Voltammetric detection of the interactions between RNO2 and electron acceptors in aqueous medium at highly boron doped diamond electrode (HBDDE)

This paper describes the electrochemical behavior of the nitrofurazone (NFZ), in predominantly aqueous medium, in the absence and presence of glutathione (reduced form) (GSH), l-cysteine (Cys) and O₂ using a highly boron doped diamond electrode (HBDDE). In presence of [Thiol] ≥ 3.7 × 10⁻² mol L⁻¹ NFZ is directly reduced to RNO-Thiol adducts in an electrochemical process involving two electrons and two protons. On the other side, O₂ acts as a RNO₂^•− scavenger and the velocity constant for the reaction, kO₂, is 60 L mol⁻¹ s⁻¹. The process is catalytic and can be used to the analytical determination of NFZ in the range of 9.9 × 10⁻⁷ ≤ [NFZ] ≤ 1.1 × 10⁻⁵ mol L⁻¹ at pH 8.0, with sensitivity of 2.2 × 10⁶ μA mol⁻¹ cm⁻² and detection limit of 3.4 × 10⁻⁷ mol L⁻¹. The analytical parameters were similar to those obtained at pH 4.0 using the direct reduction of NFZ to the respective amine derivative in a process involving six electrons and six protons. The characterization of NFZ global reduction process in aqueous medium and at relative low scan rate, 100 mV s⁻¹, was only possible due the intrinsic superficial characteristics of the HBDDE, which stabilize the RNO₂⁻ free radical, allowing to work in a large potential window, without losing the RNO₂⁻ oxidation signal.     

Thermal stability of polyhydroxyalkanoates

In this study, we examined the thermal decomposition of polyhydroxyalkanoates (PHAs) such as the homopolymer poly(3‐hydroxybutyrate) and the copolymer poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate). They are biodegradable polymers that can replace plastics produced from nonrenewable resources, such as polypropylene. The biopolymers we analyzed were commercial PHAs [obtained by means of pure cultures, with hydroxyvalerate (HV) contents of 0 and 10.4 mol %] and biopolymers produced in our laboratories (by means of an enriched activated sludge at two different organic loads, 8.5 and 20 gCOD/L, with a HV content of 20 mol %). To process these biopolymers, it is important to know their thermal stability. For this reason, thermal degradation in air by means of dynamic thermogravimetry (TG) was carried out. The TG data were adjusted to the nth‐order general analytical equation to evaluate the best order of the reaction, the temperatures of the onset and end of thermal decomposition, and the kinetic parameters. The latter were also calculated by means of other integral and differential methods and compared to those obtained by the general analytical solution. Finally, the influence of the preparation method (pure and mixed cultures and HV content within the biopolymer) on thermal stability was analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2111–2121, 2006     

Effect of hydroxyl content on the morphology and properties of epoxy/poly(styrene-co-allylalcohol) blends

Blends based on epoxy resin and random copolymers, poly(styrene-co-allylalcohol) (PS-co-PA), were studied. Two PS-co-PA copolymers, with different hydroxyl content, and a polyallylalcohol (PA) homopolymer were used to analyze the effect of polyalcohol content. The polymers presented similar values of molar mass. The miscibility of noncured mixtures and the thermal transition behavior of cured blends were investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). Its morphology was studied using both scanning and transmission electron microscopy (SEM and TEM). While the epoxy/PA blends are homogenous materials, because of the epoxy/hydroxyl reaction, PS-co-PA/epoxy blends shows separated phases. In these blends, the presence of a third glass transition, whose value is an intermediate between those of pure components, and the presence of a well-defined interfacial layer between PS-co-PA domains and epoxy matrix indicates a secondary epoxy/hydroxyl reaction. The modification of epoxy resin with PS-co-PA provides significant increase in the storage modulus measured by DMTA. POLYM. ENG. SCI., 47:1580–1588, 2007. © 2007 Society of Plastics Engineers     

A white emitting poly(phenylenevinylene)

