Gold nanoparticle assisted synthesis of MoS2 monolayers by chemical vapor deposition.

The use of metal nanoparticles is an established paradigm for the synthesis of semiconducting one-dimensional nanostructures. In this work we study their effect on the synthesis of two-dimensional semiconducting materials, by using gold nanoparticles for chemical vapor deposition growth of two-dimensional molybdenum disulfide (MoS2). In comparison with the standard method, the employment of gold nanoparticles allows us to obtain large monolayer MoS2 flakes, up to 20 µm in lateral size, even if they are affected by the localized overgrowth of MoS2 bilayer and trilayer islands. Important modifications of the optical and electronic properties of MoS2 triangular domains are reported, where the photoluminescence intensity of the A exciton is strongly quenched and a shift to a positive threshold voltage in back-gated field effect transistors is observed. These results indicate that the use of gold nanoparticles influences the flake growth and properties, indicating a method for possible localized synthesis of two-dimensional materials, improving the lateral size of monolayers and modifying their properties.

Wave-Vector Dependence of the Dynamics in Supercooled Metallic Liquids.

We present a detailed investigation of the wave-vector dependence of collective atomic motion in Au_{49}Cu_{26.9}Si_{16.3}Ag_{5.5}Pd_{2.3} and Pd_{42.5}Cu_{27}Ni_{9.5}P_{21} supercooled liquids close to the glass transition temperature. Using x-ray photon correlation spectroscopy in a previously uncovered spatial range of only a few interatomic distances, we show that the microscopic structural relaxation process mimics the structure and presents a marked slowing down at the main average interparticle distance. This behavior is accompanied by dramatic changes in the shape of the intermediate scattering functions, which suggest the presence of large dynamical heterogeneities at length scales corresponding to a few particle diameters. A ballisticlike mechanism of particle motion seems to govern the structural relaxation of the two systems in the highly viscous phase, likely associated with hopping of caged particles in agreement with theoretical studies.

Direct measurement of DNA-mediated adhesion between lipid bilayers.

Multivalent interactions between deformable mesoscopic units are ubiquitous in biology, where membrane macromolecules mediate the interactions between neighbouring living cells and between cells and solid substrates. Lately, analogous artificial materials have been synthesised by functionalising the outer surface of compliant Brownian units, for example emulsion droplets and lipid vesicles, with selective linkers, in particular short DNA sequences. This development extended the range of applicability of DNA as a selective glue, originally applied to solid nano and colloidal particles. On very deformable lipid vesicles, the coupling between statistical effects of multivalent interactions and mechanical deformation of the membranes gives rise to complex emergent behaviours, as we recently contributed to demonstrate [Parolini et al., Nat. Commun., 2015, 6, 5948]. Several aspects of the complex phenomenology observed in these systems still lack a quantitative experimental characterisation and a fundamental understanding. Here we focus on the DNA-mediated multivalent interactions of a single liposome adhering to a flat supported bilayer. This simplified geometry enables the estimate of the membrane tension induced by the DNA-mediated adhesive forces acting on the liposome. Our experimental investigation is completed by morphological measurements and the characterisation of the DNA-melting transition, probed by in situ Förster Resonant Energy Transfer spectroscopy. Experimental results are compared with the predictions of an analytical theory that couples the deformation of the vesicle to a full description of the statistical mechanics of mobile linkers. With at most one fitting parameter, our theory is capable of semi-quantitatively matching experimental data, confirming the quality of the underlying assumptions.

Controlling the dynamics of a bidimensional gel above and below its percolation transition.

The morphology and the microscopic internal dynamics of a bidimensional gel formed by spontaneous aggregation of gold nanoparticles confined at the water surface are investigated by a suite of techniques, including grazing-incidence x-ray photon correlation spectroscopy (GI-XPCS). The range of concentrations studied spans across the percolation transition for the formation of the gel. The dynamical features observed by GI-XPCS are interpreted in view of the results of microscopic imaging; an intrinsic link between the mechanical modulus and internal dynamics is demonstrated for all the concentrations. Our work presents an example of a transition from a stretched to a compressed correlation function actively controlled by quasistatically varying the relevant thermodynamic variable. Moreover, by applying a model proposed some time ago by Duri and Cipelletti [Europhys. Lett. 76, 972 (2006)] we are able to build a master curve for the shape parameter, whose scaling factor allows us to quantify a "long-time displacement length." This characteristic length is shown to converge, as the concentration is increased, to the "short-time localization length" determined by pseudo-Debye-Waller analysis of the initial contrast. Finally, the intrinsic dynamics of the system is then compared with that induced by means of a delicate mechanical perturbation applied to the interface.

