Artículos de revistas sobre el tema "Sem Benelli"

This study presents a new locality record of poisonous pufferfish, Lagocephalus sceleratus (Gmelin, 1789), one of the 18 worst invader fish species identified globally by IUCN, from the Sea of Marmara caught by a commercial purse seine fishing vessel while fishing anchovy on 22 February 2021. Previously, this invasive species was first recorded at the Gelibolu peninsula in the Sea of Marmara between September 2007 and October 2008. Lagocephalus sceleratus recorded in this study is larger in size with 142 mm total length than previous records (126 mm in 2007; 95 mm in 2008) for the Sea of Marmara. The presently reported record represents the first documented occurrence of this species in the Erdek Bay of the Sea of Marmara and the third documented record for the entire Sea of Marmara.

The presented review article describes a number of some important developed, implemented and already used software products, information systems, and other digital solutions that are essential for the effective functioning of the agro-industrial complex of the republic. Important global trends in the development of modern agriculture are considered, the benefi ts received by farmers from the use of various digital technologies are discussed, the need to accelerate the current pace of introduction of various elements of precision farming and livestock systems into Belarusian agriculture is noted.

En el período de enero a junio del 2009 se indagó el benefi ciado de cacao en 49 fi ncas de productores socios de la cooperativa CACAONICA en el municipio de Waslala, Nicaragua. El propósito del estudio fue generar información de los costos, tiempos y puntos críticos del benefi ciado en las fi ncas, y realizar un análisis FODA sobre la factibilidad de implementar el modelo de acopio de cacao en baba en dos centros comunitarios. Se aplicaron encuestas a productores y entrevistas semi-estructuradas al equipo técnico de CACAONICA y otros informantes claves vinculados con la comercialización local del cacao. Se elaboró una matriz clasifi cándose la información en relación a las variables tiempo, área de siembra, rendimientos y participación de la familia en la labores poscosecha del cacao. Todas las fi ncas visitadas poseen certifi cación orgánica. Treinta de los productores poseen áreas pequeñas de cacao (aproximadamente de una ha) y 19 cultivan entre 1.5 a siete ha. El benefi ciado de cacao en la fi nca se compone de tres etapas y seis actividades: etapa 1 (cosecha y extracción-selección de semillas), etapa 2 (fermentación y secado) y etapa 3 (empacado y transporte). El proceso de benefi ciado se constituye de 21.7 días calendarios, sin embargo, el tiempo real requerido en días hombre resultó ser 9.14, con un costo de USD 40.33 para benefi ciar 45.45 kg de cacao (un qq ). La etapa 1 resultó ser la más costosa del proceso de benefi ciado (USD 30.13 por cada 45.45 kg). Los puntos críticos que afectan la calidad del benefi ciado del grano son: fermentación (41%) y secado (31%). El punto de equilibrio del benefi ciado en fi nca es 361.8 kg ha-1 ciclo-1. Rendimientos por debajo de este umbral signifi can que el cacaotal no retribuye los costos invertidos por el agricultor. La participación de la familia en el benefi ciado del cacao es relevante, especial atención requiere la participación de la mujer. La gran mayoría de los productores (69%) perciben como buena estrategia implementar el acopio de cacao en baba en benefi cios centralizados, y ratifi caron su participación siempre y cuando el pago sea contra entrega del grano (USD 48.87 por cada 45.45 kg). El éxito del nuevo sistema de acopio dependerá de la gestión de capital para el acondicionamiento de la instalación, la compra del grano a los productores, la definición de rutas lógicas de acopio en las comunidades, el equipamiento básico y la capacitación oportuna al personal técnico responsable de los centros de acopio.La Calera, Vol. 14. Nº 22, p. 5-12 / mayo 2014

Na obra “Alucinações musicais” Oliver Sacks, professor de neurologia Clínica na Columbia University, New York, relata casos de homens e mulheres que, em condições neurológicas raras, reagem à música de forma incomum: alguns não conseguem ouvi-la, e outros simplesmente ouvem música todo o tempo, mesmo sem nenhuma melodia tocando. Há descrição de casos em que, após um acidente, a pessoa desenvolve um talento musical que antes não existia. O livro oferece uma fascinante coletânea de fenômenos interligando neurologia, fisiologia e música, mostrando que a música pode sobreviver a danos cerebrais devastadores. Unitermos. Encéfalo, Música, Fisiologia, Dano Encefálico. Citação. Benetti IC. Resenha do livro “Alucinações musicais: relatos sobre a música e o cérebro”.

The host–guest interaction of p-nitro benzaldehyde as guest β-Cyclodextrins have been investigated which have significant applications in the field of medicine such as controlled drug delivery. The 1H NMR study confirms the formation of inclusion complex while surface tension and conductivity studies support the formation inclusion complex with 1:1 stoichiometry. The stoichiometry of the inclusion complex was also supported with Job’s plot method by UV-Visible spectroscopy. FT-IR spectra and SEM study also support the inclusion process. Association constants of the inclusion complexes have been calculated using the Benesi–Hildebrand method, while the thermodynamic parameters have been estimated with the help of van’t Hoff equation.

We report on dramatic change in Sakurai’s object (RA: 17h52m32.7s, DEC: −17d41’07”, J2000.0). Discovered by the Japanese amateur astronomer Y. Sakurai in Feb. 1996, this object was first classified as a slow nova (Nakano S., Sakurai Y., Hazen M., McNaught R.H., Benetti S., Duerbeck H.W., Leibundgut B., 1996, IAU Circ. 6322). Further study revealed a spectrum rich in C, N and O-lines, but poor in hydrogen, as well as an old planetary nebula surrounding the star; it was then realized that this might be a star undergoing a late He-flash (Benetti, S. et al. 1996, IAU Circ. 6325). Despite the fact that 10 to 20% of all low mass stars will experience a late He-flash (Iben I. Jr., MacDonald J., 1996), it is an extremely rare observational event, due to its short duration. The most recent example is V605 Aql/A58 in 1919 (Eitter W.C., 1987, ESO Messenger, 14: see also Clayton C.G., De Marco O., 1997, AJ for a review).In March 1997 we discovered dramatic change in the optical spectrum of Sakurai’s object using the 2.5 m Du Pont telescope at Las Campanas, Chile. The dominating features now are the prominent bands of CN (bandheads at 388.8 and 421.6 nm) and C2 (Swan-Bands at 439.2, 473.7, 516.5, 558.5 and 565.5 nm)(Kerber F., Gratl, H., Roth, M., 1997, IAU Circ. 6601) that were not evident a year ago (Duerbeck, H.W., Benetti, S., 1996, ApJ 468, L111).

Summary Market of volunteers in Poland, especially those ones with specialized skills, is limited. An important reservoir of volunteer work are the universities. Non-governmental organizations should consider sustained cooperation with them. Volunteers predisposed to provide administrative support could be sought among the students of management. This article aims to answer the following questions: Are students of management want to get involved in the activities of non-governmental organizations? What are the motives of involvement in voluntary dominate among them? What benefi ts do they see, in collaboration with NGO’s? What actions can take the managers of these organizations to motivate volunteers?

Dysfunction of the basal ganglia and the brain nuclei interconnected with them leads to disturbances of movement and cognition, including disordered timing of movement and perceptual timing deflcits. Patients with Parkinson's disease (PD) were studied in temporal reproduction tasks. We examined PD patients when brain dopamine (DA) transmission was impaired (OFF state) and when DA transmission was reestablished, at the time of maximal clinical beneflt following administration of levodopa + apomorphine (ON state). Patients reproduced target times of 8 and 21 sec trained in blocked trials with the peak interval procedure, which were veridical in the ON state, comparable to normative performance by healthy young and aged controls (Experiment 1). In the OFF state, temporal reproduction was impaired in both accuracy and precision (variance). The 8-sec signal was reproduced as longer and the 21-sec signal was reproduced as shorter than they actually were (Experiment 1). This fimigrationfl effect was dependent upon training of two different durations. When PD patients were trained on 21 sec only (Experiment 2), they showed a reproduction error in the long direction, opposite to the error produced under the dual training condition of Experiment 1. The results are discussed as a mutual attraction between temporal processing systems, in memory and clock stages, when dopaminergic regulation in the striatum is dysfunctional.

Features of the species and spatial structure of macrobenthic sublittoral communities in a lagoon ecosystem on the Green Cape (the White Sea) were studied. 31 invertebrate species and 3 species of sea grasses and algae (Zostera marina, Cladophora sericea, and Fucus vesiculosus) were found in the sublittoral of the surveyed lagoon. The data on the species composition, diversity and spatial structure of macrobenthos communities indicate the predominance of littoral brackish-water and marine euryhaline macrobenthos species (Hydrobia ulvae, Tubificoides benedii, Chironomus salinarius, and Macoma balthica) in the coastal region of the lagoon, marine euryhaline littoral and sublittoral species (mainly polychaetes Heteromastus filiformis, Polydora ciliata, and Capitella capitata) in the central deeper region, and marine sublittoral less euryhaline species (Pontoporeia femorata, Anonyx nugans, Nereimyra punctata, Terebellides stroemi, Astarte montagui, Micronephthys minuta, and Atylus carinatus) at the exit from the lagoon. The ecosystem of the Green Cape lagoon belongs to lagoons significantly fenced off from the sea with depleted specific fauna (many littoral species) and largely influenced by carbon load and salinity. The reduced connection of the lagoon with the sea due to the continued rise of the White Sea coast (4 mm per year in this area) will contribute to a decrease in the species diversity and the predominance of few small eurytopic invertebrate species resistant to organic load, oxygen deficiency, and desalination.

This research is to see the influence of managerial, institutional, and public ownership and the size of top milMgernent on the value of companies with the return on assets as the controlling variable. This study nkes the benefi* of 67 samples of companies during the period of 2005-2007, which are listed in the Indonesia Stock Exchmrge (BED.By using double regression, it indicates that the managerial ownership and the size of top management have a positive inJluence on the value of the companies. The institutional ownership and the public ownership do not have any influences on thevalue of the companies.Keywords: tnanogerial, institutional, public, the size of top mantagernent, return on assets (ROA), thevalue of company.

A cationic derivative of pullulan was obtained by grafting reaction and used together with dextran sulfate to form polysaccharide-based nanohydrogel cross-linked via electrostatic interactions between polyions. Due to the polycation-polyanion interactions nanohydrogel particles were formed instantly and spontaneously in water. The nanoparticles were colloidally stable and their size and surface charge could be controlled by the polycation/polyanion ratio. The morphology of the obtained particles was visualized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The resulting structures were spherical, with hydrodynamic diameters in the range of 100–150 nm. The binding constant (Ka) of a model drug, piroxicam, to the cationic pullulan (C-PUL) was determined by spectrophotometric measurements. The value of Ka was calculated according to the Benesi—Hildebrand equation to be (3.6 ± 0.2) × 103 M−1. After binding to cationic pullulan, piroxicam was effectively entrapped inside the nanohydrogel particles and released in a controlled way. The obtained system was efficiently taken up by cells and was shown to be biocompatible.

The paper is devoted to the study of the volume and value of biological resources of beekeeping, the feasibility and possibility of developing beekeeping on the basis of melliferous resources available in the Russian Federation. Beekeeping is an important branch of agriculture, since bee pollination of entomophilic agricultural plants is one of the most eff ective agricultural techniques, which leads to an increase in the yield of entomophilic agricultural plants by up to 300 %. The development of beekeeping on a national scale is possible only with serious state support. For such participation of the state, it is necessary to have a clear understanding of the state of the industry, the biological resources of beekeeping and the prospects for development. In this regard, there is a need to analyze the feed base of beekeeping in the Russian Federation, determine potential honey reserves and prospects for the development of beekeeping in the Russia. We have touched on the topic of melliferous resources of entomophilic plants in this paper. The melliferous resources of Russia calculated in diff erent versions have been considered. The volume of melliferous resources, potential honey reserves, and the number of bee colonies that can be maintained based on the available melliferous resources in Russia have been given. The evaluation of the profi t that can be obtained with the development of beekeeping in Russia and proper pollination of entomophilic crops and wild entomophilic plants has been made. It has been noted that the melliferous resources of Russia theoretically allow to contain up to 30 million bee colonies and receive up to 452 million kg of commercial honey, which can meet the scientifi cally-based norms of honey consumption for all Russians. The total benefi t from proper pollination of entomophilic cultural and wild plants in Russia has been evaluated at an impressive amount approaching 1 trillion rubles per year.

Lysine of feed proteins is incorporated into tissue proteins without any preliminary changes. It is an indispensable precursor in the synthesis of collagen, participates in the formation of carnitine, which plays an important role in fat metabolism. Lysine activates hematopoiesis, promotes calcium absorption, and has a benefi cial eff ect on protein metabolism and the state of the nervous system. It is used in the synthesis of proteins necessary for the formation of skeletal tissues and enzymes, is an important component of several peptide hormones. The purpose of the work was to study the eff ect of compound feed with diff erent levels of sunfl ower and soybean meal with the addition of lysine in the form of sulfate on the productivity of laying hens. The eff ect of lysine sulfate on the productivity of laying hens and the quality of eggs was studied. The physiological and biochemical justifi cation of the possibility of its use in compound feed of diff erent structures was given. With an increase in the level of soy meal input into the feed to 15 % and the inclusion of lysine sulfate in the feed, the fat digestibility increased by 0,6 abs.%, nitrogen-free extractive substances by 1,4 abs.%. Lysine in the form of sulfate had a positive infl uence on the digestibility and use of essential nutrients in all experimental groups. The results of the production check confi rmed the zootechnical data obtained in the experiments and showed the economic effi ciency of using lysine sulfate in compound feed for laying hens of the industrial herd of the egg productivity. The data obtained indicate the feasibility of using lysine sulfate in compound feed for laying hens.

