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Circularly polarized luminescence activity from new cationic water soluble Sm(iii) and Eu(iii) complexes is triggered by one- and two-photon absorption processes. The Eu(iii) complex is shown to be an efficient NIR-to-RED probe in cellulo.

Protecting the health of pregnant women from environmental stressors is crucial for reducing the burden of non-communicable diseases. In industrially contaminated sites, this action is particularly challenging due to the heterogeneous pollutant mixtures in environmental matrices. Aim of this study was to evaluate distribution patterns of mercury, hexacholobenzene and polychlorobyfenils in the serum of 161 pregnant women recruited in the framework of the NEHO cohort and living both inside and outside the National Priority Contaminated Site (NPCS) of Priolo. Food macro-categories were determined, and serum levels of contaminants were used to perform k-means cluster analysis and identify the role of food in pollutant transfer from the environment. Two groups of mothers with high and low measured pollutant levels were distinguished. Concentrations in mothers in the high-exposure cluster were at least twofold for all the evaluated pollutants (pHighlights- HCB, PCBs and Hg were measured in pregnant women from a highly contaminated area- Pregnant women’s exposure profiles were obtained through k-means cluster analysis- Distance of residence from emission sources only partially explains exposure levels- Maternal age and food consumption appear to primarily drive contaminant levelsAbstract Figure

During pregnancy, maternal nutrition and lifestyle play a critical role in influencing fetal development and newborn health outcomes. The aim of this study is to investigate the factors influencing the adherence to dietary patterns in pregnant women living in highly contaminated areas, and whether women with higher environmental risk perception manifest different nutritional behaviors during pregnancy. Food consumption data on 816 pregnant women from the Neonatal Environment and Health Outcomes (NEHO) residential birth cohort were analyzed. Dietary patterns were computed by principal component analysis. A multinomial logistic regression was also applied to identify sociodemographic, lifestyle, and pregnancy-related determinants of adherence to dietary patterns during pregnancy. Three patterns of food consumption—explaining 24.9% of the total variance—were identified as “prudent”, “high energy”, and “vegetarian” patterns. Results suggest that food choices during pregnancy follow a social gradient and align with other health behaviors during pregnancy: older, better educated, and physically active women with higher risk perception are more likely to follow healthier dietary patterns. Knowledge about what is eaten can contribute to dietary choices. Interventions to improve the prenatal nutrition knowledge of pregnant women are needed, especially concerning younger mothers and those with lower educational levels.

We report the first example of very efficient NIR Circularly Polarized Luminescence (CPL) (around 970 nm) in water, obtained thanks to the combined use of a chiral Yb complex and of poly lactic-co-glycolic acid (PLGA) nanoparticles. [YbL(tta)

to evaluate and validate the adoption of an algorithm for the identification of cases of congenital anomalies (CAs) to improve the performance of the Congenital Malformations Registry of Sicily Region (Southern Italy).an algorithm was used to identify congenital anomalies on a sample of hospital discharge records (SDO) with ICD-9-CM code between 740-759 on any of the diagnoses within the first year of life, together with a sample of healthy births equal to 5% of total births for the same period. The identified cases were evaluated through the clinical record analysis.the analysed sample was composed of 4,271 cases identified between June 2013 and December 2014 along with 3,993 SDO without any code of MC (5% of the total volume of births in the same period).positive predictive value (VPP) and negative predictive value (VPN) were computed by means of the comparison between the algorithm outcomes and the clinical record verification.4,271 potentially malformed records involving 3,381 subjects born in the Sicilian territory have been identified. Among the hospital discharge records that it was possible to verify, the application of the algorithm led to the exclusion of 924 cases: of these, 62 proved to be false negatives (VPN: 93.3). The valid cases were 1,179, while the cases to be evaluated 617: the comparison between algorithm and clinical record analysis led to a VPP of 91.7 and 72.1, respectively, for valid and to be evaluated.the tested algorithm proved to be a useful tool for identifying SDO potentially related to congenital anomalies. In the overall sample, the algorithm provided an outcome consistent with the clinical record assessment in 87.4% (2,379) of cases.

BackgroundBirth cohorts of women living in highly industrialized areas provide an ideal setting for studying the correlation between environmental exposure and health.ObjectivesTo evaluate serum microRNA expression in response to environmental contaminants in 68 healthy pregnant women from the NEHO birth cohort.MethodsSerum contaminants were determined by GC-MS/MS and ICP-MS/MS. Serum microRNA expression was determined by qPCR. Associations between miRNA ΔCTs and single serum element levels were tested by linear regression models, while whole mixture effect was studied by WQS regression analysis.ResultsIn separate regression models, a positive association was found between miR-223 ΔCT and concentrations of Se and Zn, while a negative association between miR-30b and Hg levels was observed. Similar regression models were also conducted using tertiles of each chemical as independent variables. In this setting, the Let-7a ΔCT was decreased in the comparison between medium and low tertiles of Se. The highest tertiles of Zn and p,p’-DDE showed a significant association with increasing levels of miR-223 ΔCT with respect to the lower tertile; moreover, miR-30b ΔCT was reduced in the comparison between high and low tertiles of Hg. The observed data were confirmed by fold-change analysis. A WQS analysis built on tertiles of contaminant distribution revealed a significant mixture effect on the expression of the analyzed miRNAs. The inverse association between Let-7a ΔCT and the WQS index was dominated by Zn, Se, Cu, Hg and HCB. Moreover, miR-223 ΔCT was positively associated with the WQS index, where p,p’-DDE, Zn and Se showed the greatest contributions to the association. Conversely, the reduction of miR-30b ΔCT was mainly driven by Hg and Se.DiscussionThis study allowed us to characterize the role of prolonged exposure to environmental contaminants influencing the expression of circulating miRNAs in the serum of women in the last trimester of pregnancy.