Heterogeneous and anisotropic dynamics of a 2D gel.

We report x-ray photon correlation spectroscopy (XPCS) results on bidimensional (2D) gels formed by a Langmuir monolayer of gold nanoparticles. The system allows an experimental determination of the fourth order time correlation function, which is compared to the usual second order correlation function and to the mechanical response measured on macroscopic scale. The observed dynamics is anisotropic, heterogeneous and superdiffusive on the nanoscale. Different time scales, associated with fast heterogeneous dynamics inside 2D cages and slower motion of larger parts of the film, can be identified from the correlation functions. The XPCS results are discussed in view of other experimental results and models of three-dimensional gel dynamics.

[Dose and effect biomarkers in the diagnosis of asbestos-related diseases and health surveillance of exposed workers]. / Gli indicatori biologici di dose ed effetto nella diagnostica delle patologie asbesto-correlate e nella sorveglianza sanitaria degli ex-esposti.

The aim of the study was to assess the reliability of the indicators of dose and effect in the health monitoring of asbestos exposed workers. In 49 cases out of 158 studied workers (31%) asbestos-related diseases were diagnosed following ATS criteria (2004). Using nonparametric statistical methods (permutation tests) 6 variables were analyzed with respect to asbestos-related diseases and working sectors, demonstrating a difference in the concentration of amphiboles (p < 0.01), greater in patients with asbestosis and workers involved in asbestos removal from railway carriages. There was not a correlation between mesothelin and amphiboles, chrysotile and total fibers concentrations (Spearman test).

Identification and quantitation of vitamins K1 and K3 in cosmetic products for facial skin protection.

A simple and rapid analytical method was developed for the determination of vitamins K1 and K3 in facial anti-rash creams. The procedure is based on an ultrasonic extraction of the cosmetic sample with dimethylacetamide, in the presence of an internal standard, followed by HPLC separation. HPLC was performed using a C18 column and spectrophotometric detection at 333 nm. A linear gradient elution was carried out starting with 50% acetonitrile-methanol (75:25 v/v) and water up to 100% acetonitrile-methanol for 5 min. Linearity was established over the concentration range from 0.2 to 1.0 mg/ml for vitamin K1 and from 0.02 to 0.1 mg/ml for vitamin K3, with LOD values of 100 ng and 20 ng injected, respectively. The accuracy was verified by spiking experiments on model cosmetic samples. The proposed method has been successfully applied for the analysis of commercial samples of creams.

[Mortality in a cohort of sugar refinery workers in Arezzo Province, Italy]. / Mortalità negli addetti di uno zuccherificio nell'aretino.

BACKGROUND AND OBJECTIVES: The aim of this study was to investigate mortality of a cohort of 1,767 male workers employed in a sugar refinery plant located in the Province of Arezzo, Italy, where asbestos had been used from the 1960's for the insulation of thermohydraulic systems and for furnaces. In 1987-88 workers removed the asbestos-cement insulation from the plant. METHODS: The cohort was composed by male workers who were employed in the plant between 1 March 1962 and 1 February 1996, and had worked for at least 2 months. Follow-up started on 1 March 1962, and ended on 31 May, 2003. The population mortality for Tuscany Region was used as the reference. The relative risk was estimated by Standardized Mortality Ratio (SMR) and the confidence intervals were calculated at a 95% level (95% CI). RESULTS: The majority of workers were employed during the summer only. Significant decreases in mortality were observed for overall mortality (SMR = 78; 95% CI = 69-88), all cancers (SMR = 80; 95% CI = 65-97), cardiovascular diseases (SMR = 64; 95% CI = 50-81), lung cancer (SMR = 66; 95% CI = 43-98), and gastrointestinal diseases (SMR = 53; 95% CI = 26-98). Non-significant increases were observed for kidney cancer (SMR = 229; 95% CI = 92-472), and diseases of the nervous system (SMR = 155; 95% CI = 71-294). Kidney cancer mortality for workers employed for > = 5 years was significantly higher (SMR = 508; 95% CI = 105-1485). CONCLUSIONS: Mortality for asbestos-related diseases did not show any increase. The higher kidney cancer mortality for workers employed for > = 5 years could be due to exposures to various carcinogens, that occurred not only in the sugar refinery plant, given that the workers were seasonal and did other jobs during the rest of the year. Asbestos-related deaths could occur in the future among some workers who in 1987-88 were employed on the removal of asbestos-cement insulation from the plant.