The association between science and production is gradually developing due to the arrival of new information and discoveries about the composition of feed and the transformation of nutrients in the body of cows. One of the most important links in the formation of animal productivity during lactation is the use of new feed products and feed additives in feeding. The results of scientific and economic experiment on the use of protein concentrate “Agro-Matic” in feeding of highly productive lactating cows of Ayrshire breed are contained the article. The inclusion of protein concentrate “AgroMatic” in the daily rations of lactating cows in the amount of 1,0 and 1,5 kg/head/day increases the level of indigestible protein by 6,1 and 8,9 %, respectively. The use of protein concentrate in the amount of 1,5 kg in cows feeding helps to increase the digestibility of nutrients in rations the quality of milk and the productivity of cows. When feeding protein concentrate in the amount of 1,5 kg the milk productivity of cows during the period of increasing the milk yield was 4297,5 kg of milk, the yield of essential and dispensable amino acids with milk was significantly higher. The yield of milk protein in cows that received protein concentrate in the ration in the amount of 1,0 kg was 137,7 kg, and when using 1,5 kg – 141,4 kg, which was signifi cantly higher than in the control group by 10,2 and 13,6 kg, respectively. The use of protein concentrate “Agro-Matic” in the ration had a benefi cial eff ect on the digestibility of protein. The digestibility of raw protein of the feed mixture with the inclusion of 1,5 kg of protein concentrate was 71,1 % compared to 68,0 % in the basic ration, which are used at the Maysky complex in the “Plemzavod Maysky”

Among feed additives, probiotics used in animal husbandry are of great interest, containing live microorganisms that belong to the normal, physiologically justifi ed microfl ora of the intestinal tract and have a positive eff ect on the animal’s body. Newly created drugs (eff ective microorganisms – EM-drugs) are a set of microorganisms that have a benefi cial eff ect, clean all living things from pathogenic microfl ora and harmful chemical compounds. The purpose of the work was to establish the optimal doses of feeding the probiotic drug “Baikal EM 1” in the rations of dry and lactating cows in connection with the eff ectiveness of milk production. The researches have been carried out on cows of Black-and-White breed in the NE “Ufi mskoe” of the Bashkir Scientifi c and Research Institute of Agriculture, where the feed base and the condition of the production facilities met the veterinary requirements. The optimal dose and methods of application of the drug “Baikal EM 1” of probiotic action in the rations of cows in the Republic of Bashkortostan have been determined and tested. The positive infl uence of the probiotic drug on the processes of rumen digestion, digestibility and assimilation of nutrients, physiological and biochemical status, milk productivity, reproductive functions, the quality of the off spring and its livability has been established. The eff ect of using the drug “Baikal EM 1” in diff erent dosages on hematological parameters, digestibility and assimilation of nutrients, and nitrogen metabolism has been studied. The economic justifi cation of the use of the probiotic drug “Baikal EM 1” in the rations of cows has been given. It has been found that the most eff ective from the zootechnical, biological and economic points of view is to use the probiotic drug “Baikal EM 1” in the dose of 50 ml/head/day.

Background: The need for blood services in Indonesia are still high. These were related to the high number of maternal deaths from hemorrhage during and after childbirth. The National Health Insurance (JKN) provide great opportunities for ensuring the needs of the community blood transfusion services. Presidential Decree No. 12 of 2013 article 22 paragraph 1a.6 mentioned that blood transfusions became one of the health care benefi ts package in the fi rst degree. The purpose of this study to analyze the benefi ts package in the regulation of blood transfusion services, especially in health centers. Methods: This study was conducted in Surabaya. The analysis was performed on the results of Focus Group Discussion with actor implementing policies (health center, Indonesian Cross Red/PMI, Hospitals, and BPJS), by content analysis. Results: The blood transfusion services benefi t package had not been able to do in Health Center (Puskesmas/FKTP), especially Puskesmas in Surabaya. Package benefi ts of blood transfusion services confl ict with other policies. Theauthority to give a blood transfusion was not a health center (puskesmas) but the hospital. The technical requirements of medical support blood transfusion services in health centers did not according to the standard. Referral service was the most likely carried out by the health center when encountered cases of maternal urgency requiring blood transfusions. Conclusion: Package benefi ts of blood transfusion services in Presidential Decree No. 12 of 2013 article 22 contradicted by other policies already set. Availability of medical requirements that support these services had not been fulfilled. Blood transfusion services could not currently be implemented in Puskesmas Surabaya. Recommendation: The content of Presidential Decree no. 12 of 2013 article 22 requires the revision, that the blood transfusion service could only be carried out in health facilities provided medical technical requirements, both human resources and supporting infrastructure. Abstrak Latar Belakang: Kebutuhan pelayanan darah di Indonesia masih tinggi. Ini terkait masih tingginya jumlah kematian ibu akibat perdarahan saat dan pascamelahirkan. Jaminan Kesehatan Nasional (JKN) memberikan peluang terjaminnya kebutuhan masyarakat terhadap pelayanan transfusi darah. Peraturan Presiden (Perpres) no. 12 tahun 2013 pasal 22 ayat 1a.6 menyebutkan bahwa transfusi darah menjadi salah satu paket manfaat di pelayanan kesehatan tingkat pertama. Tujuan kajian untuk menganalisis paket manfaat pelayanan transfusi darah di puskesmas dalam Perpres tersebut. Metode: Kajian ini merupakan studi implementasi kebijakan Perpres no. 12 tahun 2013 yang dilakukan di Surabaya. Analisis dilakukan terhadap hasil FGD dengan aktor pelaksana kebijakan (Puskesmas, PMI, Rumah sakit, dan BPJS), secara content analysis. Hasil: Paket manfaat pelayanan transfusi darah belum dapat dilakukan di FKTP, khususnya Puskesmas di Surabaya, karena bertentangan dengan perundang-undangan yang lebih tinggi dan ditetapkan sebelumnya. Pemberian transfusi merupakan kewenangan rumah sakit. Persyaratan teknis medis penunjang pelayanan transfusi darah di puskesmas belum memenuhi standar. Puskesmas hanya berwenang merujuk ketika menjumpai kasus kegawatan maternal yang memerlukan transfusi darah. Kesimpulan: Pelayanan transfusi darah dalam Perpres no. 12 tahun 2013 pasal 22 kontradiktif dengan kebijakan lain. Pelayanan transfusi darah belum dapat dilaksanakan di Puskesmas Kota Surabaya, karena belum memenuhi persyaratan tranfusi darah yang aman. Rekomendasi: Isi Perpres no. 12 tahun 2013 pasal 22 perlu direvisi, bahwa pelayanan transfusi darah hanya dapat dilakukan di fasilitas kesehatan yang memenuhi persyaratan teknis medisnya, SDM dan sarana prasarana penunjangnya.

The Asian tiger mosquito ( Aedes albopictus ) is an invasive species that has the potential to transmit infectious diseases such as dengue and chikungunya fever. Using high-resolution observations and regional climate model scenarios for the future, we investigated the suitability of Europe for A. albopictus using both recent climate and future climate conditions. The results show that southern France, northern Italy, the northern coast of Spain, the eastern coast of the Adriatic Sea and western Turkey were climatically suitable areas for the establishment of the mosquito during the 1960–1980s. Over the last two decades, climate conditions have become more suitable for the mosquito over central northwestern Europe (Benelux, western Germany) and the Balkans, while they have become less suitable over southern Spain. Similar trends are likely in the future, with an increased risk simulated over northern Europe and slightly decreased risk over southern Europe. These distribution shifts are related to wetter and warmer conditions favouring the overwintering of A. albopictus in the north, and drier and warmer summers that might limit its southward expansion.

Pesquisa feita em 2017 intitulada Monitor de Propriedade de Mídia (MOM) e organizada pela Repórteres Sem Fronteiras mostra que o Brasil apresenta os piores indicadores para a pluralidade na mídia entre 12 países em desenvolvimento. Quatro das principais redes de TV brasileiras somam mais de 71% de toda a audiência do país. Em contramão a estes conglomerados midiáticos existe o conceito de mídia livre caracterizada por ser uma mídia alternativa aos modelos de comunicação oligárquicos que compõem o cenário midiático brasileiro. Diante deste contexto o presente artigo tem como objetivo analisar os discursos que o coletivo brasileiro Intervozes faz sobre si mesmo ao se denominar como uma mídia livre e democrática. O corpus deste estudo compreende quatro textos do site oficial do Intervozes a saber: Quem somos, Carta de Princípios, Áreas de Atuação Direitos Humanos e Comunicação Pública e Popular. Ancorados sobre o pressuposto teórico metodológico da Análise do Discurso (AD) que entende que todo discurso é uma construção social com o intuito de gerar sentidos, este estudo recorre aos teóricos Benetti (2008), Ferreira (2010), Foucault (1995), Orlandi (1999), Paulillo (1997), Pinto (2002), entre outros, para abordar sobre condições de produção e formação discursiva. Também abordamos sobre comunicação e democracia a partir da visão de Chauí (2018), Kucinsky (2003), Vilela (2018) e outros. Os resultados apontam para um discurso com caráter auto afirmativo no sentido que o Intervozes se entende como um agente transformador enquanto novo meio de comunicação e deseja reforçar no leitor esse sentido.

Como casi todos los conceptos fi losófi cos, el de «validez normativa» tiene altos grados de ambigüedad y de vaguedad. En este trabajo me encargo de analizar la postura de distintos autores que han tratado de dar respuesta a la pregunta ¿qué significa que una norma sea «válida»? Para ello, tomo como hilo conductor la obra de Ernesto Garzón Valdés. Esto se debe a que los trabajos de Ernesto Garzón dedicados a este tema, le ofrecen al lector un análisis crítico y comprensivo de algunas de las posturas teóricas más relevantes sobre el concepto de validez normativa. Asimismo, trabajar a través de su obra tiene un doble benefi cio: por un lado, no sólo nos permite conocer a fondo la postura teórica de autores que pertenecen a distintas corrientes del pensamiento, como Hans Kelsen, H.L.A. Hart, Francisco Suárez o von Wright por ejemplo, sino que, por el otro, nos permite conocer la postura del mismo Garzón y sus críticas a los diferentes modelos conceptuales.

Through the delivery of eco systemic services (ES), the ecosystems of an area provide irreplaceable support to the quality of life of its inhabitants and the basic factors for lasting economic development. These services constitute the natural capital of a geographical area and also a sort of insurance policy against extreme events. The fi rst results of an original and fast method are presented here. It was found that each year Italian eco systems deliver goods and benefi ts equivalent (if their absence is hypothesised) to euro 71.3 billion. The trends for these values are more important: in just ten years some provinces seem to have lost more than 3% of their total value and up to 18% in the case of specifi c Ess. The prospects for Ess integrated in geographical assessment and planning could be supported by development strategies that are more aware of ecological processes and that are more farsighted.

The decision by the EU Council of Heads of State or of Government at the beginning of May, that eleven Member States would form an Economic and Monetary Union on 1 January 1999, occasioned little surprise: financial markets and economic commentators had become increasingly convinced over the preceding months that EMU would start on time with a membership extending beyond the six ‘core’ countries—France, Germany, the Benelux countries and Austria—to include also Finland, Ireland, Italy, Portugal and Spain. What was not widely expected was that the ECOFIN and HoSoG Councils on 1–2 May appear to have spent little time debating the economic case for including each of the eleven countries but to have been preoccupied instead with a heated political row about who should be appointed President of the European Central Bank.This note assesses the possible consequences that this cavalier approach to the vital question of membership of monetary union might have for the conduct of policy in Stage 3 and the future viability of EMU. It examines the economic evidence that had been presented to the Councils to see whether their judgement that the economies of all eleven countries are sufficiently convergent is warranted. It also considers whether the unseemly compromise through which the dispute about the ECB Presidency was resolved will prejudice the political independence of the ECB in its conduct of monetary policy.

Abstract. Tropospheric ozone (O3) is an important air pollutant that affects human health, ecosystems, and climate. The contributions of O3 precursor emissions from different geographical source regions to the O3 concentration can help to quantify the effects of local versus remotely transported precursors on the O3 concentration in a certain area. This study presents a “tagging” approach within the WRF-Chem model that attributes O3 concentration in several European receptor regions to nitrogen oxide (NOx) emissions from within and outside of Europe during April–September 2010. We also examine the contribution of these different precursor sources to various O3 metrics and their exceedance events. Firstly, we show that the spatial distributions of simulated monthly mean MDA8 from tagged O3 source regions and types for late spring, summer, and early autumn 2010 varies with season. For summer conditions, O3 production is dominated by national and intra-European sources, while in the late spring and early autumn intercontinental transported O3 is an important contributor to the total O3 concentration. We have also identified shipping activities in the Mediterranean Sea as an important source of O3 for the Mediterranean countries, as well as the main contributor to high modelled MDA8 O3 concentration in the Mediterranean Basin itself. Secondly, to have a better understanding of the origin of MDA8 O3 exceedances, we compare modelled and observed values of MDA8 O3 concentration in the Po Valley and Germany–Benelux receptor regions, revealing that the contribution from local sources is about 41 % and 38 % of modelled MDA8 O3 during the exceedance days, respectively. By examining the relative contributions of remote NOx sources to modelled and observed O3 exceedance events, we determine that model underrepresentation of long-range O3 transport could be contributing to a general underestimation of modelled O3 exceedance events in the Germany–Benelux receptor region. Thirdly, we quantify the impact of local vs. non-local NOx precursors on O3 production for each European receptor region using different O3 metrics. The comparison between mean, MDA8 and 95th percentile O3 metrics accentuates the importance of large contributions from locally emitted NOx precursors to the high end of the O3 distribution. When we compare the vegetation and health metrics, we notice that the SOMO35 and AOT40 indexes exhibit rather similar behaviour, while the W126 index accentuates the importance of local emissions. Overall, this study highlights the importance of a tagging approach to quantify the contribution of local and remote sources to the MDA8 O3 concentration during several periods as well to different O3 metrics. Moreover, this method could be applied to assess different mitigation options.

Climate change has intensifi ed in recent years. The resulting climatic disasters are no longer a distant future, but a diffi cult reality. This subject has been un-derestimated for too long. The aim of this article is to highlight our ineptitude and the mistakes we have made as tenants of this planet, and to fi nd and analyse solutions that would be most eff ective and at the same time most benefi cial to the most disadvantaged. The climate change was caused by man, among others through the burning of fossil fuels, intensive farming, or clearing and burning forests. Mainly a man who lives in highly developer part of the world. The con-sequences of climate change, such as the rise in average temperatures, rising sea and ocean levels, and weather extremes aff ect mainly underdeveloped regions, which due to their diffi cult economic situation, have in fact contributed least to change. The Paris Agreement recognised that losses and damage resulting from weather extremes are indeed caused by climate change. Unfortunately, it was also made clear that countries aff ected by such damage have no right to claim damages for this reason. The problem is being tackled by insurance companies that off er climate risk insurance, as well as climate lawsuits.

