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Fibrin stabilizing factor (FXIII) plays a crucial role in blood clotting, tissue repair, and immune defense. FXIII deficiency after trauma can lead to prolonged wound healing due to persistent infections or coagulation disorders. The aim of this study was to describe the prevalence of acquired FXIII deficiency after trauma and to provide a description of the time-course changes of important coagulation parameters in relation to FXIII activity. In this context, patient characteristics, laboratory data, and treatment modalities were examined with respect to their influence on FXIII activity. Furthermore, the effects of in vitro administration of FXIII on clot firmness and outcomes in patients with severe traumatic brain injury were investigated.Two trauma cohorts (A and B) were examined prospectively in a two-center study, and another (cohort C) was examined retrospectively. In cohort A (trauma patients, n=880) routine laboratory tests were conducted, and FXIII activity was measured. In cohort B (polytrauma patients, n=26), additional clinical parameters were collected, and in-vitro FXIII administration and rotational thromboelastometry (ROTEM) analyses were performed. In cohort C (polytrauma patients with severe traumatic brain injury [sTBI], n=84), the impact of initially measured FXIII activity on clinical outcomes after sTBI was investigated using the modified Rankin Scale (mRS) at least 6 months after trauma.The prevalence of FXIII activity70% in cohort A was 12.4%, with significant differences in age, Hb, fibrinogen, and Hct levels, platelet count, aPTT, and INR (vs. prevalence of FXIII activity70%). Cohort B showed a decrease in FXIII activity from 85% to 58% after 7 days. FXIII deficiency correlated with time after trauma, aPTT, and fibrinogen level, lactate, and Hb levels. In-vitro administration of FXIII showed a positive influence on clot firmness due to improved maximum clot firmness (MCF in FIBTEM) and reduced maximum lysis (ML in EXTEM). Finally, a significant difference in FXIII activity between patients after sTBI with good and poor clinical outcomes was observed 6 months after trauma.We demonstrated that trauma-associated FXIII deficiency is a common coagulation disorder, with FXIII deficiency increasing further in the first 7 days after trauma, the period of early surgical care. In vitro administration of FXIII was able to demonstrate significant clot stabilizing effects. For trauma patients with sTBI, FXIII activity could serve as a prognostic parameter, as it differed significantly between patients with good and poor clinical outcomes.

Polyphosphate kinases (PPKs) have become popular biocatalysts for nucleotide 5'-triphosphate (NTP) synthesis and regeneration. Two unrelated families are described: PPK1 and PPK2. They are structurally unrelated and use different catalytic mechanisms. PPK1 enzymes prefer the usage of adenosine 5'-triphosphate (ATP) for polyphosphate (polyP) synthesis while PPK2 enzymes favour the reverse reaction. With the emerging use of PPK enzymes in biosynthesis, a deeper understanding of the enzymes and their thermodynamic reaction course is of need, especially in comparison to other kinases. Here, we tested four PPKs from different organisms under the same conditions without any coupling reactions. In comparison to other kinases using phosphate donors with comparably higher phosphate transfer potentials that are characterised by reaction yields close to full conversion, the PPK-catalysed reaction reaches an equilibrium in which about 30% ADP is left. These results were obtained for PPK1 and PPK2 enzymes, and are supported by theoretical data on the basic reaction. At high concentrations of substrate, the different kinetic preferences of PPK1 and PPK2 can be observed. The implications of these results for the application of PPKs in chemical synthesis and as enzymes for ATP regeneration systems are discussed.

Secondary transports of patients from one hospital to another are indicated for medical reasons or to address local constraints in capacity. In particular, interhospital transports of critically ill infectious patients present a logistical challenge and can be key in the effective management of pandemic situations. The state of Saxony in Germany has two characteristics that allow for an extensive evaluation of secondary transports in the pandemic year 2020/2021. First, all secondary transports are centrally coordinated by a single institution. Second, Saxony had the highest SARS-CoV-2 infection rates and the highest COVID-19 associated mortality in Germany. This study evaluates secondary interhospital transports from March 2019 to February 2021 in Saxony with a detailed analysis of transport behaviour during the pandemic phase March 2020 to February 2021. Our analysis includes secondary transports of SARS-CoV-2 patients and compares them to secondary transports of non-infectious patients. In addition, our data show differences in demographics, SARS-CoV-2- incidences, ICU occupancy of COVID-19 patients, and COVID-19 associated mortality in all three regional health clusters in Saxony. In total, 12,282 secondary transports were analysed between March 1st, 2020 and February 28th, 2021, of which 632 were associated with SARS-CoV-2 (5.1%) The total number of secondary transports changed slightly during the study period March 2020 to February 2021. Transport capacities for non-infectious patients were reduced due to in-hospital and out-of-hospital measures and could be used for transport of SARS-CoV-2 patients. Infectious transfers lasted longer despite shorter distance, occurred more frequently on weekends and transported patients were older. Primary transport vehicles were emergency ambulances, transport ambulances and intensive care transport vehicles. Data analysis based on hospital structures showed that secondary transports in correlation to weekly case numbers depend on the hospital type. Maximum care hospitals and specialized hospitals show a maximum of infectious transports approximately 4 weeks after the highest incidences. In contrast, standard care hospitals transfer their patients at the time of highest SARS-CoV-2 case numbers. Two incidence peaks were accompanied by two peaks of increased secondary transport. Our findings show that interhospital transfers of SARS-CoV-2 and non-SARS-CoV-2 patients differ and that different hospital care levels initiated secondary transports at different times during the pandemic.