Background: Few studies have examined the impact of urban greenspace exposure on lung function in children-adolescents, and the available evidence is still inconsistent. The aim of the current study was to verify the hypothesis that the effects of greenspace exposure vary with differing levels of lung function of children-adolescents. Methods: Between November 2005 and May 2006, 2150 children-adolescents (age-range: 10-15 years) living in the city of Palermo were enrolled in a cross-sectional survey. Parents were interviewed through a modified version of the Italian Studies on Respiratory Disorders in Children and the Environment (SIDRIA) questionnaire. All children-adolescents performed spirometry and were tested for allergic sensitization. Exposures to greenspace and grey space at the home addresses were measured using the CORINE land-cover classes. Parametric quantile regression models were applied for assessing the association between greenspace exposure and spirometry parameters, accounting for possible confounders and effect modifiers. A p-value lower than 0.05 was considered statistically significant. Results: From the 1st to the 21st percentile, children-adolescents living within greenspace had higher FEV1 than those living within grey space. In particular, the estimated effects were: 1st (? = 0.238 L, p = 0.01), 5th (? = 0.140 L, p = 0.01), 10th (? = 0.097 L, p = 0.015), and 15th (? = 0.073 L, p = 0.025). Similarly, from the 1st to the 29th percentile, children-adolescents living within greenspace had higher FVC than those living within grey space. In particular, the estimated effects were: 1st (? = 0.367 L, p = 0.0003), 5th (? = 0.215 L, p = 0.0003), 10th (? = 0.150 L, p = 0.0004), and 15th (? = 0.112 L, p = 0.001). No significant associations were found for FEV1/FVC, FEF25-75 and FEF25-75/FVC. Conclusion: Quantile regression techniques may provide new insights into the evaluation of the association between greenspace exposure and lung function in children-adolescents, showing substantially heterogeneous effects from lower to higher quantiles of spirometry parameters. These results may help implementing policies for planning sustainable housing and surrounding greenspaces.

There is growing evidence that environmental pollutants can induce epigenetic modifications altering the balance of miRNAs and inducing the onset of pathological conditions in animals. In this study, we measured the serum concentration of a suite of inorganic and organic pollutants (Cu, Zn, Se, Hg, HCB, p,p'-DDE, PCBs) and their association to serum miR-30b, miR-223 and Let-7a microRNA expression in 68 healthy pregnant women from the NEHO birth cohort sited in a highly industrialized area. The effects of the pollutants on the modulation of circulating miRNAs' expression were first investigated using linear continuous regression models with a single-compound approach showing that miR-223 expression was significantly associated with serum concentration of Se and Zn (pSe = 0.0336; pZn = 0.0225) and miR-30b was associated with Hg levels (pHg = 0.019). Furthermore, when contaminants were categorized into tertiles, miR-223 and miR-30b showed a positive association with higher tertiles of Zn, p,p'-DDE (pZn = 0.023; pDDE = 0.041) and Hg (pHg = 0.008), respectively. Moreover, Let-7a expression was exclusively influenced by medium tertiles levels of Se (low vs medium tertiles, p = 0.001). Simultaneous exposure to multi-pollutant mixture was approached by WQS regression model. Statistical analysis shows a driving effect of Zn, Se, Cu, Hg and HCB on significant increased expression of Let-7a (p = 0.045). Mercury and Se significantly amplified the expression for miR-30b (p = 0.038). Differently, the combined effect of p,p'-DDE, Zn and Se decreased miR-223 expression (p = 0.0001). The documented modified expression of circulating miRNAs in the serum of pregnant women, exposed to low-medium dose contaminants mixtures offers innovative early-warning approaches to human health risk assessment.

Objectives: to evaluate and validate the adoption of an algorithm for the identification of cases of congenital anomalies (CAs) to improve the performance of the Congenital Malformations Registry of Sicily Region (Southern Italy). Design: an algorithm was used to identify congenital anomalies on a sample of hospital discharge records (SDO) with ICD-9-CM code between 740-759 on any of the diagnoses within the first year of life, together with a sample of healthy births equal to 5% of total births for the same period. The identified cases were evaluated through the clinical record analysis. Setting and participants: the analysed sample was composed of 4,271 cases identified between June 2013 and December 2014 along with 3,993 SDO without any code of MC (5% of the total volume of births in the same period). Main outcome measures: positive predictive value (VPP) and negative predictive value (VPN) were computed by means of the comparison between the algorithm outcomes and the clinical record verification. Results: 4,271 potentially malformed records involving 3,381 subjects born in the Sicilian territory have been identified. Among the hospital discharge records that it was possible to verify, the application of the algorithm led to the exclusion of 924 cases: of these, 62 proved to be false negatives (VPN: 93.3). The valid cases were 1,179, while the cases to be evaluated 617: the comparison between algorithm and clinical record analysis led to a VPP of 91.7 and 72.1, respectively, for valid and to be evaluated. Conclusions: the tested algorithm proved to be a useful tool for identifying SDO potentially related to congenital anomalies. In the overall sample, the algorithm provided an outcome consistent with the clinical record assessment in 87.4% (2,379) of cases.