Chikungunya virus disease (chikungunya) is a mosquito-borne infectious disease reported in at least 50 countries, mostly in the tropics. It has spread around the globe within the last two decades, with local outbreaks in Europe. The vector mosquito Aedes albopictus (Diptera, Culicidae) has already widely established itself in southern Europe and is spreading towards central parts of the continent. Public health authorities and policymakers need to be informed about where and when a chikungunya transmission is likely to take place. Here, we adapted a previously published global ecological niche model (ENM) by including only non-tropical chikungunya occurrence records and selecting bioclimatic variables that can reflect the temperate and sub-tropical conditions in Europe with greater accuracy. Additionally, we applied an epidemiological model to capture the temporal outbreak risk of chikungunya in six selected European cities. Overall, the non-tropical ENM captures all the previous outbreaks in Europe, whereas the global ENM had underestimated the risk. Highly suitable areas are more widespread than previously assumed. They are found in coastal areas of the Mediterranean Sea, in the western part of the Iberian Peninsula, and in Atlantic coastal areas of France. Under a worst-case scenario, even large areas of western Germany and the Benelux states are considered potential areas of transmission. For the six selected European cities, June–September (the 22th–38th week) is the most vulnerable time period, with the maximum continuous duration of a possible transmission period lasting up to 93 days (Ravenna, Italy).

La propuesta que pretender introducir este artículo consiste en analizar y<br />estudiar en profundidad la labor política y personal de la congresista republicana estadounidense<br />Edith Nourse Rogers, por el estado de Massachusetts. Esta congresista fue hasta el<br />año 2011 la representante con la carrera política más extensa en la historia del Congreso, lo<br />cual valida la originalidad del presente estudio.<br />Edith Nourse Rogers fue una mujer con un impacto signifi cativo en la historia política<br />estadounidense, cambiando para siempre tanto la vida de muchas mujeres estadounidenses<br />como la de los veteranos de guerra. Para las primeras, por medio de la creación de un cuerpo<br />específi co femenino en el ejército (WAAC – WAC), mientras que para los segundos defendía<br />la creación de hospitales por todo el país así como la implantación de diversos benefi cios y<br />compensaciones económicas y sociales.<br />Pero incomprensiblemente, la fi gura de esta congresista ha sido bastante poco estudiada<br />y no se le ha reconocido su valía y relevancia para el país. De ahí que esta investigación<br />sea pionera a la par que especialmente apreciable y signifi cativa desde un punto de vista<br />histórico y político

La osteoporosis es una enfermedad metabólica que produce un hueso cuantitativamente defi ciente, de mala calidad y propenso a fracturas la cual es tratada con Calcio. A pesar de que se conocen los efectos benéfi cos de este elemento, recientes informes lo asocian con complicaciones cardiovasculares. Teniendo en cuenta lo anterior esta revisión buscó plasmar el estado del arte y los conceptos más recientes sobre el uso de Calcio en la osteoporosis así como establecer si el riesgo cardiovascular atribuido a este agente es real. Pensamos particularmente que los benefi cios del calcio como elemento terapéutico para el tratamiento coadyuvante de la osteoporosis exceden los potenciales efectos deletéreos que le asignan. Y que probablemente el presunto riesgo de enfermedad cardiovascular inducida por el calcio sea una falsa alarma y se convierta en otro más de los mitos frecuentes postulados en medicina. Se puede concluir afi rmando que el papel del calcio como elemento mineral es muy importante para el tejido óseo, si bien es cierto que estos agentes se vienen cuestionando en algunos aspectos como seguridad cardiovascular entre otros, definitivamente tanto el calcio como la Vitamina D no son los elementos más potentes en el arsenal terapéutico contra la enfermedad, pero sus défi cits son los más sencillos de identificar y los más fáciles de corregir.

Abstract. High surface ozone concentrations, which usually occur when photochemical ozone production takes place, pose a great risk to human health and vegetation. Air quality models are often used by policy makers as tools for the development of ozone mitigation strategies. However, the modeled ozone production is often not or not enough evaluated in many ozone modeling studies. The focus of this work is to evaluate the modeled ozone production in Europe indirectly, with the use of the ozone–temperature correlation for the summer of 2010 and to analyze its sensitivity to precursor emissions and meteorology by using the regional air quality model, the Comprehensive Air Quality Model with Extensions (CAMx). The results show that the model significantly underestimates the observed high afternoon surface ozone mixing ratios (≥ 60 ppb) by 10–20 ppb and overestimates the lower ones (< 40 ppb) by 5–15 ppb, resulting in a misleading good agreement with the observations for average ozone. The model also underestimates the ozone–temperature regression slope by about a factor of 2 for most of the measurement stations. To investigate the impact of emissions, four scenarios were tested: (i) increased volatile organic compound (VOC) emissions by a factor of 1.5 and 2 for the anthropogenic and biogenic VOC emissions, respectively, (ii) increased nitrogen oxide (NOx) emissions by a factor of 2, (iii) a combination of the first two scenarios and (iv) increased traffic-only NOx emissions by a factor of 4. For southern, eastern, and central (except the Benelux area) Europe, doubling NOx emissions seems to be the most efficient scenario to reduce the underestimation of the observed high ozone mixing ratios without significant degradation of the model performance for the lower ozone mixing ratios. The model performance for ozone–temperature correlation is also better when NOx emissions are doubled. In the Benelux area, however, the third scenario (where both NOx and VOC emissions are increased) leads to a better model performance. Although increasing only the traffic NOx emissions by a factor of 4 gave very similar results to the doubling of all NOx emissions, the first scenario is more consistent with the uncertainties reported by other studies than the latter, suggesting that high uncertainties in NOx emissions might originate mainly from the road-transport sector rather than from other sectors. The impact of meteorology was examined with three sensitivity tests: (i) increased surface temperature by 4 ∘C, (ii) reduced wind speed by 50 % and (iii) doubled wind speed. The first two scenarios led to a consistent increase in all surface ozone mixing ratios, thus improving the model performance for the high ozone values but significantly degrading it for the low ozone values, while the third scenario had exactly the opposite effects. Overall, the modeled ozone is predicted to be more sensitive to its precursor emissions (especially traffic NOx) and therefore their uncertainties, which seem to be responsible for the model underestimation of the observed high ozone mixing ratios and ozone production.

The conductometric study of the products of the proton transfer reactions of C-acids (nitriles, nitroalkanes, and 2,4,6-trinitrotoluene) with the strong amine bases (1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,8-bis(dimethylamino)naphthalene (DMAN), and piperidine) in acetonitrile shows their large degree of dissociation into free ions. The dissociation constant values have been estimated at 25 °C to be larger than 1 × 10−4 M. This weakens the formalism commonly accepted in spectrophotometric kinetic studies of these systems of reactions, based on the assumption that the product is an ion pair. Spectrophotometric equilibrium and kinetic measurements provided evidence that reverse reaction is a second-order process (pseudo-first order because cation concentration is controlled by side reactions). The influence of the common cation (TMGH+) on the equilibria of the proton abstraction from 2-methyl-1-(4-nitrophenyl)-1-nitropropane and 4-nitrophenylcyanomethane with TMG base in acetonitrile at 25 °C was examined and was found to be compatible with the assumption of large dissociation of the reaction product for free ions. "Equilibrium constants" estimated by the Benesi and Hildebrand method (which assumes an ion-pair product) decreased with increasing concentration of added TMGH+ cation, but these "equilibrium constants" multiplied by [TMGH+] are constant. The observed pseudo-first-order rate constants of the proton transfer reaction, measured at large excess of the base over C-acid, grow with the cation concentration due to the increase of the backward reaction rate. The concentration of added common cation shows a negligible influence on the observed rate constants of deuteron transfer reaction. Thus, as a result of side reactions, in which extra amounts of cation are formed, some second-order rate constants [Formula: see text] and also kinetic isotope effects (KIEs) [Formula: see text] that have been measured in acetonitrile can be substantially overestimated. Keywords: ion-pair dissociation, proton transfer reactions, kinetic isotope effects.

Abstract. Emissions from the marine transport sector are one of the least-regulated anthropogenic emission sources and contribute significantly to air pollution. Although strict limits were introduced recently for the maximum sulfur content in marine fuels in the SECAs (sulfur emission control areas) and in EU ports, sulfur emissions outside the SECAs and emissions of other components in all European maritime areas have continued to increase in the last two decades. We have used the air quality model CAMx (Comprehensive Air Quality Model with Extensions) with and without ship emissions for the year 2006 to determine the effects of international shipping on the annual as well as seasonal concentrations of ozone, primary and secondary components of PM2.5, and the dry and wet deposition of nitrogen and sulfur compounds in Europe. The largest changes in pollutant concentrations due to ship emissions were predicted for summer. Concentrations of particulate sulfate increased due to ship emissions in the Mediterranean (up to 60 %), the English Channel and the North Sea (30–35 %), while increases in particulate nitrate levels were found especially in the north, around the Benelux area (20 %), where there were high NH3 land-based emissions. Our model results showed that not only are the atmospheric concentrations of pollutants affected by ship emissions, but also depositions of nitrogen and sulfur compounds increase significantly along the shipping routes. NOx emissions from the ships, especially in the English Channel and the North Sea, cause a decrease in the dry deposition of reduced nitrogen at source regions by moving it from the gas phase to the particle phase which then contributes to an increase in the wet deposition at coastal areas with higher precipitation. In the western Mediterranean region, on the other hand, model results show an increase in the deposition of oxidized nitrogen (mostly HNO3) due to the ship traffic. Dry deposition of SO2 seems to be significant along the shipping routes, whereas sulfate wet deposition occurs mainly along the Scandinavian and Adriatic coasts. The results presented in this paper suggest that evolution of NOx emissions from ships and land-based NH3 emissions will play a significant role in future European air quality.

On the basis of analysis of integration processes between Nordic, Benelux countries and post-soviet states in Europe the author expresses hesitations in accepting the integration experiences gained by the EU as the criterion of efficiency and the pattern for the post-Soviet space. He does not consider that an involvement of all countries with market economy into processes of regional integration, if they do not try to achieve certain political aims through integration, is the universal regularity in the globalized world. In these cases neither free trade zones nor custom unions can be considered as integration stages, but they continue to be the tools for further development of trade. The author proposes to assess the EU evolution with regard to the legal norms of international organizations, where state sovereignty of members is strengthened, not given up to supernational bodies. In case the idea of reestablishment of an unified state on the remains of the former USSR, linked to the necessity to hand over the recently acquired sovereignty to it, is laid down to the ground for practical measures of integration, this kind of integration will hardly be attractive to the potential post-Soviet participants. This perspective is hardly desired for Russia either. The integration path of the EU reflects the peculiarities of the European situation and specific interests of its member states. Many details of the EU activity are not applicable to other integration groupings in Europe and membership criteria in every of them is not universal. Any efforts to construct integration processes in the post-Soviet space in accordance to the EU model without proper consideration to integration experiences of other countries and to political, economic, social, cultural, demographic, military peculiarities of the countries concerned seem to be not acceptable and founded.

The interaction between colloidal gold nanoparticles (AuNPs) and lysozyme (Lyz) has been studied through spectroscopic and microscopic measurements, molecular docking simulation and colorimetric measurements to investigate corona formation and the mechanism, affinity, number of sites and stoichiometry of binding. Molecular docking simulation endorses that, at physiological pH, the interaction between basic NH2 group of arginine and citrate ions is predominant than the interaction between citrate ions and the positive surface charge of the bare AuNPs that result in the desorption of citrate ions from Au surfaces and finally, electrostatic interaction between [Formula: see text] group of arginine and positive charge surface of AuNPs results in the adsorption of Lyz on Au surfaces. As observed from Benesi–Hildebrand and fluorescence analyses, the ground state complex formation between Lyz and AuNPs requires several minutes, which is approximately 11 min in the present work to attain stoichiometric ratio 1:1. CD spectra indicate insignificant or no conformational change in the secondary structure of Lyz in the presence of AuNPs. The time variation of LSPR peak position and peak height in the presence of Lyz have been studied extensively through spectroscopic and microscopic measurements. Detailed discussion on the probable time-specific roles of change in local dielectric constant, plasmon coupling and electrostatic interaction on these variations has been presented. Colorimetric change of the AuNPs-Lyz system with time has been analyzed by measuring the red, blue and green color fractions as well as its correlation with the process of corona formation and aggregation has been investigated to propose a novel naked eye colorimetric approach of studying these processes in AuNPs-Lyz system.

Abstract. The focus of this modeling study is on the role of ammonia in European air quality in the past as well as in the future. Ammonia emissions have not decreased as much as the other secondary inorganic aerosol (SIA) precursors – nitrogen oxides (NOx) and sulfur dioxide (SO2) – since the 1990s and are still posing problems for air quality and the environment. In this study, air quality simulations were performed with a regional chemical transport model at decadal intervals between 1990 and 2030 to understand the changes in the chemical species associated with SIA under varying land and ship emissions. We analyzed the changes in air concentrations of ammonia, nitric acid, ammonium, particulate nitrate and sulfate as well as changes in the dry and wet deposition of ammonia and ammonium. The results show that the approximately 40 % decrease in SIA concentrations between 1990 and 2010 was mainly due to reductions in NOx and SO2 emissions. The ammonia concentrations on the other hand decreased only near the high-emission areas such as the Netherlands and northern Italy by about 30 %, while there was a slight increase in other parts of Europe. Larger changes in concentrations occurred mostly during the first period (1990–2000). The model results indicate a transition period after 2000 for the composition of secondary inorganic aerosols due to a larger decrease in sulfate concentrations than nitrate. Changes between 2010 and 2030 – assuming the current legislation (CLE) scenario – are predicted to be smaller than those achieved earlier for all species analyzed in this study. The scenario simulations suggest that if ship emissions will be regulated more strictly in the future, SIA formation will decrease especially around the Benelux area, North Sea, Baltic Sea, English Channel and the Mediterranean region, leaving more ammonia in the gas phase, which would lead to an increase in dry deposition. In the north of the domain, the decrease in SIA would be mainly due to reduced formation of particulate nitrate, while the change around the Mediterranean would be caused mainly by decreased sulfate aerosol concentrations. One should also keep in mind that potentially higher temperatures in the future might increase the evaporation of ammonium nitrate to form its gaseous components NH3 and HNO3. Sensitivity tests with reduced NOx and NH3 emissions indicate a shift in the sensitivity of aerosol formation from NH3 towards NOx emissions between 1990 and 2030 in most of Europe except the eastern part of the model domain.