The species delimitation of the marine bivalve species complex Aequiyoldia eightsii in South America and Antarctica is complicated by mitochondrial heteroplasmy and amplification bias in molecular barcoding. In this study, we compare different data sources (mitochondrial cytochrome c oxidase subunit I (COI) sequences; nuclear and mitochondrial SNPs). Whilst all the data suggest that populations on either side of the Drake Passage belong to different species, the picture is less clear within Antarctic populations, which harbor three distinct mitochondrial lineages (p-dist ≈ 6%) that coexist in populations and in a subset of individuals with heteroplasmy. Standard barcoding procedures lead to amplification bias favoring either haplotype unpredictably and thus overestimate the species richness with high confidence. However, nuclear SNPs show no differentiation akin to the trans-Drake comparison, suggesting that the Antarctic populations represent a single species. Their distinct haplotypes likely evolved during periods of temporary allopatry, whereas recombination eroded similar differentiation patterns in the nuclear genome after secondary contact. Our study highlights the importance of using multiple data sources and careful quality control measures to avoid bias and increase the accuracy of molecular species delimitation. We recommend an active search for mitochondrial heteroplasmy and haplotype-specific primers for amplification in DNA-barcoding studies.

When an organism makes a long-distance transition to a new habitat, the associated environmental change is often marked and requires physiological plasticity of larvae, juveniles, or other migrant stages. Exposing shallow-water marine bivalves (Aequiyoldia cf. eightsii) from southern South America (SSA) and the West Antarctic Peninsula (WAP) to changes in temperature and oxygen availability, we investigated changes in gene expression in a simulated colonization experiment of the shores of a new continent after crossing of the Drake Passage, and in a warming scenario in the WAP. Bivalves from SSA were cooled from 7°C (in situ) to 4°C and 2°C (future warmed WAP conditions), WAP bivalves were warmed from 1.5°C (current summer in situ) to 4°C (warmed WAP), gene expression patterns in response to thermal stress by itself and in combination with hypoxia were measured after 10 days. Our results confirm that molecular plasticity may play a vital role for local adaptation. Hypoxia had a greater effect on the transcriptome than temperature alone. The effect was further amplified when hypoxia and temperature acted as combined stressors. The WAP bivalves showed a remarkable ability to cope with short-term exposure to hypoxia by switching to a metabolic rate depression strategy and activating the alternative oxidation pathway, whilst the SSA population showed no comparable response. In SSA, the high prevalence of apoptosis-related differentially expressed genes especially under combined higher temperatures and hypoxia indicated that the SSA Aequiyoldia are operating near their physiological limits already. While the effect of temperature per se may not represent the single most effective barrier to Antarctic colonization by South American bivalves, the current distribution patterns as well as their resilience to future conditions can be better understood by looking at the synergistic effects of temperature in conjunction with short-term exposure to hypoxia.

