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Showing papers by "University of Münster published in 2022"


Journal ArticleDOI
TL;DR: In this paper, a comprehensive review of the impact of organic matter, Fe oxides, and related biogeochemical processes on As mobilization to aquifers has been presented, including ternary complexes involving both Fe and organic matter.

39 citations


Journal ArticleDOI
TL;DR: In this article , a comprehensive review of the impact of organic matter (DOM) and Fe oxides on As mobilization to aquifers has been presented, including ternary complexes involving both Fe and DOM.

39 citations


Journal ArticleDOI
17 Feb 2022
TL;DR: In this paper , the authors analyzed fecal and saliva samples from SARS-CoV-2 infected and post COVID-19 patients and controls considering multiple influencing factors during hospitalization.
Abstract: There is a growing debate about the involvement of the gut microbiome in COVID-19, although it is not conclusively understood whether the microbiome has an impact on COVID-19, or vice versa, especially as analysis of amplicon data in hospitalized patients requires sophisticated cohort recruitment and integration of clinical parameters. Here, we analyzed fecal and saliva samples from SARS-CoV-2 infected and post COVID-19 patients and controls considering multiple influencing factors during hospitalization. 16S rRNA gene sequencing was performed on fecal and saliva samples from 108 COVID-19 and 22 post COVID-19 patients, 20 pneumonia controls and 26 asymptomatic controls. Patients were recruited over the first and second corona wave in Germany and detailed clinical parameters were considered. Serial samples per individual allowed intra-individual analysis. We found the gut and oral microbiota to be altered depending on number and type of COVID-19-associated complications and disease severity. The occurrence of individual complications was correlated with low-risk (e.g., Faecalibacterium prausznitzii) and high-risk bacteria (e.g., Parabacteroides ssp.). We demonstrated that a stable gut bacterial composition was associated with a favorable disease progression. Based on gut microbial profiles, we identified a model to estimate mortality in COVID-19. Gut microbiota are associated with the occurrence of complications in COVID-19 and may thereby influencing disease severity. A stable gut microbial composition may contribute to a favorable disease progression and using bacterial signatures to estimate mortality could contribute to diagnostic approaches. Importantly, we highlight challenges in the analysis of microbial data in the context of hospitalization.

33 citations


Journal ArticleDOI
17 Jan 2022
TL;DR: In this paper , a new catalytic approach to the selective functionalization of strong C-F bonds in polyfluorinated aliphatic esters and amides is presented.
Abstract: Selective C-F bond functionalization of perfluoalkyl units has huge potential towards accessing functionalized organofluorinated compounds, but remains challenging due to the high C-F bond strength and inherent selectivity challenges. We report a new catalytic approach to the selective functionalization of strong C-F bonds in polyfluorinated aliphatic esters and amides. This simple reaction proceeds in mild and operational fashion with divergent conversions, including hydrodefluorination, defluoroalkylation, and defluoroalkenylation, affording a diverse array of important partially fluorinated motifs. Straightforward downstream chemistry towards fluorinated alcohols, amines and drug derivatives highlights the potential of the protocol.

28 citations


Journal ArticleDOI
TL;DR: In this article, the authors theoretically motivate and apply a system-level theory of change framework that identifies central mechanisms and four distinct pathways, through which bio-based transformation can generate positive or negative outcomes in multiple domains of the Sustainable Development Goals.

26 citations


Journal ArticleDOI
TL;DR: In this paper, the authors considered whether the long-term concentration of fine particulate matter of different sizes changes the number of detected coronavirus infections and number of COVID-19 fatalities in Germany.

25 citations


Journal ArticleDOI
TL;DR: In this paper, a multisalt-based solid polymer electrolyte (XSPE) network based on multi-isalt chemistry is synthesized using photopolymerization reaction, which outperforms the conventional single salt-based XSPEs.

