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Biogenic sources contribute to cloud condensation nuclei (CCN) in the clean marine atmosphere, but few measurements exist to constrain climate model simulations of their importance. The chemical composition of individual atmospheric aerosol particles showed two types of sulfate-containing particles in clean marine air masses in addition to mass-based Estimated Salt particles. Both types of sulfate particles lack combustion tracers and correlate, for some conditions, to atmospheric or seawater dimethyl sulfide (DMS) concentrations, which means their source was largely biogenic. The first type is identified as New Sulfate because their large sulfate mass fraction (63% sulfate) and association with entrainment conditions means they could have formed by nucleation in the free troposphere. The second type is Added Sulfate particles (38% sulfate), because they are preexisting particles onto which additional sulfate condensed. New Sulfate particles accounted for 31% (7 cm −3 ) and 33% (36 cm −3 ) CCN at 0.1% supersaturation in late-autumn and late-spring, respectively, whereas sea spray provided 55% (13 cm −3 ) in late-autumn but only 4% (4 cm −3 ) in late-spring. Our results show a clear seasonal difference in the marine CCN budget, which illustrates how important phytoplankton-produced DMS emissions are for CCN in the North Atlantic.

In 50% of all infertility cases, the male is subfertile or infertile, however, the underlying mechanisms are often unknown. Even when assisted reproductive procedures such as in vitro fertilization and intracytoplasmic sperm injection are performed, the causes of male factor infertility frequently remain elusive. Since the overall activity of cells is closely linked to their metabolic capacity, we analyzed a panel of 180 metabolites in human sperm and seminal plasma and elucidated their associations with spermiogram parameters. Therefore, metabolites from a group of 20 healthy donors were investigated using a targeted LC-MS/MS approach. The correlation analyses of the amino acids, biogenic amines, acylcarnitines, lysophosphatidylcholines, phosphatidylcholines, sphingomyelins and sugars from sperm and seminal plasma with standard spermiogram parameters revealed that metabolites in sperm are closely related to sperm motility, whereas those in seminal plasma are closely related to sperm concentration and morphology. This study provides essential insights into the metabolome of human sperm and seminal plasma and its associations with sperm functions. This metabolomics technique could be a promising screening tool to detect the factors of male infertility in cases where the cause of infertility is unclear.

Background: Human life without sperm is not possible. Therefore, it is alarming that the fertilizing ability of human spermatozoa is continuously decreasing. The reasons for that are widely unknown, but there is hope that metabolomics-based investigations may be able to contribute to overcoming this problem. This review summarizes the attempts made so far. Methods: We will discuss liquid chromatography–mass spectrometry (LC-MS), gas chromatography (GC), infrared (IR) and Raman as well as nuclear magnetic resonance (NMR) spectroscopy. Almost all available studies apply one of these methods. Results: Depending on the methodology used, different compounds can be detected, which is (in combination with sophisticated methods of bioinformatics) helpful to estimate the state of the sperm. Often, but not in all cases, there is a correlation with clinical parameters such as the sperm mobility. Conclusions: LC-MS detects the highest number of metabolites and can be considered as the method of choice. Unfortunately, the reproducibility of some studies is poor, and, thus, further improvements of the study designs are needed to overcome this problem. Additionally, a stronger focus on the biochemical consequences of the altered metabolite concentrations is also required.

ObjectivesThe objective of this study was to investigate the role of infections in the pathogenesis of Kawasaki disease.MethodsThe investigation was a nationwide epidemiological case-control study, comprising all cases of Kawasaki disease diagnosed in Sweden 1987–2018. Controls were randomly sampled from the general population, matched on sex, age, and area of residency. Data on infections were obtained from the Swedish National Patient Register, which prospectively collects data on all Swedish residents. Infections were classified by organ system, infectious agent and by temporal proximity to Kawasaki disease diagnosis date. Prescription of antibiotics and infections in family members were also considered in separate analyses.ResultsThe study comprised n=1774 (61% male) cases and n=17 731 controls. Overall, a history of infections was associated with Kawasaki disease with an OR of 2.3 (95% CI 2.0 to 2.5). Respiratory, skin, urogenital and gastrointestinal tract infections were all associated with Kawasaki disease. Temporal stratification revealed a prominent clustering of infections during the weeks before a Kawasaki diagnosis, but also higher frequencies of infections several months preceding Kawasaki disease with OR ranging from 5.1 (95% CI 3.6 to 7.1) 15–28 days to 1.3 (95% CI 1.1 to 1.6) 181–365 days prior Kawasaki disease. A dose–response relationship was observed, with repeated infections associating with higher ORs of Kawasaki.ConclusionsThe findings suggest that infections are closely linked with Kawasaki disease, and with a wider temporal association than previously known. Further, the data imply that many different agents may induce the disease.

