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Our ability to predict future climate change relies on our understanding of current and future CO2 fluxes, particularly on a regional scale (100-1000 km). CO2 regional sources and sinks are still poorly understood. Inverse transport modeling, a method often used to quantify these fluxes, relies on atmospheric CO2 measurements. One of the main challenges for the transport models used in the inversions is to properly reproduce CO2 vertical gradients between the boundary layer and the free troposphere, as these gradients impact on the partitioning of the calculated fluxes between the different model regions. Vertical CO2 profiles are very well suited to assess the performances of the models. In this paper, we conduct a comparison between observed and modeled CO 2 profiles recorded during two CAATER campaigns that occurred in May 2001 and October 2002 over Western Europe, as described in a companion paper. We test different combinations between a global transport model (LMDZt), a mesoscale transport model (CHIMERE), and different sets of biospheric fluxes, all chosen with a diurnal cycle (CASA, SiB2 and ORCHIDEE). The vertical profile comparison shows that: 1) in most cases the influence of the biospheric flux is small but sometimes not negligible, ORCHIDEE giving the best results in the present study; 2) LMDZt is most of the time too diffuse, as it simulates a too high boundary layer height; 3) CHIMERE better reproduces the observed gradients between the boundary layer and the free troposphere, but is sometimes too variable and gives rise to incoherent structures. We conclude there is a need for more vertical profiles to conduct further studies to improve the parameterization of vertical transport in the models used for CO 2 flux inversions. Furthermore, we use a modeling method to quantify CO 2 fluxes at the regional scale from a chosen observing point, coupling influence functions from the transport model LMDZt (that works quite well at the synoptic scale) with information on the space-time distribution of fluxes. This modeling method is compared to a dual tracer method (the so-called Radon method) for a case study on 25 May 2001 during which simultaneous well-correlated in situ CO2 and Radon 222 measurements have been collected. Both methods give a similar result: a flux within the Radon 222 method uncertainty (35%), that is an atmospheric CO2 sink of -4.2 -2 -1 to -4.4 gCm-1 day-1 . We have estimated the uncertainty of the modeling method to be at least 33% on average, and even more for specific individual events. This method allows the determination of the area that contributed to the CO 2 observed concentration. In our case, the observation point located at 1700ma.s.l. in the north of France, is influenced by an area of 1500x700 km² that covers the Benelux region, part of Germany and western Poland. Furthermore, this method allows deconvolution between the different contributing fluxes. In this case study, the biospheric sink contributes 73% of the total flux, fossil fuel emissions for 27%, the oceanic flux being negligible. However, the uncertainties of the influence function method need to be better assessed. This could be possible by applying it to other cases where the calculated fluxes can be checked independently, for example at tall towers where simultaneous CO2 and Radon 222 measurements can be conducted. The use of optimized fluxes (from atmospheric inversions) and of mesoscale models for atmospheric transport may also significantly reduce the uncertainties. [ABSTRACT FROM AUTHOR]

Our ability to predict future climate change relies on our understanding of current and future CO2 fluxes, particularly at the scale of regions (100-1000 km). Nowadays, CO2 regional sources and sinks are still poorly known. Inverse transport modeling, a method often used to quantify these fluxes, relies on atmospheric CO2 measurements. One of the main challenge for the transport models used in the inversions is to reproduce properly CO2 vertical gradients between the boundary layer and the free troposphere, as these gradients impact on the partitioning ot the calculated fluxes between the different model regions. Vertical CO2 profiles are very well suited to assess the performances of the models. In this paper, we conduct a comparison between observed and modeled CO2 profiles recorded during two CAATER campaigns that occurred in May 2001 and October 2002 over western Europe, and that we have described in a companion paper. We test different combinations between a global transport model (LMDZt), a mesoscale transport model (CHIMERE), and different sets of biospheric fluxes, those latter all chosen to have a diurnal cycle (CASA, SiB2 and ORCHIDEE). The vertical profile comparison shows that: (1) in most cases the influence of the biospheric flux is small but sometimes not negligeable, ORCHIDEE giving the best results in the present study; (2) LMDZt is most of the time too diffusive, as it simulates a too high boundary layer height; (3) CHIMERE reproduces better the observed gradients between the boundary layer and the free troposphere, but is sometimes too variable and gives rise to incoherent structures. We conclude there is a need for more vertical profiles to conduct further studies that will help to improve the parameterization of vertical transport in the models used for CO2 flux inversions. Furthermore, we use a modeling method to quantify CO2 fluxes at the regional scale from any observing point, coupling influence functions from the transport model LMDZt (that works quite well at the synoptic scale) with information on the space-time distribution of fluxes. This modeling method is compared to a dual tracer method (the so-called Radon method) for a case study on 25 May 2001 during which simultaneous well-correlated in-situ CO2 and Radon 222 measurements have been collected. Both methods give a similar flux within the Radon 222 method uncertainty (35%), that is an atmospheric CO2 sink of -4.2 to -4.4 gCm-2 day-1. We have estimated the uncertainty of the modeling method to be at least 33% when considering averages, even much more on individual events. This method allows the determination of the area that contributed to the CO2 observed concentration. In our case, the observation point located at 1700ma.s.l. in the North of France, is influenced by an area of 1500×700 km² that covers the Benelux region, part of Germany and western Poland. Furthermore, this method allows deconvolution between the different contributing fluxes. In this case study, the biospheric sink contributes for 73% of the total flux, fossil fuel emissions for 27%, the oceanic flux being negligeable. However, the uncertainties of the influence function method must be better assessed. This could be possible by applying it to other cases where the calculated fluxes can be checked independantly, for example at tall towers where simultaneous CO2 and Radon 222 measurements can be conducted. The use of optimized fluxes (from atmospheric inversions) and of mesoscale models for atmospheric transport may also significantly reduce the uncertainties. [ABSTRACT FROM AUTHOR]