Il capitolo descrive, nell'ambito del Progetto CISAS (Centro di studi avanzati su ambiente, ecosistema e salute umana), il disturbo olfattivo e la sua valutazione, strettamente associata alla percezione umana soggettiva.

In this work, we investigated from a theoretical point of view the dynamics of the energy transfer process from the ligand to Eu(III) ion for 12 isomeric species originating from six different complexes differing by nature of the ligand and the total charge. The cationic complexes present the general formula [Eu(L)(H2O)2] + (where L = bpcd2− = N,N′-bis(2-pyridylmethyl)- trans-1,2-diaminocyclohexane N,N′-diacetate; bQcd2− = N,N′- bis(2-quinolinmethyl)-trans-1,2-diaminocyclohexane N,N′-diacetate; and bisoQcd2− = N,N′-bis(2-isoquinolinmethyl)-trans-1,2- diaminocyclohexane N,N′-diacetate), while the neutral complexes present the Eu(L)(H2O)2 formula (where L = PyC3A3− = Npicolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate; QC3A3− = N-quinolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate; and isoQC3A3− = N-isoquinolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate). Time-dependent density functional theory (TD-DFT) calculations provided the energy of the ligand excited donor states, distances between donor and acceptor orbitals involved in the energy transfer mechanism (RL), spin-orbit coupling matrix elements, and excited-state reorganization energies. The intramolecular energy transfer (IET) rates for both singlet-triplet intersystem crossing and ligand-to-metal (and vice versa) involving a multitude of ligand and Eu(III) levels and the theoretical overall quantum yields (ϕovl) were calculated (the latter for the first time without the introduction of experimental parameters). This was achieved using a blend of DFT, Judd−Ofelt theory, IET theory, and rate equation modeling. Thanks to this study, for each isomeric species, the most efficient IET process feeding the Eu(III) excited state, its related physical mechanism (exchange interaction), and the reasons for a better or worse overall energy transfer efficiency (ηsens) in the different complexes were determined. The spectroscopically measured ϕovl values are in good agreement with the ones obtained theoretically in this work. published

Risk perception (RP) evaluation during pregnancy and its relationship with lifestyles are considered useful tools for understanding communities living in high-risk areas and preventing dangerous exposure. It is well known that exposure to pollutants and less-healthy lifestyles may result in increased disease occurrence during life. Our work investigated environmental RP through ad hoc questionnaires administered to 611 mothers within the NEHO birth cohort, recruited in three heavily contaminated areas of Southern Italy. Four different RP indices, an exploratory factorial analysis (EFA), and a latent class analysis were evaluated from questionnaires. The highest values of risk perception index were observed in the Milazzo site (0.64 ± 0.16) and the lowest in the Crotone site (0.5 ± 0.18). EFA revealed four latent factors, including different items describing environmental pollution, and subjects were classified into four latent classes with different RP indices. Significant RP profiles were different among the sites (p &lt, 0.001). Our results did not demonstrate any association between RP and lifestyles during pregnancy. Improving healthy lifestyle behaviours, particularly in polluted areas, would generate co-benefits by preventing further risk factors. As remediation interventions can take a long time, it needs to improve healthy lifestyles in residents until remediation is completed.

In this paper, we present a comparative study of the redox properties of the icosahedral [Rh

BACKGROUND Several studies have reported a low prevalence of current smoking among hospitalized COVID-19 cases; however, no definitive conclusions can be drawn. OBJECTIVE We investigated the association of tobacco smoke exposure with nasopharyngeal swab (NPS) test results for SARS-CoV-2 infection and disease severity accounting for possible confounders. METHODS The nationwide, self-administered, cross-sectional web-based Italian National Epidemiological Survey on COVID-19 (EPICOVID19) was administered to an Italian population of 198,822 adult volunteers who filled in an online questionnaire between April 13 and June 2, 2020. For this study, we analyzed 6857 individuals with known NPS test results. The associations of smoking status and the dose-response relationship with a positive NPS test result and infection severity were calculated as odds ratios (ORs) with 95% CIs by means of logistic and multinomial regression models adjusting for sociodemographic, clinical, and behavioral characteristics. RESULTS Out of the 6857 individuals (mean age 47.9 years, SD 14.1; 4516/6857, 65.9% female), 63.2% (4334/6857) had never smoked, 21.3% (1463/6857) were former smokers, and 15.5% (1060/6857) were current smokers. Compared to nonsmokers, current smokers were younger, were more educated, were less affected by chronic diseases, reported COVID-19–like symptoms less frequently, were less frequently hospitalized, and less frequently tested positive for COVID-19. In multivariate analysis, current smokers had almost half the odds of a positive NPS test result (OR 0.54, 95% CI 0.45-0.65) compared to nonsmokers. We also found a dose-dependent relationship with tobacco smoke: mild smokers (adjusted OR [aOR] 0.76, 95% CI 0.55-1.05), moderate smokers (aOR 0.56, 95% CI 0.42-0.73), and heavy smokers (aOR 0.38, 95% CI 0.27-0.53). This inverse association also persisted when considering the severity of the infection. Current smokers had a statistically significantly lower probability of having asymptomatic (aOR 0.50, 95% CI 0.27-0.92), mild (aOR 0.65, 95% CI 0.53-0.81), and severe infections (aOR 0.27, 95% CI 0.17-0.42) compared to those who never smoked. CONCLUSIONS Current smoking was negatively associated with SARS-CoV-2 infection with a dose-dependent relationship. Ad hoc experimental studies are needed to elucidate the mechanisms underlying this association. CLINICALTRIAL ClinicalTrials.gov NCT04471701; https://clinicaltrials.gov/ct2/show/NCT04471701