Currently, spermiogram analysis is the most relevant method used to clarify the potential infertility of a couple. However, in some cases, the reasons for infertility remain obscure. Smoking is among the factors that have been described to adversely affect male fertility. Smoking increases oxidative stress and thus promotes various pathological processes. Comparative studies, particularly those on metabolomic changes in sperm and seminal plasma caused by smoking, have not yet been published. Thus, the present pilot study aimed at the mass spectrometric characterization of the metabolomes of specimens from both smoking and nonsmoking subjects and the comparison of the evaluated data in terms of sperm apoptosis and spermiogram parameters. The results provided evidence that the conventional spermiogram is not altered in smokers compared to nonsmokers. However, a more careful investigation of sperm cells by metabolomic profiling reveals profound effects of smoking on sperm: first, nitrogen oxide synthase, a marker of oxidative stress, is activated. Second, the uptake of fatty acids into sperm mitochondria is reduced, leading to an impaired energy supply. Third, phenylalanine hydroxylation and tryptophan degradation, which are both indications of altered tetrahydrobiopterin biosynthesis, are reduced. Moreover, flow cytometry approaches indicated increased sperm caspase-3 activity, a sign of apoptosis. The present study clearly shows the negative effects of smoking on semen quality. Especially for idiopathic cases, metabolomic profiling can help to shed light on male subfertility or infertility. Summary sentence The combination of spermiogram parameters with metabolomic profiling reveals oxidative stress markers, reduced mitochondrial fatty acid uptake and altered tetrahydrobiopterin biosynthesis, indicating negative effects of smoking on semen quality. Graphical Abstract

A comprehensive X-ray topography analysis of two selected aluminum nitride (AlN) bulk crystals is presented. We compare surface inspection X-ray topography in back-reflection geometry with high-energy transmission topography in the Lang and Laue configuration using the monochromatic Kα1 excitation wavelength of copper, silver, and tungsten, respectively. A detailed comparison of the results allows the assessment of both the high- and low-energy X-ray topography methods with respect to performance and structural information, giving essential feedback for crystal growth. This is demonstrated for two selected AlN freestanding faceted crystals up to 8 mm in thickness grown in all directions using the physical vapor transport (PVT) method. Structural defects of all facets of the crystals are determined using the X-ray topography in back-reflection geometry. The mean threading dislocation densities are 480 ± 30 cm−2 for both crystals of either the Al- or N-face. Clustering of dislocations could be observed. The m-facets show the presence of basal plane dislocations and their accumulation as clusters. The integral transmission topographs of the 101¯0 (m-plane) reflection family show that basal plane dislocations of the screw type in 131¯21¯0 directions decorate threading dislocation clusters. Three-dimensional section transmission topography reveals that the basal plane dislocation clusters mainly originate at the seed boundary and propagate in the 131¯21¯0 direction along the growth front. In newly laterally grown material, the Borrmann effect has been observed for the first time in PVT-grown bulk AlN, indicating very high structural perfection of the crystalline material in this region. This agrees with a low mean FWHM of 10.6 arcsec of the 101¯0 reflection determined through focused high-energy Laue transmission mappings. The latter method also opens the analysis of the ∆2θ-shift correlated to the residual stress distribution inside the bulk crystal, which is dominated by dislocation clusters. Contrary to Lang transmission topography, the de-focused high-energy Laue transmission penetrates the 8 mm-thick crystal enabling a defect analysis in the bulk.

Rivers are rich in biodiversity and act as ecological corridors for plant and animal species. With climate change and increasing anthropogenic water demand, more frequent and prolonged periods of drying in river systems are expected, endangering biodiversity and river ecosystems. However, understanding and predicting the hydrological mechanisms that control periodic drying and rewetting in rivers is challenging due to a lack of studies and hydrological observations, particularly in non-perennial rivers. Within the framework of the Horizon 2020 DRYvER (Drying River Networks and Climate Change) project, a hydrological modelling study of flow intermittence in rivers is being carried out in three European catchments (Spain, Finland, France) characterised by different climate, geology, and anthropogenic use. The objective of this study is to represent the spatio-temporal dynamics of flow intermittence at the reach level in mesoscale river networks (between 120 and 350 km2). The daily and spatially distributed flow condition (flowing or dry) is predicted using the J2000 distributed hydrological model coupled with a random forest classification model. Observed flow condition data from different sources (water level measurements, photo traps, citizen science applications) are used to build the predictive model. This study aims to evaluate the impact of the observed flow condition dataset (sample size, spatial and temporal representativity) on the performance of the predictive model. Results show that the hybrid modelling approach developed in this study allows the spatio-temporal patterns of drying to be accurately predicted in the three catchments, with a sensitivity criterion above 0.9 for the prediction of dry events in the Finnish and French case studies and 0.65 in the Spanish case study. This study shows the value of combining different data sources of observed flow condition to reduce the uncertainty in predicting flow intermittence.