In this issue, Ramonet et al. revealed a positive trend in European, atmospheric CO2 concentrations relative to a marine, North Atlantic reference baseline, for the years 2001–2006. The observed build up mainly occurred during the cold season where it reaches a 0.8 ppm yr−1 at low-altitude stations to a 0.3 ppm yr−1 at mid-altitude stations. We explore the cause of this build-up using the mesoscale model CHIMERE. We first model the observed trends, using interannually varying fluxes and transport, then suppress the interannual variability in fluxes or aspects of transport to elucidate the cause. The run with no interannual variability in fluxes still matches observed trends suggesting that transport is the major cause. Separate runs varying either boundary layer height or winds show that changes in boundary layer height explain the trends at low-altitude stations within the continents while changes in wind regimes drive changes elsewhere. [ABSTRACT FROM AUTHOR]

Introduction: Rubinstein-Taybi syndrome (RSTS) is a rare genetic syndrome caused primarily by a mutation in the CREBBP gene found on chromosome 16. Patients with RSTS are at greater risk for a variety of medical problems, including upper airway obstruction and aspiration. Childhood interstitial lung disease (ILD) thus far has not been definitively linked to RSTS. Here we present three patients with RSTS who developed ILD and discuss possible mechanisms by which a mutation in CREBBP may be involved in the development of ILD., Methods: Routine hematoxylin and eosin staining was performed on lung biopsy tissue for histological analysis. Immunofluorescent staining was performed on lung biopsy tissue for markers of fibrosis, surfactant deficiency and histone acetylation. Cases 1 and 2 had standard clinical microarray analysis. Case 3 had whole exome sequencing. Bioinformatics analyses were performed to identify possible causative genes using ToppGene., Results: Computed tomography images in all cases showed consolidated densities overlying ground glass opacities. Lung histopathology revealed accumulation of proteinaceous material within alveolar spaces, evidence of fibrosis, and increased alveolar macrophages. Immunofluorescent staining showed increase in surfactant protein C staining, patchy areas of increased anti-smooth muscle antibody staining, and increased staining for acetylated histone 2 and histone 3 lysine 9., Discussion: Clinical characteristics, radiographic imaging, lung histopathology, and immunofluorescent staining results shared by all cases demonstrated findings consistent with ILD. Immunofluorescent staining suggests two possible mechanisms for the development of ILD: abnormal surfactant metabolism and/or persistent activation of myofibroblasts. These two pathways could be related to dysfunctional CREBBP protein., (© 2021 Wiley Periodicals LLC.)