In New Zealand in the 1990s, labour market decentralization and new employment legislation precipitated a sharp decline in unionism and collective bargaining coverage; trends that continued well into the 2000s even after the introduction of the more supportive Employment Relations Act 2000 (ERA). The ERA prescribed new bargaining rules, which included a good faith obligation, increased union rights and promoted collective bargaining as the key to building productive employment relationships (Anderson, 2004; May and Walsh, 2002). In this respect the ERA provided scope for increased collective bargaining and union renewal (Harbridge and Thickett, 2003; May, 2003a and 2003b; May and Walsh, 2002). Despite these predictions and the ERA's overall intent, the decline in collective bargaining coverage begun in the 1990s has continued unabated in the private sector. It has naturally been questioned why the ERA has not reversed, or at least halted, this downward trend. So far research has focused on the impact of the legislation itself and much less on employer behaviour and perceptions, or on their contribution to these trends. This article addresses the paucity of employer focused research in New Zealand. The research explores views of employers on the benefi ts of collective bargaining, how decisions to engage or not engage in collective bargaining are made and the factors instrumental to them. It is demonstrated that the preferred method of setting pay and conditions continues to be individual bargaining. This is especially so for organizations with less than 50 employees, by far the largest majority of fi rms in New Zealand. Frequently, these smaller organizations see no perceived benefits from collective bargaining. Overall, these fi ndings suggest that despite a decade of supportive legislation there are few signs that the 20 year decline in collective bargaining coverage in New Zealand will be reversed.

Abstract. The summer drought of 2015 affected a large portion of continental Europe and was one of the most severe droughts in the region since summer 2003. The summer of 2015 was characterized by exceptionally high temperatures in many parts of central and eastern Europe, with daily maximum temperatures 2 °C higher than the seasonal mean (1971–2000) over most of western Europe, and more than 3 °C higher in the east. It was the hottest and climatologically driest summer over the 1950–2015 study period for an area stretching from the eastern Czech Republic to Ukraine. For Europe, as a whole, it is among the six hottest and driest summers since 1950. High evapotranspiration rates combined with a lack of precipitation affected soil moisture and vegetation and led to record low river flows in several major rivers, even beyond the drought-hit region. The 2015 drought developed rather rapidly over the Iberian Peninsula, France, southern Benelux and central Germany in May and reached peak intensity and spatial extent by August, affecting especially the eastern part of Europe. Over the summer period, there were four heat wave episodes, all associated with persistent blocking events. Upper-level atmospheric circulation over Europe was characterized by positive 500 hPa geopotential height anomalies flanked by a large negative anomaly to the north and west (i.e., over the central North Atlantic Ocean extending to northern Fennoscandia) and another center of positive geopotential height anomalies over Greenland and northern Canada. Simultaneously, the summer sea surface temperatures (SSTs) were characterized by large negative anomalies in the central North Atlantic Ocean and large positive anomalies in the Mediterranean basin. Composite analysis shows that the western Mediterranean SST is strongly related to the occurrence of dry and hot summers over the last 66 years (especially over the eastern part of Europe). The lagged relationship between the Mediterranean SST and summer drought conditions established in this study can provide valuable skill for the prediction of drought conditions over Europe on interannual to decadal timescales.

Abstract. The CALIOPE air quality modelling system is developed and applied to Europe with high spatial resolution (12 km × 12 km). The modelled daily-to-seasonal aerosol variability over Europe in 2004 is evaluated and analysed. Aerosols are estimated from two models, CMAQv4.5 (AERO4) and BSC-DREAM8b. CMAQv4.5 calculates biogenic, anthropogenic and sea salt aerosol and BSC-DREAM8b provides the natural mineral dust contribution from North African deserts. For the evaluation, we use daily PM10, PM2.5 and aerosol components data from 55 stations of the EMEP/CREATE network and total, coarse and fine aerosol optical depth (AOD) data from 35 stations of the AERONET sun photometer network. Annual correlations between modelled and observed values for PM10 and PM2.5 are 0.55 and 0.47, respectively. Correlations for total, coarse and fine AOD are 0.51, 0.63, and 0.53, respectively. The higher correlations of the PM10 and the coarse mode AOD are largely due to the accurate representation of the African dust influence in the forecasting system. Overall PM and AOD levels are underestimated. The evaluation of the aerosol components highlights underestimations in the fine fraction of carbonaceous matter (EC and OC) and secondary inorganic aerosols (SIA; i.e. nitrate, sulphate and ammonium). The scores of the bulk parameters are significantly improved after applying a simple model bias correction based on the observed aerosol composition. The simulated PM10 and AOD present maximum values over the industrialized and populated Po Valley and Benelux regions. SIA are dominant in the fine fraction representing up to 80% of the aerosol budget in latitudes north of 40° N. In southern Europe, high PM10 and AOD are linked to the desert dust transport from the Sahara which contributes up to 40% of the aerosol budget. Maximum seasonal ground-level concentrations (PM10 > 30 μg m−3) are found between spring and early autumn. We estimate that desert dust causes daily exceedances of the PM10 European air quality limit value (50 μg m−3) in large areas south of 45° N with more than 75 exceedances per year in the southernmost regions.

Abstract. Emissions from the marine transport sector are one of the least regulated anthropogenic emission sources and contribute significantly to air pollution. Although strict limits were introduced recently for the maximum sulfur content in marine fuels in the SECAs (sulfur emission control areas) and in the EU ports, sulfur emissions outside the SECAs and emissions of other components in all European maritime areas have continued to increase in the last two decades. We have used the air quality model CAMx with and without ship emissions for the year 2006 to determine the effects of international shipping on the annual as well as seasonal concentrations of ozone, primary and secondary components of PM2.5 and the dry and wet deposition of nitrogen and sulfur compounds in Europe. Our results suggest that emissions from international shipping affect the air quality in northern and southern Europe differently and their contributions to the air concentrations vary seasonally. The largest changes in pollutant concentrations due to ship emissions were predicted for summer. Increased concentrations of the primary particle mass were found only along the shipping routes whereas concentrations of the secondary pollutants were affected over a larger area. Concentrations of particulate sulfate increased due to ship emissions in the Mediterranean (up to 60 %), in the English Channel and the North Sea (30–35 %) while increases in particulate nitrate levels were found especially in the north, around the Benelux area (20 %) where there were high NH3 land-based emissions. Our model results showed that not only the atmospheric concentrations of pollutants are affected by ship emissions, but also depositions of nitrogen and sulfur compounds increase significantly along the shipping routes. NOx emissions from the ships especially in the English Channel and the North Sea, cause a decrease in the dry deposition of reduced nitrogen at source regions by moving it from the gas-phase to the particle phase which then contributes to an increase in the wet deposition at coastal areas with higher precipitation. In the western Mediterranean region on the other hand, model results show an increase in the deposition of oxidized nitrogen (mostly HNO3) due to the ship traffic. Dry deposition of SO2 seems to be significant along the shipping routes whereas sulfate wet deposition occurs mainly along the Scandinavian and Adriatic coasts. The results presented in this paper suggest that evolution of NOx emissions from ships and land-based NH3 emissions will play a significant role in the future European air quality.

Abstract. A nine-year air quality simulation is conducted from 2000 to 2008 over Europe using the Polyphemus/Polair3D chemical-transport model (CTM) and then evaluated against the measurements of the European Monitoring and Evaluation Programme (EMEP). The spatial distribution of PM2.5 over Europe shows high concentrations over northern Italy (36 μg m−3) and some areas of eastern Europe, France, and Benelux, and low concentrations over Scandinavia, Spain, and the easternmost part of Europe. PM2.5 composition differs among regions. The operational evaluation shows satisfactory model performance for ozone (O3). PM2.5, PM10, and sulfate (SO42−) meet the performance goal of Boylan and Russell (2006). Nitrate (NO3−) and ammonium (NH4+) are overestimated, although NH4+ meets the performance criteria. The correlation coefficients between simulated and observed data are 63% for O3, 57% for PM10, 59% for PM2.5, 57% for SO42−, 42% for NO3−, and 58% for NH4+. The comparison with other recent one-year model simulations shows that all models overestimate nitrate. The performance of PM2.5, sulfate, and ammonium is comparable to that of the other models. The dynamic evaluation shows that the response of PM2.5 to changes in meteorology differs depending on location and the meteorological variable considered. Wind speed and precipitation show a strong negative day-to-day correlation with PM2.5 and its components (except for sea salt, which shows a positive correlation), that tends towards 0 as the day lag increases. On the other hand, the correlation coefficient is near constant for temperature, for any day lag and PM2.5 species, but it may be positive or negative depending on the species and, for sulfate, depending on the location. The effects of precipitation and wind speed on PM2.5 and its components are better reproduced by the model than the effects of temperature. This is mainly due to the fact that temperature has different effects on the PM2.5 components, unlike precipitation and wind speed which impact most of the PM2.5 components in the same way. These results suggest that state-of-the-science air quality models reproduce satisfactorily the effect of meteorology on PM2.5 and, therefore, are suitable to investigate the effects of climate change on particulate air quality.

Abstract. The CALIOPE high-resolution air quality modelling system is developed and applied to Europe (12 km × 12 km, 1 h). The modelled daily to seasonal aerosol variability over Europe in 2004 have been evaluated and analysed. The aerosols are estimated from two models, CMAQv4.5 (AERO4) and BSC-DREAM8b. CMAQv4.5 calculates biogenic, anthropogenic and sea salt aerosol and BSC-DREAM8b provides the natural mineral dust contribution from North African deserts. For the evaluation, we use daily PM10/PM2.5 and chemical composition data from 54 stations of the EMEP/CREATE network and coarse and fine aerosol optical depth (AOD) data from 35 stations of the AERONET sun photometer network. The model achieves daily PM10 and PM2.5 correlations of 0.57 and 0.47, respectively, and total, coarse and fine AOD correlations of 0.51, 0.63, and 0.53, respectively. The higher correlations of the PM10 and the coarse mode AOD are largely due to the accurate representation of the African dust influence in the forecasting system. Overall PM and AOD levels are underestimated. The evaluation of the chemical composition highlights underestimations of the modelled fine fractions particularly for carbonaceous matter (EC and OC) and secondary inorganic aerosols (SIA; i.e. nitrates, sulphates and ammonium). The scores of the bulk parameters are significantly improved after applying a simple model bias correction based on the chemical composition observations. SIA are dominant in the fine fractions representing up to 80 % of the aerosol budget in latitudes beyond 40° N. The highest aerosol concentrations are found over the industrialized and populated areas of the Po Valley and the Benelux regions. High values in southern Europe are linked to the transport of coarse particles from the Sahara desert which contributes up to 40 % of the total aerosol mass. Close to the surface, maxima dust seasonal concentrations (>30 μg m–3) are found between spring and early autumn. We estimate that desert dust causes daily exceedances of the PM10 European air quality threshold (50 μg m–3) in large areas south of 45° N reaching up to more than 75 days per year in the southernmost regions.

Abstract. A 9 yr air quality simulation is conducted from 2000 to 2008 over Europe using the Polyphemus/Polair3D chemical-transport model (CTM) and then evaluated against the measurements of the European Monitoring and Evaluation Programme (EMEP). The spatial distribution of PM2.5 over Europe shows high concentrations over northern Italy (36 μg m−3) and some areas of Eastern Europe, France, and Benelux, and low concentrations over Scandinavia, Spain, and the easternmost part of Europe. PM2.5 composition differs among regions. The operational evaluation shows satisfactory model performance for ozone (O3). PM2.5, PM10, and sulfate (SO4=) meet the performance goal of Boylan and Russell (2006). Nitrate (NO3−) and ammonium (NH4+) are overestimated, although NH4+ meets the performance criterion. The correlation coefficients between simulated and observed data are 63% for O3, 57% for PM10, 59% for PM2.5, 57% for SO4=, 42% for NO3−, and 58% for NH4+. The comparison with other recent 1 yr model simulations shows that all models overestimate nitrate. The performance of PM2.5, sulfate, and ammonium is comparable to that of the other models. The dynamic evaluation shows that the response of PM2.5 to changes in meteorology differs depending on location and the meteorological variable considered. Wind speed and precipitation show a strong negative day-to-day correlation with PM2.5 and its components (except for sea salt, which shows a positive correlation), which tends towards 0 as the day lag increases. On the other hand, the correlation coefficient is near constant for temperature, for any day lag and PM2.5 species, but it may be positive or negative depending on the species and, for sulfate, depending on the location. The effects of precipitation and wind speed on PM2.5 and its components are better reproduced by the model than the effects of temperature. This is mainly due to the fact that temperature has different effects on the PM2.5 components, unlike precipitation and wind speed, which impact most of the PM2.5 components in the same way. These results suggest that state-of-the-science air quality models reproduce satisfactorily the effect of meteorology on PM2.5 and therefore are suitable to investigate the effects of climate change on particulate air quality, although uncertainties remain concerning semivolatile PM2.5 components.

Background:Behcet’s disease is a systemic autoimmune vasculitis that typically involves mucocutaneous surfaces, the eyes and the skin with varying manifestations. Skin ulceration often secondary to pathergy is a common feature.Objectives:To raise awareness of breast ulceration as a clinical manifestation in Behcet’s disease.Methods:We report a case of complex Bechet’s disease associated with severe refractory breast ulceration successfully treated with cyclophosphamide.Results:A 27 year old female patient presented to the rheumatology department with a non-healing lesion on her face secondary to a cat scratch. She reported previous episodes of ulceration usually as a result of minor trauma such as IV cannulation, as well as a two year history of severe oral and genital ulceration. She had also been diagnosed with ‘colitis’ requiring iliocaecal resection two years prior to presentation. Previous treatments for her bowel included azathioprine, infliximab, adalimumab and vedolizumab. Over the next three years she developed recurrent eye involvement in the form of scleritis with ongoing oral and genital ulceration. Further treatment under our care included ustekinumab, entanercept, benepali, certolizumab and tacrolimus with background prednisolone. She then developed a small area of broken skin on her left breast which continued to extend and ulcerate despite treatment with IV steroids. Tissue biopsy showed deep focal vasculitis with intravascular thrombi. Anticoagulation was commenced and she was treated with tocilizumab IV for 3 months with no clinical improvement. Involvement extended to include 80 percent of the breast surface and the nipple self-amputated. Due to the severity and extent of the ulceration which was extremely painful and distressing, she was given 3 months of IV cyclophosphamide at a dose of 15mg/kg every 2-3 weeks. The ulceration showed rapid clinical improvement (see Figure 1).Figure 1.Breast ulceration before and after 3 months of cyclophosphamide treatmentConclusion:Involvement of the breast in systemic vasculitides (such as GPA or PAN) has been reported, although usually manifesting as a palpable mass with diagnosis on biopsy 1. Similar presentations in Behcet’s disease have been recognised 2, although much less commonly. Our case demonstrates that severe breast ulceration can be a clinical manifestation of this condition and can be refractory to usual therapies.References:[1]Ren J, Liu J, Su J, Zhang J, Zhao J. Systemic vasculitis involving the breast: a case report and literature review. Rheumatol Int. 2019 Aug;39(8):1447-1455[2]Soleto MJ, Marcos L. Behçet’s disease involving the breast. Eur Radiol. 2002 Dec;12 Suppl 3:S98-S100. doi: 10.1007/s00330-002-1420-4.Disclosure of Interests:None declared

