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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.
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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.
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DNA/química , Bicamadas Lipídicas/química , Lasers , Microscopia Confocal , Fosfatidilcolinas/químicaRESUMO
HYPOTHESIS: In order to understand the basic mechanisms affecting emulsion stability, the intrinsic dynamics of the drop population must be investigated. We hypothesize that transient ballistic motion can serve as a marker of interactions between drops. In 1G conditions, buoyancy-induced drop motion obscures these interactions. The microgravity condition onboard the International Space Station enable this investigation. EXPERIMENTS: We performed Diffusing Wave Spectroscopy (DWS) experiments in the ESA Soft Matter Dynamics (SMD) facility. We used Monte Carlo simulations of photon trajectory to support data analysis. The analysis framework was validated by ground-based characterizations of the initial drop size distribution (DSD) and the properties of the oil/water interface in the presence of surfactant. FINDINGS: We characterized the drop size distribution and found to be bi-disperse. Drop dynamics shows transient ballistic features at early times, reaching a stationary regime of primarily diffusion-dominated motion. This suggests different ageing mechanisms: immediately after emulsification, the main mechanism is coalescence or aggregation between small drops. However at later times, ageing proceeds via coalescence or aggregation of small with large drops in some emulsions. Our results elucidate new processes relevant to emulsion stability with potential impact on industrial processes on Earth, as well as enabling technologies for space exploration.
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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.
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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).
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Asbestose/diagnóstico , Doenças Profissionais/diagnóstico , Exposição Ocupacional/efeitos adversos , Vigilância da População , Adulto , Idoso , Idoso de 80 Anos ou mais , Biomarcadores/análise , Feminino , Humanos , Masculino , Pessoa de Meia-IdadeRESUMO
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.
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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.
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Cromatografia Líquida de Alta Pressão/métodos , Cosméticos/química , Vitamina K 1/análise , Vitamina K 3/análise , Humanos , Pele , Espectrofotometria UltravioletaRESUMO
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.
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Indústria Alimentícia , Doenças Profissionais/mortalidade , Adolescente , Adulto , Causas de Morte , Seguimentos , Humanos , Itália/epidemiologia , Masculino , Pessoa de Meia-IdadeRESUMO
Nasal cancer has a number of causative agents; exposures to most of the established nasal carcinogens occur in the workplace. An increased risk of nasal cancer has been ascertained in shoe-making and shoe-repairing, but the results for leather goods manufacture and leather tanning don't provide adequate evidence of carcinogenicity. Findings from two epidemiological studies carried out in Italy (a case/control study and a case/series report) add further information on this issue. The case/control study was performed in the provinces of Siena (Tuscany), Verona and Vicenza (Venetia) including 96 cases and 378 controls. A significant increased risk (Odds Ratio: 6.8; 90% C.I. = 1.9-25) of sinonasal cancer was found for the employ in the whole leather industry; Odds Ratio of 8.3 (C.I. = 1.9-36) and 5.0 (C.I. = 0.92-28) were associated with shoe-making and leather tanning. The case/series report is based on 110 patients accepted in some Italian hospitals during last three years (1990-1993): 26 cases had worked in the leather industry; adenocarcinoma is the most frequent type observed. Chromium salts and natural tannins are indicated as possible aetiological agents.
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Neoplasias Nasais/epidemiologia , Doenças Profissionais/epidemiologia , Curtume , Estudos de Casos e Controles , Humanos , Itália/epidemiologia , Razão de Chances , Fatores de Risco , Inquéritos e QuestionáriosRESUMO
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.
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Vidro , Neoplasias/mortalidade , Doenças Profissionais/mortalidade , Adulto , Idoso , Causas de Morte , Estudos de Coortes , Humanos , Itália , Masculino , Pessoa de Meia-Idade , Sistema de RegistrosRESUMO
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).
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Organofosfatos/urina , Adolescente , Adulto , Fatores Etários , Análise de Variância , Poluição Ambiental , Feminino , Contaminação de Alimentos , Humanos , Itália , Masculino , Pessoa de Meia-Idade , Organofosfatos/metabolismo , Organotiofosfatos/urina , Software , Inquéritos e QuestionáriosRESUMO
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.
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Adjuvantes Imunológicos/metabolismo , Envelhecimento/fisiologia , Bolsa de Fabricius/citologia , Bolsa de Fabricius/enzimologia , Galinhas , Enzimas/metabolismo , Extratos do Timo/metabolismo , Animais , Técnicas ImunoenzimáticasRESUMO
Plasma zinc levels in patients of both sexes suffering from an heterogeneous group of dermopathies were examined and compared with those in patients suffering from psychiatric-neurologic pathologies, in which recent literature has also suggested the role of low zinc levels. The results of the study show a prevalence of effective zinc deficiency in 9.2% of dermatologic patients and 3.9% of neurologic patients, as well as low plasma zinc levels with a different mean, mode and s.d. in comparison to other patients in the control group. These results were statistically significant. The findings are discussed and compared with those reported in the literature.
