Preparation and voltammetric characterization of electrodes coated with Langmuir-Schaefer ultrathin films of Nafion®

Ultrathin films of Nafion® perfluorinated polymer were deposited on indium-tin oxide electrodes (ITO) by using Langmuir-Schaefer (LS) technique, after optimization of the subphase composition conditions. Morphological characteristics of these coatings were obtained by Atomic Force Microscopy (AFM). Nafion® LS films showed a good uniformity and complete coverage of the electrode surface, however a different organization degree of the polymer layer was evidenced with respect to thin films deposited by spin-coating. ITO electrodes modified with Nafion® LS coatings preconcentrate by ion-exchange electroactive cations, such as Ru[(NH3)6]3+, dissolved in diluted solutions. The electroactive species is retained by the Nafion® LS coated ITO also after transfer of the modified electrode into pure supporting electrolyte. This allowed the use of the ruthenium complex as voltammetric probe to test diffusion phenomena within the Nafion® LS films. Apparent diffusion coefficients (Dapp) of Ru[(NH3)6]3+ incorporated in Nafion® LS films were obtained by voltammetric measurements. Dapp values decrease slightly by increasing the amount of ruthenium complex incorporated in the ultrathin film. They are significantly lower than values typical for recasted Nafion® films, in agreement with the highly condensed nature of the Nafion® LS fims. Filmes ultrafinos do polímero perfluorado Nafion® foram depositados em eletrodos de óxido índio-titânio (ITO) usando a técnica de Langmuir-Scaefer (LS), depois da otimização das condições de composição da subfase. As características morfológicas das camadas foram obtidas por Microscopia de Força Atômica (AFM). Filmes de Nafion® LS mostraram boa uniformidade e cobertura completa da superfície do eletrodo. No entanto, diferentes graus de organização das camadas poliméricas ficaram evidentes com respeito a filmes finos depositados por revestimento rotacional. Eletrodos ITO modificados com camadas de Nafion® LS, pré-concentrados por cátions eletroativos de troca iônica, como o Ru[(NH3)6]3+, dissolveram-se em soluções diluídas. A espécie eletroativa foi retida pelo ITO com camada de Nafion® LS, mesmo depois da mudança do eletrodo modificado para eletrodo de suporte purificado. Isto possibilitou o uso do complexo de rutênio como padrão voltamétrico para o teste do fenômeno de difusão nos filmes de Nafion® LS. Os coeficientes de difusão aparentes (Dapp) do Ru[(NH3)6]3+ incorporado no filme de Nafion® LS foram obtidos por medidas voltamétricas. Os valores de Dapp diminuíram levemente com o aumento da quantidade de complexo de rutênio incorporado no filme ultrafino e foram significativamente mais baixos do que os valores para filmes de Nafion® recapados, em acordo com a natureza altamente condensada dos filmes de Nafion® LS

Is depression a real risk factor for acute myocardial infarction mortality? A retrospective cohort study

Background: Depression has been associated with a higher risk of cardiovascular events and a higher mortality in patients with one or more comorbidities. This study investigated whether continuative use of antidepressants (ADs), considered as a proxy of a state of depression, prior to acute myocardial infarction (AMI) is associated with a higher mortality afterwards. The outcome to assess was mortality by AD use. Methods: A retrospective cohort study was conducted in the Veneto Region on hospital discharge records with a primary diagnosis of AMI in 2002-2015. Subsequent deaths were ascertained from mortality records. Drug purchases were used to identify AD users. A descriptive analysis was conducted on patients' demographics and clinical data. Survival after discharge was assessed with a Kaplan-Meier survival analysis and Cox's multiple regression model. Results: Among 3985 hospital discharge records considered, 349 (8.8%) patients were classified as AD users'. The mean AMI-related hospitalization rate was 164.8/100,000 population/year, and declined significantly from 204.9 in 2002 to 130.0 in 2015, but only for AD users (-40.4%). The mean overall follow-up was 4.64.1years. Overall, 523 patients (13.1%) died within 30days of their AMI. The remainder survived a mean 5.3 +/- 4.0years. After adjusting for potential confounders, use of antidepressants was independently associated with mortality (adj OR=1.75, 95% CI: 1.40-2.19). Conclusions: Our findings show that AD users hospitalized for AMI have a worse prognosis in terms of mortality. The use of routinely-available records can prove an efficient way to monitor trends in the state of health of specific subpopulations, enabling the early identification of AMI survivors with a history of antidepressant use