Background The aim of this study was to assess the usefulness of adding thoracic CT to abdominal CT in intensive care unit (ICU) patients with signs of infection after abdominopelvic surgery. Methods 143 thoracoabdominal CTs of ICU patients with signs of infection after abdominopelvic surgery were retrospectively reviewed for thoracic pathologies. It was determined if pathologic findings were visible only on thoracic CT above the diaphragmatic dome or also on abdominal CT up to the diaphragmatic dome. All thoracic pathologies visible only above the diaphragmatic dome were retrospectively analyzed by an ICU physician in terms of clinical relevance. Diagnostic and therapeutic efficacy of thoracic CT were assessed with regard to an infectious focus and to other pathologic findings. Results 297 pathologic thoracic findings were recorded. 26 of the 297 findings could only be detected on images obtained above the diaphragmatic dome (in 23 of 143 CTs). A change in patient management was initiated due to only one of the 26 supradiaphragmatic findings. Diagnostic efficacy of thoracic CT in addition to abdominal CT to identify an infectious focus was 3.5% (95%-CI: 0.5–6.5%) and therapeutic efficacy was 0.7% (95%-CI: 0–2.1%). With regard to all pathologic thoracic findings, diagnostic efficacy was 16.1% (95%-CI: 10.1–22.1%) and therapeutic efficacy remained at 0.7%. Conclusions Additional thoracic CT to detect an infectious focus in ICU patients after abdominopelvic surgery leads to identification of the focus in only 3.5% and to changes in patient management in only 0.7%. Other relevant findings are more common (16.1%), but very rarely affect patient management.

In this work, the activity and thermostability of horseradish peroxidase (HRP) in betaine-based natural deep eutectic systems (NADESs) was measured and studied by molecular simulations.

Saccharides are still commonly isolated from biological feedstock by crystallization from aqueous solutions. Precise thermodynamic data on solubility are essential to optimize the downstream crystallization process. Solubility modeling, in turn, requires knowledge of melting properties. In the first part of this work, following our previous work on amino acids and peptides, D-α-glucose, D-β-fructose, D-sucrose, D-α-galactose, and D-α-xylose were investigated with Fast Scanning Calorimetry (FSC) in a wide scanning rate range (2000 K·s−1 to 10000 K·s−1). Using the experimental melting properties of saccharides from FSC allowed successfully modeling aqueous solubility for D-sucrose and D-α-galactose with the equation of state PC-SAFT. This provides cross-validation of the measurement methods to determine accurate experimental melting properties with FSC. Unexpectedly, the experimental FSC melting temperatures, extrapolated to zero scanning rates for thermal lag correction, were higher than results determined with DSC and available literature data. To clarify this inconsistency, FSC measurements towards low scanning rates from 10000 K·s−1 to 1 K·s−1 (D-α-glucose, D-β-fructose, D-sucrose) overlapping with the scanning rates of DSC and literature data were combined. At scanning rates below 1000 K·s−1, the melting properties followed a consistent non-linear trend, observed in both the FSC and the literature data. In order to understand the non-linear decrease of apparent melting temperatures with decreasing heating rate, the endothermic peaks were investigated in terms of isoconversional kinetics. The activation energies in the non-linear dependency region are in the range of 300, Food biophysics;Bd 17. 2022, H. 2, S.181-197

Zusammenfassung Hintergrund Die komplexe und dynamische Situation im aktuellen Pandemiegeschehen erfordert eine regional abgestimmte und vernetzte Zusammenarbeit in der Gesundheitsversorgung zwischen den verschiedenen Akteuren des Gesundheitswesens, dem stationaren Sektor sowie dem offentlichen Gesundheitsdienst. Ziel der Untersuchung war, das Versorgungsmanagement hinsichtlich der regionalen Vernetzungs- und Kommunikationsstrukturen wahrend der COVID-19-Pandemie im Jahr 2020 zu beleuchten. Methode Im Rahmen des vom Bundesministerium fur Bildung und Forschung (BMBF) geforderten Projekts „egePan Unimed“ wurde im November 2020 allen Vorstanden der 35 deutschen Universitatskliniken ein Online-Fragebogen zum Pandemiemanagement zugesandt. Im Zentrum des Fragebogens standen die Kernthemen Regionale Vernetzung, Krisenmanagement, Datenaustausch und Kommunikation mit politischen Akteuren. Der Fragebogen bestand aus 37 geschlossenen und drei offenen Fragen. Nach der Pilotierung erfolgte die Einladung zur Befragung dreimal per E-Mail und einmal telefonisch. Ergebnisse Von den befragten Universitatskliniken (n = 25, Response 71,4%) bestand bei 68% eine abgestimmte Zusammenarbeit mit anderen regionalen Krankenhausern und bei 86% mit Vertretern des Offentlichen Gesundheitsdienstes (OGD). Eine koordinierte Zusammenarbeit mit dem ambulanten Sektor wurde seltener (26%) angegeben. 84% der Universitatskliniken gaben an, eine Leitungsfunktion im Rahmen eines regionalen COVID-19-Pandemiemanagements innezuhaben. Ein Datenaustausch im Zuge des Pandemiemanagements fand bei 75% mit regionalen Kliniken und bei 67% mit uberregionalen Kliniken statt. Schlussfolgerung Zur Bewaltigung der regionalen medizinischen Versorgung wahrend der COVID-19-Pandemie im Jahr 2020 nahmen Universitatskliniken sehr haufig eine koordinierende Rolle im komplexen pandemischen Versorgungsgeschehen ein. Es bestanden dabei haufig strukturierte Kooperationen mit regionalen Kliniken und Gesundheitsamtern und vergleichsweise selten mit dem ambulanten Versorgungsbereich. Gerade diese Zusammenarbeit hatte jedoch das Potenzial, Uberbelegungen von Kliniken zu verhindern.