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Transtornos Mentais/sangue , Doenças do Sistema Nervoso/sangue , Dermatopatias/sangue , Zinco/deficiência , Feminino , Humanos , Masculino , Zinco/sangueRESUMO
"Trans-placental" exposure to polycyclic aromatic hydrocarbons (PAHs) in newborn babies of mothers smoking during pregnancy was investigated and compared with that in newborn babies of non smoking mothers. PAHs intake was evaluated by measuring urinary levels of 1-hydroxypyrene, a pyrene metabolita and a biological index of exposure. 42 mothers-babies couples (31 smoking and 11 non smoking mothers) were examined. Urinary concentrations of 1-hydroxypyrene in 42 controls, 18 non smoking and 24 smoking women, were determined at the same time. Mean values of 1-hydroxypyrene in non smoking women in labour and their babies were 0.15 (SD 0.11) and 0.15 (SD 0.10) micrograms/g creatinine respectively. In controls the mean was 0.15 (SD 0.09) micrograms/g creat. Mean values of 0.23 (SD 0.17) and 0.20 (SD 0.15) micrograms/g creatinine were determined in smoking mothers and their newborn babies, whereas in smoking controls 1-hydroxypyrene was 0.42 (SD 0.45) micrograms/g creatinine. The highest levels of 1-hydroxypyrene were detected in smokers (both controls and women in labour). Babies of smoking mothers also showed a higher mean value of 1-hydroxypyrene than babies of non smokers. However the only statistically significant difference found was between smoking and non smoking controls.
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Troca Materno-Fetal , Mutagênicos/metabolismo , Compostos Policíclicos/metabolismo , Pirenos/metabolismo , Fumar/urina , Adulto , Feminino , Humanos , Recém-Nascido , Masculino , Gravidez , Terceiro Trimestre da GravidezRESUMO
The treatment of liver metastases should be addressed in a multidisciplinary way, considering the manifold therapeutic options available, for each of which corresponds a particular indication. The best results are obtainable with resective surgery in cases in which there is a partial involvement of the liver (25-50%) and a variable intra-hepatic distribution (monolobar), situations that correspond to Gennari stages I and II. In the authors' experience, the extent of the liver resection does not influence possible survival and oncologically correct resections should be carried out such as segmentectomies, pluri-segmentectomies or wedge resection in compliance with the principle of removing at least 1.5 cm of healthy perineoplastic tissue. The authors reserve major hepatectomies to special situations: voluminous metastases, diffuse involvement of a single lobe, topographic localisation contraindicating segmentary resection.
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Carcinoma/secundário , Carcinoma/terapia , Neoplasias Colorretais/patologia , Neoplasias Hepáticas/secundário , Neoplasias Hepáticas/terapia , Carcinoma/mortalidade , Carcinoma/patologia , Quimioterapia do Câncer por Perfusão Regional , Neoplasias Colorretais/mortalidade , Terapia Combinada , Etanol/administração & dosagem , Floxuridina/administração & dosagem , Hepatectomia/métodos , Humanos , Neoplasias Hepáticas/mortalidade , Neoplasias Hepáticas/patologia , Estadiamento de Neoplasias , PrognósticoRESUMO
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.
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Arte , Vidro , Adulto , Idoso , Causas de Morte , Estudos de Coortes , Feminino , Seguimentos , Humanos , Itália/epidemiologia , Masculino , Pessoa de Meia-Idade , Neoplasias/mortalidade , Doenças Profissionais/mortalidade , Distribuição por SexoRESUMO
The Authors analyze a series of 441 patients affected by carcinoma of the colon operated on between June 1980 and November 1993. The incidence of the different stages of the disease according to Dukes resulted comparable to that reported in the literature as well as the incidence of morbidity and mortality. Recostruction was performed in all cases with mechanical sutures (T-L for the right colon and L-T for the left colon) and without protection enterostomy. Long-term results evaluated by actuarial methods were influenced by the stage of the disease, and not by sex or duration of symptoms. The need of early diagnosis as well as oncologically correct surgical technique is furthermore confirmed. The importance of clinical trials on adjuvant chemotherapy is emphasized in order to improve survival in patients operated for stage B and C colon cancer.
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Neoplasias do Colo/cirurgia , Adulto , Idoso , Idoso de 80 Anos ou mais , Neoplasias do Colo/mortalidade , Feminino , Seguimentos , Humanos , Masculino , Pessoa de Meia-Idade , Taxa de SobrevidaRESUMO
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.