Light-mediated methodologies for the reduction of acylazolium species generated during N-heterocyclic carbene (NHC)-catalyzed reactions have been developed. Employing the simple amine, DIPEA, as the terminal reductant, products resulting from overall 2-electron or 4-electron-reduction processes could be obtained using either a photocatalytic approach under blue light irradiation or directly under UV-A light irradiation without an additional photocatalyst. Moreover, under the same photocatalyst-free conditions, UV-A-light-mediated reduction could be achieved using triethylsilane as the only reductant with subsequent desilylation and NHC elimination with fluoride delivering the corresponding aldehyde product.
Weniger anzeigenThis meta-analysis aimed to evaluate the efficacy of automated activity monitoring (AAM) in detecting estrous expression and ovulatory status in cows during the voluntary waiting period (VWP). A comprehensive literature search was conducted in PubMed, ScienceDirect, and Google Scholar using specific search terms. Inclusion criteria focused on studies that assessed estrous expression within the VWP using modern AAM systems alongside blood progesterone (P4) measurements. Four manuscripts involving 2,198 cows were included. Data extraction was performed by a single investigator and validated by a coauthor. The analysis considered estrous expression and ovulatory status determined through serial blood P4 measurements. Cows were classified based on P4 concentrations and estrus alerts into true positive, false positive, true negative, and false negative categories. Statistical analyses were conducted using MedCalc, incorporating 7 experimental groups from the selected manuscripts. The pooled proportion of ovulatory cows with P4 ≥1 ng/mL by 49 DIM (in most studies) was 79.8% (95% CI: 74.9%–84.3%), with significant heterogeneity (I2 = 86.1%). The proportion of cows with estrous expression detected by AAM by 60 DIM (in most studies) was 64.0% (95% CI: 48.3%–78.3%), also showing significant heterogeneity (I2 = 98.1%). Sensitivity and specificity of AAM systems to identify ovulatory cows were 70.3% (95% CI: 55.1%–83.4%) and 60.0% (95% CI: 42.5%–76.3%), respectively, both with significant heterogeneity. Positive predictive value was 88.1% (95% CI: 84.9%–91.0%), and negative predictive value was 35.3% (95% CI: 26.3%–44.7%), indicating variability among experimental groups. The findings suggest that although AAM systems show promise in confirming ovulation in early lactation, the lack of estrus detection by AAM does not confirm anovulatory status. The heterogeneity in the data suggests there might be inconsistencies in the precision or configuration of the AAM systems across farms and studies.
Weniger anzeigenResearch on temporary organizations such as projects acknowledges the interplay between the temporary and the permanent. However, we still lack deeper understanding of the processes responsible for (re)producing and transforming permanent structures for temporary organizing. We present an ethnography of collaborative emergency response operations in a major German city – a setting providing an example of temporary organizing including more permanent structures drawn from intra- and interorganizational processes. Revealing the recursive interplay between the permanent and temporary across multiple levels, we explore practices of temporary organizing in situations that require both routine and highly situated responses. We also show how more permanent structures are co-fabricated in the process of temporary organizing. Furthermore, our study addresses the intricate interplay between organizing for the temporary and the permanent in relation to the tensions associated with the duality of stability and change. Finally, we outline implications for the effectiveness of emergency management and planning.
Weniger anzeigenBackground: Upon arriving in host countries, forcibly displaced people face psychological, cultural, as well as sociostructural challenges. Access to mental health and psychosocial support (MHPSS) remains limited, affecting both refugees and host country structures. Digital services offer promise in addressing these challenges, given their potential for scalability and accessibility. Despite the increasing use of digital MHPSS, cultural and contextual adaptation remains insufficiently documented, requiring systematic documentation.
Objective: This study aims (1) to assess the psychosocial needs of newly arrived refugees in Switzerland and identify potential digital support solutions and (2) to participatorily develop and culturally adapt the Sui app to address those needs for Arabic-speaking refugees.
