Bond energy/eond order relationships for N-O linkages and a quantitative measure of ionicity: the rôle of nitro groups in hydrogen bonding

The nitro group is active in metabolic systems and can be found as an integral part of a number of useful curative drugs and many toxic substances. The basis for much of this activity is not fully understood. It is not necessarily caused directly by through-bond electronic effects but may also be due to direct H-bonding to nitro or to indirect interference by the nitro group with existing H-bonding. An unusual effect of a nitro substituent on kinetic results from urethane addition/elimination reactions (Scheme 1) has been ascribed to some form of self-association, which was neither specified nor quantified. To investigate self-association phenomena caused by a nitro group, a bond energy/bond order formula for N–O bonds has been developed and then used to interpret relative amounts of covalent and ionic contributions to total N–O bond energy. Calculated bond energies were then used to obtain enthalpies of formation for H-bonds to nitro groups in crystals and in solution. Similar results from solution data reveal that direct H-bonding to nitro is much weaker than in crystals, unless intramolecular H-bonding can occur. The results revealed that the 'self-association' effects observed for nitro substituents in urethanes (Scheme 1) were not caused by nitro participating directly in intermolecular bonding to NH of another urethane but by an indirect intramolecular action of the nitro group on pre-existing normal NH–O amide/amide type H-bonding

3-( E )-But-2-enoxy-1,2-benzisothiazole 1,1-dioxide: unusual C—O—C ether bond lengths and reactivity

Ethers such as the title compound, C~HIINO3S, (1), rearrange thermally to give N-allyl isomers, (2), in high yield. The X-ray structure determination of the title ether shows a central C--O--C linkage which has one very short (notional) C--O single bond and one exceptionally long single C--O bond. The thermal migration of allyl from the O to the N atom involves the breaking of one of the ether bonds in (1) and a shortening of the other as it becomes a formal carbonyl group in the product (2). The rearrangement is thus considerably assisted by the ground-state structure of the starting ether, in which the bond to be broken is already stretched and the one that is to form a carbonyl group is already a substantial partial double bond

Joint effects of chlorpyrifos and mancozeb to the terrestrial isopod Porcellionides pruinosus: a multiple biomarker approach

The exposure to pesticides by non-target soil biota has long been regarded as a serious downside of modern agriculture regimes and subject of heated debate. Of utmost relevance is the exposure to pesticide mixtures since their effects have shown not to necessarily reflect the individual toxicity of its components and even the simple addition of effects may lead to consequences not clearly anticipated. In this work, a multiple biomarker approach was employed to identify the mechanistic and time-effects underlying several single and mixture treatments of chlorpyrifos and mancozeb in juveniles and adults of the terrestrial isopod Porcellionides pruinosus. The effects of both pesticides and mixture at recommended doses were mostly transitory under these controlled conditions and one-pulse exposure. While imbalances were identified on detoxification and oxidative stress-related enzymes, isopods generally showed the ability to recover until the end of the experiment. Juveniles showed, however, higher vulnerability than adults. The most notorious differences between life stages occurred in energy-related parameters where distinct performances and stress-handling behaviours were observed, suggesting higher metabolic costs in juveniles. Our results stress that understanding the time-dependence of the underlying mechanisms governing the joint-effects of pesticides can help assessing and anticipating mixtures’ effects. Moreover, it is also emphasized the importance taking life stage-related differences in consideration when evaluating the environmental risks of pesticides and pesticide mixtures

Thermal rearrangement of 3-allyloxy-1,2-benzisothiazole 1,1-dioxides: an unusual inversion of products of sigmatropic [3,3]-shift to give the [1,3]-Isomers

3-Allyloxy-1,2-benzisothiazole 1,1-dioxides isomerize thermally to give [3,3]- and [1,3]-products 6 of sigmatropic shift, of which the former reacts further to give solely the [1,3]-isomer

Gut and faecal bacterial community of the terrestrial isopod porcellionides pruinosus: potential use for monitoring exposure scenarios