A white emitting copolymer with the polyphenylenevinylene (PPV) structure is obtained via the Stille cross-coupling reaction. Substitution of hydrogen atoms with fluorine atoms on the vinylene units of poly(1,4-dialkoxyphenylenevinylene) shifts the emission from orange-red to blue. White emission is obtained by combining dialkoxyphenylenedifluorovinylene and dialkoxyphenylenevinylene units in proper ratio. The two complementary emitters are obtained separately by Stille polymerization reaction. Then, the two reaction mixtures are combined without purification in different ratios and further reacted in similar experimental conditions. A white luminescent material is obtained using 99/1 mixing ratio. OLED devices fabricated with this copolymer shows near-white emission with CIE (0.30, 0.40) and excellent stability in the range 10–200 cd/m².     

3-dimensional microscope analysis of bone and tooth surface modifications: comparisons of fossil specimens and replicas

Cut-marks on fossil bones and teeth are an important source of evidence in the reconstruction of ancient butchery practices. The analysis of butchery marks has allowed archaeologists to interpret aspects of past subsistence strategies and the behavior of early humans. Recent advances in optical scanning microscopy allow detailed measurements of cut-mark morphology to be undertaken. An example of this technology is the Alicona 3D InfiniteFocus imaging microscope, which has been applied recently to the study of surface modifications on bones and teeth. Three-dimensional models generated by the Alicona microscope have been used to identify cross-sectional features of experimental cut-marks that are characteristic for specific cutting actions (e.g., slicing, chopping, scraping) and different tool types (e.g., metal versus stone tools). More recently, this technology has been applied successfully to the analysis of ～500,000 year-old cut-marked animal bones from Boxgrove (U.K.), as well as cannibalized 14,700 cal BP year-old human bones from Gough's Cave (U.K.). This article describes molding methods used to replicate fragile prehistoric bones and teeth, where image quality was adversely affected by specimen translucency and reflectivity. Alicona images generated from molds and casts are often of better quality than those of the original specimen.     

Structure and secretory activity of cultured chondrocytes from patients with osteoarthritis.

Cartilage samples were taken from OA patients in order to describe and quantify pro-inflammatory mediators. Samples were cultured under aseptic conditions in Dulbecco's modified Eagle medium at 37 degrees C for 10 days. Control samples, taken from non-inflammatory cartilage, were cultured under the same conditions. The levels of NO(-)2 and NO(-)3 were measured in the supernatant using a spectrophotometric assay. The activity of MMP-1 was quantified by ELISA. The concentration of NO(-)x was 47.3 +/- 4.1 microM in the OA cartilague and 10.7 +/- 1.8 microM in the controls. The average MMP-1 activity was 3,650 +/- 387 ng/ml in the OA cartilage and 2,150 +/- 190 ng/ml in the control samples. These increased values of MMP-1 and NO(-)x observed in the OA cartilage suggest a higher catabolic activity. A morphological analysis of OA chondral tissue using light microscopy shows that the surface of the tissue is characterized by the presence of aggregated chondrocytes or "clones" but in the deeper areas isolated cells are found. These results could be a significant contribution towards the identification of biological markers indicating the presence of OA activity.     

A finite element method comparison of wear in two metal-on-metal total hip prostheses

The contact mechanics of two metal-on-metal (MOM) total hip prostheses was studied by means of the finite element method (FEM). The purpose of the work was to compare two total hip replacements (Durom and Metasul) with regard to the amount of wear debris released. Wear on the bearing surfaces was evaluated following Reye hypotheses from the pressure distribution, computed by means of three-dimensional FEM models; an approximate analytical model based on Hertz contact theory has also been developed and discussed. The results show that in the dry friction condition the Durom joint releases almost twice as much wear volume as produced by the Metasul joint. Therefore, while Durom implants can improve hip stability by increasing the prosthetic impingement-free range of motion (PIF-ROM), Metasul prostheses can be a valuable solution whenever wear represents a critical choice factor.     