Geocoding health data with Geographic Information Systems: a pilot study in northeast Italy for developing a standardized data-acquiring format

Introduction. Geographic Information Systems (GIS) have become an innovative and somewhat crucial tool for analyzing relationships between public health data and environment. This study, though focusing on a Local Health Unit of northeastern Italy, could be taken as a benchmark for developing a standardized national data-acquiring format, providing a step-by-step instructions on the manipulation of address elements specific for Italian language and traditions. Methods. Geocoding analysis was carried out on a health database comprising 268,517 records of the Local Health Unit of Rovigo in the Veneto region, covering a period of 10 years, starting from 2001 up to 2010. The Map Service provided by the Environmental Research System Institute (ESRI, Redlands, CA), and ArcMap 10.0 by ESRI\uae were, respectively, the reference data and the GIS software, employed in the geocoding process. Results. The first attempt of geocoding produced a poor quality result, having about 40% of the addresses matched. A procedure of manual standardization was performed in order to enhance the quality of the results, consequently a set of guiding principle were expounded which should be pursued for geocoding health data. High-level geocoding detail will provide a more precise geographic representation of health related events. Conclusions. The main achievement of this study was to outline some of the difficulties encountered during the geocoding of health data and to put forward a set of guidelines, which could be useful to facilitate the process and enhance the quality of the results. Public health informatics represents an emerging specialty that highlights on the application of information science and technology to public health practice and research. Therefore, this study could draw the attention of the National Health Service to the underestimated problem of geocoding accuracy in health related data for environmental risk assessment

Enzymes Encapsulated within Alginate Hydrogels: Bioelectrocatalysis and Electrochemiluminescence Applications

A simple procedure to incorporate enzymes (horseradish peroxidase, HRP, and lactate oxidase, LOx) within alginate hydrogels is reported with electrochemiluminescence (ECL) used to detect the enzymatic reactions with the corresponding substrates. First, HRP and LOx were successfully immobilized into CaCO3 microspheres, followed by the electrostatic layer-by-layer deposition of a nanoshell onto the microspheres, and finally by their dispersion into alginate solution. The as-prepared dispersion was drop cast onto the glassy carbon electrodes and cross-linked by the external and internal gelation methods using Ca2+ cations. The enzymes encapsulated within the alginate hydrogels were characterized using cyclic voltammetry and kinetic studies performed using ECL. The results showed that the enzymatic activity was significantly maintained as a result of the immobilization, with values of the apparent Michaelis-Menten constants estimated as 7.71 ± 0.62 and 8.41 ± 0.43 μM, for HRP and LOx, respectively. The proposed biosensors showed good stability and repeatability with an estimated limit of detection of 5.38 ± 0.05 and 0.50 ± 0.03 μM for hydrogen peroxide and lactic acid, respectively. The as-prepared enzymes encapsulated within the alginate hydrogels showed good stability up to 28 days from their preparation. The sensitivity and selectivity of the enzymes encapsulated within the alginate hydrogels were tested in real matrices (HRP, hydrogen peroxide, in contact lens solution; LOx, lactic acid in artificial sweat) showing the sensitivity of the ECL detection methods for the detection of hydrogen peroxide and lactic acid in real samples

A new interpolation method to measure delta evolution and sediment flux: Application to the late Holocene coastal plain of the Argens River in the western Mediterranean

Rapid environmental changes along the Mediterranean coasts influenced the sedimentary dynamics, shoreline position and human settlements in deltaic areas over the last millennia. An innovative and multiproxy approach using geostatistical modelling was developed to estimate geomorphic evolution and sediment fluxes in deltaic areas, while palaeoecological conditions and environmental changes were assessed from geochemistry and cluster analyses of molluscan fauna. This method was applied to the coastal plain of the Argens River in southern France. Depositional environments of prodelta, delta front, river channel, floodplain, marsh and abandoned channel were identified from the study of facies associations. The late Holocene sediment flux in the Argens River bayhead delta ranged from 15,800 ± 2300 to 52,000 ± 8500 m3·yr−1. The highest rate of sediment deposition between 2500 and 2000 cal yr BP was associated with increased river flooding in southeastern France. A general decrease in subaqueous sediment flux over the past 2500 years was primarily controlled by a decrease in accommodation space and delta slope. From 500 to 0 cal yr BP, a sharp increase in subaerial sediment flux probably due to hydroclimatic change was contemporaneous with a period of high flood frequency during the Little Ice Age. A southward shift of the North Atlantic westerlies combined with either a negative phase of the East Atlantic/West Russian pattern or a negative phase of the East Atlantic pattern coupled to a northward migration of the intertropical convergence zone could have led to increased fluvial activity in the lower Argens valley during the late Holocene