In this paper, we present a comparative study of the redox properties of the icosahedral [Rh12E(CO)27]n− (n = 4 when E = Ge or Sn and n = 3 when E = Sb or Bi) family of clusters through in situ infrared spectroelectrochemistry experiments and density functional theory computational studies. These clusters show shared characteristics in terms of molecular structure, being all E-centered icosahedral species, and electron counting, possessing 170 valence electrons as predicted by the electron-counting rules, based on the cluster-borane analogy, for compounds with such metal geometry. However, in some cases, clusters of similar nuclearity, and beyond, may show multivalence behavior and may be stable with a different electron counting, at least on the time scale of the electrochemical analyses. The experimental results, confirmed by theoretical calculations, showed a remarkable electron-sponge behavior for [Rh12Ge(CO)27]4− (1), [Rh12Sb(CO)27]3− (3), and [Rh12Bi(CO)27]3− (4), with a cluster charge going from −2 to −6 for 1 and 3 and from −2 to −7 for cluster 4, making them examples of molecular electron reservoirs. The [Rh12Sn(CO)27]4− (2) derivative, conversely, presents a limited ability to exist in separable reduced cluster species, at least within the experimental conditions, while in the gas phase it appears to be stable both as a penta- and hexa-anion, therefore showing a similar redox activity as its congeners. As a fallout of those studies, during the preparation of [Rh12Sb(CO)27]3−, we were able to isolate a new species, namely, [Rh11Sb(CO)26]2−, which presents a Sb-centered nido-icosahedral metal structure possessing 158 cluster valence electrons, in perfect agreement with the polyhedral skeletal electron pair theory.

Pregnant women living in industrially contaminated sites (ICSs) are exposed to environmental contaminants through different pathways, and thus children’s health may be affected by pollutants. We created the Neonatal Environment and Health Outcomes (NEHO) longitudinal birth cohort in three ICSs in the Mediterranean area of southern Italy, collecting comprehensive information on personal data and lifestyles by questionnaire. Through multiple correspondence analysis, we identified possible clusters of enrolled women, and a neural network classifier analysis (NNCA) was performed to identify variables capable of predicting the attrition rate of the study. NEHO recruited 845 mother–child pairs over two years. The mothers’ mean age was 31.1 ± 5.2 SD years. We found significant differences in socioeconomic status (SES) among the three evaluated ICS, and an overall 11.1% prevalence of mothers who actively smoked during pregnancy. Active smoking during pregnancy was strongly associated with the lowest socioeconomic level (p &lt, 0.0001). By means of the NNCA, we found that smoking during pregnancy and the lowest education level characterized the cluster with the highest attrition rate (p &lt, 0.001). Our results demonstrate that reason for public health concern still exists regarding smoking during pregnancy and that SES influences both lifestyles, producing negative pregnancy outcomes and a higher survey attrition rate.

Il capitolo descrive l'attività svolta, nell'ambito del Progetto CISAS (Centro di studi avanzati su ambiente, ecosistema e salute umana), per l'arruolamento e la conduzione della coorte residenziale di nascita NEHO (Neonatal Environment and Health Outcomes) nelle tre aree a rischio ambientale di Milazzo, Priolo e Crotone.

Questo capitolo è una sintesi dei risultati più rilevanti emersi dalle attività del progetto CISAS, Centro internazionale di studi avanzati sull'ambiente, l'ecosistema e la salute umana, quelli che i protagonisti ritengono più promettenti per gli sviluppi della ricerca su ambiente e salute e degli interventi di bonifica delle aree inquinate , presidio prioritario per la prevenzione dei danni sulla salute delle persone e delle comunità.

Il progetto CISAS, Centro internazionale di studi avanzati sull'ambiente l'ecosistema e la salute umana, mira a comprendere i processi chimico fisici e biologici che regolano la distribuzione dei contaminanti in varie matrici ambientali e il loro impatto su ecosistema e salute umana partendo da tre casi studio dei Siti di bonifica di interessi nazionale, SIN: il SIN di Augusta/Priolo, il SIN di Milazzo, e il SIN di Crotone.

Stabilised sulfur ylides are synthetically appealing compounds, which reactivity under Brønsted acid catalysis has been poorly explored. Herein, we report a new catalyst- and substrate- dependent chemodivergent reaction between stabilised sulfur ylides and salicylaldehydes, leading to the (suprising) formation of 2H-chromenes or dihydrobenzofurans products. Particular attention was set on the unusual mechanisms involved. Two unique reaction routes including two ylide units in the reactions are proposed. These pathways were validated by performing a selectivity switch in some cases, enabled by the modulation of the nucleophilicity of the sulfur ylide, and by the loading of the Brønsted acid catalyst in the reaction.