During the summer of 2018, a widespread drought developed over Northern and Central Europe. The increase in temperature and the reduction of soil moisture have influenced carbon dioxide (CO 2 ) exchange between the atmosphere and terrestrial ecosystems in various ways, such as a reduction of photosynthesis, changes in ecosystem respiration, or allowing more frequent fires. In this study, we characterize the resulting perturbation of the atmospheric CO 2 seasonal cycles. 2018 has a good coverage of European regions affected by drought, allowing the investigation of how ecosystem flux anomalies impacted spatial CO 2 gradients between stations. This density of stations is unprecedented compared to previous drought events in 2003 and 2015, particularly thanks to the deployment of the Integrated Carbon Observation System (ICOS) network of atmospheric greenhouse gas monitoring stations in recent years. Seasonal CO 2 cycles from 48 European stations were available for 2017 and 2018. Earlier data were retrieved for comparison from international databases or national networks. Here, we show that the usual summer minimum in CO 2 due to the surface carbon uptake was reduced by 1.4 ppm in 2018 for the 10 stations located in the area most affected by the temperature anomaly, mostly in Northern Europe. Notwithstanding, the CO 2 transition phases before and after July were slower in 2018 compared to 2017, suggesting an extension of the growing season, with either continued CO 2 uptake by photosynthesis and/or a reduction in respiration driven by the depletion of substrate for respiration inherited from the previous months due to the drought. For stations with sufficiently long time series, the CO 2 anomaly observed in 2018 was compared to previous European droughts in 2003 and 2015. Considering the areas most affected by the temperature anomalies, we found a higher CO 2 anomaly in 2003 (+3 ppm averaged over 4 sites), and a smaller anomaly in 2015 (+1 ppm averaged over 11 sites) compared to 2018. This article is part of the theme issue 'Impacts of the 2018 severe drought and heatwave in Europe: from site to continental scale'.

An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al 3+ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 μm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ethnopharmacological Relevance: Historical development of the Journal of Ethnopharmacology, the International Society of Ethnopharmacology, and the first definition of ethnopharmacology., Aim of the Study: To present the background to, and the people involved, in the foundation of the journal and the society., Materials and Methods: Personal recollections, archival documents and photographs., Results: A concise review of the early years of the JEP and the ISE, and the development of the first definition of ethnopharmacology., Conclusions: The definition of ethnopharmacology as an interdisciplinary science, and its establishment as a journal and a society was timely, filled a need, and opened up publication and meeting possibilities for scientists from various academic fields. Most important has been, and continues to be, the bridges created between people from all cultures and all countries., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Detailed studies on hydrogen evolution by decamethylruthenocene ([Cp* 2 Ru II ]) highlighted that metallocenes are capable of photoreducing hydrogen without the need for an additional sensitizer. Electrochemical, gas chromatographic, and spectroscopic (UV/Vis, 1 H and 13 C NMR) measurements corroborated by DFT calculations indicated that the production of hydrogen occurs by a two-step process. First, decamethylruthenocene hydride [Cp* 2 Ru IV (H)] + is formed in the presence of an organic acid. Subsequently, [Cp* 2 Ru IV (H)] + is reversibly reduced in a heterolytic reaction with one-photon excitation leading to a first release of hydrogen. Thereafter, the resultant decamethylruthenocenium ion [Cp* 2 Ru III ] + is further reduced with a second release of hydrogen by deprotonation of a methyl group of [Cp* 2 Ru III ] + . Experimental and computational data show spontaneous conversion of [Cp* 2 Ru II ] to [Cp* 2 Ru IV (H)] + in the presence of protons. Calculations highlight that the first reduction is endergonic (ΔG 0 =108 kJ mol -1 ) and needs an input of energy by light for the reaction to occur. The hydricity of the methyl protons of [Cp* 2 Ru II ] was also considered., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The concept of efficient electrolysis by linking photoelectrochemical biphasic H 2 evolution and water oxidation processes in the cathodic and anodic compartments of an H-cell, respectively, is introduced. Overpotentials at the cathode and anode are minimised by incorporating light-driven elements into both biphasic reactions. The concepts viability is demonstrated by electrochemical H 2 production from water splitting utilising a polarised water-organic interface in the cathodic compartment of a prototype H-cell. At the cathode the reduction of decamethylferrocenium cations ([Cp 2 *Fe (III) ] + ) to neutral decamethylferrocene (Cp 2 *Fe (II) ) in 1,2-dichloroethane (DCE) solvent takes place at the solid electrode/oil interface. This electron transfer process induces the ion transfer of a proton across the immiscible water/oil interface to maintain electroneutrality in the oil phase. The oil-solubilised proton immediately reacts with Cp 2 *Fe (II) to form the corresponding hydride species, [Cp 2 *Fe (IV) (H)] + . Subsequently, [Cp 2 *Fe (IV) (H)] + spontaneously undergoes a chemical reaction in the oil phase to evolve hydrogen gas (H 2 ) and regenerate [Cp 2 *Fe (III) ] + , whereupon this catalytic Electrochemical, Chemical, Chemical (ECC') cycle is repeated. During biphasic electrolysis, the stability and recyclability of the [Cp 2 *Fe (III) ] + /Cp 2 *Fe (II) redox couple were confirmed by chronoamperometric measurements and, furthermore, the steady-state concentration of [Cp 2 *Fe (III) ] + monitored in situ by UV/vis spectroscopy. Post-biphasic electrolysis, the presence of H 2 in the headspace of the cathodic compartment was established by sampling with gas chromatography. The rate of the biphasic hydrogen evolution reaction (HER) was enhanced by redox electrocatalysis in the presence of floating catalytic molybdenum carbide (Mo 2 C) microparticles at the immiscible water/oil interface. The use of a superhydrophobic organic electrolyte salt was critical to ensure proton transfer from water to oil, and not anion transfer from oil to water, in order to maintain electroneutrality after electron transfer. The design, testing and successful optimisation of the operation of the biphasic electrolysis cell under dark conditions with Cp 2 *Fe (II) lays the foundation for the achievement of photo-induced biphasic water electrolysis at low overpotentials using another metallocene, decamethylrutheneocene (Cp 2 *Ru (II) ). Critically, Cp 2 *Ru (II) may be recycled at a potential more positive than that of proton reduction in DCE.