19 citations


Journal ArticleDOI
TL;DR: In this paper , a transition-metal-free radical 1,2-difunctionalization of unactivated alkenes via FSO2 -radical addition with subsequent vicinal alkynylation to access β-alkynyl-fluorosulfonylalkanes is presented.
Abstract: Sulfonyl fluorides have found widespread use in chemical biology and drug discovery. The development of synthetic methods for the introduction of the sulfonyl fluoride moiety is therefore of importance. Herein, a transition-metal-free radical 1,2-difunctionalization of unactivated alkenes via FSO2 -radical addition with subsequent vicinal alkynylation to access β-alkynyl-fluorosulfonylalkanes is presented. Alkynyl sulfonyl fluorides are introduced as highly valuable bifunctional radical trapping reagents that also serve as FSO2 -radical precursors. The β-alkynyl-fluorosulfonylalkanes obtained in these transformations can be readily diversified by using SuFEx click chemistry to obtain sulfonates and sulfonamides.

16 citations


Journal ArticleDOI
TL;DR: In this paper , the enantioselective II /IIII catalysis was used to intercept the transient iodonium intermediate using simple nitriles, which function as both the solvent and nucleophile.
Abstract: The regio- and enantio-selective, intermolecular vicinal fluoroamination of α-trifluoromethyl styrenes has been achieved by enantioselective II /IIII catalysis. Leveraging C2 -symmetric resorcinol-based aryl iodide catalysts, it has been possible to intercept the transient iodonium intermediate using simple nitriles, which function as both the solvent and nucleophile. In situ Ritter reaction provides direct access to the corresponding amides (up to 89 % yield, e.r. 93 : 7). This main group catalysis paradigm inverts the intrinsic regioselectivity of the uncatalyzed process, thereby providing facile access to tertiary, benzylic stereocenters bearing both CF3 and F groups. Privileged phenethylamine pharmacophores can be generated in which there is complete local partial charge inversion (CF3δ- /Fδ- versus CH3δ+ /Hδ+ ). Crystallographic analyses of representative β-fluoroamide products reveal highly pre-organized conformations that manifest the stereoelectronic gauche effect.

15 citations


Journal ArticleDOI
TL;DR: In this article, the relationship between self-efficacy for motivational regulation and three dimensions of satisfaction with academic studies with respect to the potential underlying mechanisms in terms of the expectancy, value, and cost components of motivation, controlling for relevant covariates.

14 citations


Journal ArticleDOI
TL;DR: In this paper , the authors highlight the recent development of highly reductive photocatalytic systems for the reduction of challenging substrates (substrates with very negative reduction potentials) with super electron donors for C-C and C-X (X = H, B, P, S, Sn) bond formations via single or multiphoton excitation is highlighted.
Abstract: The recent development of highly reductive photocatalytic systems for the reduction of challenging substrates (substrates with very negative reduction potentials) with super electron donors for C–C and C–X (X = H, B, P, S, Sn) bond formations via single- or multiphoton excitation is highlighted. Several elegant strategies, including consecutive photo-induced electron transfer (conPET), electrochemically mediated photoredox catalysis (e-PRC), or tandem photoredox strategy, play a significant role in highly reductive photocatalytic systems. These highly reductive photocatalytic systems provide a new strategy for the reduction of inert substrates under mild conditions with adjustable photosensitizers, showing an advantage to the direct UVC photolysis, electrolysis, and classical transition-metal catalysis via two-electron activation. Reductive organic transformations, which are important in both academia and industry to generate valuable chemicals, have been widely investigated. However, the reductive transformations of inert substrates still face many challenges, such as high cost and potential safety issues arising from strong reductants in excess, UVC light irradiation, or strong current density for electrolysis. In this context, visible-light photocatalysis has emerged as an ideal approach to provide highly reductive systems for the activation of inert substrates via single-electron reduction under mild conditions. In this review, we highlight some recent contributions to this field, classify them as single- or multiphoton excitation systems, elucidate the mechanisms with different super electron donors, and analyze their structural features on reducibility. Furthermore, the limitations and potential applications of this field will be discussed. Reductive organic transformations, which are important in both academia and industry to generate valuable chemicals, have been widely investigated. However, the reductive transformations of inert substrates still face many challenges, such as high cost and potential safety issues arising from strong reductants in excess, UVC light irradiation, or strong current density for electrolysis. In this context, visible-light photocatalysis has emerged as an ideal approach to provide highly reductive systems for the activation of inert substrates via single-electron reduction under mild conditions. In this review, we highlight some recent contributions to this field, classify them as single- or multiphoton excitation systems, elucidate the mechanisms with different super electron donors, and analyze their structural features on reducibility. Furthermore, the limitations and potential applications of this field will be discussed. proton-transfer reactions play critical roles in biology and chemistry, in which a proton is transferred from one atom to another atom. substrates with very negative reduction potentials, Ered < –2.0 V. reductants that are needed and consumed in stoichiometric amounts for the reduction of catalyst in the reaction. a reductive reaction of a substrate that proceeds by transferring one electron. highly aggressive species that can force chemical transformations of otherwise unreactive molecules. an activation mode for a substrate being reduced or oxidized while gaining or losing two electrons.