Identification of cells secreting a thymostimulin-like substance and examination of some histoenzymatic pathways in aging avian primary lymphatic organs: II. Bursa of Fabricius.

The Bursa of Fabricius of 15 day, 1-, 3-, and 6 month-old adult chickens (White Leghorn strain) were studied by histological and histochemical staining, histoenzymatic reactions (LDH, SDH, a-GPDH, NAD, NADPH, Ca++-dependent ATP-ase, pH 8.5) and by anti-thymostimulin immunoreaction. Positive reactions for mucopolysaccharides and enzymatic activities were located in the epithelia of the follicles, i.e. in follicle-associated-epithelium (FAE), inter-follicle-epithelium (IFE) and in different epithelial compartments of cortical and medullary zones. Positive reaction for thymostimulin-like (TS-like) substance was restricted to FAE cells and weakly to the basal lamina of IFE. In 6-month-old chickens, the FAE cells disappeared; the phenomenon of bursal regression was evident, although not all the follicles were involved. In the few still normal follicles, the good reactivity to the enzymes tested suggests that residual physiological activity is still present, even if reduced.

Mortality due to asbestos-related causes among railway carriage construction and repair workers.

The objective of this study was to further clarify the cancer risk associated with asbestos exposure in railway carriage construction and repair. The cohort included 734 subjects employed between 1 January 1945 and 31 December 1969. Vital status was ascertained at 31 December 1997. Mortality was investigated in the time span 1970-97. Forty-two subjects (6%) were lost to follow-up and eight causes of death (4%) could not be ascertained. The overall mortality was not above the expected value. Among neoplastic diseases, excesses were observed for lung standardized mortality ratio (SMR) = 124; 90% confidence interval (CI) = 87-172; 26 obs), pleura (SMR = 1,327; CI = 523-2,790; 5 obs), larynx (SMR = 240; CI = 95-505; 5 obs), liver (SMR = 241; CI = 126-420; 9 obs), pancreas (SMR = 224; CI = 98-443; 6 obs) and multiple myeloma (SMR = 429; CI = 117-1,109; 3 obs). The observed excess of lung and pleural neoplasms can be causally related to asbestos exposure in the manufacture of railway carriages. A causal role of asbestos exposure in the raised SMRs from laryngeal and pancreatic neoplasms and multiple myeloma cannot be conclusively proven.

Cancer mortality of art glass workers in Tuscany, Italy.

OBJECTIVES: This study considers the cause-specific mortality from cancer among art glass workers employed in 17 industrial facilities in Tuscany, Italy. METHODS: A cohort of 3390 workers, 3180 men and 210 women, employed at least 1 year, was taken from company payrolls. It was followed between the year each factory started operation, mostly the mid-1950s, and 31 December 1993. The cause-specific expected mortality from cancer was computed for men relative to Tuscany rates, specified for gender, 5-year age groups, and calendar year. Separate analyses were carried out for the job title of maker and former and for batch mixers. RESULTS: For 3180 men, the observed mortality was above the expected for larynx [standardized mortality ratio (SMR) 166, 90% confidence interval (90% CI) 90-282], lung (SMR 123, 90% CI 100-151), stomach (SMR 105, 90% CI76-142), and brain (SMR 150, 90%CI 71-282) cancer. Increases for these causes were also found for the makers and formers. Mortality from larynx and lung cancer increased with latency, and significantly increased SMR values were observed for > or =21 years since first exposure. The increasing pattern was also present after adjustment for smoking. CONCLUSIONS: The results showed consistently increased mortality from larynx and lung cancer in the overall cohort and among makers and formers. Stomach and brain cancer was also increased in the overall cohort and among the makers and formers.