Background Several studies have reported a low prevalence of current smoking among hospitalized COVID-19 cases; however, no definitive conclusions can be drawn. Objective We investigated the association of tobacco smoke exposure with nasopharyngeal swab (NPS) test results for SARS-CoV-2 infection and disease severity accounting for possible confounders. Methods The nationwide, self-administered, cross-sectional web-based Italian National Epidemiological Survey on COVID-19 (EPICOVID19) was administered to an Italian population of 198,822 adult volunteers who filled in an online questionnaire between April 13 and June 2, 2020. For this study, we analyzed 6857 individuals with known NPS test results. The associations of smoking status and the dose-response relationship with a positive NPS test result and infection severity were calculated as odds ratios (ORs) with 95% CIs by means of logistic and multinomial regression models adjusting for sociodemographic, clinical, and behavioral characteristics. Results Out of the 6857 individuals (mean age 47.9 years, SD 14.1; 4516/6857, 65.9% female), 63.2% (4334/6857) had never smoked, 21.3% (1463/6857) were former smokers, and 15.5% (1060/6857) were current smokers. Compared to nonsmokers, current smokers were younger, were more educated, were less affected by chronic diseases, reported COVID-19–like symptoms less frequently, were less frequently hospitalized, and less frequently tested positive for COVID-19. In multivariate analysis, current smokers had almost half the odds of a positive NPS test result (OR 0.54, 95% CI 0.45-0.65) compared to nonsmokers. We also found a dose-dependent relationship with tobacco smoke: mild smokers (adjusted OR [aOR] 0.76, 95% CI 0.55-1.05), moderate smokers (aOR 0.56, 95% CI 0.42-0.73), and heavy smokers (aOR 0.38, 95% CI 0.27-0.53). This inverse association also persisted when considering the severity of the infection. Current smokers had a statistically significantly lower probability of having asymptomatic (aOR 0.50, 95% CI 0.27-0.92), mild (aOR 0.65, 95% CI 0.53-0.81), and severe infections (aOR 0.27, 95% CI 0.17-0.42) compared to those who never smoked. Conclusions Current smoking was negatively associated with SARS-CoV-2 infection with a dose-dependent relationship. Ad hoc experimental studies are needed to elucidate the mechanisms underlying this association. Trial Registration ClinicalTrials.gov NCT04471701; https://clinicaltrials.gov/ct2/show/NCT04471701

Sulfur ylides first disclosed in 1930 started to gain more attention in the 1960s, thanks mainly to the studies by Corey and Chaykovsky on their use for the preparation of strained rings. More recently, the chemistry of these compounds has experienced important growth, in part due to the similarity of their reactivities with diazo compounds. This short review provides an overview on the great assortment of reactions of sulfoxonium ylides, outlining a comparison between the chemistry of these ylides and their congeners: sulfonium ylides and diazo compounds. Insertion reactions, cyclisation reactions and ring-opening reactions are highlighted, giving particular attention to catalytic asymmetric methodologies.

Industrial areas are characterized by the dispersion of environmental stressors that could possibly have long-term detrimental effects on both human health and the environment. Environmental contamination has been indicated to be one of the major risks for reproductive health. In this context, the effects of environmental pollution on pregnant women living in heavily polluted areas is of special interest. In fact, fetal development is a crucial phase due to the dynamic interaction between the maternal/external environments and the developing organs and tissues. Moreover, following Barker's postulate of the intrauterine origin of health and disease, the events occurring in this time window could affect future health. Birth cohorts provide the most suitable design for assessing the association between early-life and possible long-term health outcomes in highly contaminated sites. By providing an assessment of the early life environment throughout the collection of biological samples, birth cohorts offer the opportunity to study in-depth several possible confounders and outcomes by means of questionnaires and follow-ups based on clinical evaluations and bio-specimen samplings. The exposome comprises the totality of exposures from conception onwards; the birth cohort approach allows the integration of the exposures as a whole, including those related to socioeconomic status, with "omics" data from biological samples collected at birth and throughout life. In the characterization of the "fetal exposome," the placenta represents a highly informative and scarcely considered organ. For this purpose, the "Neonatal Environment and Health Outcomes" (NEHO) birth cohort has been established by enrolling pregnant women residing in contaminated sites and in surrounding areas.

The reactivity of [Rh7(CO)16]3– with SbCl3 has been deeply investigated with the aim of finding a new approach to prepare atomically precise metalloid clusters. In particular, by varying the stoichiometric ratios, the reaction atmosphere (carbon monoxide or nitrogen), the solvent, and by working at room temperature and low pressure, we were able to prepare two large carbonyl clusters of nanometer size, namely, [Rh20Sb3(CO)36]3– and [Rh21Sb2(CO)38]5–. A third large species composed of 28 metal atoms was isolated, but its exact formulation in terms of metal stoichiometry could not be incontrovertibly confirmed. We also adopted an alternative approach to synthesize nanoclusters, by decomposing the already known [Rh12Sb(CO)27]3– species with PPh3, willing to generate unsaturated fragments that could condense to larger species. This strategy resulted in the formation of the lower-nuclearity [Rh10Sb(CO)21PPh3]3– heteroleptic cluster instead. All three new compounds were characterized by IR spectroscopy, and their molecular structures were fully established by single-crystal X-ray diffraction studies. These showed a distinct propensity for such clusters to adopt an icosahedral-based geometry. Their characterization was completed by ESI-MS and NMR studies. The electronic properties of the high-yield [Rh21Sb2(CO)38]5– cluster were studied through cyclic voltammetry and in situ infrared spectroelectrochemistry, and the obtained results indicate a multivalent nature., The reactivity of [Rh7(CO)16]3− with SbCl3 has been deeply investigated as a new approach to prepare atomically precise metal nanoparticles. By varying the reaction conditions, we obtained three large carbonyl nanoclusters, [Rh20Sb3(CO)36]3−, [Rh21Sb2(CO)38]5−, and [Rh28−xSbx(CO)44]6−, and the lower-nuclearity [Rh10Sb(CO)21PPh3]3− species. They have all been characterized through X-ray diffraction, IR spectroscopy, and other techniques based on their specific nature. Spectroelectrochemical studies on [Rh21Sb2(CO)38]5− unravelled its multivalent nature.