Journal ArticleDOI
12 Feb 2022-Cells
TL;DR: In this article , the authors explored quantitative phase imaging with digital holographic microscopy (DHM) as a time-resolved in vitro assay to quantify effects caused by three different types of organic nanoparticles in development for medical use.
Abstract: Cytotoxicity quantification of nanoparticles is commonly performed by biochemical assays to evaluate their biocompatibility and safety. We explored quantitative phase imaging (QPI) with digital holographic microscopy (DHM) as a time-resolved in vitro assay to quantify effects caused by three different types of organic nanoparticles in development for medical use. Label-free proliferation quantification of native cell populations facilitates cytotoxicity testing in biomedical nanotechnology. Therefore, DHM quantitative phase images from measurements on nanomaterial and control agent incubated cells were acquired over 24 h, from which the temporal course of the cellular dry mass was calculated within the observed field of view. The impact of LipImage™ 815 lipidots® nanoparticles, as well as empty and cabazitaxel-loaded poly(alkyl cyanoacrylate) nanoparticles on the dry mass development of four different cell lines (RAW 264.7, NIH-3T3, NRK-52E, and RLE-6TN), was observed vs. digitonin as cytotoxicity control and cells in culture medium. The acquired QPI data were compared to a colorimetric cell viability assay (WST-8) to explore the use of the DHM assay with standard biochemical analysis methods downstream. Our results show that QPI with DHM is highly suitable to identify harmful or low-toxic nanomaterials. The presented DHM assay can be implemented with commercial microscopes. The capability for imaging of native cells and the compatibility with common 96-well plates allows high-throughput systems and future embedding into existing experimental routines for in vitro cytotoxicity assessment.

Journal ArticleDOI
TL;DR: In this article , a photoredox catalyzed 1,3-oxyalkynylation of aryl cyclopropanes with ethylnylbenziodoxolones (EBXs) in an atom-economic fashion is described.

Journal ArticleDOI
01 Jan 2022-Icarus
TL;DR: Woo et al. as mentioned in this paper used high-resolution N-body simulations of terrestrial planet formation to study the assembly of Earth in unprecedented detail, focusing on its collisional history, and found that more than 90% of giant impacts (GIs) on Earth occur within 80 Myr in the EJS simulations, matching the possible early timing of the Moon-forming GI based on the ages recorded by various meteoritic samples.