The importance of sex as a risk factor for hospital readmissions due to pulmonary diseases

BACKGROUND: Pulmonary diseases are a common and costly cause of 30-day readmissions. Few studies have focused on the difference in risk for rehospitalization between men and women in older patients. In this study we analyzed the association between sex and the risk of readmission in a cohort of patients admitted to the hospital for chronic obstructive pulmonary disease (COPD) exacerbation and other major pulmonary diseases. METHODS: This was a retrospective cohort study based on administrative data collected in the Veneto Region in 2016. We included 14,869 hospital admissions among residents aged 6565\u2009years for diagnosis related groups (DRGs) of the most common disorders of the respiratory system: bronchitis and asthma, pneumonia, pulmonary edema, respiratory failure, and COPD. Multilevel logistic regressions were performed to test the association between 30-day hospital readmission and sex, adjusting for confounding factors. RESULTS: For bronchitis and asthma, male patients had significantly higher odds of 30-day readmission than female patients (adjusted odds ratio (aOR), 2.07; 95% confidence interval (CI), 1.11-3.87). The odds of readmission for men were also significantly higher for pneumonia (aOR, 1.40; 95% CI, 1.13-1.72), for pulmonary edema and respiratory failure (aOR, 1.28; 95% CI, 1.05-1.55), and for COPD (aOR, 1.34; 95% CI, 1.00-1.81). CONCLUSIONS: This study found that male sex is a major risk factors for readmission in patients aged more than 65\u2009years with a primary pulmonary diagnosis. More studies are needed to understand the underlying determinants of this phenomena and to provide targets for future interventions

Relationship between programmed cell death and the cell cycle in the tobacco BY-2 cell line

Ethylene is an established plant growth regulator linked with programmed cell death (PCD). To investigate the relationship between the cell cycle and PCD, ethylene was used to see if it induced mortality in a cell cycle specific manner. Tobacco BY-2 cultures synchronized with aphidicolin were treated with ethylene. Cell cycle progression and mortality, measured at hourly intervals, showed distinct peaks of mortality at the G2/M boundary and S-phase. In conjunction with this, DNA fragmentation increased at G2/M. Furthermore, ethylene caused a significant reduction in cell size of the cycling population. Simultaneous addition of silver nitrate with ethylene ameliorated ethylene-induced G2/M mortality, although a toxic effect of silver alone was evident. Due to the toxicity of silver, 1-MCP, an alternative chemical for blocking ethylene receptors was used. 1-MCP neither affected the BY-2 cell cycle nor mortality levels. In addition, 1-MCP ameliorated ethylene-induced G2/M mortality. To balance the chemical approaches to blocking ethylene receptors, tobacco BY-2 cells were transformed with Atetrl that encodes a dominant insensitive form of the Arabidopsis ETR1 ethylene receptor. Atetrl expression caused a massive perturbation to the tobacco BY-2 cell cycle, especially in S-phase, and resulted in high levels of mortality throughout the cell cycle. Ethylene treatment caused a doubling of G2 duration but did not affect temporal distribution of mortality. However, ethylene treatment generated a peak of mortality in S-phase. These results suggest that ethylene induces PCD at G2/M through the known ethylene signaling pathway. Furthermore, it confirms that 1-MCP and Atetrl result in ethylene insensitivity. To examine the G2/M transition, Spcdc25, a positive regulator of G2/M in fission yeast was transformed into the tobacco BY-2 cell line. This resulted in premature entry into mitosis, a shortened cell cycle, and reduced cell size. This was similar to Spcdc25 over-expression in fission yeast and suggests the presence of a CDC25-like phosphatase in plants.EThOS - Electronic Theses Online ServiceGBUnited Kingdo