Special issue The Weddell Sea and the ocean off Dronning Maud Land: unique oceanographic conditions shape circumpolar and global processes – a multi-disciplinary study (OS/BG/TC inter-journal SI).-- 30 pages, 5 figures.-- Data availability: The data (sets) used for the illustrations in some figures are referenced in the figure captions: bathymetry (water depth) in Fig. 1 (Dorschel et al., 2022); bathymetry in Figs. 2a and 3 (Arndt et al., 2013); and sea ice, chlorophyll, and temperature in Fig. 4 (Lavergne et al., 2019, and http://oceandata.sci.gsfc.nasa.gov/, last access: 23 August 2022). No addition data sets were used in this publication, Systematic long-term studies on ecosystem dynamics are largely lacking from the East Antarctic Southern Ocean, although it is well recognized that they are indispensable to identify the ecological impacts and risks of environmental change. Here, we present a framework for establishing a long-term cross-disciplinary study on decadal timescales. We argue that the eastern Weddell Sea and the adjacent sea to the east, off Dronning Maud Land, is a particularly well suited area for such a study, since it is based on findings from previous expeditions to this region. Moreover, since climate and environmental change have so far been comparatively muted in this area, as in the eastern Antarctic in general, a systematic long-term study of its environmental and ecological state can provide a baseline of the current situation, which will be important for an assessment of future changes from their very onset, with consistent and comparable time series data underpinning and testing models and their projections. By establishing an Integrated East Antarctic Marine Research (IEAMaR) observatory, long-term changes in ocean dynamics, geochemistry, biodiversity, and ecosystem functions and services will be systematically explored and mapped through regular autonomous and ship-based synoptic surveys. An associated long-term ecological research (LTER) programme, including experimental and modelling work, will allow for studying climate-driven ecosystem changes and interactions with impacts arising from other anthropogenic activities. This integrative approach will provide a level of long-term data availability and ecosystem understanding that are imperative to determine, understand, and project the consequences of climate change and support a sound science-informed management of future conservation efforts in the Southern Ocean, Stefanie Arndt, Heike Link and Christoph Held have received financial support from the Deutsche Forschungsgemeinschaft (DFG) in the framework of the priority programme 1158 “Antarctic Research with Comparative Investigations in Arctic Sea Ice Areas”. The article processing charges for this open-access publication were covered by the Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research (AWI), With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S)

The solvent is of prime importance in biomass conversion as it influences dissolution, reaction kinetics, catalyst activity and thermodynamic equilibrium of the reaction system. So far, activity-based models were developed to predict kinetics and equilibria, but the influence of the catalyst on kinetics has not been succesfully predicted by thermodynamic models. In this work, the thermodynamic model ePC-SAFT advanced was used to predict the activities of the reactants and of the catalyst at various conditions (temperature, reactant concentrations, γ-valerolactone GVL cosolvent addition, catalyst concentration) for the homogeneously acid-catalyzed esterification of levulinic acid (LA) with ethanol. Different kinetic models were applied, and it was found that the catalyst influence on kinetics could be predicted correctly by simultaneously solving the dissociation equilibrium of H

In the deep sea, the phylogeny and biogeography of only a few taxa have been well studied. Although more than 200 species in 32 genera have been described for the asellote isopod families Desmosomatidae Sars, 1897 and Nannoniscidae Hansen, 1916 from all ocean basins, their phylogenetic relationships are not completely understood. There is little doubt about the close relationship of these families, but the taxonomic position of a number of genera is so far unknown. Based on a combined morphological phylogeny using the Hennigian method with a dataset of 107 described species and a molecular phylogeny based on three markers (COI, 16S, and 18S) with 75 species (most new to science), we could separate Desmosomatidae and Nannoniscidae as separate families. However, we could not support the concept of the subfamilies Eugerdellatinae Hessler, 1970 and Desmosomatinae Hessler, 1970. Most genera of both families were well supported, but several genera appear as para- or even polyphyletic. Within both families, convergent evolution and analogies caused difficulty in defining apomorphies for phylogenetic reconstructions and this is reflected in the results of the concatenated molecular tree. There is no biogeographic pattern in the distribution as the genera occur over the entire Atlantic and Pacific Ocean, showing no specific phylogeographical pattern. Poor resolution at deep desmosomatid nodes may reflect the long evolutionary history of the family and rapid evolutionary radiations. Supplementary Information The online version contains supplementary material available at 10.1007/s13127-021-00509-9.