Journal ArticleDOI
TL;DR: In this paper , the authors evaluated the effect of the clinically widely used antifungal itraconazole and the antidepressant fluoxetine for a repurposing against EBOV infection.
Abstract: Ebola virus disease (EVD) is a severe and frequently lethal disease caused by Ebola virus (EBOV). The latest occasional EVD outbreak (2013-2016) in Western African, which was accompanied by a high fatality rate, showed the great potential of epidemic and pandemic spread. Antiviral therapies against EBOV are very limited, strain-dependent (only antibody therapies are available) and mostly restricted to symptomatic treatment, illustrating the urgent need for novel antiviral strategies. Thus, we evaluated the effect of the clinically widely used antifungal itraconazole and the antidepressant fluoxetine for a repurposing against EBOV infection. While itraconazole, similar to U18666A, directly binds to and inhibits the endosomal membrane protein Niemann-Pick C1 (NPC1), fluoxetine, which belongs to the structurally unrelated group of weakly basic, amphiphile so-called "functional inhibitors of acid sphingomyelinase" (FIASMA) indirectly acts on the lysosome-residing acid sphingomyelinase via enzyme detachment leading to subsequent lysosomal degradation. Both, the drug-induced endolysosomal cholesterol accumulation and the altered endolysosomal pH, might interfere with the fusion of viral and endolysosomal membrane, preventing infection with EBOV. We further provide evidence that cholesterol imbalance is a conserved cross-species mechanism to hamper EBOV infection. Thus, exploring the endolysosomal host-pathogen interface as a suitable antiviral treatment may offer a general strategy to combat EBOV infection.

Journal ArticleDOI
TL;DR: In this article , electrical resistivity models of the structure beneath the Tariat and Chuluut volcanic zones with the goal of imaging the volcanic system from surface to mantle source are presented.

Journal ArticleDOI
TL;DR: In this paper, the authors used magnetotelluric data collected from the Tariat and Chuluut volcanic zones in central Mongolia to generate and analyze electrical resistivity models of the structure of the volcanic system.

Journal ArticleDOI
TL;DR: In this article, the authors used high-precision iron isotopic data of 23 iron meteorites from nine major chemical groups to identify the origin and nature of the material that built the terrestrial planets.

Journal ArticleDOI
TL;DR: In this article, the effects of actual and perceived physical fitness have been investigated from a variable-centered approach, however, the accuracy of the perceived physically fitness remains unconsidered, especially in children due to greater egocentricity and hence less comparison processes.

Journal ArticleDOI
TL;DR: The authors employed deep learning and several other techniques to extract credit-relevant information from user-generated text on Lending Club and showed that even short pieces of usergenerated text can improve credit default predictions significantly.


Journal ArticleDOI
TL;DR: In this article, an anti-cooperative supramolecular polymerization by attenuated growth exhibited by self-assembling units of two electron-donor benzo[1,2-b:4,5-b′]dithiophene derivatives and the electron-acceptor 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) (compound 2) is reported.
Abstract: Anti-cooperative supramolecular polymerization by attenuated growth exhibited by self-assembling units of two electron-donor benzo[1,2-b:4,5-b′]dithiophene (BDT) derivatives (compounds 1a and 1b) and the electron-acceptor 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) (compound 2) is reported. Despite the apparent cooperative mechanism of 1 and 2, AFM imaging and SAXS measurements reveal the formation of small aggregates that suggest the operation of an anti-cooperative mechanism strongly conditioned by an attenuated growth. In this mechanism, the formation of the nuclei is favoured over the subsequent addition of monomeric units to the aggregate, which finally results in short aggregates. Theoretical calculations show that both the BDT and BODIPY motifs, after forming the initial dimeric nuclei, experience a strong distortion of the central aromatic backbone upon growth, which makes the addition of successive monomeric units unfavourable and impedes the formation of long fibrillar structures. Despite the anti-cooperativity observed in the supramolecular polymerization of 1 and 2, the combination of both self-assembling units results in the formation of small co-assembled aggregates with a similar supramolecular polymerization behaviour to that observed for the separate components.