Abstract. Aerosols play an important role in Europe and the Mediterranean area where different sources of natural and anthropogenic particles are present. Among them ammonium and nitrate (A&amp;N) aerosols may have a growing impact on regional climate. In this study, their representation in coarse and fine modes has been introduced in the prognostic aerosol scheme of the ALADIN-Climate regional model. This new aerosol scheme is evaluated over Europe and the Mediterranean Sea, using two twin simulations over the period 1979–2016 with and without A&amp;N aerosols. This evaluation is performed at local and regional scales, using surface stations and satellite measurements. Despite an overestimate of the surface nitrate concentration, the model is able to reproduce its spatial pattern including local maxima (Benelux, Po Valley). Concerning the simulated aerosol optical depth (AOD), the inclusion of A&amp;N aerosols significantly reduces the model bias compared to both AERONET stations and satellite data. Our results indicate that A&amp;N aerosols can contribute up to 40 % of the total AOD550 over Europe, with an average of 0.07 (550 nm) over the period 2001–2016. Sensitivity studies suggest that biases still present are related to uncertainties associated with the annual cycle of A&amp;N aerosol precursors (ammonia and nitric acid). The decrease in sulfate aerosol production over Europe since 1980 produces more free ammonia in the atmosphere leading to an increase in A&amp;N concentrations over the studied period. Analyses of the different aerosol trends have shown for the first time to our knowledge that, since 2005 over Europe, A&amp;N AOD550 and A&amp;N shortwave (SW) direct radiative forcing (DRF) are found to be higher than sulfate and organics, making these the species with the highest AOD and the highest DRF. On average over the period 1979–2016, the A&amp;N DRF is found to be about −1.7 W m−2 at the surface and −1.4 W m−2 at the top of the atmosphere (TOA) in all sky conditions over Europe, with regional maxima located at the surface over the Po Valley (−5 W m−2). Finally, the dimming effect of A&amp;N aerosols is responsible for a cooling of about −0.2∘ C over Europe (summer), with a maximum of −0.4 ∘C over the Po Valley. Concerning precipitation, no significant impact of A&amp;N aerosols has been found.

Abstract. Most of the global fossil fuel CO2 emissions arise from urbanized and industrialized areas. Bottom-up inventories quantify them but with large uncertainties. In 2010–2011, the first atmospheric in situ CO2 measurement network for Paris, the capital of France, began operating with the aim of monitoring the regional atmospheric impact of the emissions coming from this megacity. Five stations sampled air along a northeast–southwest axis that corresponds to the direction of the dominant winds. Two stations are classified as rural (Traînou – TRN; Montgé-en-Goële – MON), two are peri-urban (Gonesse – GON; Gif-sur-Yvette – GIF) and one is urban (EIF, located on top of the Eiffel Tower). In this study, we analyze the diurnal, synoptic and seasonal variability of the in situ CO2 measurements over nearly 1 year (8 August 2010–13 July 2011). We compare these datasets with remote CO2 measurements made at Mace Head (MHD) on the Atlantic coast of Ireland and support our analysis with atmospheric boundary layer height (ABLH) observations made in the center of Paris and with both modeled and observed meteorological fields. The average hourly CO2 diurnal cycles observed at the regional stations are mostly driven by the CO2 biospheric cycle, the ABLH cycle and the proximity to urban CO2 emissions. Differences of several µmol mol−1 (ppm) can be observed from one regional site to the other. The more the site is surrounded by urban sources (mostly residential and commercial heating, and traffic), the more the CO2 concentration is elevated, as is the associated variability which reflects the variability of the urban sources. Furthermore, two sites with inlets high above ground level (EIF and TRN) show a phase shift of the CO2 diurnal cycle of a few hours compared to lower sites due to a strong coupling with the boundary layer diurnal cycle. As a consequence, the existence of a CO2 vertical gradient above Paris can be inferred, whose amplitude depends on the time of the day and on the season, ranging from a few tenths of ppm during daytime to several ppm during nighttime. The CO2 seasonal cycle inferred from monthly means at our regional sites is driven by the biospheric and anthropogenic CO2 flux seasonal cycles, the ABLH seasonal cycle and also synoptic variations. Enhancements of several ppm are observed at peri-urban stations compared to rural ones, mostly from the influence of urban emissions that are in the footprint of the peri-urban station. The seasonal cycle observed at the urban station (EIF) is specific and very sensitive to the ABLH cycle. At both the diurnal and the seasonal scales, noticeable differences of several ppm are observed between the measurements made at regional rural stations and the remote measurements made at MHD, that are shown not to define background concentrations appropriately for quantifying the regional (∼ 100 km) atmospheric impact of urban CO2 emissions. For wind speeds less than 3 m s−1, the accumulation of local CO2 emissions in the urban atmosphere forms a dome of several tens of ppm at the peri-urban stations, mostly under the influence of relatively local emissions including those from the Charles de Gaulle (CDG) Airport facility and from aircraft in flight. When wind speed increases, ventilation transforms the CO2 dome into a plume. Higher CO2 background concentrations of several ppm are advected from the remote Benelux–Ruhr and London regions, impacting concentrations at the five stations of the network even at wind speeds higher than 9 m s−1. For wind speeds ranging between 3 and 8 m s−1, the impact of Paris emissions can be detected in the peri-urban stations when they are downwind of the city, while the rural stations often seem disconnected from the city emission plume. As a conclusion, our study highlights a high sensitivity of the stations to wind speed and direction, to their distance from the city, but also to the ABLH cycle depending on their elevation. We learn some lessons regarding the design of an urban CO2 network: (1) careful attention should be paid to properly setting regional (∼ 100 km) background sites that will be representative of the different wind sectors; (2) the downwind stations should be positioned as symmetrically as possible in relation to the city center, at the peri-urban/rural border; (3) the stations should be installed at ventilated sites (away from strong local sources) and the air inlet set up above the building or biospheric canopy layer, whichever is the highest; and (4) high-resolution wind information should be available with the CO2 measurements.

The life of people with disabilities are marked by adverse situations, like architectural barriers, communication barriers and attitudinal barriers, This group also suffers from violent situations in their daily lifes, such as physical and verbal aggression. In the current scientific production, there is few researches that investigates the discourse of the person victim of violence, a fact that, on one hand, may characterize some ignorance of the situations experienced by these people, and, on the other hand, may result in discredit of the discourse of people with disabilities. The objective of this research was to investigate the violence experienced by people with disabilities through a case study of a young person with physical disability. The research was descriptive and had a qualitative nature, using the theoretical framework of the Sociology of disability, Violence and Stigma. Semi-structured interview was conducted, using Comprehensive Sociology as a data analysis tool. The results showed that insults and exclusions are a part of the daily life of the young, actions that can be classified as bullying. The young experience several conflicts in the school environment, having some of these conflicts resolved through the mediation of professionals. Violence against people with disabilities is a dynamic and recurring phenomenon, requiring prevention and intervention programs in the school and other researches on the theme that focuses on the victim point of view.ResumoA vida das pessoas com deficiência é marcada por situações adversas, como barreiras físicas, comunicacionais e atitudinais. Esse grupo também sofre de situações violentas em seu cotidiano, como agressões físicas e verbais. Na produção científica atual se notam poucas pesquisas que investigam o discurso da própria pessoa vítima de violência, fato esse que, de um lado, pode caracterizar desconhecimento das situações vividas por essas pessoas e, por outro, pode resultar em um descrédito em relação ao discurso das pessoas com deficiência. Nesse sentido, o objetivo desta pesquisa foi investigar as violências vividas por pessoas com deficiência por meio de um estudo de caso de um jovem com deficiência física. A pesquisa realizada foi descritiva e de natureza qualitativa, utilizando-se do referencial teórico da Sociologia da Deficiência, da Violência e do Estigma. Foi realizada entrevista a partir de um roteiro semiestruturado de questões, sendo utilizada a Sociologia Compreensiva como ferramenta de análise dos dados. Os resultados mostraram que xingamentos e exclusões fazem parte do cotidiano do jovem com deficiência, ações tais que podem, legalmente, ser tidas como bullying. O jovem vive diversos conflitos no ambiente escolar, tendo alguns desses conflitos resolvidos a partir da mediação de profissionais. A violência contra as pessoas com deficiência é um fenômeno dinâmico e recorrente, são necessários programas de prevenção e de intervenção no ambiente escolar, além de outras pesquisas sobre a temática que focalizem a perspectiva da vítima.Palavras-chave: Violência, Pessoas com deficiência, Estigma, Bullying.Keywords: Violence, Disabled Persons, Stigma, Bullying.ReferencesABRAMOVAY, M. Cotidiano das escolas: entre violências. Brasília, DF: Unesco, Observatório de Violência, Ministério da Educação 2006.AMARAL, L. A. Sobre crocodilos e avestruzes: falando de diferenças físicas, preconceitos e sua superação. In: Diferenças e preconceito na escola: alternativas teóricas e práticas. Volume 5. São Paulo: Summus, 1998. p. 11-30.ARANHA, M. S. F. Paradigmas da relação da sociedade com as pessoas com deficiência. Revista do Ministério Público do Trabalho, v. 11, n. 21, p. 160-173, 2001.BARROS, A. C. M. W.; DESLANDES, S. F.; BASTOS, O. M. A violência familiar e a criança e o adolescente com deficiências. Cadernos de Saúde Pública, v. 32, 2016.BENETTI, D. S. Efeitos de um treino de habilidades para a vida junto a adolescentes com deficiência intelectual e em situação de acolhimento. 2015. Tese (Doutorado em Educação e Ciências Humanas). Programa de Pós-Graduação em Educação Especial. Universidade Federal de São Carlos, 2015.BIANCHETTI, L. Os trabalhos e os dias dos deuses e dos homens: a mitologia como fonte para refletir sobre normalidade e deficiência. Revista Brasileira de Educação Especial, v. 7, n. 1, p. 61-75, 2001.BONI, V.; QUARESMA, S. J. Aprendendo a entrevistar: como fazer entrevistas em Ciências Sociais. Em Tese, v. 2, n. 1, p. 68-80, 2005.BORGES, L.; CAMPOS, J. A. P. P. Fatores determinantes ao ingresso de alunos com deficiência no ensino médio. Psicologia Educacional, São Paulo, n. 44, p. 79-91, jun. 2017.BOTELHO, R. G.; SOUZA, J. M. C. Bullying e educação física na escola: características, casos, conseqüências e estratégias de intervenção. Revista de Educação Física/Journal of Physical Education, v. 76, n. 139, 2007.BRANDÃO, E. C.; MATIAZI, L. D. Bullying: Violência socioeducacional – desafio permanente. Pedagogia em Ação, v. 9, n. 1, p. 17-33, 2017.BRASIL. Estatuto da Pessoa com Deficiência. Lei Brasileira de Inclusão. Lei nº 13.146, de 6 de julho de 2015. Presidência da República, Brasília/DF; 2015.CHARLOT, B. A violência na escola: como os sociólogos franceses abordam essa questão. Sociologias, Porto Alegre, n. 8, p. 432-443, 2002.CUNHA, M, J.; PINTO, P. C. Representaciones mediáticas de la deficiencia: un estudio longitudinal en la prensa. Sociologia, Problemas e Práticas, Lisboa, n. 85, p. 131-147, set. 2017.EMERICH, D. R.; ALCKMIN-CARVALHO, F.; SILVA, M. H. M. Rejeição e vitimização por pares em crianças com deficiência intelectual e transtorno do espectro autista. Revista Educação Especial, v. 30, n. 58, 2017.FERNANDES, A. P. C. S.; DENARI, F. E. Pessoa com deficiência: estigma e identidade. Revista da FAEEBA Educação e Contemporaneidade, v. 26, n. 50, p. 77-89, 2017.FOUCAULT, M. Vigiar e punir: o nascimento da prisão. Tradução R. Ramalhete. 21. ed. Petrópolis, RJ: Vozes; 1999.FRASER, M. T. D.; GONDIM, S. M. G. Da fala do outro ao texto negociado: discussões sobre a entrevista na pesquisa qualitativa. Paidéia, v. 14, n. 28, p. 139-152, 2004.GOFFMAN, E. Estigma: notas sobre a manipulação da identidade deteriorada. Rio de Janeiro: Coletivo Sabotagem, 1988.GOMES, A. E. G.; REZENDE, L. K. Reflexões sobre bullying na realidade brasileira utilizando a técnica de análise de conteúdo: revisão bibliográfica. Cadernos de Pós-Graduação em Distúrbios do Desenvolvimento, v. 11, n. 1, 2018.GUIMARÃES, A. M. A dinâmica da violência escolar: conflito e ambiguidade. Campinas, SP: Editora Autores Associados, 1996.HARLOS, F. E. Sociologia da deficiência: vozes por significados e práticas (mais) inclusivas. 2012. 201 f. Dissertação (Mestrado em Educação Especial ? Educação do Indivíduo Especial) ? Universidade Federal de São Carlos, São Carlos, 2012.MAFFESOLI, M. Dinâmica da violência. São Paulo: Editora Revista dos Tribunais, 1987.MAFFESOLI, M. Elogio da razão sensível. Petrópolis, RJ: Vozes, 1998.MAFFESOLI, M. Entre o bem e o mal. Compêndio de subversão pós-moderna. Lisboa: Instituto Piaget, 2002.MAFFESOLI, M. O conhecimento comum: introdução à sociologia compreensiva. Porto Alegre: Sulina, 2007.MAGNABOSCO, M. B.; SOUZA, L. L. Educação inclusiva e as representações dos estudantes sobre seus pares com deficiência. Psicologia Escolar e Educacional, v. 22, n. 1, p. 115-122, 2018.MAZZOTTA, M. J. S.; D'ANTINO, M. E. F. Inclusão social de pessoas com deficiências e necessidades especiais: cultura, educação e lazer. Saúde e Sociedade, v. 20, p. 377-389, 2011.MENDES, C. S. Prevenção da violência escolar: avaliação de um programa de intervenção. Revista da Escola de Enfermagem da USP, v. 45, n. 3, p. 581-588, 2011.MENDES, E. G. Breve histórico da educação especial no Brasil. Revista Educación y Pedagogía, v. 22, n. 57, maio/ago. 2010.MOREIRA, M. C. N.; BASTOS, O. M.; BASTOS, L. C.; SOARES, A. H. R.; SOUZA, W. D. S.; SANCHEZ, R. N. Violência contra crianças e adolescentes com deficiência: narrativas com conselheiros tutelares. Ciência e Saúde Coletiva, v. 19, p. 3869-3878, 2014.ORGANIZAÇÃO MUNDIAL DA SAÚDE (OMS). CIF: Classificação Internacional de Funcionalidade, Incapacidade e Saúde. Organização Mundial da Saúde. Lisboa; 2004.ORGANIZAÇÃO MUNDIAL DA SAÚDE (OMS). World report on violence and health. World Health Organization. Geneva; 2002.PAULINO, V. C.; CAIADO, K. R. M. A construção do conceito de deficiência por estudantes sem deficiência, a partir de suas histórias de vida. Educação em Foco, v. 20, n. 32, p. 35-59, 2017.SÃO PAULO. Serviço de Acolhimento Institucional para Crianças e Adolescentes. Prefeitura Municipal de São Paulo. 2017. Disponível em: <https://www.prefeitura.sp.gov.br/cidade/secretarias/assistencia_social/protecao_social_especial/index.php?p=28980>. Acesso em: 6 set. 2019.SILVA, F. R.; ASSIS, S. G. Prevenção da violência escolar: uma revisão da literatura. Educação e Pesquisa, São Paulo, v. 44. 2018.SILVA, J. L. D.; OLIVEIRA, W. A. D.; SILVA, M. A. I. D.; PEREIRA, B. O.; CECILIO, S. Estudo exploratório sobre as concepções e estratégias de intervenção de professores em face do bullying escolar. Psicologia, Sa?o Paulo, Brasil, v. 17, n. 3, p. 189-199, 2015.SIMMEL, G. A natureza sociológica do conflito. In: MORAES FILHO, E. (Org.). Simmel. São Paulo: Ática, 1983. p. 122-134.STELKO-PEREIRA, A. C.; WILLIAMS, L. C. A. Reflexões sobre o conceito de violência escolar e a busca por uma definição abrangente. Temas Psicológicos, Ribeirão Preto/SP, v. 18, n. 1, p. 45-55, 2010.STELKO-PEREIRA, A. C. Avaliação de um programa preventivo de violência escolar: planejamento, implantação e eficácia. 2012. 193 f. Tese (Doutorado em Psicologia), Universidade Federal de São Carlos, São Carlos. 2012.VIEIRA, C. M.; DENARI, F. E. Programa informativo sobre deficiência mental e inclusão: mudanças nas atitudes sociais de crianças sem deficiência. Revista Brasileira de Educação Especial, Marília/SP, v. 18, n. 2, p. 265-282, 2012.WILLIAMS, L. C. A. Sobre deficiência e violência: reflexões para uma análise de revisão de área. Revista Brasileira de Educação Especial, v. 9, n. 2, p. 141-154, 2003.YIN, R. K. Estudo de caso: planejamento e método. Porto Alegre, RS: Bookman, 2001.e3308080

