Volcano correlations for the reactivity of surface-confined cobalt N4-macrocyclics for the electrocatalytic oxidation of 2-mercaptoacetate

We have investigated the electrocatalytic activity of several substituted and unsubstituted cobalt–phthalocyanines of substituted tetraphenyl porphyrins and of vitamin B12, for the electro-oxidation of 2-mercaptoacetate, with the complexes pre-adsorbed on a pyrolytic graphite electrode. Several N4-macrocyclic were used to have a wide variety of Co(II)/(I) formal potentials. The electrocatalytic activity, measured as current at constant potential, increases with the Co(II)/(I) redox potential for porphyrins as Co–pentafluorotetraphenylporphyrin larger than Co–tetrasulfonatotetraphenylporphyrin larger than Co-2,2′,2″,2‴tetra-aminotetraphenylporphyrin and decreases for cobalt phthalocyanines as Co-3,4-octaethylhexyloxyphthalocyanine > Co–octamethoxyphthalocyanine > Co–tetranitrophthalocyanine Co–tetraaminophthalocyanine > Co–unsubstituted phthalocyanine > Co–tetrasulfonatophthalocyanine > Co–perfluorinated phthalocyanine. Vitamin B12 exhibits the maximum activity. A correlation of log I (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. This clearly shows that the search for better catalysts for this reaction point to those N4-macrocyclic complexes with Co(II)/(I) formal potentials close to −0.84 V versus SCE, which correspond to an optimum situation for the interaction of the thiol with the active site

Tuning the redox properties of Co-N4 macrocyclic complexes for the catalytic electrooxidation of glucose

Graphite electrodes modified with four different cobalt N4 macrocyclics, namely Co tetrapentapyridinophthalocyanine, (CoTPenPyrPc), Co tetrapyridinoporphyrazine (CoTPyPz), Co octa(hydroxyethylthio)phthalocyanine (CoOEHTPc) and Co tetranitrophthalocyanine (CoTNPc) exhibit catalytic activity for the oxidation of glucose in alkaline media. The purpose of this work is to establish correlations between the catalytic activity of these complexes and their redox potential. The activity of the different modified electrodes was tested by linear voltammetry under hydrodynamic conditions using the rotating disk technique. Tafel plots constructed from mass-transport corrected currents give slopes ranging from 0.080 to 0.160 V/decade for the different catalysts which suggests that a first one-electron step is rate controlling with the symmetry of the energy barrier depending on the nature of the ligand of the Co complex. A plot of log I versus the Co(II)/(I) formal potential gives a volcano curve that also includes catalysts studied previously. This illustrates the concept that the formal potential of the catalyst needs to be tuned to a certain value for achieving maximum activity. A theoretical interpretation of these results is given in terms of Langmuir isotherms for the adsorption of glucose on the Co sites of the surface-confined metal complexes

Pharmaceutical pollution of the world's rivers

Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytical methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world's rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals

Improving the interaction between aluminum surfaces and polymer coatings

To better understand the effect of surface treatments on the efficiency of protective coatings of aluminum alloys, this study assessed different surface treatments for the aluminum alloy AA2024, including mechanical polishing, chemical etching and Ar-plasma pretreatment followed by deposition of poly(methyl methacrylate). Surface morphology, surface chemical analysis and wettability of the treated samples were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy and contact angle, respectively. Open circuit potential and electrochemical impedance spectroscopy were carried out in a 0.1 M solution of Na2SO4 as a function of exposure time. SEM images revealed that a homogeneous and well incorporated poly-(methyl methacrylate) coating was obtained by using Ar-plasma as a pretreatment. XPS spectra showed that the Al–O/Al–OH intensity ratio of the Ar-plasma pretreated samples does not show clear dependence on angle measurement, which indicates that Al(OH) and Al2O3 are not homogenously distributed on the sample surfaces. Al2O3 does not completely cover the aluminum surface, leaving some areas exposed. The measurements of the hysteresis angle showed that the Ar-plasma pretreatment favors chemical heterogeneity, which in turn increases the hydrophilicity of the coated samples, resulting in lower wettability and a greater hysteresis angle. The electrochemical results showed that the Ar-plasma pretreatment significantly improves the protective capacity of poly(methyl methacrylate)

Variación anual de las propiedades insecticidas de Peumus boldus sobre Sitophilus zeamais Annual variation of insecticide properties of Peumus boldus on Sitophilus zeamais

El objetivo del presente trabajo fue determinar la variación anual en las propiedades insecticidas de Peumus boldus Molina, en el control de Sitophilus zeamais Motschulsky, bajo condiciones de laboratorio. El polvo de hojas de P. boldus se evaluó durante 12 meses, en concentraciones de 0,5, 1 y 2% (p/p). Se evaluaron 36 tratamientos con tres repeticiones, en un diseño experimental completamente al azar, con un arreglo factorial. Se determinó el porcentaje de mortalidad y emergencia de insectos adultos e inmaduros y pérdida de peso y germinación del grano. La mayor mortalidad se obtuvo en los meses de agosto y septiembre de 2003, para las tres concentraciones con un 100%, mientras que la menor fue en mayo de 2003, cuando solo la concentración de 2% fue próxima a 100% de mortalidad. La menor emergencia de insectos adultos y pérdida de peso se obtuvieron en los mismos tratamientos. El efecto sobre estados inmaduros fue menor que contra adultos, y la germinación de los granos de maíz fue afectada por los polvos de P. boldus. Las propiedades insecticidas del polvo de hojas de P. boldus no son estables durante el año, Mayo es el mes con la menor eficacia insecticida, y la germinación de las semillas se ve afectada por el polvo.<br>The objective of this work was to determine the annual variation of Peumus boldus Molina insecticidal properties for the control of Sitophilus zeamais Motschulsky, under laboratory conditions. The powder of P. boldus leaves was evaluated, during 12 months, in 0.5, 1, and 2% (w/w) concentrations. Thirty-six treatments, with three replications, were evaluated in a completely randomized experimental design, with a factorial arrangement. Evaluations were made for adult and immature insect percentage mortality and emergence, grain weight loss and seed germination. The greatest mortality was obtained in August and September 2003, in the three concentrations with 100%, and the lowest mortality was registered in May 2003, when only 2% (w/w) reached almost 100% mortality. The lowest adult insect emergence and weight loss were obtained in the same treatments. The effect on immature stages was lower than on adults; and grain germination was affected by P. boldus powders. Insecticidal properties of P. boldus leaves powder are not stable during the year; May is the month with lesser insecticide efficacy; and the powder affects grain germination