Chemical research in synthesizing metal nanoparticles has been a major topic in the last two decades, as nanoparticles can be of great interest in many fields such as biology, catalysis, and nanotechnology. However, as their chemical and physical properties are size-dependent, the reliable preparation of nanoparticles at a molecular level is highly desirable. Despite the remarkable advances in recent years in the preparation of thiolate- or p-MBA or PA-protected gold and silver nanoclusters (p-MBA = p-mercaptobenzoic acid; PA = phenylalkynyl), as well as the large palladium clusters protected by carbonyl and phosphine ligands that initially dominated the field, the synthesis of monodispersed and atomically precise nanoparticles still represents a great challenge for chemists.Carbonyl cluster compounds of high nuclearity have become more and more part of a niche chemistry, probably owing to their handling issues and expensive synthesis. However, even in large size, they are known at a molecular level and therefore can play a relevant role in understanding the structures of nanoparticles in general. For instance the icosahedral pattern, proper of large gold nanoparticles, is also found in some Au-Fe carbonyl cluster compounds.Rh clusters in general can also be employed as precursors in homo- and heterogeneous catalysis, and the possibility of doping them with other elements at the molecular level is an important additional feature. The fact that they can be obtained as large crystalline species, with dimensions of about 2 nm, allows one to place them not only in the nanometric regime, but also in the ultrafine-metal-nanoparticle category, which lately has been attracting growing attention. In fact, such small nanoparticles possess an even higher density of active catalytic sites than their larger (up to 100 nm) equivalents, hence enhancing atom efficiency and reducing the cost of precious-metal catalysts. Finally, the clusters' well-defined morphology could, in principle, contribute to expand the studies on the shape effects of nanocatalysts.In this Account, we want to provide the scientific community with some insights on the preparation of rhodium-containing carbonyl compounds of increasing nuclearity. Among them, we present the synthesis and molecular structures of two new heterometallic nanoclusters, namely, [Rh23Ge3(CO)(41)](5-) and [Rh16Au6(CO)(36)](6-), which have been obtained by reacting a rhodium-cluster precursor with Ge(II) and Au(III) salts. The growth of such clusters is induced by redox mechanisms, which allow going from mononuclear complexes up to clusters with over 20 metal atoms, thus entering the nanosized regime.

Cigarette smoke is the main source of indoor chemical and toxic elements. Cadmium (Cd), Thallium (Tl), Lead (Pb) and Antimony (Sb) are important contributors to smoke-related health risks. Data on the association between Rare Earth Elements (REE) Cerium (Ce) and Lanthanum (La) and domestic smoking are scanty. To evaluate the relationship between cigarette smoke, indoor levels of PM2.5 and heavy metals, 73 children were investigated by parental questionnaire and skin prick tests. The houses of residence of 41 "cases" and 32 "controls" (children with and without respiratory symptoms, respectively) were evaluated by 48-hours PM2.5 indoor/outdoor monitoring. PM2.5 mass concentration was determined by gravimetry; the extracted and mineralized fractions of elements (As, Cd, Ce, La, Mn, Pb, Sb, Sr, Tl) were evaluated by ICP-MS. PM2.5 and Ce, La, Cd, and Tl indoor concentrations were higher in smoker dwellings. When corrected for confounding factors, PM2.5, Ce, La, Cd, and Tl were associated with more likely presence of respiratory symptoms in adolescents. We found that: i) indoor smoking is associated with increased levels of PM2.5, Ce, La, Cd, and Tl and ii) the latter with increased presence of respiratory symptoms in children

The reaction of the [Rh7(CO)16]3− cluster anion with Ge2+ salts, in different stoichiometric ratios and under different atmospheres, leads to the formation of new heterometallic Rh–Ge clusters, representing the first known examples of Rh carbonyl compounds containing interstitial germanium atoms. More specifically, under N2 the reaction progressively affords the new [Rh13Ge(CO)25]3− and [Rh14Ge2(CO)30]2− clusters in good yields, with the Ge atoms located in cubic and square-anti-prismatic cavities, respectively. However, under a CO atmosphere, the [Rh13Ge(CO)25]3− derivative undergoes a significant structural and chemical rearrangement giving the new compound, [Rh12Ge(CO)27]4−, where Ge is hosted in an icosahedral metal cage. All species have been characterized by IR spectroscopy and ESI mass spectrometry, and their structures have been elucidated by single-crystal X-ray diffraction. Additionally, preliminary biological tests on the [Rh13Ge(CO)25]3− and [Rh14Ge2(CO)30]2− clusters show that they are cytotoxic to various cell lines.