Prediction of percutaneous absorption from physicochemical data: a model based on data of in vitro experiments.

Correlations between in vitro percutaneous absorption data and physicochemical properties of industrial chemicals are evaluated in order to develop predictive mathematical models based on said properties. Percutaneous diffusion of 16 pounds of occupational interest, eight of which were polycyclic aromatic hydrocarbons (acenaphthene, anthracene, benzo(a)anthracene, chrysene, phenanthrene, fluorene, naphthalene, pyrene), six organophosphorus insecticides (acephate, chlorpyrifos, dimethoate, fenitrothion, methamidophos, omethoate) and two phenoxycarboxylic herbicides (2,4-D, MCPA), were tested in vitro using monkey (Cercopithecus aetiops) skin. The test apparatus consisted of nine static diffusion cells with normal saline, gentamycin sulphate and 4% bovine serum albumin as receiving solution. Test compounds were applied at various concentrations in 30 microliters of acetone solution and determined, in the receiving phase, by chemical analysis. Values for ln Kow (octanol/water partition coefficient) were correlated with experimentally determined values of the permeability constant Kp (r = 0.90, P < 0.001) and lag time (r = 0.81, P < 0.01). Analysis of variance in a model of multiple linear regression between Kp, ln Kow and water solubility [water] of the compounds, showed that the data had a highly significant fit (P < 0.0001). A more general model which also included molecular weight (MW) and vapour pressure was evaluated as well, but the two variables made no substantial difference. Multiple regression analysis between lag time, ln Kow and [water] was significant (P < 0.0001), whereas introduction of vapour pressure and MW as independent variables did not significantly improve the predictive effect on lag time. Our experimental system, therefore, enables the values of Kp and lag time to be predicted with reasonable precision on the basis of ln Kow and [water] values, using the algorithm derived from the multiple linear regression equation.

Cohort study of art glass workers in Tuscany, Italy: mortality from non-malignant diseases.

This investigation studies cause-specific mortality of art glass workers employed in 17 industrial facilities in Tuscany, Italy. A cohort of 3,390 workers employed for at least 1 year was enumerated from company payrolls. Follow-up was between the start of employment in each factory and 31 December 1993. The cause-specific expected mortality was computed relative to Tuscany rates and specified for gender, 5-year age groups and calendar year. Separate analyses were carried out for the jobs of makers and formers and for batch mixers. Among males (3, 180 individuals) observed mortality for non-cancer causes was higher than expected for hypertensive disease [standardized mortality ratio (SMR) = 178, 90% confidence interval (90% CI) = 96-301], pneumoconiosis (SMR = 200, 90% CI = 94-376) and diseases of the genitourinary system (SMR = 169, 90% CI = 95-279). Increases for the above causes were shown also among makers and formers: hypertensive disease (SMR = 182, 90% CI = 85-341), pneumoconiosis (SMR = 250, 90% CI = 109-493) and diseases of the genitourinary system (SMR = 224, 90% CI = 121-380). For batch mixers an increase was present for cerebrovascular disease. The observed mortality for cancer causes was above the expected for cancers of the larynx, lung, stomach and brain. This study points to the existence for Tuscan glass workers of health effects in addition to cancer; previously observed carcinogenic effects were also confirmed.

[A cohort study of art glass workers in the Empoli area]. / Studio di coorte dei lavoratori del vetro artistico nel territorio empolese.