Journal ArticleDOI
TL;DR: In this paper , the authors show that only ls-tim flies can synchronise their behaviour to semi-natural conditions typical for Northern European summers, suggesting that this functional gain is driving the Northward ls-Tim spread.
Abstract: Daily temporal organisation offers a fitness advantage and is determined by an interplay between environmental rhythms and circadian clocks. While light:dark cycles robustly synchronise circadian clocks, it is not clear how animals experiencing only weak environmental cues deal with this problem. Like humans, Drosophila originate in sub-Saharan Africa and spread North up to the polar circle, experiencing long summer days or even constant light (LL). LL disrupts clock function, due to constant activation of CRYPTOCHROME, which induces degradation of the clock protein TIMELESS (TIM), but temperature cycles are able to overcome these deleterious effects of LL. We show here that for this to occur a recently evolved natural timeless allele (ls-tim) is required, encoding the less light-sensitive L-TIM in addition to S-TIM, the only form encoded by the ancient s-tim allele. We show that only ls-tim flies can synchronise their behaviour to semi-natural conditions typical for Northern European summers, suggesting that this functional gain is driving the Northward ls-tim spread.

Journal ArticleDOI
TL;DR: In this article , the authors used computational methods and in situ NMR spectroscopy to study the hydrogenation of 2-methylbenzofuran promoted by the chiral ruthenium(ii)bis-SINpEt complex.
Abstract: The chiral ruthenium(ii)bis-SINpEt complex is a versatile and powerful catalyst for the hydrogenation of a broad range of heteroarenes. This study aims to provide understanding of the active form of this privileged catalyst as well as the reaction mechanism, and to identify the factors which control enantioselectivity. To this end we used computational methods and in situ NMR spectroscopy to study the hydrogenation of 2-methylbenzofuran promoted by this system. The high flexibility and conformational freedom of the carbene ligands in this complex lead to the formation of a chiral pocket interacting with the substrate in a "lock-and-key" fashion. The non-covalent stabilization of the substrate in this particular pocket is an exclusive feature of the major enantiomeric pathway and is preserved throughout the mechanism. Substrate coordination leading to the minor enantiomer inside this pocket is inhibited by steric repulsion. Rather, the catalyst exhibits a "flat" interaction surface with the substrate in the minor enantiomer pathway. We probe this concept by computing transition states of the rate determining step of this reaction for a series of different substrates. Our findings open up a new approach for the rational design of chiral catalysts.

Journal ArticleDOI
TL;DR: In this paper , the degradation mechanisms of negative electrodes based on nanoparticles like silicon are analyzed using both in situ and ex-in situ scanning electron microscopy and energy-dispersive X-ray spectroscopy.
Abstract: Understanding the degradation mechanisms of negative electrodes based on nanoparticles like silicon is key for developing solutions against active material cracking, pulverization, or extensive growth of the solid electrolyte interphase (SEI). Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) are common ex situ methods for post mortem analysis of lithium (ion) battery materials. Beyond that, in situ/operando methods provide more accurate insights but require specially designed cells and electrolytes with a high evaporation temperature. This study combines aspects of in situ and ex situ SEM/EDX measurements to enable detailed insights on the degradation mechanisms of silicon nanoparticle-based electrodes during charge/discharge cycling. Therein, a protective quasi in situ environment was ensured by handling electrodes of repeatedly disassembled cells under an inert atmosphere and performing a same-spot analysis by SEM and EDX in the pristine state and after formation and subsequent cycles. This so-called quasi in situ analysis allowed accurate tracking of the degradation mechanisms such as irreversible expansion, cracking, and pulverization of active material particles and evolution of the SEI. Thus, extensive irreversible volume expansion of silicon nanoparticles was detected during charge/discharge cycling at low C rates, while higher C rates facilitated pulverization. Furthermore, EDX analysis revealed pronounced SEI growth at conductive additive-rich areas.

