99 research outputs found

    Synthesis of Liquid Core−Shell Particles and Solid Patchy Multicomponent Particles by Shearing Liquids Into Complex Particles (SLICE)

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    We report a simple method that uses (i) emulsion shearing with oxidation to make core–shell particles, and (ii) emulsion shearing with surface-tension driven phase segregation to synthesize particles with complex surface compositions and morphologies. Subjecting eutectic gallium–indium, a liquid metal, to shear in an acidic carrier fluid we synthesized smooth liquid core–shell particles 6.4 nm to over 10 μm in diameter. Aggregates of these liquid particles can be reconfigured into larger structures using a focused ion beam. Using Field’s metal melts we synthesized homogeneous nanoparticles and solid microparticles with different surface roughness and/or composition through shearing and phase separation. This extension of droplet emulsion technique, SLICE, applies fluidic shear to create micro- and nanoparticles in a tunable, green, and low-cost approach

    Assembled Monolayers Depends upon the Roughness of the Substrate and the Orientation of the Terminal Moiety

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    The origin of the odd even effect in properties of self-assembled monolayers (SAMs) and/or technologies derived from them is poorly understood. We report that hydrophobicity and, hence, surface wetting of SAMs are dominated by the nature of the substrate (surface roughness and identity) and SAM tilt angle, which influences surface dipoles/orientation of the terminal moiety. We measured static contact angles (theta(s)) made by water droplets on n-alkanethiolate SAMs with an odd (SAM(O)) or even (SAM(E)) number of carbons (average theta(s) range of 105.8-112.1 degrees). When SAMs were fabricated on smooth template-stripped metal (M-TS) surfaces [root-mean-square (rms) roughness = 0.36 +/- 0.01 nm for Au-TS and 0.60 +/- 0.04 nm for Ag-TS], the odd-even effect, characterized by a zigzag oscillation in values of theta(s), was observed. We, however, did not observe the same effect with rougher as-deposited (M-AD) surfaces (rms roughness = 2.27 +/- 0.16 nm for Au-AD and 5.13 +/- 0.22 nm for Ag-AD). The odd-even effect in hydrophobicity inverts when the substrate changes from Au-TS (higher theta(s) for SAM(E) than SAM(O), with average Delta theta(s) (vertical bar n - (n + 1)vertical bar) approximate to 3 degrees) to Ag-TS (higher theta(s) for SAM(O) than SAM(E), with average Delta theta(s) (vertical bar n - (n + 1)vertical bar) approximate to 2 degrees). A comparison of hydrophobicity across Ag-TS and Au-TS showed a statistically significant difference (Student\u27s t test) between SAM(E) (Delta theta(s) (vertical bar Ag evens - Au evens vertical bar) approximate to 5 degrees; P \u3c 0.01) but failed to show statistically significant differences on SAM(O) (Delta theta(s) (vertical bar Ag odds) (- Au odds vertical bar) approximate to 1 degrees; p \u3e 0.1). From these results, we deduce that the roughness of the metal substrate (from comparison of M-AD versus M-TS) and orientation of the terminal -CH2CH3 (by comparing SAM(E) and SAM(O) on Au-TS versus Ag-TS) play major roles in the hydrophobicity and, by extension, general wetting properties of n-alkanethiolate SAMs

    A Systematic Approach to Study Electoral Fraud

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    Integrity of elections relies on fair procedures at di?erent stages of the election process, and fraud can occur in many instances and di?erent forms. This paper provides a general approach for the detection of fraud. While most existing contributions focus on a single instance and form of fraud, we propose a more encompassing approach, testing for several empirical implications of di?erent possible forms of fraud. To illustrate this approach we rely on a case of electoral irregularities in one of the oldest democracies: In a Swiss referendum in 2011, one in twelve municipalities irregularly destroyed the ballots, rendering a recount impossible. We do not know whether this happened due to sloppiness, or to cover possible fraudulent actions. However, one of our statistical tests leads to results, which points to irregularities in some of the municipalities, which lost their ballots: they reported significantly fewer empty ballots than the other municipalities. Relying on several tests leads to the well known multiple comparisons problem. We show two strategies and illustrate strengths and weaknesses of each potential way to deal with multiple tests

    Bone mineral density and the subsequent risk of cancer in the NHANES I follow-up cohort