This work aimed to characterize the gut and faeces bacterial communities (BC) of Porcellionides pruinosus using high-throughput sequencing. Isopods were collected from the field and kept in laboratory conditions similar to those normally applied in ecotoxicology tests. Faeces and purged guts of isopods (n=3 × 30) were analysed by pyrosequencing the V3-V4 region of 16 S rRNA encoding gene. Results showed that gut and faecal BCs were dominated by Proteobacteria, particularly by an OTU (Operational Taxonomic Unit) affiliated to genus Coxiella. Diversity and richness values were statistically higher for faecal BC, mainly due to the occurrence of several low-abundance phylotypes. These results may reflect faecal carriage of bacterial groups that cannot settle in the gut. BCs of P. pruinosus comprised: (1) common members of the soil microbiota, (2) bacterial symbionts, (3) bacteria related to host metabolic/ecological features, and (4) bacterial etiological agents. Comparison of BC of this isopod species with the BC from other invertebrates revealed common bacterial groups across taxa. The baseline information provided by this work will assist the design and data interpretation of future ecotoxicological or biomonitoring assays where the analysis of P. pruinosus BC should be included as an additional indicator.publishe

Effects of external nutrient sources and extreme weather events on the nutrient budget of a Southern European coastal lagoon

The seasonal and annual nitrogen (N), phosphorus (P), and carbon (C) budgets of the mesotidal Ria Formosa lagoon, southern Portugal, were estimated to reveal the main inputs and outputs, the seasonal patterns, and how they may influence the ecological functioning of the system. The effects of extreme weather events such as long-lasting strong winds causing upwelling and strong rainfall were assessed. External nutrient inputs were quantified; ocean exchange was assessed in 24-h sampling campaigns, and final calculations were made using a hydrodynamic model of the lagoon. Rain and stream inputs were the main freshwater sources to the lagoon. However, wastewater treatment plant and groundwater discharges dominated nutrient input, together accounting for 98, 96, and 88 % of total C, N, and P input, respectively. Organic matter and nutrients were continuously exported to the ocean. This pattern was reversed following extreme events, such as strong winds in early summer that caused upwelling and after a period of heavy rainfall in late autumn. A principal component analysis (PCA) revealed that ammonium and organic N and C exchange were positively associated with temperature as opposed to pH and nitrate. These variables reflected mostly the benthic lagoon metabolism, whereas particulate P exchange was correlated to Chl a, indicating that this was more related to phytoplankton dynamics. The increase of stochastic events, as expected in climate change scenarios, may have strong effects on the ecological functioning of coastal lagoons, altering the C and nutrient budgets.Portuguese Science and Technology Foundation (FCT) [POCI/MAR/58427/2004, PPCDT/MAR/58427/2004]; Portuguese Science and Technology Foundation (FCT

Metal alloys, matrix inclusions and manufacturing techniques of Moinhos de Golas collection (North Portugal): a study by micro-EDXRF, SEM–EDS, optical microscopy and X-ray radiography

"Article:820"A collection of 35 metallic artefacts comprising various typologies, some of which can be attributed to the Bronze Age and others to later periods, were studied to provide detailed information on elemental composition, manufacturing techniques and preservation state. Elemental analysis by micro-EDXRF and SEM–EDS was performed to investigate the use of different alloys and to study the presence of microstructural heterogeneities, as inclusions. X-ray radiography, optical microscopy and SEM–EDS were used to investigate manufacturing techniques and degradation features. Results showed that most of the artefacts were produced in a binary bronze alloy (Cu–Sn) with 10–15 wt% Sn and a low concentration of impurities. Other artefacts were produced in copper or in brass, the latest with varying contents of Zn, Sn and Pb. A variety of inclusions in the metal matrices were also found, some related to specific types of alloys, as (Cu–Ni)S2 in coppers, or ZnS in brasses. Microstructural observations revealed that the majority of the artefacts were subjected to cycles of thermomechanical processing after casting, being evident that among some artefacts different parts were subjected to distinct treatments. The radiographic images revealed structural heterogeneities related to local corrosion processes and fissures that seem to have developed in wear-tension zones, as in the handle of some daggers. Radiographic images were also useful to detect the use of different materials in one particular brass artefact, revealing the presence of a possible Cu–Sn solder.This work was funded by FEDER funds through the COMPETE 2020 Programme and National Funds through FCT— Fundação para a Ciência e a Tecnologia under the project UID/CTM/ 50025/2013 to CENIMAT/I3N. C2 TN/IST authors gratefully acknowledge the FCT support through the UID/Multi/04349/2013 project. EF acknowledges FCT for the grant SFRH/BPD/97360/2013. JF acknowledge FCT for the grant SFRH/BD/65143/2009. Part of this project has been done in the framework of the FCT project ENARDAS (PTDC/HISARQ/112983/2009).info:eu-repo/semantics/publishedVersio