A new fluorimetric and colorimetric dual-mode probe, 4-bromo-2-(hydrazonomethyl) phenol (BHP) has been synthesized and successfully utilized for the recognition of Cd2+/F‒ ions in DMSO/H2O (9:1, v/v) system. The probe displays dual channel of detection via fluorescence enhancement and colorimetric changes upon binding with F‒ and Cd2+ ions respectively. The Job’s plot analysis, ESI-MS studies, Density Functional Theoretical (DFT) calculations, 1H NMR and 19F NMR titration results were confirmed and highly supported the 1:1 binding stoichiometry of the probe was complexed with Cd2+/F‒ ions. Furthermore, intracellular detection of F‒ ions in HeLa cells and fluorescence imaging analysis in Zebrafish embryos results of the probe BHP might be used to reveal their potential applications in a biological living system. Introduction The quantification and detection of toxic metal ions in diverse fields have fascinated more attention in recent years due to their prominent and significant roles in clinical diagnosis and ecological system.1–6 Besides metal ions, anions also play an exclusive role in a variety of chemical and biological processes.7–12 In earlier, analytical methods for the detection of cations/anions has required highly sophisticated and expensive instruments such as atomic absorption spectrometry, inductively coupled plasma mass spectrometry, ion sensitive electrodes, and gas and ion chromatography. Amid, fluorescent techniques have more expedient in terms of rapidness, excellent sensitivity and selectivity, low cost, easy and feasible detection. In addition, optical detection mode analysis is a more appropriate method because of their potential features such as easy handling, real-time analysis and different signal output modes.13–16 Besides, colorimetric assays are more feasible and potent tool as they provide a simple visible authentication for analyte detection in the absence of instruments and tedious techniques. In this perspective, the recent research area has been mainly focused to design the novel multi-functional fluorometric and colorimetric sensors for the detection of ions in the different environments. Cadmium (Cd2+) is one of the important hazardous heavy transition metal ions17 in the environment due its carcinogenic nature. The higher accumulation of Cd2+ ion and inhalation of Cd-dust prompts more awful health issues in human like cancer, cardiovascular diseases, kidneys and liver damage.18 Furthermore, the Cd2+ ion has more advantages in several industries such as pigments in plastics, electroplating and batteries, etc. On the other hand, fluoride ions play an ample role in dental health and in the treatment of osteoporosis.19–22 The excess of fluoride ingestion prompted severe disease in human health like gastric and kidney problems.23 In some remote areas, the high level contamination of fluoride ions in drinking water triggered bone disease such as fluorosis.24–31 Thus, to develop and synthesize novel multifunctional probe for the detection and quantification of both cations and anions is a highly anticipated and imperative task. Scheme 1. Synthesis of probe BHP Herein, we have fabricated and synthesized a novel chromogenic and fluorogenic assay based on bromo substituted salicylhydrazone moiety for the colorimetric and fluorometric detection of F‒ ions and colorimetric detection of Cd2+ ions in DMSO/H2O (9:1, v/v) system. The UV-visible and fluorescence spectral analysis of BHP with Cd2+/F‒ ions exposed an outstanding ratiometric absorbance and colorimetric responses towards F‒ ions and also showed a visible colorimetric response towards Cd2+ ions. The fluorescence enhancement of BHP with F‒ ion was highly evaluated by DFT calculations. As well, the cell viability experimental results of BHP can be used for the detection of F‒ ions in both HeLa cells and Zebrafish embryos via high content analysis system. Experimental Methods 2.1 Materials All the chemicals used in the present study were in the analytical reagent grade and solvents used were of HPLC grade. Reagents were used as such received without any further purification. Metal ions such as K+, Na+, Ca2+, Mg2+, Fe2+, Fe3+, Ag+, Zn2+, Mn2+, Cu2+, Co2+, Ni2+, Cd2+, Al3+, Cr3+, Pb2+ and Hg2+ were purchased from Merck and S.D. Fine chemicals. The anions of Cl-, Br-, I-, SCN-, CN-, H2PO4-, HSO4-, NO3-, AcO- and F- were purchased as their tetrabutylammonium salts from Sigma–Aldrich Pvt. Ltd. Absorption measurements were performed on JASCO V-630 spectrophotometer in 1 cm path length quartz cuvette with a volume of 2 mL at room temperature. Fluorescence measurements were made on a JASCO and F- 4500 Hitachi Spectrofluorimeter with excitation slit set at 5.0 nm band pass and emission at 5.0 nm band pass in 1 cm ×1 cm quartz cell. 1H and 13C NMR spectra were obtained on a Bruker 300 MHz NMR instrument with TMS as internal reference using DMSO-d6 as solvent. Standard Bruker software was used throughout. 19F NMR spectra were recorded at 293K on BRUKER 400 MHz FT-NMR spectrometers using DMSO-d6 as solvent. ElectroSpray Ionisation Mass Spectrometry (ESI-MS) analysis was performed in the positive/negative ion mode on a liquid chromatography-ion trap mass spectrometer (LCQ Fleet, Thermo Fisher Instruments Limited, US). Fluorescence microscopic imaging measurements were determined using Operetta High Content Imaging System (PerkinElmer, US) 2.2. Synthesis of (E)-4-bromo-2-(hydrazonomethyl) phenol, BHP An absolute alcoholic solution (50 ml) of 5-bromosalicylaldehyde (0.5gm, 2.49 mmol) was refluxed under hydrazine hydrate (in excess) for 5 hr and the pale yellow color solid product was collected after recrystallized with ethanol and ethyl acetate mixture (yield, 95 %). 1H NMR (300 MHz, DMSO-d6) δ (ppm): 8.92 (s, 1H), 11.89 (s, 1H), 7.53 (d, J = 8.7 Hz, 1H), 6.94 (d, J = 5.8 Hz, 1H); 13C NMR (75 MHz, DMSO-d6) δ (ppm): 161.36, 158.51, 135.84, 131.82, 120.86, 119.69, 106.72. 2.3 Photophysical analysis of BHP The optical mode analysis of BHP towards various cations/anions in DMSO/H2O (9:1, v/v) system was carried out by using absorbance and fluorescence spectroscopy. UV-visible and fluorescence analysis of BHP with cations were gauged by using their corresponding acetate salts of metal ions. Tetrabutylammonium salts of competing anions were used for the anionic sensing analysis. 2.4 Computational Studies The optimized geometrical and ground state energy level calculations of BHP were obtained by Density functional theoretical (DFT) calculations were executed using Gaussian 09 program 32 with the 6-311G basis set. The optimized geometries and the fluorescence enhancement of probe BHP complexed with Cd2+/F- ions were attained by DFT-B3LYP level theory using 6-311G and LANL2DZ basis sets. 2.5 Cytotoxicity studies HeLa cell lines were procured from the National Center for Cell Science (NCCS), Pune, India. Cell lines are kept in the Dulbecco's Modified Eagle's medium (DMEM) supplemented with 10% fetal bovine serum (FBS), 1% antimycotic and antibiotic solution was used in this study. The cells were kept in an incubator at 25 °C with humidified atmosphere comprising 5% of CO2 and 95% of air. HeLa cells were loaded over the wells of 96 well-culture plates with a density of 1 x 104 cells/well. After 48 h of incubation, previous DMEM medium was exchanged with new medium and BHP (dissolved in DMSO) was added in the range of 0-200 µM to all the wells and further incubated over 3h. Cytotoxicity of BHP was measured by using MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay. After incubation of HeLa cells with BHP, the medium was detached. Further, 100 μl of DMSO was added and the resulting formazan crystals were dissolved in DMSO. The cell viability was determined by measuring the absorbance of each well at 540-660 nm (formation of formazan) using a microplate reader. 2.6 In vivo fluorescence analysis in Zebrafish embryos The fluorescence imaging analysis was performed in four days old embryos. The embryos were seeded over F- ion alone for 2 h in the E3 medium. The E3 medium was prepared by dissolving 5.0 mM NaCl, 0.17mM KCl, 0.33mM CaCl2, 0.33mM MgSO4 ingredients in H2O (2L) and the pH 7.2 was adjusted by adding NaOH. The embryos were thoroughly washed with E3 medium. Successively, incubated embryos were sowed over 25 mM of BHP (in DMSO) solution for 3h. Further, embryos were washed again with E3 medium and fixed in 10% methyl cellulose solution for the good oriented images. The fluorescent images of BHP-F- were logged using high content screening microscopy. (Excitation wavelength of 482 nm and emission wavelength range of 500-700 nm). Results and discussion The probe, (E)-4-bromo-2-(hydrazonomethyl) phenol (BHP) has been synthesized by one step condensation between hydrazine and 5-bromosalicylaldehyde in ethanol (yield, 95 %) as shown in Scheme 1. The structure of the probe BHP was confirmed via 1H, 13C NMR analysis (Figure S1-S2, See ESI) 3.1. UV–vis spectral analysis of cations with BHP To investigate the cation sensing events of BHP towards different cations in DMSO/H2O (9:1, v/v) system by using UV-vis and fluorescence titration experiments. Initially, free probe BHP exhibited an absorption band at 367 nm and further addition of mono, di and trivalent cations such as Li+, K+, Ag+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Fe2+, Hg2+, Na+, Mg2+, Ca2+, Pb2+, Fe3+ and Cr3+ exhibited tiny changes in absorption spectr due to their weak interaction towards BHP except Cd2+ ion as shown in Figure 1. Interestingly, upon titrated with Cd2+ ion, a new absorption band appeared at 470 nm due to the highly resonance induced charge transfer ability of bromo substituted salicyl moiety while the solution turns into dark yellow color from pale yellow. Increasing addition of Cd2+ ion results gradual reduction of both higher and lower energy bands at 367 nm and 470 nm respectively as depicted in Figure 2. Figure 1. UV-vis spectra of BHP (10 µM) with different cations (5 × 10-3 M) in DMSO/H2O (9: 1, v/v) system. Figure 2. UV-vis spectra of BHP (10 µM) with Cd2+ (0 – 100 µM) in DMSO/H2O (9: 1, v/v) system Besides, fluorescence response of probe BHP towards various cations such as Li+, K+, Ag+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Fe2+, Hg2+, Na+, Mg2+, Ca2+, Pb2+, Fe3+ and Cr3+ including Cd2+ ion have been inspected in DMSO/H2O (9:1, v/v) system. Initially, the probe BHP displayed low intensed fluorescence band in free state. Addition of other commonly coexistent metal ions including Cd2+ ions exhibited trivial changes in fluorescence spectra. From these results, it is concluded that the probe BHP could serve as an excellent colorimetric assay for the detection of Cd2+ ions. 3.2. The sensing analysis of BHP towards anions Moreover, the anion binding attraction of BHP towards anions have been investigated in DMSO/H2O (9:1, v/v) system via both UV-visible and fluorescence spectral techniques. Initially the probe BHP showed the absorption band at 367 nm. Upon titrated with other anions such as Cl‒, Br‒, I‒, NO3‒, AcO‒, HSO4‒, H2PO4‒ and CN‒ were failed to alter the absorbance of the probe BHP except F‒ ions as shown in Figure 3a. Moreover, the incremental addition of F‒ ions (0-50 µM), the higher energy band at 367 nm was decreased along with the increment in new absorption band at 482 nm results an excellent ratiometric response. The new low energy band observed at 482 nm due to the deprotonation of–OH group present in salicyl moiety initiated by hydrogen bonding [Figure 3b]. At that affair, the solution turns into orange color from pale yellow and it was simply discerned by naked eye [Figure 4]. Besides, under identical condition, the fluorescence titration experiment of BHP was carried out in the presence of different anions. Interestingly, the probe BHP displayed low intensed fluorescence band at 601 nm and the other competing anions were failed to affect the fluorescence intensity except F‒ ions as shown in [Figure 5a]. Further, the incremental addition of F‒ ions triggers the enhancement in intensity results an excellent “turn on” fluorescence response due to the deprotonation and the inhibition of charge transfer state stimulated by resonance around the moiety [Figure 5b]. 3.3. Competitive experiments To gauge the selectivity and recognizing ability of BHP, competitive analysis was performed in the presence of varying concentration of F‒ ion (0-50 µM). Initially, the probe was treated with 5 × 10-3 M of different anions such as, CN-, I-, Br-, Cl-, NO2-, CH3COO-, H2PO4- and HSO4-. The other common competing anions were failed to bind with the probe BHP except F- ion [Figure 6 (a) and (b)]. From these observations, it is ensured that BHP could act as an excellent selective and sensitve chromogenic receptor for F- ions in real time monitoring and different biological applications. Figure 3 (a): UV-vis spectra of BHP with 5 × 10-3 M of other anions in DMSO/H2O (9: 1 v/v) system. (b) UV-visible spectra of BHP (5 µM) with F‒ (0-50 µM) in DMSO/H2O (9: 1 v/v) system. Figure 4. Naked eye detection of F‒ ions with BHP under visible light (top) and UV-lamp (bottom) and BHP with Cd2+ visible light only (bottom). Figure 5 (a): Fluorescence spectra of BHP (5µM) with 5 × 10-3 M of other anions in DMSO/H2O (9: 1, v/v) system. Excitation at 482 nm. Slit width is 5 nm. (b) Fluorescence spectra of BHP (5µM) with F‒ (0-50 µM) in DMSO/H2O (9: 1, v/v) system. Excitation at 482 nm. Slit width is 5 nm. Figure 6 (a): Selectivity analysis of F‒ ion with BHP in the presence of competing anions. Excitation at 480 nm, Slit width = 5 nm. (b) The blue bars represent the change of the fluorescence intensity of BHP with the consequent addition of other anions. The pink bars represent the addition of the competing anions to BHP. Excitation at 480 nm, Slit width = 5 nm. 3.4. Job’s plot analysis and calculation of binding constant of BHP for Cd2+/F‒ ions Furthermore, the Job’s plot [Figure 7(a) and (b)] analysis based on UV-visible and fluorescence titration experiments results confirmed the 1:1 binding stoichiometry of BHP with both Cd2+/F‒ ions respectively. To further support the binding stoichiometry of BHP with Cd2+/F‒ions, ESI-MS spectral analysis were performed. The ESI-MS spectral analysis of BHP-Cd2+/BHP-F‒ disclosed peaks at 327.45/258.28 corresponds to [BHP+Cd2++Na+]/[BHP+F‒+H++Na+] respectively (Figure S3-S4, See ESI). Furthermore, the 1:1 binding stoichiometry of BHP with F− ions was confirmed via 1H NMR titration profile (Figure 8) and 19F NMR. The deprotonation of ‒OH group present in the salicyl moiety was initiated by hydrogen bonding and the plausible binding mode of BHP with Cd2+ and F‒ ion is shown in Scheme 2. Further, the absorbance and fluorescence intensity changes of Cd2+ ions (A472 nm) and F‒ ions (A482 nm, I603 nm) were plotted against [Cd2+] and [F‒] respectively provided a good linear relationship between both BHP and Cd2+/F‒ ions (Figure S5, S6 and S7, See ESI). From absorbance and fluorescence titration profile, the binding constant values of BHP for Cd2+/F‒ ions were calculated using modified Benesi-Hildebrand method ions (Figure S8, S9 and S10, See ESI). The binding constant values of BHP with Cd2+ ions were found to be 4.26 ×10-4 M from UV-visible titration profile. Similarly, the binding constant values of BHP with F‒ ions were estimated to be 6.03 ×10-3 M / and 3.01 × 10-4 M from UV-visible and fluorescence titration profile respectively. The detection limits (LOD) of F‒ were calculated to be 0.05 nM respectively. Moreover, the LOD values of BHP signifies that the probe might be utilized for the quantitative determination of F‒ ions in environment and real system. Figure 7 (a) Job’s plot for BHP with F‒ ion. (b) Job’s plot for BHP with Cd2+ ion Scheme 2. Binding mode of BHP with Cd2+/F‒ ions 3.5. 1H NMR titrations of BHP with F- ions In addition, to confirm and highly supported the 1:1 binding stoichiometry of probe with F- ions, 1H NMR titrations was performed. Upon addition of F- ion (0.5 equiv), the proton signal corresponds to phenolic –OH group at 11.14 ppm was gradually decreased. Further, addition of 1 equiv. of F- ions to BHP showed the complete disappearance of –OH proton signal as depicted in Figure 8. Moreover, the binding stoichiometric ratio of F- ion with BHP was further supported by 19F NMR experiment. The (H2F)- signal appeared at -124.33 ppm (Figure S11-S12, See ESI) confirms the deprotonation process arose from phenolic –OH proton. Figure 8 1H NMR titration of BHP with F- (0-1equiv) in DMSO-d6 3.6. DFT calculations of BHP with Cd2+/F- ion To recognize the fluorescence enhancement of probe BHP after complexation with F-, DFT calculations were accomplished. The optimized structures of BHP, BHP-Cd2+ and BHP-F- were obtained using DFT/B3LYP-6-311G and B3LYP/LanL2DZ basis sets respectively. The frontier molecular orbital diagram obtained from optimized structure of BHP is presented in Figure 9. Upon binding with Cd2+ ion, the HOMO and LUMO are delocalized over the entire salicyl unit and their energy gap was reduced. It is noteworthy that inhibition of charge transfer in probe BHP renders the reduction of absorbance at 367 nm and 470 nm. Moreover, Complexation of F- ion to the probe BHP leads to lowering of HOMO-LUMO energy gap. In the presence of F-, HOMO and LUMO are distributed over the whole molecule of BHP. From these results, the F- ion was efficiently binded and complexed with BHP than Cd2+ ion. Figure 9. Frontier molecular orbital diagram of BHP, BHP-Cd2+and BHP-F‒ 3.7. Live cell Imaging analysis of BHP in HeLa cells / Zebrafish embryos The cell viability or cytotoxicity analysis of BHP (0–200 µM) against Human HeLa cells were performed using MTT assay. In 100 µM of BHP, cell viability was obtained as too high as 98%. (Figure S13, See ESI). Hence, the probe was sucessfully used for live cell imaging analysis of F- ions in Figure 10. Live cell fluorescence imaging analysis of BHP in HeLa cells. (a) Bright field images of HeLa cells incubated with BHP (25 µM) for 3h (b) Fluorescence merged images of HeLa cells incubated with BHP (25 µM) (c) Fluorescence image of HeLa cells incubated with BHP (25 µM) alone (d) Fluorescence image of HeLa cells incubated with BHP (25 µM) and 25 µM of F‒ ions for 1 h HeLa cells. Further, the HeLa cells were pre-treated with 25 µM of BHP alone for 3 h. Then HeLa cells were seaded with 25 µM of F- ions for 1h. In the absence of F- ions, the probe BHP exposed a weak yellow fluorescence. However, addition of F- ions to the probe BHP induced a bright orange fluorescence (Figure 10). These results endorsed that the probe BHP can be successfully utilized for the intracellular fluorescence imaging analysis of F- ions in HeLa cells. Besides, the exceptional cell viability output of BHP has been further explored in four days Zebrafish embryos. Zebrafish has positioned as a well-known vertebrate model in numerous biological applications. From this perspective, we have utilized also zebrafish embryos as a living animal model to expose the excellent imaging potential of BHP for the detection of F‒ ion in the biological environment (Figure 11) . Figure 11. Fluorescence imaging analysis of F‒ ion in 4 days old Zebrafish embryos developed with BHP and various concentrations of F‒ ion (a) bright field images of BHP (25 µM) alone, (b) fluorescence merged images of BHP and F- ion (25 µM) (c) fluorescence image of BHP (25 µM) alone (d) 25 µM of F‒ ion for 2 h continuously incubated with BHP (25 µM) for 3 h. 3.8. Evaluation of BHP with previous reports The probe BHP has valid and multi features such as single step synthesis, dual-mode recognition, turn-on fluorescence response and colorimetric change. The probe BHP displayed unique sensing property among other dual sensors. Table S1 compares the sensing performance of BHP with recently reported F‒ receptors. Amid, BHP exhibits too low limit of detection when compared with other previously reported chemoreceptors cited in table S1. Also, the limit of detection of BHP is within the range of recommended limits set by both EPA and WHO for F‒ Ions. Moreover, the fluorescence imaging experiments inferred that the probe BHP can be utilized as potential tool for mapping F‒ ion distribution in HeLa cells and Zebrafish embryos. Conclusions We have designed and synthesized a new chromogenic and fluorogenic probe based on salicylhydrazone derivative for the selective and sensitive detection of both Cd2+/F- ions by colorimetrically and fluorimetrically respectively. As per our knowledge, it is a novel simple hydrazone receptor for sensing carcinogenic heavy metal Cd2+ via colorimetric method and biologically significant F‒ ion by both colorimetric and fluorimetric methods. The binding constant value of Cd2+ ion was found to be 4.26×10-4 M by UV-visible method where as 6.03×10-3 and 3.01×10-4 M for F- ion by both UV-visible and fluorescence methods respectively. The limit of detection was found to be 0.05 nM for F- ion. The excellent biological potential of BHP has been successfully utilized for the detection of F- ions in Zebrafish embryos and human HeLa cells. Acknowledgments The authors acknowledge the financial support from the Council of Scientific and Industrial Research, Extramural Research, New Delhi, India (Grant No. 01(2901)17/EMR-II. The Department of Science and Technology, SERB, Extramural Major Research Project (Grant No. EMR/2015/000969), Department of Science and Technology, CERI, New Delhi, India (Grant No. DST/TM/CERI/C130(G) and we acknowledge the DST-FIST, DST-PURSE,DST-IRPHA, UPE programme and UGC-NRCBS, SBS, MKU for providing instrumentation facilities. References Jäkle, F. Chem. Rev. 2010, 110, 3985. Chen, X.; Zhou, Y.; Peng, X.; Yoon, J. Chem. Soc. 2010, 39, 2120. Kim, H. N.; Guo, Z.; Zhu, W.; Yoon J.; Tian, H. Chem. Soc. Rev. 2011, 40, 79. Zhang, J. F.; Zhou, Y.; Yoon, J.; Kim, J. S. Chem. Soc. Rev. 2011, 40, 3416. Zhou, Y.; Yoon, J. Chem. Soc. Rev. 2012, 41, 52. Chen, X.; Pradhan, T.; Wang, F.; Kim, J. S.; Yoon, J. Chem. Rev. 2012, 112, 1910. Wade, C. R.; Broomsgrove, A. E. J.; Aldridge, S.; Gabbaï, F. P. Chem. Rev. 2010, 110, Gale, P. A. Chem. Soc. Rev. 2010, 39, 3746. Wenzel, M.; Hiscock, J. R.; Gale P. A. Chem. Soc. Rev. 2012, 41, 480. Xu, Z.; Chen, X.; Kim, H. N.; Yoon, J. Chem. Soc. Rev. 2010, 39, 127. Galbraith, E.; James, T. D.; Chem. Soc. Rev. 2010, 39, 3831. Xu, Z.; Kim, S. K.; Yoon, J. Chem. Soc. Rev. 2010, 39, 1457. Zhou,Y.; Xu, Z.; Yoon, J.; Chem. Soc. Rev. 2011, 40, Quang, D. T.; Kim, J. S. Chem. Rev. 2010, 110, 6280. Zhou, Y.; Zhang, J. F.; Yoon, J.; Chem. Rev. 2014, 114, 5511. Martínez-Máñez, R.; Sancenón, F. Fluorogenic and chromogenic chemosensors and reagents for anions, 2003. Waisberg, M.; Joseph, P.; Hale, B.; Beyersmann, D. Toxicology. 2003, 192, 95. McFarland, C. N.; Bendell-Young, L. I.; Guglielmo, C.; Williams, T. D. J. Environ. Monit. 2002, 4, Nordberg, G. F.; Herber R. F. M.; Alessio, L. Cadmium in the Human Environment, Oxford University Press, Oxford, UK, 1992. Akula, M.; Thigulla, Y.; Nag, A.; Bhattacharya, RSC Adv. 2015, 5, 57231. Michael Kleerekoper. Clin. North Am. 2018, 65, 441. Erdal, S.; Buchanan, S. N.; Environ. Health Perspect. 2005, 113, Michigami, Y.; Kuroda, Y.; Ueda, K.; Yamamoto, Y.; Anal. Chim. 1993, 274, 299. Sivamani, J.; Siva, A. Sens. Actuators, B, 2017, 242, 423. Sarveswari, S.; Jesin Beneto, A.; Siva, A. Sens. Actuators, B, 2017, 245, 428. Sivamani, J.; Sadhasivam, V.; Siva, A.; Sens. Actuators, 2017, 246, 108. Jesin Beneto, A.; Siva, A.; Sens. Actuators, 2017, 247, 526. Krishnaveni, K.; Iniya, M.; Jeyanthi, D.; Siva, A.; Chellappa, D. Spectrochim. Acta A. 2018, 205, 557. Krishnaveni, K.; Murugesan, S.; Siva, A. New J. 2019, 4, 9021. Krishnaveni, K.; Iniya, M.; Siva, A.; Vidhyalakshmi, N.; Ramesh, U.; Sasikumar, S.; Murugesan, S.; J. Mol. 2020, 1217, 128446. Krishnaveni, K.; Harikrishnan, M.; Murugesan S.; Siva, A. Microchem. J. 2020, 159, 105543. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, V.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Peralta, J. E. Jr.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski J.; Fox, D. J. Gaussian 09, Revision A. 02, Gaussian, Inc., Wallingford C T, York, 1991.