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    BACKGROUD: Bone mineral density (BMD) is a marker of long-term estrogen exposure. BMD measurement has been used in this context to investigate the association of estrogen with breast cancer risk in three cohorts. In order to assess further BMD as a predictor of estrogen related cancer risk, the association of BMD with colorectal and corpus uteri cancer was investigated in the NHANES I Epidemiologic Followup Study (NHEFS) cohort along with breast cancer and prostate cancer. METHODS: Participants were members of the NHEFS cohort who had BMD measurement in 1974–1975. Age, race, and BMI adjusted rate ratios and 95% confidence intervals were calculated for incidence of cancers of the corpus uterus, breast, colorectum, prostate, and of osteoporosis and hip fracture related to baseline BMD. RESULTS: Data were available for 6046 individuals. One hundred cases of breast cancer, 94 prostate cancers, 115 colorectal cancers, 29 uterine cancers, 110 cases of hip fracture and 103 cases of osteoporosis were reported between 1974 and 1993. Hip fracture and osteoporosis were both significantly inversely associated with BMD. Uterine cancer was positively associated (p = 0.005, test for linear trend) and colorectal cancer negatively associated (p = 0.03) with BMD. No association was found between elevated BMD and incidence of breast cancer (p = 0.74) or prostate cancer (p = 0.37) in the overall cohort, although a weak association was seen between BMD and subsequent breast cancer incidence when BMD was measured in post-menopausal women (p = 0.04). CONCLUSION: The findings related to cancers of the uterus and colorectum as well as the weak association of BMD with breast cancer strengthen the use of BMD as a marker of estrogen exposure and cancer risk

    cis-Expression QTL Analysis of Established Colorectal Cancer Risk Variants in Colon Tumors and Adjacent Normal Tissue

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    Genome-wide association studies (GWAS) have identified 19 risk variants associated with colorectal cancer. As most of these risk variants reside outside the coding regions of genes, we conducted cis-expression quantitative trait loci (cis-eQTL) analyses to investigate possible regulatory functions on the expression of neighboring genes. Forty microsatellite stable and CpG island methylator phenotype-negative colorectal tumors and paired adjacent normal colon tissues were used for genome-wide SNP and gene expression profiling. We found that three risk variants (rs10795668, rs4444235 and rs9929218, using near perfect proxies rs706771, rs11623717 and rs2059252, respectively) were significantly associated (FDR q-value ≤0.05) with expression levels of nearby genes (<2 Mb up- or down-stream). We observed an association between the low colorectal cancer risk allele (A) for rs10795668 at 10p14 and increased expression of ATP5C1 (q = 0.024) and between the colorectal cancer high risk allele (C) for rs4444235 at 14q22.2 and increased expression of DLGAP5 (q = 0.041), both in tumor samples. The colorectal cancer low risk allele (A) for rs9929218 at 16q22.1 was associated with a significant decrease in expression of both NOL3 (q = 0.017) and DDX28 (q = 0.046) in the adjacent normal colon tissue samples. Of the four genes, DLGAP5 and NOL3 have been previously reported to play a role in colon carcinogenesis and ATP5C1 and DDX28 are mitochondrial proteins involved in cellular metabolism and division, respectively. The combination of GWAS findings, prior functional studies, and the cis-eQTL analyses described here suggest putative functional activities for three of the colorectal cancer GWAS identified risk loci as regulating the expression of neighboring genes

    School Effects on the Wellbeing of Children and Adolescents

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    Well-being is a multidimensional construct, with psychological, physical and social components. As theoretical basis to help understand this concept and how it relates to school, we propose the Self-Determination Theory, which contends that self-determined motivation and personality integration, growth and well-being are dependent on a healthy balance of three innate psychological needs of autonomy, relatedness and competence. Thus, current indicators involve school effects on children’s well-being, in many diverse modalities which have been explored. Some are described in this chapter, mainly: the importance of peer relationships; the benefits of friendship; the effects of schools in conjunction with some forms of family influence; the school climate in terms of safety and physical ecology; the relevance of the teacher input; the school goal structure and the implementation of cooperative learning. All these parameters have an influence in promoting optimal functioning among children and increasing their well-being by meeting the above mentioned needs. The empirical support for the importance of schools indicates significant small effects, which often translate into important real-life effects as it is admitted at present. The conclusion is that schools do make a difference in children’s peer relationships and well-being

    Global, regional, and national age-sex specific all-cause and cause-specific mortality for 240 causes of death, 1990-2013: A systematic analysis for the Global Burden of Disease Study 2013