Journal ArticleDOI
01 Jan 2022
TL;DR: In this paper, skin-derived ABCB5+ mesenchymal stem cells were used to dampen the sustained IL-1β-driven inflammation present in chronic wounds.
Abstract: A significant number of chronic venous ulcers (CVUs) fail to heal despite guideline-conform standards of care. Skin-derived ABCB5+ mesenchymal stem cells can dampen the sustained IL-1β‒driven inflammation present in chronic wounds. On the basis of their wound healing‒facilitating effects in a mouse CVU model and an autologous first-in-human study, ABCB5+ mesenchymal stem cells have emerged as a potential candidate for cell-based advanced therapy of nonhealing CVUs. In this interventional, multicenter, single-arm, phase I/IIa clinical trial, subjects whose CVUs had emerged as standard therapy resistant received one or two topical applications of 1 × 106 allogeneic ABCB5+ mesenchymal stem cells per cm2 wound area, in addition to standard treatment. Of 83 treatment-emergent adverse events, only three were judged related to the cell product; they were mild or moderate and recovered without sequelae. Wound size markedly decreased from baseline to week 12, resulting in a median wound size reduction of 76% (full analysis set, n = 31), 78% (per-protocol set, n = 27), and 87% (subset of responders, n = 21). In conclusion, the study treatment was well-tolerated and safe. The treatment elicited a profound wound size reduction within 12 weeks, identifying ABCB5+ mesenchymal stem cells as a potential candidate for adjunctive therapy of otherwise incurable CVUs. These results justify the conduct of a larger, randomized, controlled trial to confirm clinical efficacy.

Journal ArticleDOI
TL;DR: The authors showed that inactivation of Disp in Shh-expressing human cells impairs proteolytic Shh release from its lipidated terminal peptides, a process called ectodomain shedding.
Abstract: The Sonic hedgehog (Shh) pathway controls embryonic development and tissue homeostasis after birth. Long-standing questions about this pathway include how the dual-lipidated, firmly plasma membrane-associated Shh ligand is released from producing cells to signal to distant target cells and how the resistance-nodulation-division transporter Dispatched 1 (Disp, also known as Disp1) regulates this process. Here, we show that inactivation of Disp in Shh-expressing human cells impairs proteolytic Shh release from its lipidated terminal peptides, a process called ectodomain shedding. We also show that cholesterol export from Disp-deficient cells is reduced, that these cells contain increased cholesterol amounts in the plasma membrane, and that Shh shedding from Disp-deficient cells is restored by pharmacological membrane cholesterol extraction and by overexpression of transgenic Disp or the structurally related protein Patched 1 (Ptc, also known as Ptch1; a putative cholesterol transporter). These data suggest that Disp can regulate Shh function via controlled cell surface shedding and that membrane cholesterol-related molecular mechanisms shared by Disp and Ptc exercise such sheddase control.

Journal ArticleDOI
TL;DR: In this paper, the vibrational sum-frequency generation (SFG) was applied to study β-escin adsorption layers at the air-water interface as a function of electrolyte pH and compare the results from SFG spectroscopy to complementary experiments that have addressed the surface tension and surface dilational rheology.

Journal ArticleDOI
TL;DR: In this article , the contribution of epigenetic mechanisms to the evolution of resistance to pathogen selection has been investigated, highlighting DNA methylation, histone acetylation, and microRNAs in mediating the transgenerational inherited transcriptional reprogramming of defense-related gene expression.
Abstract: Insects resist infection by natural selection that favors the survival and reproduction of the fittest phenotypes. Although the genetic mechanisms mediating the evolution of insect resistance have been investigated, little is known about the contribution of epigenetic mechanisms. Gene expression in response to a pathogen selection pressure is regulated by different mechanisms affecting chromatin plasticity. Whether transgenerational inheritance of genome-wide epigenetic marks contributes to the heritable manifestation of insect resistance is presently debated. Here, we review the latest works on the contributions of chromatin remodeling to insect immunity and adaptation to pathogens. We highlight DNA methylation, histone acetylation, and microRNAs in mediating the transgenerational inherited transcriptional reprogramming of defense-related gene expression and the evolution of insect resistance.