Metazoans normally possess a single lineage of mitochondria inherited from the mother (♀-type mitochondria) while paternal mitochondria are absent or eliminated in fertilized eggs. In doubly uniparental inheritance (DUI), which is specific to the bivalve clade including the ocean quahog, Arctica islandica, ♂-type mitochondria are retained in male gonads and, in a few species, small proportions of ♂-type mitochondria co-exist with ♀-type in somatic tissues. To the best of our knowledge, we report, for the first time in metazoan, the natural occurrence of male and female individuals with exclusively ♂-type mitochondria in somatic tissues of the bivalve A. islandica. Mitochondrial genomes differ by ~5.5% at DNA sequence level. Exclusive presence of ♂-type mitochondria affects mitochondrial complexes partially encoded by mitochondrial genes and leads to a sharp drop in respiratory capacity. Through a combination of whole mitochondrial genome sequencing and molecular assays (gene presence and expression), we demonstrate that 1) 11% of individuals of an Icelandic population appear homoplasmic for ♂-type mitochondria in somatic tissues, 2) ♂-type mitochondrial genes are transcribed and 3) individuals with ♂-type mitochondria in somatic cells lose 30% of their wild-type respiratory capacity. This mitochondrial pattern in A. islandica is a special case of DUI, highlighted in individuals from both sexes with functional consequences at cellular and conceivably whole animal level., Dégletagne et al. report on an unusual case of doubly uniparental inheritance in the ocean quahog, Arctica isladica. Some individuals in an Icelandic population present homoplasmic presence of male-type mitochondrial genes in somatic tissues, which appears to confer some changes in respiratory capacity in some environmental conditions.

The suitability of phenyl–based deep eutectic solvents (DESs) as absorbents for toluene absorption was investigated by means of thermodynamic modeling and molecular dynamics (MD). The thermodynamic models PC–SAFT and COSMO–RS were used to predict the vapor–liquid equilibrium (VLE) of DES–toluene systems. PC–SAFT yielded quantitative results even without using any binary fitting parameters. Among the DESs consisting of three different HBAs and three different HBDs (phenol, levulinic acid, ethylene glycol), [TEBAC][PhOH] was considered as the most suitable absorbent. Systems with [TEBAC][PhOH] had lowest equilibrium pressures of the considered DES–toluene mixtures, the best thermodynamic characteristics (i.e., Henry’s law constant, excess enthalpy, free energy of solvation of toluene), and the highest self–diffusion coefficient of toluene. The molecular–level mechanism was explored by MD simulations, indicating that [TEBAC][PhOH] has the strongest interaction of HBA–/HBD–toluene compared to the other DESs under study. This work provides guidance to rationally design novel DESs for efficient aromatic VOCs absorption.

To validate the use of horseradish peroxidase (HRP) in natural deep eutectic systems (NADES), five different betaine-based NADES were characterized in terms of water content, water activity, density, and viscosity experimentally and by thermodynamic modeling. The results show that the NADES under study have a water activity of about 0.4 at 37 °C for water contents between 14 and 22 wt %. The densities of the studied NADES had values between 1.2 and 1.3 g

Proton activity, which is usually expressed as a pH value, is among the most important properties in the design of chemical and biochemical processes as it determines the dissociation of species in aqueous mixtures. This article addresses the prediction of pH values in multiphase systems based on the IUPAC definition via proton activity. The required proton activity coefficients were predicted using the thermodynamic equation of state ePC-SAFT advanced. The developed framework considers reaction equilibria and phase equilibria (vapor–liquid and liquid–liquid) to predict pH in the equilibrated liquid phases., Chem. Commun.;58(60)

Sour-gas absorption is the main unit operation used in refineries and petrochemical and natural gas processing plants for the effective reduction of climate-wrecking gases, mainly CO2 and H2S. Abso...

In downstream processes for peptides, crystallization is still used as the state-of-the-art separation step for which the knowledge about the solubility of each single compound is mandatory. Since ...