Redox electrocatalysis (catalysis of electron-transfer reactions by floating conductive particles) is discussed from the point-of-view of Fermi level equilibration, and an overall theoretical framework is given. Examples of redox electrocatalysis in solution, in bipolar configuration, and at liquid-liquid interfaces are provided, highlighting that bipolar and liquid-liquid interfacial systems allow the study of the electrocatalytic properties of particles without effects from the support, but only liquid-liquid interfaces allow measurement of the electrocatalytic current directly. Additionally, photoinduced redox electrocatalysis will be of interest, for example, to achieve water splitting.

The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene, Cp 2 *Ru II (Cp*=C 5 Me 5 ), is reported. The use of a metallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer. The mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1 H NMR) measurements. The photoactivated hydride involved was characterized spectroscopically and the resulting [Cp 2 *Ru III ] + species was electrochemically regenerated in situ on a fluorinated tin oxide electrode surface. A promising internal quantum yield of 25 % was obtained. Optimal experimental conditions- especially the use of weakly coordinating solvent and counterions-are discussed., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein the synthesis, characterization, and organization of a first-generation dendritic fulleropyrrolidine bearing two pending porphyrins are reported. Both the dendron and the fullerene derivatives were synthesized by Cu(I) -catalyzed alkyne-azide cycloaddition (CuAAC). The electron-donor-acceptor conjugate possesses a shape that allows the formation of supramolecular complexes by encapsulation of C60 within the jaws of the two porphyrins of another molecule. The interactions between the two photoactive units (i.e., C60 and Zn-porphyrin) were confirmed by cyclic voltammetry as well as by steady-state and time-resolved spectroscopy. For example, a shift of about 85 mV was found for the first reduction of C60 in the electron-donor-acceptor conjugate compared with the parent molecules, which indicates that C60 is included in the jaws of the porphyrin. The fulleropyrrolidine compound exhibits a rich polymorphism, which was corroborated by AFM and SEM. In particular, it was found to form supramolecular fibrils when deposited on substrates. The morphology of the fibrils suggests that they are formed by several rows of fullerene-porphyrin complexes., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

SWNT-porphyrin/phthalocyanine conjugates are described and fully characterised; their optical and electrochemical properties are investigated.

A very long half-life of paroxetine (195 h instead of the usual value of around 16 h) was measured after an overdose with 2 g paroxetine and 1 g clorazepate in a patient who was an extensive cytochrome P4502D6 metabolizer. The patient recovered well without any clinically significant complications. A consequence of the close monitoring of paroxetine levels in this patient was that it was decided not to reintroduce any other antidepressant despite her suicide attempt, until normal levels of paroxetine had been reached, which took over 1 month.

We report the findings of the analysis of 75 different nutritional supplements bought through the internet. Seven products (all from the class of prohormones) contained other hormone substances than indicated on the labels, and two further products contained ephedrine and caffeine without a clear indication on the labels.

Forensic scientists have long detected the presence of drugs and their metabolites in biological materials using body fluids such as urine, blood and/or other biological liquids or tissues. For doping analysis, only urine has so far been collected. In recent years, remarkable advances in sensitive analytical techniques have encouraged the analysis of drugs in unconventional biological samples such as hair, saliva and sweat. These samples are easily collected, although drug levels are often lower than the corresponding levels in urine or blood. This chapter reviews recent studies in the detection of doping agents in hair, saliva and sweat. Sampling, analytical procedures and interpretation of the results are discussed in comparison with those obtained from urine and blood samples.