The reaction of [Rh7(CO)16]3– with BiCl3 under N2 and at room temperature results in the formation of the new heterometallic [Bi@Rh12(CO)27]3– cluster in high yields. Further controlled addition of BiCl3 leads first to the formation of the dimeric [(Bi@Rh12(CO)26)2Bi]5– and the closo-[Bi@Rh14(CO)27Bi2]3– species in low yields, and finally, to the [Bi@Rh17(CO)33Bi2]4– cluster. All clusters were spectroscopically characterized by IR and electrospray ionization mass spectrometry, and their molecular structures were fully determined by X-ray diffraction studies. Notably, they represent the first examples of Bi atoms interstitially lodged in metallic cages that, in this specific case, are all based on an icosahedral geometry. Moreover, [Bi@Rh14(CO)27Bi2]3– forms an exceptional network of infinite zigzag chains in the solid state, thanks to intermolecular Bi–Bi distances.

The reactivity of [Rh7(CO)16]3- with SbCl3 has been deeply investigated with the aim of finding a new approach to prepare atomically precise metalloid clusters. In particular, by varying the stoichiometric ratios, the reaction atmosphere (carbon monoxide or nitrogen), the solvent, and by working at room temperature and low pressure, we were able to prepare two large carbonyl clusters of nanometer size, namely, [Rh20Sb3(CO)36]3- and [Rh21Sb2(CO)38]5-. A third large species composed of 28 metal atoms was isolated, but its exact formulation in terms of metal stoichiometry could not be incontrovertibly confirmed. We also adopted an alternative approach to synthesize nanoclusters, by decomposing the already known [Rh12Sb(CO)27]3- species with PPh3, willing to generate unsaturated fragments that could condense to larger species. This strategy resulted in the formation of the lower-nuclearity [Rh10Sb(CO)21PPh3]3- heteroleptic cluster instead. All three new compounds were characterized by IR spectroscopy, and their molecular structures were fully established by single-crystal X-ray diffraction studies. These showed a distinct propensity for such clusters to adopt an icosahedral-based geometry. Their characterization was completed by ESI-MS and NMR studies. The electronic properties of the high-yield [Rh21Sb2(CO)38]5- cluster were studied through cyclic voltammetry and in situ infrared spectroelectrochemistry, and the obtained results indicate a multivalent nature.

Prenatal smoking exposure and early-life respiratory infections are major determinants of asthma during childhood. We investigate the factors influencing allergic sensitization (AS), asthma, and lung function in children and the balance between individual and environmental characteristics at different life stages. 1714 children aged 7&ndash, 16 years and living in southern Italy were investigated using a parental questionnaire, skin prick tests, and spirometry. We found 41.0% AS prevalence: among children without parental history of asthma, male sex, maternal smoking during pregnancy (MatSmoke), and acute respiratory diseases in the first two years of life (ARD2Y) were significant risk factors for AS. MatSmoke was associated (OR = 1.79) with ARD2Y, and this association was influenced by sex. ARD2Y was, in turn, a significant risk factor (OR = 8.53) for childhood current asthma, along with AS (OR up to 3.03) and rhinoconjuctivitis (OR = 3.59). Forced mid-expiratory flow (FEF25&ndash, 75%) was negatively affected by ARD2Y, with a sex-related effect. Thus, males exposed to MatSmoke had significantly lower FEF25&ndash, 75% than unexposed males. Despite the difficulty of discriminating among the complex interactions underlying the development of allergic respiratory diseases, ARD2Y appears to strongly influence both asthma and lung function during childhood. In turn, ARD2Y is influenced by prenatal exposure to tobacco smoke with a sex-dependent effect.

The reaction of [Ni6(CO)12]2– as a [NBu4]+ salt in CH2Cl2 with 0.8 equiv of PCl3 afforded [Ni14P2(CO)22]2–. In contrast, the reactions of [Ni6(CO)12]2– as a [NEt4]+ salt with 0.4–0.5 equiv of POCl3 afforded [Ni22–xP2(CO)29–x]4– (x = 0.84) or [Ni39P3(CO)44]6– by using CH3CN and thf as a solvent, respectively. Moreover, by using 0.7–0.9 mol of POCl3 per mole of [NEt4]2[Ni6(CO)12] both in CH3CN and thf, [Ni23–xP2(CO)30–x]4– (x = 0.82) was obtained together with [Ni22P6(CO)30]2– as a side product. [Ni23–xP2(CO)30–x]4– (x = 0.82) and [Ni22P6(CO)30]2– were separated owing to their different solubility in organic solvents. All the new molecular nickel phosphide carbonyl nanoclusters were structurally characterized through single crystal X-ray diffraction (SC-XRD) as [NBu4]2[Ni14P2(CO)22] (two different polymorphs, P21/n and C2/c), [NEt4]4[Ni23–xP2(CO)30–x]·CH3COCH3·solv (x = 0.82), [NEt4]2[Ni22P6(CO)30]·2thf, [NEt4]4[Ni22–xP2(CO)29–x]·2CH3COCH3( x = 0.84) and [NEt4]6[Ni39P3(CO)44]·C6H14·solv. The metal cores’ sizes of these clusters range from 0.59 to 1.10 nm, and their overall dimensions including the CO ligands are 1.16–1.63 nm. In this respect, they are comparable to ultrasmall metal nanoparticles, molecular nanoclusters, or atomically precise metal nanoparticles. The environment of the P atoms within these molecular Ni–P–CO nanoclusters displays a rich diversity, that is, Ni5P pentagonal pyramid, Ni7P monocapped trigonal prism, Ni8P bicapped trigonal prism, Ni9P monocapped square antiprism, Ni10P sphenocorona, Ni10P bicapped square antiprism, and Ni12P icosahedron., Five new molecular nickel phosphide carbonyl clusters have been obtained displaying overall sizes in the range 1.16−1.63 nm and very diverse environments for the phosphide atoms.