Precursor solubility is a crucial factor in industrial applications, dominating the outcome of reactions and purification steps. The outcome and success of thermodynamic modelling of this industrially important property with equations of states, such as Perturbed‐Chain Statistical Associating Fluid Theory (PC‐SAFT), vastly depends on the quality of the pure‐component parameters. The pure‐component parameters for low‐volatile compounds such as ionic liquids (ILs) have been commonly estimated using mixture properties, e. g. the osmotic pressure of aqueous solutions. This leads to parameters that depend on the solvent, and transferability to other mixtures often causes poor modeling results. Mixture‐independent experimental properties would be a more suitable basis for the parameter estimation offering a way to universal parameter sets. Model parameters for ILs are available in the literature [10.1016/j.fluid.2012.05.029], but they were estimated using pure‐IL density data. The present work focuses on a step towards a more universal estimation strategy that includes new experimental vapor‐pressure data of the pure IL. ILs exhibit an almost negligible vapor pressure in magnitude of usually 10−5 Pa even at elevated temperatures. In this work, such vapor‐pressure data of a series of 1‐ethyl‐3‐methyl‐imidazolium‐based [C2mim]‐ILs with various IL‐anions (e. g. tetrafluoroborate [BF4]−, hexafluorophosphate [PF6]−, bis(trifluoromethylsulfonyl)imide [NTf2]−) were experimentally determined and subsequently used for PC‐SAFT parameter estimation. The so‐determined parameters were used to predict experimental molecular precursor solubility in ILs and infinitely diluted activity coefficients of various solvents in ILs. The parameters were further compared to modeling results using classical parametrization methods (use of liquid‐density data only for the molecular PC‐SAFT and the ion‐based electrolyte PC‐SAFT). As a result, the modeled precursor solubilities using the new approach are much more precise than using the classical parametrization methods, and required binary parameters were found to be much smaller (if needed). In sum, including the pure‐component vapor‐pressure data of ILs opens the door towards parameter estimation that is not biased by mixture data. This procedure might be suitable also for polymers and for all kind of ionic species but needs extension to ion‐specific parametrization in the long term., The conventional way to fit ionic liquid parameters of equations of state to density is compared using a new method. The experimental vapor pressures as well as the density have been used as input to the model parameter estimation. The work was performed within the framework of the EOS PC‐SAFT (perturbed‐chain statistical associating fluid theory). The new method allows modeling density and vapor pressure accurately, and still allows for an improved modeling of the solubility of precursors in ionic liquids.

S‐alkyltetrahydrothiophenium, [CnTHT]+ bis(trifluorosulfonyl)imide, [NTf2]− room temperature ionic liquids (ILs) and tetraphenylborate, [BPh4]− salts with alkyl chain lengths from C4 to C10 have been prepared. The ILs and salts were characterized and their purity verified by 1H‐ and 13C‐nuclear magnetic resonance, elemental analysis, ion chromatography, Karl‐Fischer titration, single crystal X‐ray diffraction as well as thermogravimetric analysis. The experimentally determined density and viscosity decrease with increasing temperature. The experimental solubility of the [CnTHT][NTf2]‐ILs in water (75 to 2.2 mg/L for C4 to C10) was modelled with very good agreement by Perturbed Chain Statistical Associating Fluid Theory (PC‐SAFT), based on the extremely low vapor pressures for the [CnTHT][NTf2]‐ILs measured in this work (4.15 to 0.037 ⋅ 10−7×psat for C4 to C10). PC‐SAFT is able to predict and correlate different thermodynamic properties by estimating the Helmholtz residual energy.

Deep eutectic solvents have appeared as potential solvents for improving the extraction of polyphenols from vegetable or fruit matrixes. Since gallic acid is abundant in these sources, it is consid...

ERC-2016-CoG 725034 HE 7165/6-1 CH 1922/1-1 The use of water as a component of deep eutectic systems (DES) has raised some questions regarding its influence on the nature of the mixture. Does it form a DES or an aqueous solution and what is the role of water? In this work, the nature of citric acid:l-arginine:water mixtures was explored through phase equilibria studies and spectroscopic analysis. In a first step, PC-SAFT was validated as a predictive tool to model the water influence on the solid liquid equilibria (SLE) of the DES reline using the individual-component approach. Hence, activity coefficients in the ternary systems citric acid:l-arginine:water and respective binary combinations were studied and compared using ePC-SAFT. It was observed that the water-free mixtures citric acid:l-arginine showed positive deviation from Raoult's law, while upon addition of water strong negative deviation from Raoult's law was found, yielding melting depressions around 100 K. Besides these strong interactions, pH was found to become acidic (pH = 3.5) upon water addition, which yields the formation of charged species ([H2Cit]- and [l-arg]+). Thus, the increased interactions between the molecules upon water addition might be caused by several mechanisms such as hydrogen bonding or ionic forces, both being induced by water. For further investigation, the liquid mixtures citric acid:l-arginine:water were studied by FTIR and NMR spectroscopy. FTIR spectra disproved a possible solubility enhancement caused by salt formation between citric acid and l-arginine, while NMR spectra supported the formation of a hydrogen bonding network different from the binary systems citric acid:water and l-arginine:water. Either being a DES or other type of non-ideal solution, the liquefaction of the studied systems is certainly caused by a water-mediator effect based on the formation of charged species and cross interactions between the mixture constituents. This journal is publishersversion published