Climate and land use changes, as well as human water use and flow alteration, are causing worldwide shifts in river flow dynamics. During the last decades, low flows, flow intermittence, and drying have increased in many regions of the world, including Europe. This trend is projected to continue and amplify in the future, resulting in more frequent and intense hydrological droughts. However, due to a lack of data and studies on temporary rivers in the past, little is known about the processes governing the development of flow intermittence and drying, their timing and frequency, or their long-term evolution under climate change. Moreover, understanding the impact of climate change on the drying up of rivers is crucial to assess the impact of climate change on aquatic ecosystems, including the biodiversity and functional integrity of freshwater systems. This study is one of the first to present future projections of drying in intermittent river networks and to analyse future changes in the drying patterns at a high spatial and temporal resolution. Flow intermittence projections were produced using a hybrid hydrological model forced with climate projection data from 1985 until 2100 under three climate scenarios in six European drying river networks. The studied watershed areas are situated in different biogeographic regions, located in Spain, France, Croatia, Hungary, Czechia, and Finland, and their areas range from 150 to 350 km2. Additionally, flow intermittence indicators were developed and calculated to assess (1) changes in the characteristics of the drying spells at the reach scale and (2) changes in the spatial extent of drying in the river network at various time intervals. The results for all three climate scenarios show that drying patterns are projected to increase and expand in time and space, despite differences in the amplitude of changes. Temporally, in addition to the average frequency of drying events, the duration increases over the year. Seasonal changes are expected to result in an earlier onset and longer persistence of drying throughout the year. Summer drying maxima are likely to shift to earlier in the spring, with extended drying periods or additional maxima occurring in autumn and extending into the winter season in some regions. A trend analysis of extreme events shows that the extreme dry spells observed in recent years could become regular by the end of the century. Additionally, we observe transitions from perennial to intermittent reaches in the future.

Purpose The anesthetic-conserving device AnaConDa ® , a miniature vaporizer, allows volatile sedation in the intensive care unit (ICU). We investigated the effects of isoflurane sedation on cerebral and systemic physiology parameters in neuromonitored ICU stroke patients. Methods Included in the study were 19 consecutive ventilated patients with intracerebral hemorrhage (12), subarachnoid hemorrhage (4), and ischemic stroke (3) who were switched from intravenous propofol or midazolam to inhalative isoflurane sedation for an average of 3.5 days. During the sedation transition, the following parameters were assessed: mean arterial pressure (MAP), intracranial pressure (ICP), cerebral perfusion pressure (CPP), middle cerebral artery mean flow velocity (MFV) and cerebral fractional tissue oxygen extraction (FTOE), as well as systemic cardiopulmonary parameters and administered drugs. Results After the first hour, mean ICP showed an increase of 2.1 mmHg that was not clinically relevant. Likewise, MFV did not change. MAP and CPP, however, decreased by 6.5 and 6.3 mmHg, respectively. FTOE was reduced slightly from 0.24 to 0.21 ( p  = 0.03). Over an observation period of 12 h, ICP remained stable, while MAP and thus CPP showed distinct decreases (CPP: −10 mmHg at 6 h, p  < 0.001; −7.5 mmHg at 12 h, p  = 0.005, when compared to preswitch levels) despite a 1.5-fold increase in vasopressor administration. Conclusions We suggest that that it is possible to reach sufficient sedation levels in cerebrovascular ICU patients by applying volatile isoflurane long-term without a relevant increase in ICP, if baseline ICP values are low or only moderately elevated. However, caution should be exercised in view of isoflurane’s decreasing effect on MAP and CPP. Multimodal neuromonitoring is strongly recommended when applying this off-label sedation method.

The reaction of [(OC)5MnBr] with substituted 3-(2-pyridyl)pyrazoles) 2-PyPzRH (1a-l) in methanol or diethyl ether yields the yellow to orange manganese(I) complexes [(OC)3Mn(Br)(2-PyPzRH)] (2a-l), the substituents R being phenyl (a), 1-naphthyl (b), 2-anthracenyl (c), 1-pyrenyl (d), 4-bromophenyl (e), 3-bromophenyl (f), duryl (g), 2-pyridyl (h), 2-furanyl (i), 2-thienyl (j), ferrocenyl (k), and 1-adamantyl (l). The carbonyl ligands are arranged facially, leading to three chemically different CO ligands due to different trans-positioned Lewis donors. The diversity of the substituent R demonstrates that this photoCORM backbone can easily be varied with a negligible influence on the central (OC)3MnBr fragment, because the structural parameters and the spectroscopic data of this unit are very similar for all these derivatives. Even the ferrocenyl complex 2k shows a redox potential for the ferrocenyl subunit which is identical to the value of the free 5-ferrocenyl-3-(2-pyridyl)pyrazole (1k). The ease of variation of the starting 5-substituted 3-(2-pyridyl)pyrazoles) offers a modular system to attach diverse substituents at the periphery of the photoCORM complex.