The investigation aimed at studying cause-specific mortality of art glass workers employed in 17 industrial facilities in Tuscany, Italy. A cohort of 3390 workers employed for at least 1 year was obtained from company payrolls. Follow-up was between the year each factory started operations, mostly in the mid-fifties, and the end of 1993. The cause specific expected mortality was computed relative to Tuscany rates, specified for gender, 5-year age groups and calendar year. Separate analyses were carried out for the job titles of makers, batch mixers and grinders. For males, 3180 individuals, the observed mortality for cancer causes was above the expected for the lung [standardized mortality ratio (SMR) 123, 10 observed (Obs)], larynx (SMR 166, 10 Obs), stomach (SMR 105, 30 Obs) and brain (SMR 150, 7 Obs). For non-cancer causes observed mortality was above expected for hypertensive diseases (SMR 178, 10 Obs) and diseases of the genitourinary system (SMR 169, 11 Obs). Increases for the above listed causes were shown also among makers. Mortality for larynx and lung cancer increased with time since first exposure and significantly increased SMRs were observed for 21 or more years since first exposure: this pattern was still present with smoking adjustment. The results showed consistently increased mortality for lung and larynx cancer in the overall cohort and among makers. Stomach cancer, brain cancer, hypertensive diseases and diseases of the genitourinary system were also increased in the overall cohort and among makers.

In vitro percutaneous penetration of methyl-parathion from a commercial formulation through the human skin.

OBJECTIVE: To compare in vitro percutaneous absorption of methyl-parathion dissolved in an acetone vehicle and in the form of a commercial formulation. METHODS: Penetration through the human skin was measured in Franz diffusion cells with full thickness skin from a human cadaver as the membrane. The two tailed non-parametric Mann-Whitney U test was used to compare the cumulative diffusion of methyl-parathion in the receptor fluid of the cells at various time intervals. RESULTS: In vitro skin penetration of methyl-parathion was significantly higher with the commercial formulation. The percentage of the applied dose absorbed after 24 hours was 5.20% v 1.35%. The mean lag time was < 8 hours. CONCLUSION: Assessments of uptake and internal dose after exposure to pesticides should be based on the commercial products rather than active ingredients, because of the crucial role of the vehicle, as shown in this study.

Urinary excretion of alkylphosphates in the general population (Italy).

Xenobiotic residues and their metabolites in biological fluids of the general population are an important indicator of exposure to toxic substances dispersed in the environment. Urine samples collected from 124 subjects living in SW Tuscany, Italy were analyzed for alkylphosphates (dimethylphosphate, dimethylthiophosphate, dimethyldithiophosphate, diethylphosphate, diethylthiophosphate, diethyldithiophosphate), aspecific metabolites of organophosphorus insecticides. The compound most frequently found was dimethylthiophosphate which was detectable in 99% of the subjects analyzed, with a geometric mean of 70.7 nmol/g creatinine. The other substances were found in the following percentages of our population, at the following mean concentrations: dimethylphosphate, 87%, 62.8 nmol/g creat.; dimethyldithiophosphate, 48%, 21.1 nmol/g creat.; diethylphosphate, 81%, 27.4 nmol/g creat.; diethylthiophosphate, 73%, 22.8 nmol/g creat.; diethyldithiophosphate, 7%, 13.7 nmol/g creatinine. Subjects eating food (fruit, meat, vegetables) that was not their own produce showed higher urinary concentrations of nearly all the compounds. The other variables considered (sex, age, residence, alcohol, smoking, sampling period) seem to affect the percentages of positive values of the various substances but to different degrees. Age and source of foods were the most important variables for dimethylthiophosphate excretion when mean values were analyzed by Student's t-test and analysis of variance (ANOVA).

Serum erythropoietin and blood lead concentrations.

The aim of the study was to test the hypothesis that high blood lead levels are associated with depressed serum erythropoietin concentrations in workers occupationally exposed to lead. The results in exposed workers and in a control group of unexposed subjects were compared. Blood lead values were < or = 20 micrograms/dl in unexposed subjects and > or = 30 micrograms/dl in exposed subjects. The two groups of exposed workers and the control population were matched for sex and age. Hemoglobin levels were not affected by blood lead values and did not differ significantly between the three groups. The two-tailed, nonparametric Mann-Whitney U-test was used to compare unpaired groups. The Spearman rank correlation test was used to evaluate the dose-effect relationship between Pb and EPO. The analysis of the data indicate that erythropoietin values are significantly lower in exposed subjects than a controls. However no correlation was demonstrated between blood lead concentrations and erythropoietin in any group.