The burden of mental disorders, substance use disorders and self-harm among young people in Europe, 1990-2019 : Findings from the Global Burden of Disease Study 2019

Background Mental health is a public health issue for European young people, with great heterogeneity in resource allocation. Representative population-based studies are needed. The Global Burden of Disease (GBD) Study 2019 provides internationally comparable information on trends in the health status of populations and changes in the leading causes of disease burden over time. Methods Prevalence, incidence, Years Lived with Disability (YLDs) and Years of Life Lost (YLLs) from mental disorders (MDs), substance use disorders (SUDs) and self-harm were estimated for young people aged 10-24 years in 31 European countries. Rates per 100,000 population, percentage changes in 1990-2019, 95% Uncertainty Intervals (UIs), and correlations with Sociodemographic Index (SDI), were estimated. Findings In 2019, rates per 100,000 population were 16,983 (95% UI 12,823 - 21,630) for MDs, 3,891 (3,020 4,905) for SUDs, and 89.1 (63.8 - 123.1) for self-harm. In terms of disability, anxiety contributed to 647.3 (432 -912.3) YLDs, while in terms of premature death, self-harm contributed to 319.6 (248.9-412.8) YLLs, per 100,000 population. Over the 30 years studied, YLDs increased in eating disorders (14.9%;9.4-20.1) and drug use disorders (16.9%;8.9-26.3), and decreased in idiopathic developmental intellectual disability (-29.1%;23.8-38.5). YLLs decreased in self-harm (-27.9%;38.3-18.7). Variations were found by sex, age-group and country. The burden of SUDs and self-harm was higher in countries with lower SDI, MDs were associated with SUDs. Interpretation Mental health conditions represent an important burden among young people living in Europe. National policies should strengthen mental health, with a specific focus on young people. Funding The Bill and Melinda Gates Foundation Copyright (C) 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)Peer reviewe

MAMMALS IN PORTUGAL : A data set of terrestrial, volant, and marine mammal occurrences in P ortugal

Mammals are threatened worldwide, with 26% of all species being includedin the IUCN threatened categories. This overall pattern is primarily associatedwith habitat loss or degradation, and human persecution for terrestrial mam-mals, and pollution, open net fishing, climate change, and prey depletion formarine mammals. Mammals play a key role in maintaining ecosystems func-tionality and resilience, and therefore information on their distribution is cru-cial to delineate and support conservation actions. MAMMALS INPORTUGAL is a publicly available data set compiling unpublishedgeoreferenced occurrence records of 92 terrestrial, volant, and marine mam-mals in mainland Portugal and archipelagos of the Azores and Madeira thatincludes 105,026 data entries between 1873 and 2021 (72% of the data occur-ring in 2000 and 2021). The methods used to collect the data were: live obser-vations/captures (43%), sign surveys (35%), camera trapping (16%),bioacoustics surveys (4%) and radiotracking, and inquiries that represent lessthan 1% of the records. The data set includes 13 types of records: (1) burrowsjsoil moundsjtunnel, (2) capture, (3) colony, (4) dead animaljhairjskullsjjaws, (5) genetic confirmation, (6) inquiries, (7) observation of live animal (8),observation in shelters, (9) photo trappingjvideo, (10) predators dietjpelletsjpine cones/nuts, (11) scatjtrackjditch, (12) telemetry and (13) vocalizationjecholocation. The spatial uncertainty of most records ranges between 0 and100 m (76%). Rodentia (n=31,573) has the highest number of records followedby Chiroptera (n=18,857), Carnivora (n=18,594), Lagomorpha (n=17,496),Cetartiodactyla (n=11,568) and Eulipotyphla (n=7008). The data setincludes records of species classified by the IUCN as threatened(e.g.,Oryctolagus cuniculus[n=12,159],Monachus monachus[n=1,512],andLynx pardinus[n=197]). We believe that this data set may stimulate thepublication of other European countries data sets that would certainly contrib-ute to ecology and conservation-related research, and therefore assisting onthe development of more accurate and tailored conservation managementstrategies for each species. There are no copyright restrictions; please cite thisdata paper when the data are used in publications.info:eu-repo/semantics/publishedVersio

Riociguat treatment in patients with chronic thromboembolic pulmonary hypertension: Final safety data from the EXPERT registry

Objective: The soluble guanylate cyclase stimulator riociguat is approved for the treatment of adult patients with pulmonary arterial hypertension (PAH) and inoperable or persistent/recurrent chronic thromboembolic pulmonary hypertension (CTEPH) following Phase