Rapid regional warming causing glacial retreat and melting of ice caps in Antarctica leads benthic filter-feeders to be exposed to periods of food shortage and high respiratory impairment as a consequence of seasonal sediment discharge in the West Antarctic Peninsula coastal areas. The molecular physiological response and its fine-tuning allow species to survive acute environmental stress and are thus a prerequisite to longer-term adaptation to changing environments. Under experimental conditions, we analyzed here the metabolic response to changes in suspended sediment concentrations, through transcriptome sequencing and enzymatic measurements in a highly abundant Antarctic ascidian. We found that the mechanisms underlying short-term response to sedimentation in Cnemidocarpa verrucosa sp. A involved apoptosis, immune defense, and general metabolic depression. These mechanisms may be understood as an adaptive protection against sedimentation caused by glacial retreat. This process can strongly contribute to the structuring of future benthic filter-feeder communities in the face of climate change.

Research on the thermodynamics of electrolytes is timeless, and modeling an electrolyte solution might be considered to be a golden oldie, which was, is, and will be important in the design of proc...

Four ionic liquids (ILs) consisting of the bis(trifluoromethylsulfonyl)imide anion paired with a phosphonium, pyridinium, imidazolium, or thiolanium cation were investigated as potential solvents t...

The Southern Ocean is one of the most isolated marine ecosystems, characterized by high levels of endemism, diversity, and biomass. Ascidians are among the dominant groups in Antarctic benthic assemblages; thus, recording the evolutionary patterns of this group is crucial to improve our current understanding of the assembly of this polar ocean. We studied the genetic variation within Cnemidocarpa verrucosa sensu lato, one of the most widely distributed abundant and studied ascidian species in Antarctica. Using a mitochondrial and a nuclear gene (COI and 18S), the phylogeography of fifteen populations distributed along the West Antarctic Peninsula and Burdwood Bank/MPA Namuncurá (South American shelf) was characterized, where the distribution of the genetic distance suggested the existence of, at least, two species within nominal C. verrucosa. When reevaluating morphological traits to distinguish between genetically defined species, the presence of a basal disk in one of the genotypes could be a diagnostic morphological trait to differentiate the species. These results are surprising due to the large research that has been carried out with the conspicuous C. verrucosa with no differentiation between species. Furthermore, it provides important tools to distinguish species in the field and laboratory. But also, these results give new insights into patterns of differentiation between closely related species that are distributed in sympatry, where the permeability of species boundaries still needs to be well understood., The evidence presented here allowed to delimitate two species within the conspicuous Antarctic ascidian C. verrucosa: two monophyletic groups were obtained, and congruent mitochondrial/nuclear species delimitation was demonstrated. Our results once again emphasize that species identities, even for highly abundant and well‐studied species on small local scales, must be assessed rather than assumed.

Purpose To investigate the outcome of local intra-arterial papaverine infusion therapy in patients with non-occlusive mesenteric ischemia (NOMI), and factors influencing survival, in comparison with a conservative approach. Methods From 2013 to 2019, patients with NOMI confirmed by imaging were included in a retrospective two-center study. According to different in-house standard procedures, patients were treated in each center either conservatively or interventionally by a standardized local infusion of intra-arterial papaverine into the splanchnic arteries. Thirty-day mortality and factors influencing the outcome, such as different demographics and laboratories, were compared between groups using Kaplan–Meier survival analysis and Cox regression, respectively. Results A total of 66 patients with NOMI were included, with n = 35 treated interventionally (21 males, mean age 67.7 ± 12.3 years) and n = 31 treated conservatively (18 females, mean age 71.6 ± 9.6 years). There was a significant difference in 30-day mortality between the interventional (65.7%; 12/35 survived) and the conservative group (96.8%; 1/31 survived) (hazard ratio 2.44; P = 0.005). Thresholds associated with a worse outcome of interventional therapy are > 7.68 mmol/l for lactate, Conclusion Local intra-arterial papaverine infusion therapy in patients with NOMI significantly increases survival rate in comparison with conservative treatment. High lactate levels, low pH and high base excess, and high demand for catecholamines are associated with a poor outcome. Level of Evidence Level III.