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    Background Up-to-date evidence on levels and trends for age-sex-specific all-cause and cause-specific mortality is essential for the formation of global, regional, and national health policies. In the Global Burden of Disease Study 2013 (GBD 2013) we estimated yearly deaths for 188 countries between 1990, and 2013. We used the results to assess whether there is epidemiological convergence across countries. Methods We estimated age-sex-specific all-cause mortality using the GBD 2010 methods with some refinements to improve accuracy applied to an updated database of vital registration, survey, and census data. We generally estimated cause of death as in the GBD 2010. Key improvements included the addition of more recent vital registration data for 72 countries, an updated verbal autopsy literature review, two new and detailed data systems for China, and more detail for Mexico, UK, Turkey, and Russia. We improved statistical models for garbage code redistribution. We used six different modelling strategies across the 240 causes; cause of death ensemble modelling (CODEm) was the dominant strategy for causes with sufficient information. Trends for Alzheimer's disease and other dementias were informed by meta-regression of prevalence studies. For pathogen-specific causes of diarrhoea and lower respiratory infections we used a counterfactual approach. We computed two measures of convergence (inequality) across countries: the average relative difference across all pairs of countries (Gini coefficient) and the average absolute difference across countries. To summarise broad findings, we used multiple decrement life-tables to decompose probabilities of death from birth to exact age 15 years, from exact age 15 years to exact age 50 years, and from exact age 50 years to exact age 75 years, and life expectancy at birth into major causes. For all quantities reported, we computed 95% uncertainty intervals (UIs). We constrained cause-specific fractions within each age-sex-country-year group to sum to all-cause mortality based on draws from the uncertainty distributions. Findings Global life expectancy for both sexes increased from 65·3 years (UI 65·0-65·6) in 1990, to 71·5 years (UI 71·0-71·9) in 2013, while the number of deaths increased from 47·5 million (UI 46·8-48·2) to 54·9 million (UI 53·6-56·3) over the same interval. Global progress masked variation by age and sex: for children, average absolute differences between countries decreased but relative differences increased. For women aged 25-39 years and older than 75 years and for men aged 20-49 years and 65 years and older, both absolute and relative differences increased. Decomposition of global and regional life expectancy showed the prominent role of reductions in age-standardised death rates for cardiovascular diseases and cancers in high-income regions, and reductions in child deaths from diarrhoea, lower respiratory infections, and neonatal causes in low-income regions. HIV/AIDS reduced life expectancy in southern sub-Saharan Africa. For most communicable causes of death both numbers of deaths and age-standardised death rates fell whereas for most non-communicable causes, demographic shifts have increased numbers of deaths but decreased age-standardised death rates. Global deaths from injury increased by 10·7%, from 4·3 million deaths in 1990 to 4·8 million in 2013; but age-standardised rates declined over the same period by 21%. For some causes of more than 100 000 deaths per year in 2013, age-standardised death rates increased between 1990 and 2013, including HIV/AIDS, pancreatic cancer, atrial fibrillation and flutter, drug use disorders, diabetes, chronic kidney disease, and sickle-cell anaemias. Diarrhoeal diseases, lower respiratory infections, neonatal causes, and malaria are still in the top five causes of death in children younger than 5 years. The most important pathogens are rotavirus for diarrhoea and pneumococcus for lower respiratory infections. Country-specific probabilities of death over three phases of life were substantially varied between and within regions. Interpretation For most countries, the general pattern of reductions in age-sex specific mortality has been associated with a progressive shift towards a larger share of the remaining deaths caused by non-communicable disease and injuries. Assessing epidemiological convergence across countries depends on whether an absolute or relative measure of inequality is used. Nevertheless, age-standardised death rates for seven substantial causes are increasing, suggesting the potential for reversals in some countries. Important gaps exist in the empirical data for cause of death estimates for some countries; for example, no national data for India are available for the past decade. Funding Bill &amp; Melinda Gates Foundation

    Molecular Dynamics and Stochastic Kinetics of Hydrogen Combustion

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    There is increasing evidence that emissions from burning fossil fuels drive climate change, necessitating a global transition to cleaner sources of energy, like hydrogen. However, many fundamental problems remain unsolved regarding the complex chemistry of combustion, with potential implications for the overall efficient utilization and safe storage of this fuel. For example, while hydrogen is an energy-dense, clean, and renewable energy carrier, it also has a propensity to auto-ignite and has a wide flammability range. These are ultimately macroscopic consequences of the microscopic reaction events. More efforts are needed to create robust theoretical frameworks that translate between these levels of description. The main focus of this dissertation will be novel theoretical methods that give a new perspective on explosion limits – the pressure/temperature boundaries that divide explosive and nonexplosive chemistry. From several kinetic mechanisms that model the non-equilibrium pathways of hydrogen oxidation, the explosion limits can be determined by the coexistence of two competing reactive phases in an ensemble of simulated trajectories. This novel perspective of chemical explosions is independent of the fuel and could have wider applicability beyond hydrogen. In addition to discussing new theoretical frameworks for explosion limits, this document also includes research conducted with cutting-edge reactive molecular dynamics. The ability to simulate the atomistic dynamics of reactive processes could be an indispensable tool, but as of now, more benchmarking is required. This dissertation highlights some of the steps taken towards validation of a reactive molecular dynamics force field and showcase the results of hydrogen combustion simulations with this atomistic model
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