Seiring dengan kemajuan perkembangan mengenai pengembangan wilayah dan otonomi daerah, maka setiap daerah dituntut untuk mengembangkan wilayahnya termasuk desa/kelurahan. Hal ini berakibat pada pemanfaatan SDM secara mandiri. Menurut Kementerian Desa, Pembangunan Daerah Tertinggal dan Transmigrasi (Kemendes PDTT), untuk meningkatkan kesejahteraan dan pemerataan pembangunan, maka penggunaan dana desa harus diawasi dan dibina secara benar. Salah satu peran penting dalam mendorong percepatan pembangunan saat ini dibutuhkan pengawasan agar dana desa tidak diselewengkan melalui proses pengadaan barang/jasa pemerintah dengan baik dan benar. Mitra yang bekerjasama dalam kegiatan Ibm ini akan dilakukan bimbingan dan sosialisasi adalah desa yang memiliki tingkat pembangunan yang rendah di kawasan sekitar Politeknik Negeri Banyuwangi. Adapun Fokus sosialisasi adalah para perangkat desa disetiap desa/mitra yang sudah disurvey sebelumnya diantaranya Desa Labanasem, Gintangan, Bareng, Benelan Lor dan Karang Bendo. Pada laporan kemajuan pelaksanaan kegiatan ini, peserta total yang sudah dilakukan pelatihan sebanyak 66 orang, meliputi: 25 orang dari desa Labanasem, 10 orang dari Bareng, 11 orang dari Benelan Lor, 10 orang desa Gintangan dan 10 orang dari desa Karang Bendo. Setiap desa mitra mendapatkan sertifikat bagi pesertanya dan modul tentang tata cara pengadaan di Desa sesuai Peraturan Lembaga Kebijakan Pengadaan Barang/Jasa Pemerintah.

