars (Stuart, Sioux, and Pawnee). The analytes were separated on a C30 column kept at 15 °C, under isocratic non-aqueous reversed-phase (NARP) conditions, in only 18 min and detected by atmospheric pressure chemical ionization–tandem mass spectrometry (APCI-MS/MS). The HPLC-APCI-MS/MS method was validated, according to the main FDA guidelines, and then applied for the characterization of the real samples. Analytes were extracted by cold saponification with recoveries greater than 87%. The limits of detection (LOD) and limits of quantification (LOQ) were in the range of 0.3–10 μg/100 mg and 1–30 μg/100 mg, respectively. Compared to other nuts, vitamin E composition of pecan nuts (Carya illinoinensis) has only partially been elucidated. Results have evidenced the prevalence of γ-forms for both Ts and T3 s and clear quantitative differences of the identified vitamers among the studied cultivars. The richest variety in vitamin E was Sioux with a total content of about ∼ 32 mg/100 g wet weight, followed by Stuart (∼16 mg/100 g) and Pawnee (∼9 mg/100 g).

Bacterial canker of

Bacterial canker of Actinidia, caused by the bacterium Pseudomonas syringae pv. actinidiae (Psa), is the most serious disease of these plants worldwide. Leaves of three species of Actinidia, namely A. chinensis var. chinensis, A. chinensis var. deliciosa and A. arguta, having different degrees of tolerance to Psa, were analyzed by Nuclear Magnetic Resonance spectroscopy. Aqueous extracts of leaves were studied and several metabolites, classified as organic acids, amino acids, carbohydrates, phenols and other metabolites, were identified by 1D and 2D NMR experiments and quantified. The metabolic profiles of these species were compared through univariate statistical analysis ANOVA and multivariate PCA. Levels of metabolites with known antibacterial activity, such as caffeic and chlorogenic acids, were observed to be higher in the A. arguta samples. Moreover, these metabolites have different Pearson correlation patterns among the three Actinidia species, suggesting a difference at the phenylpropanoid biosynthetic pathway.

The metabolic profiling of pistachio (Pistacia vera) aqueous extracts from two different cultivars, namely ‘Bianca’ and ‘Gloria’, was monitored over the months from May to September employing high field NMR spectroscopy. A large number of water-soluble metabolites were assigned by means of 1D and 2D NMR experiments. The change in the metabolic profiles monitored over time allowed the pistachio development to be investigated. Specific temporal trends of amino acids, sugars, organic acids and other metabolites were observed and analysed by multivariate Partial Least Squares (PLS) analysis. Statistical analysis showed that while in the period from May to September there were few differences between the two cultivars, the ripening rate was different.

New methodology has been developed for the synthesis of so-called sapphyrins, pentapyrrolic “expanded porphyrins”. An efficient approach involving acid-catalyzed condensation of 1,19-diunsubstituted a,c-biladienes and 3,4-dialkylpyrrole-2-carbaldehydes eliminates the preparation of bipyrrolic intermediates and allows the synthesis of sapphyrins with an unsymmetrical array of peripheral substituents. The β-substitution pattern of 2,3,13,17-tetraethyl-7,8,12,18,22,23-hexamethylsapphyrin has been unambiguously confirmed by single crystal X-ray crystallography. 1H NMR spectra of the dication salts of sapphyrins are strongly dependent upon the counterions, and the pattern of resonances observed in solution is related to the stacking interactions between the macrocycles.

Health-care workers handling antineoplastic agents may be exposed to extremely low doses of these drugs. Very sensitive and specific analytical methods are therefore needed for biological monitoring. The aim of this study was to develop and validate a method for trace level determination of doxorubicin, epirubicin, daunorubicin and idarubicin in human urine, using epi-daunorubicin as an internal standard. Solid-phase extraction (SPE) was used for sample preparation. Urine samples were loaded onto Bond Elut C18 cartridges. The analytes were eluted in methylene chloride/2-propanol (1:1, v/v) and then evaporated to dryness. The residue was reconstituted with the mobile phase prior to high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) analysis. Quantitation of each analyte was performed using the multiple reaction monitoring (MRM) method. The urine assay was linear over the range 0.1-2.0 microg/L, with a lower limit of quantification (LLOQ) of 0.10 microg/L for doxorubicin and epirubicin, and 0.03 microg/L for daunorubicin and idarubicin. The respective limits of detection (LODs) were 0.04 and 0.01 microg/L. The precision and accuracy of the assay were determined on three different days. The within-series precision was found to be always less than 13.9% for all the analytes. The overall precision expressed as relative standard deviation (RSD) was always less than 10.6%. The recovery of anthracyclines was assessed at two concentrations of the range tested (0.1 and 2.0 microg/L) and it ranged from 87.7% (daunorubicin) to 102.0% (doxorubicin) and from 79.1% (daunorubicin) to 90.7% (idarubicin) for the lower and the higher level, respectively, with a RSD always less than 9.1%. The uncertainty of the present assay was also evaluated and the combined uncertainty was always less than 20% over all the days of the validation study. This is the first method that makes use of LC/MS/MS for the biological monitoring of occupational exposure to anthracyclines.

The separation of paraquat, diquat, and difenzoquat bipyridilium herbicides and ethyl viologen as internal standard is shown. The separation has been carried out using a fused silica capillary with a high-sensitivity detection cell for a capillary electrophoresis system and with a diode array detector. The experiments have been performed using phosphate buffer 50 mM at pH = 4 and pH = 7. The effect of methanol has also been studied when used as an organic modifier. Different voltages and electrokinetic conditions have been used to optimize the separation. Twenty Kv voltage and 10 Kv for 3 sec for injection have been found to be reliable conditions of separation at pH 4 without organic modifier.

New methodology has been developed for the synthesis of so-called sapphyrins, pentapyrrolic “expanded porphyrins”. An efficient approach involving acid-catalyzed condensation of 1,19-diunsubstituted a,c-biladienes and 3,4-dialkylpyrrole-2-carbaldehydes eliminates the preparation of bipyrrolic intermediates and allows the synthesis of sapphyrins with an unsymmetrical array of peripheral substituents. The β-substitution pattern of 2,3,13,17-tetraethyl-7,8,12,18,22,23-hexamethylsapphyrin has been unambiguously confirmed by single crystal X-ray crystallography. 1H NMR spectra of the dication salts of sapphyrins are strongly dependent upon the counterions, and the pattern of resonances observed in solution is related to the stacking interactions between the macrocycles.