In March 1995, a decision about cultivation of cannabis was issued by the Swiss Federal Offices of Public Health, Police and Agriculture in order to satisfy the growing interest of farmers and other people in hemp farming. It pointed out that 1)... each hemp plant contains THC and must be therefore considered a drug, 2)... no permission is required for those who grow hemp without the intention to produce drugs ... meaning that the choice of the plant variety was not restricted to those which are characterized by a low THC concentration and grown in a few countries belonging to the European Union. Claiming that natural hemp must contain significant amounts of THC and thanks to the Swiss legislation, areas dedicated to hemp cultivation develop considerably. Most hemp plants which are submitted to our laboratories by the police for THC quantification belong to the drug-type. Nowadays, a great deal of goods (food and beverages, cosmetics, drugs) made of hemp are marketed in Switzerland. Strong suspicions exist however that several of these products could be used as a screen for the illegal market of cannabis. For instance, despite financial support from the state, fiber hemp cultivation remains unsuccessful. No advantage with regard to seed productivity, edible seed and essential oils qualities and yields have been found for drug hemp over fiber hemp by agricultural research stations up to now. Several clues about the possible illicit use of hemp goods rich in THC, especially hemp tea made of flower tops and "therapeutic" pillows filled with cannabis exist. Recently, two Federal edits were issued in order to restrict the selling of hemp seedlings and of hemp foods and beverages to those containing only low amounts of THC. However, the marketing of hemp plants used for decorating remains free partly explaining the recent success of these "beautiful" plants. Broadly speaking, the Swiss and European legislations about hemp have approached mutually during the last years.

Individual differences in flank gland secretions were examined among males of the monogamous shrewCrocidura russula during the breeding and nonbreeding seasons. Gas chromatography was used to measure intra- and interindividual variation of flank gland secretions of free-ranging shrews from different populations. The number of compounds detected by gas Chromatographic analyses was correlated with body mass, flank gland size, and the presence of blood parasites in individual shrews. Very few compounds were detected from the flank gland area of juvenile males. After they reached sexual maturity, however, the number of compounds detected from the flank gland secretions increased significantly. At the beginning of the reproductive season 48 different compounds were detected from male flank gland secretions. In the middle of the breeding season 70 compounds were detected, while only 11 compounds were detected during the nonbreeding season. Few compounds were common to all males. There were more volatile compounds in the flank gland secretions of males in the beginning of the breeding season than later in the breeding season. Males from the same population had fewer differences in the elution profile of compounds than males from different populations indicating that individuals from a distinct population have similar elution profiles of compounds and that each population has its own type of elution profile. No correlations were found between the number of compounds detected by gas chromatography for each male and the male's body mass or flank gland size. Blood parasites (trypanosomes,Trypanosoma crocidurae) were found in only three of 30 males investigated.

Cocaine is a powerful reinforcer that has become a popular drug of abuse. Cocaine inhibits the reuptake of dopamine into presynaptic terminals, resulting in an overstimulation of the dopaminergic system. When cocaine and alcohol are taken together, cocaine is partially converted by a liver carboxylesterase to its ethyl homolog called ethylcocaine. In 1991, several studies demonstrated that ethylcocaine is a pharmacologically active metabolite of cocaine. Ethylcocaine was shown to be even more potent than cocaine in mediating lethality. In the USA, prevalent studies have indicated that concurrent and simultaneous abuse of cocaine with alcohol were a very common practice. In Switzerland, as far as we know, epidemiologic studies have not been carried out yet. In our laboratory, radioimmunoassays mainly sensitive to benzoylecgonine (an inert metabolite of cocaine and ethylcocaine) are used to detect cocaine abusers. Positive results are always confirmed by combined gas chromatography (GC) and mass spectrometry (MS). Recently, cocaine, ethylcocaine, methyl ecgonine and ethyl ecgonine were detected by GC/MS in urine from three people arrested after erratic driving. Their blood alcohol concentration was 2.89, 0.98 and 1.26 g/kg. In Switzerland, the influence of alcohol, cocaine and ethylcocaine on the incidence of accidents, overdose and death is not known and requires further studies. Because morbidity and mortality are exacerbated by concurrent use of alcohol and cocaine, physicians should discourage their hooked patients from consuming this deadly mixture.