AbstractThe macroecological variable of patchiness (Lloyd’s Ip index of patchiness, P) has recently been shown to be related inter- and intraspecifically to those of abundance (numbers m−2, A), and occupancy (% occurrence in samples, O) in lower latitude seagrass macrofaunas. For the first time in higher latitudes, intraspecific relationships between three spatial variables were investigated in the intertidal mudflat macrobenthos of the Scolt Head barrier island, southern North Sea (53° N, 01° E). Sampling was conducted between early July and late September 2009–2013 using 710-µm mesh for sample processing. Strong positive interspecific A-O and negative interspecific P-O and P-A relationships were present. Two of the most numerous and widespread assemblage components, however, occurred with effectively constant occupancy (Peringia ulvae, 100%, and Tubificoides benedii, 93%) across the whole 20-ha locality and therefore could not show intraspecific relationships of occupancy with other macroecological metrics. These two apart, only one other dominant species failed to show a significant positive intraspecific A-O relationship; no species showed significant P-A relations of any form; and only two showed the negative P-O ones that have been described elsewhere. The intraspecific A-O patterns appear to contrast with those of an earlier study at another North Sea locality (the Dutch Wadden Sea), although differences are more apparent than real, but the Scolt Head fauna showed fewer intraspecific P-O and P-A relations than those characterising similar circumstances in the two lower-latitude localities previously investigated. Neither developmental mode nor variation in local abundance appears to influence these patterns. A-O-P relations therefore seem widespread but may be subject to latitudinal modification.

As reforçadas propriedades intrínsecas dos materiais cerâmicos, associados à adesão resinosa fundamentam a desenvoltura de técnicas restauradoras mais simplificadas, conservadoras e sem a necessidade de preparo dental prévio seja em dentição anterior ou posterior. Assim sendo, o trabalho tem como objetivo apresentar dois casos clínicos os quais abordaram a confecção de restaurações delgadas em dissilicato de lítio cimentadas sobre diferentes áreas dos arcos dentários, enfatizando o mesmo protocolo clínico, ou seja, ausência de preparos dentais e consequentemente a cimentação resinosa adesiva das restaurações. Caso Clínico 1: laminados cerâmicos nos elementos 13, 12, 11, 21, 22 e 23; Caso Clínico 2: facetas delgadas sobre os elementos 34, 35, 36 e 37. Ambos os casos clínicos com 1 ano de acompanhamento após a cimentação das restaurações. Conclui-se que houve a recuperação da estética e da função em ambos os casos apresentados e a confiabilidade e o sucesso em longo prazo do protocolo clínico descrito estão diretamente relacionados ao substrato dentário, aos fatores de adesividade dos materiais e as propriedades intrínsecas das cerâmicas.Descritores: Cerâmica; Estética Dentária; Facetas Dentárias; Cimentos de Resina.ReferênciasMurdoch-Kinch CA, McLean ME. Minimally invasive dentistry. J Am Dent Assoc. 2003;134(1):87-95.Ericson D. The concept of minimally invasive dentistry. Dent Update. 2007;34(1):9-10,12-4,17-8.Beier US, Kapferer I, Burtscher D, Dumfahrt H. Clinical performance of porcelain laminate veneers for up to 20 years. Int J Prosthodont. 2012;25(1):79-85.D'Arcangelo C, Vadini M, D'Amario M, Chiavaroli Z, De Angelis F. Protocol for a new concept of no-prep ultrathin ceramic veneers. J Esthet Restor Dent. 2018;30(3):173-79.Vadini M, D'Amario M, De Angelis F, Falco A, D'Arcangelo C. No-prep rehabilitation of fractured maxillary incisors with partial veneers. J Esthet Restor Dent. 2016;28(6):351-58.Molina IC, Molina GC, Stanley K, Lago C, Xavier CF, Volpato CA. Partial-prep bonded restorations in the anterior dentition: long-term gingival health and predictability. A case report. Quintessence Int. 2016;47(1):9-16.Kelly JR, Benetti P. Ceramic materials in dentistry: historical evolution and current practice. Aust Dent J. 2011;56(Suppl 1):84-96.Edelhoff D, Brix O. All-ceramic restorations in different indications: a case series. J Am Dent Assoc. 2011;142(Suppl 2):14S-9S.Miranda ME, Olivieri KA, Rigolin FJ, Basting RT. Ceramic fragments and metal-free full crowns: a conservative esthetic option for closing diastemas and rehabilitating smiles. Oper Dent. 2013;38(6):567-71.Cortellini D, Canale A. Bonding lithium disilicate ceramic to feather-edge tooth preparations: a minimally invasive treatment concept. J Adhes Dent. 2012;14(1):7-10.Wolfart S, Eschbach S, Scherrer S, Kern M. Clinical outcome of three-unit lithium-disilicate glass-ceramic fixed dental prostheses: up to 8 years results. Dent Mater. 2009;25(9):e63-71.Benetti P, Della Bona A, Kelly JR. Evaluation of thermal compatibility between core and veneer dental ceramics using shear bond strength test and contact angle measurement. Dent Mater. 2010;26(8):743-50.Beier US, Kapferer I, Dumfahrt H. Clinical long-term evaluation and failure characteristics of 1,335 all-ceramic restorations. Int J Prosthodont. 2012;25(1):70-8.Veneziani M. Ceramic laminate veneers: clinical procedures with a multidisciplinary approach. Int J Esthet Dent. 2017;12(4):426-48.Anchieta RB, Rocha EP, de Almeida EO, Junior AC, Martini AP. Bonding all-ceramic restorations with two resins cement techniques: a clinical report of three-year follow-up. Eur J Dent. 2011;5(4):478-85.Peumans M, Van Meerbeek B, Lambrechts P, Vanherle G. Porcelain veneers: a review of the literature. J Dent. 2000;28(3):163-77.Barkmeier WW, Erickson RL, Kimmes NS, Latta MA, Wilwerding TM. Effect of enamel etching time on roughness and bond strength. Oper Dent. 2009;34(2):217-22.Esquivel-Upshaw J, Rose W, Oliveira E, Yang M, Clark AE, Anusavice K. Randomized, controlled clinical trial of bilayer ceramic and metal-ceramic crown performance. J Prosthodont. 2013;22(3):166-73.Martin AJ, Buschang PH, Boley JC, Taylor RW, McKinney TW. The impact of buccal corridors on smile attractiveness. Eur J Orthod. 2007;29(5):530-7.Fradeani M. Evaluation of dentolabial parameters as part of a comprehensive esthetic analysis. Eur J Esthet Dent. 2006;1(1):62-9.Borges GA, Sophr AM, de Goes MF, Sobrinho LC, Chan DC. Effect of etching and airborne particle abrasion on the microstructure of different dental ceramics. J Prosthet Dent. 2003;89(5):479-88.Fabianelli A, Goracci C, Bertelli E, Davidson CL, Ferrari M. A clinical trial of Empress II porcelain inlays luted to vital teeth with a dual-curing adhesive system and a self-curing resin cement. J Adhes Dent. 2006;8(6):427-31.Aykor A, Ozel E. Five-year clinical evaluation of 300 teeth restored with porcelain laminate veneers using total-etch and a modified self-etch adhesive system. Oper Dent. 2009;34(5):516-23.Oztürk E, Hickel R, Bolay S, Ilie N. Micromechanical properties of veneer luting resins after curing through ceramics. Clin Oral Investig. 2012;16(1):139-46.Scherrer SS, de Rijk WG, Belser UC, Meyer JM. Effect of cement film thickness on the fracture resistance of a machinable glass-ceramic. Dent Mater. 1994;10(3):172-77.Gresnigt M, Ozcan M. Esthetic rehabilitation of anterior teeth with porcelain laminates and sectional veneers. J Can Dent Assoc. 2011;77:b143.Friedman MJ. A 15-year review of porcelain veneer failure--a clinician's observations. Compend Contin Educ Dent. 1998;19(6):625-8,630,632 passim;quiz 638.Peumans M, De Munck J, Fieuws S, Lambrechts P, Vanherle G, Van Meerbeek B. A prospective ten-year clinical trial of porcelain veneers. J Adhes Dent. 2004;6(1):65-76.Fradeani M, Redemagni M, Corrado M. Porcelain laminate veneers: 6- to 12-year clinical evaluation--a retrospective study. Int J Periodontics Restorative Dent. 2005;25(1):9-17.De Munck J, Van Landuyt K, Peumans M, Poitevin A, Lambrechts P, Braem M et al. A critical review of the durability of adhesion to tooth tissue:methods and results. J Dent Res. 2005;84(2):118-32.

Objetiva-se desvelar os efeitos da aplicação de reiki no cuidado ao usuário com hipertensão arterial sistêmica.Pesquisa qualitativa, exploratória, do tipo pesquisa-ação, realizada no período de julho a dezembro de 2015 emuma Unidade Básica de Saúde, composta por duas Estratégias de Saúde da Família. Participaram 10 usuários comdiagnóstico de hipertensão arterial sistêmica. Para a coleta de dados utilizou-se três estratégias: aplicação deuma sessão de reiki, entrevista semiestruturada e observação participante. Os dados foram analisados conforme aoperacionalização de Bardin. Os principais efeitos encontrados foram: relaxamento, descanso do corpo e da mente,alívio das dores, liberação de emoções reprimidas e sobrecargas cotidianas, silêncio, tranquilidade e momentosde meditação. Concluí-se que uma sessão de reiki proporciona benefícios físicos e mentais aos usuários comhipertensão arterial sistêmica, porém sem alterar signifi cativamente os índices pressóricos.Palavras-chave: Terapias Complementares; Cuidados de Enfermagem; Hipertensão. ABSTRACTThe aim is to unveil the effects of the application of reiki in the care to the users with systemic arterialhypertension. Qualitative, exploratory, the type action research, carried out in the period from July to December2015 in a Basic Health Unit, composed of two Family Health Strategies. With 10 users with a diagnosis ofsystemic arterial hypertension. Three strategies were used to collect data: applying a reiki session, structuredinterviews and observation participant. The data were analyzed according to the Bardin operation. The maineffects were: relaxation and rest of the body and mind, pain relief, release of toxins, repressed emotions andburdens of everyday life, silence, tranquility and meditation moments. It concludes that we observed that a reikisession provides mentally and physically benefi ts to the users with systemic arterial hypertension, but withoutsignifi cantly altering the pressure rates.Keywords: Complementary Therapies, Nursing Care, Hypertension.

Objetiva-se desvelar os efeitos da aplicação de reiki no cuidado ao usuário com hipertensão arterial sistêmica.Pesquisa qualitativa, exploratória, do tipo pesquisa-ação, realizada no período de julho a dezembro de 2015 emuma Unidade Básica de Saúde, composta por duas Estratégias de Saúde da Família. Participaram 10 usuários comdiagnóstico de hipertensão arterial sistêmica. Para a coleta de dados utilizou-se três estratégias: aplicação deuma sessão de reiki, entrevista semiestruturada e observação participante. Os dados foram analisados conforme aoperacionalização de Bardin. Os principais efeitos encontrados foram: relaxamento, descanso do corpo e da mente,alívio das dores, liberação de emoções reprimidas e sobrecargas cotidianas, silêncio, tranquilidade e momentosde meditação. Concluí-se que uma sessão de reiki proporciona benefícios físicos e mentais aos usuários comhipertensão arterial sistêmica, porém sem alterar signifi cativamente os índices pressóricos.Palavras-chave: Terapias Complementares; Cuidados de Enfermagem; Hipertensão. ABSTRACTThe aim is to unveil the effects of the application of reiki in the care to the users with systemic arterialhypertension. Qualitative, exploratory, the type action research, carried out in the period from July to December2015 in a Basic Health Unit, composed of two Family Health Strategies. With 10 users with a diagnosis ofsystemic arterial hypertension. Three strategies were used to collect data: applying a reiki session, structuredinterviews and observation participant. The data were analyzed according to the Bardin operation. The maineffects were: relaxation and rest of the body and mind, pain relief, release of toxins, repressed emotions andburdens of everyday life, silence, tranquility and meditation moments. It concludes that we observed that a reikisession provides mentally and physically benefi ts to the users with systemic arterial hypertension, but withoutsignifi cantly altering the pressure rates.Keywords: Complementary Therapies, Nursing Care, Hypertension.

Beijing-Tianjin-Hebei Economic Zone is one of the most polluted areas in northern China. In recent years, pollution has become one of the most severe the environmental problems in that region, posing huge impact on the urban traffi c and threatening the public health greatly. Understanding the spatio-temporal variability and their mechanisms is important for the monitoring and control of regional air pollution. This study employed the Mann-Kendall test, statistical methods, geographical spatial analysis, aiming to explore the characteristics of air quality and its main controlling factors in this region. Temporal analysis was conducted in four largest cities to indicate the variation trend of air quality and identify the infl uence of meteorological factors, while spatial analysis was conducted based on all 13 cities of the region to clarify the socioeconomic controls on air quality. The results from trend analysis indicate an improving trend in air quality. Temperature, air pressure and wind speed are the main meteorological factors controlling air quality in the four large cities, which impose important infl uence on the migration, diffusion or settlement of pollutants. Agglomeration degree and distribution characteristics of AQI and six pollutants show great spatial heterogeneity, which is determined by topography, land-sea position, physicochemical properties of pollutants and socioeconomic factors. Principal component analysis (PCA) indicate that economic development benefi ts the improvement of air quality, while industrialization and traffi c construction aggravate air pollution. The air quality is less dependent on the level of urbanization. About 55 % of the spatial AQI changes can be explained by the socioeconomic factors, suggesting the leading contribution of human activities to air quality. This study will help deeply understand the main sources of air pollution in Beijing-Tianjin-Hebei region, and provides insights for urban planning and rational policy formulation that are conducive to air pollution control.