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La Convenzione di Minamata sul mercurio è entrata in vigore il 26 agosto 2017. L'Italia, assieme a Stati Uniti, Cina, Canada, Australia, ai paesi dell'Unione Europea e ad alcuni paesi di Africa ed Asia, rientra tra i primi paesi firmatari, ma, tra i Paesi dell'UE, l'Italia e la Spagna non hanno ancora ratificato. Nel settembre 2017 si è tenuta a Ginevra la prima conferenza, nella quale i governi provenienti da tutto il mondo si sono impegnati nella riduzione di emissioni e rilascio di mercurio a livello mondiale che minacciano l'ambiente e la salute di milioni di persone. Il progetto CISAS (Centro Internazionale di Studi avanzati su Ambiente, ecosistema e Salute umana), coordinato dal CNR (Consiglio Nazionale delle Ricerche), sta studiando l'associazione tra ambiente e salute in siti contaminati, e specificamente nei SIN (Siti di Bonifica di Interesse Nazionale) di Priolo, Milazzo e Crotone. Tra i tanti inquinanti presenti nei tre SIN, l'attenzione dei ricercatori si è concentrata anche sul mercurio, rappresentato in particolare nel SIN di Priolo, dove la preoccupazione per la contaminazione si accompagna a quella per la ritardata bonifica. L'eliminazione dovrebbe avvenire sequestrando e isolando la sostanza perché i cicli naturali non riescono né a far diminuire il mercurio né ad annullarne gli effetti negativi. La rassegna delle conoscenze che proponiamo di seguito nasce dall'esigenza di riportare il mercurio all'attenzione degli studiosi, degli operatori del settore ambientale e della sanità pubblica e degli amministratori ai diversi livelli di competenza.

Syngas and Hydrogen productions from methane are industrially carried out at high temperatures (900 &deg, C). Nevertheless, low-temperature steam reforming can be an alternative for small-scale plants. In these conditions, the process can also be coupled with systems that increase the overall efficiency such as hydrogen purification with membranes, microreactors or enhanced reforming with CO2 capture. However, at low temperature, in order to get conversion values close to the equilibrium ones, very active catalysts are needed. For this purpose, the Rh4(CO)12 cluster was synthetized and deposited over Ce0.5Zr0.5O2 and ZrO2 supports, prepared by microemulsion, and tested in low-temperature steam methane reforming reactions under different conditions. The catalysts were active at 750 &deg, C at low Rh loadings (0.05%) and outperformed an analogous Rh-impregnated catalyst. At higher Rh concentrations (0.6%), the Rh cluster deposited on Ce0.5Zr0.5 oxide reached conversions close to the equilibrium values and good stability over long reaction time, demonstrating that active phases derived from Rh carbonyl clusters can be used to catalyze steam reforming reactions. Conversely, the same catalyst suffered from a fast deactivation at 500 &deg, C, likely related to the oxidation of the Rh phase due to the oxygen-mobility properties of Ce. Indeed, at 500 &deg, C the Rh-based ZrO2-supported catalyst was able to provide stable results with higher conversions. The effects of different pretreatments were also investigated: at 500 &deg, C, the catalysts subjected to thermal treatment, both under N2 and H2, proved to be more active than those without the H2 treatment. In general, this work highlights the possibility of using Rh carbonyl-cluster-derived supported catalysts in methane reforming reactions and, at low temperature, it showed deactivation phenomena related to the presence of reducible supports.

Polybrominated diphenyl ethers (PBDEs) are widespread as flame-retardants in different types of consumer products. PBDEs present in the air or dust and their inhalation can damage human health by influencing the respiratory system. We evaluated the effects of environment relevant concentrations (0.01–1 μM) of PBDE-47, PBDE-99 and PBDE-209 on the mechanism of oxidative stress, dysregulation of cell proliferation, apoptosis, and DNA damage and repair (in term of H2AX phosphorylation ser139) in an in-vitro/ex-vivo model of bronchial epithelial cells. PBDEs (−47, −99 and −209) at the environment relevant concentrations (0.01 and 1 μM) induce oxidative stress (in term of NOX-4 expression as well as ROS and JC-1 production), activate the mechanism of DNA-damage and repair affecting Olive Tail length (comet assay) production and H2AX phosphorylation (ser139) in normal human bronchial epithelial cells. Furthermore PBDEs, although do not affect cell viability, induce cell apoptosis and single cell capacity to grow into a colony (like a cancer phenotype) in bronchial epithelial cells. Finally, PBDE-47 had a greater effect than −99 and −209. PBDE-47, -99 and −209 congeners exert cytotoxic and genotoxic effects, and play a critical role in the dysregulation of oxidative stress, damaging DNA and the related gene expression in bronchial epithelial cells. Our findings might suggest that PBDEs inhalation might have adverse effect on human health regarding pulmonary diseases in the areas of environmental pollution.