Indoor air quality in schools of a highly polluted south Mediterranean area

This study aimed at surveying lower secondary schools in southern Italy, in a highly polluted area. A community close to an industrial area and three villages in rural areas was investigated. Indoor temperature, relative humidity (RH), gaseous pollutants (CO₂ and NO₂), selected biological pollutants in indoor dust, and the indoor/outdoor mass concentration and elemental composition of PM_2.5 were ascertained. Temperature and RH were within, or close to, the comfort range, while CO₂ frequently exceeded the threshold of 1000 ppm, indicating inadequate air exchange rate. In all the classrooms, median NO₂ levels were above the WHO threshold value. Dermatophagoides p. allergen concentration was below the sensitizing threshold, while high endotoxin levels were detected in the classrooms, suggesting schools may produce significant risks of endotoxin exposure. Concentration and solubility of PM_2.5 elements were used to identify the sources of indoor particles. Indoor concentration of most elements was higher than outdoors. Resuspension was responsible for the indoor increase in soil components. For elements from industrial emission (Cd, Co, Ni, Pb, Sb, Tl, V), the indoor concentration depended on penetration from the outside. For these elements, differences in rural vs industrial concentrations were found, suggesting industrial sources may influence indoor air quality nearby schools.     

Effects of smoking bans on passive smoking exposure at work and at home. The European Community respiratory health survey

This longitudinal study investigated whether smoking bans influence passive smoking at work and/or at home in the same subjects. Passive smoking at work and/or at home was investigated in random population samples (European Community Respiratory Health Survey) in 1990‐1995, with follow‐up interviews in 1998‐2003 and 2010‐2014. National smoking bans were classified as partial (restricted to public workplaces) or global (extended to private workplaces). Multivariable analysis was accomplished by three‐level logistic regression models, where level‐1, level‐2, and level‐3 units were, respectively, questionnaire responses, subjects, and centers. Passive smoking at work was reported by 31.9% in 1990‐1995, 17.5% in 1998‐2003, and 2.5% in 2010‐2014. Concurrently, passive smoking at home decreased from 28.9% to 18.2% and 8.8%. When controlling for sex, age, education, smoking status, and ECHRS wave, the odds of passive smoking at work was markedly reduced after global smoking bans (OR = 0.45, 95% CI 0.25‐0.81), particularly among non‐smokers, while the protective effect of global smoking bans on passive smoking at home was only detected in non‐smokers. Smoking bans both in public and private workplaces were effective in reducing passive smoking at work in Europe. However, given the inefficacy of smoking bans in current smokers’ dwellings, better strategies are needed to avoid smoking indoors.     

A practical demonstration of water disinfection using TiO2 films and sunlight

The scope of this study is the assessment of the efficiency of solar disinfection by heterogeneous photocatalysis with sol-gel immobilized (titanium dioxide) TiO2 films over glass cylinders. The solar disinfection process known as SODIS was considered as a reference. Spring water naturally polluted with coliform bacteria was exposed to sunlight in plastic bottles with and without TiO2 over simple solar collectors and the disinfection effectiveness was measured. Total and fecal coliforms quantification was performed by means of the chromogenic substrate method in order to obtain the efficiency of each disinfection treatment. The disinfection with TiO2 was more efficient than the SODIS process, inactivating total coliforms as well as fecal coliforms. On a sunny day (more than 1000 W m(-2) irradiance), it took the disinfection with immobilized TiO2 15 min of irradiation to inactivate the fecal coliforms to make them undetectable. For inactivation of total coliforms, 30 min was required, so that in less than half the time it takes SODIS, the treated water complies with the microbial standards for drinking water in Mexico. Another important part of this study has been to determine the bacterial regrowth in water after the disinfection processes were tested. After SODIS, bacterial regrowth of coliforms was observed. In contrast, when using the TiO2 catalyst, coliforms regrowth was not detected, neither for total nor for fecal coliforms. The disinfection process using TiO2 kept treated water free of coliforms at least for seven days after sun irradiation. This demonstration opens the possibility of application of this simple method in rural areas of developing countries.