Purpose Postpancreatectomy hemorrhage (PPH) is one of the leading causes of mortality after pancreatic resection. Late onset PPH is most often treated using a transarterial approach. The aim of this study was to analyze risk factors for in-hospital mortality after endovascular treatment. Methods Between 2012 and 2017, patients who were treated endovascular due to PPH were identified from a retrospective analysis of a database. Risk factors for mortality were identified by univariate analysis. Results In total, 52 of the 622 patients (8.4%) underwent endovascular treatment due to PPH. The primary technical success achieved was 90.4%. In 59.6% of patients, bleeding control was achieved by placing a stent graft and in 40.4% by coil embolization. The primary 30-day and 1-year patency of the placed covered stents was 89.3% and 71.4%, respectively. The 60-day mortality was 34.6%. The reintervention rate was higher after stent graft placement compared to coiling (39.3% vs. 21.1%, P = 0.012). In the univariate analysis the need for reintervention was associated with a higher in-hospital mortality (21.2% vs. 7.7%, P = 0.049). The use of an antiplatelet agent was associated with a decreased in-hospital mortality in the univariate (11.5% vs. 25%, P = 0.024) and multivariate analysis (HR 3.1, 95% CI 1.1-9, P = 0.034), but did not increase the risk of rebleeding. Conclusion Endovascular management of delayed PPH has a high technical success rate. Stent graft placement showed a higher reintervention rate. The need for reintervention was associated with a higher in-hospital mortality but did not differ between coiling and stent graft placement.

The condensation reaction of fructose to 5-hydroxymethylfurfural (HMF) is acid-catalyzed, and it suffers from thermodynamic limitation of the conversion, poor kinetics, and consecutive reactions su...

Parallel phenotypic divergence is the independent differentiation between phenotypes of the same lineage or species occupying ecologically similar environments in different populations. We tested in the Antarctic limpet Nacella concinna the extent of parallel morphological divergence in littoral and sublittoral ecotypes throughout its distribution range. These ecotypes differ in morphological, behavioural and physiological characteristics. We studied the lateral and dorsal outlines of shells and the genetic variation of the mitochondrial gene Cytochrome Oxidase subunit I from both ecotypes in 17 sample sites along more than 2,000 km. The genetic data indicate that both ecotypes belong to a single evolutionary lineage. The magnitude and direction of phenotypic variation differ between ecotypes across sample sites; completely parallel ecotype-pairs (i.e., they diverge in the same magnitude and in the same direction) were detected in 84.85% of lateral and 65.15% in dorsal view comparisons. Besides, specific traits (relative shell height, position of shell apex, and elliptical/pear-shape outline variation) showed high parallelism. We observed weak morphological covariation between the two shape shell views, indicating that distinct evolutionary forces and environmental pressures could be acting on this limpet shell shape. Our results demonstrate there is a strong parallel morphological divergence pattern in N. concinna along its distribution, making this Antarctic species a suitable model for the study of different evolutionary forces shaping the shell evolution of this limpet.

The production of platform molecules from the valorization of lignocellulosic biomass is increasing. Among these plateform molecules, γ-valerolactone (GVL) is a promising one and could be used for different industrial applications. This molecule is synthesized from levulinic acid (LA) or alkyl levulinates (AL) through a tandem hydrogenation/cyclization (lactonization) cascade. A lot of investigations have been carried out to develop the best catalyst for the hydrogenation step by using solely LA or AL. However, one should keep in mind that in the AL production via fructose alcoholysis, there is also LA production, and both are present in the product mixture during the further conversion. To the best of our knowledge, no article exists describing the hydrogenation of LA and AL simultaneously in one-pot. Also, the literature reporting the use of solid catalyst for the second cyclization step is rare. To fill this gap, the hydrogenation of levulinic acid and butyl levulinate was studied over Ru/C and Amberlite IR-120. Several kinetic models were evaluated via Bayesian inference and K-fold approach. The kinetic assessment showed that a non-competitive Langmuir-Hinshelwood with no dissociation of hydrogen where LA, BL and H2 are adsorbed on different sites (NCLH1.2) and non-competitive Langmuir-Hinshelwood with dissociation of hydrogen where LA, BL (butyl levulinate) and H2 are adsorbed on different sites (NCLH2.2) are the best model to describe this system. The presence of LA and Amberlite IR-120 allows to increase the kinetics of cyclization steps, and in fine to accelerate the production of GVL.