Methods: We used a 2-phase adaptation process, structured using the RECAPT (Reporting Cultural Adaptation in Psychological Trials) framework to ensure systematic documentation. The preparation phase (2019-2021) included a desk review, needs assessment interviews, and conceptualization discussions. The development phase (2021-2022) included iterative development loops with a user advisory board (UAB) and a beta test, followed by final adjustments.
Results: The desk review provided 5 key insights guiding development: mental health stigma, health literacy, sociostructural aspects, adherence to digital interventions, and task-shifting approaches. Findings from the needs assessment with 22 asylum care interviewees, 2 intercultural interpreters, and 4 target group interviewees confirmed the importance of integrating sociostructural and psychological factors. Through conceptualization discussions with a consultancy agency and 4 UAB (n=9) meetings, the scope of the Sui app was drafted: 9 relevant, everyday life topics (eg, asylum process, housing, and work), 5 psychological topics (eg, stress, sleep, and emotion regulation), and 1 peer-guided chat support feature. A multilevel translation process, involving 5 Arabic speakers from different countries, ensured linguistic accessibility. This allowed the UAB to focus on surface, content, and delivery during 19 development loops. The app’s content was delivered in various formats, including text, illustrations, video testimonies, and audio exercises. The beta test revealed high acceptability, with most users engaging with the app several times a week. However, technical challenges such as slow loading times hindered the full exploration of the features. Participants valued the peer support function, highlighting the importance of faster response times and personalized messages. Based on the beta test, technical and content refinements were made to prepare the app for a future quantitative evaluation.
Conclusions: Through engagement with stakeholders and adherence to the RECAPT framework, we carefully considered the cultural and contextual circumstances of Arabic-speaking refugees newly arrived in Switzerland. The iterative participatory development process, spanning a preparation and development phase, ensured usability, accessibility, and relevance, while highlighting challenges in technical implementation and peer support. This study contributes to the existing knowledge of mental health and the needs of refugees and provides insights for future cultural adaptation of MHPSS interventions.
Weniger anzeigenWe initiate a study of local operator algebras at the boundary of infinite tensor networks, using the mathematical theory of inductive limits. In particular, we consider tensor networks in which each layer acts as a quantum code with complementary recovery, a property that features prominently in the bulk-to-boundary maps intrinsic to holographic quantum error-correcting codes. In this case, we decompose the limiting Hilbert space and the algebras of observables in a way that keeps track of the entanglement in the network. As a specific example, we describe this inductive limit for the holographic Harlow-Pastawski-Preskill-Yoshida code model and relate its algebraic and error-correction features. We find that the local algebras in this model are given by the hyperfinite type II infinity factor. Next, we discuss other networks that build upon this framework and comment on a connection between type II factors and stabilizer circuits. We conclude with a discussion of multiscale entanglement renormalization ansatz networks in which complementary recovery is broken. We argue that this breaking possibly permits a limiting type III von Neumann algebra, making them more suitable ans & auml;tze for approximating subregions of quantum field theories.
Weniger anzeigenWe unambiguously document unrest at Taftan volcano. Summit uplift was detected using Interferometric Synthetic Aperture Radar time series and its timing tightly constrained applying a new common mode filtering method. Uplift started and ended gradually lasting 10 months (July 2023 to May 2024). Uplift peaked at 11 cm/year rates, and during slowing-down several gas emission events occurred. Unrest was triggerless, uncorrelated with rainfall or seismic events. We favor internal driving processes with two possible scenarios: (a) dynamic hydrothermal alteration leading to permeability changes, shallow gas storage and pressurization, followed by opening of degassing pathways; or (b) a minor, undetected deep magmatic intrusion causing volatile exsolution and pore pressure increases within the hydrothermal system. Lack of post-unrest subsidence suggests persistence of hydrothermal high-pressure conditions at the summit and associated hazards. Our study shows how satellite imagery reveals hidden volcanic hazards at Taftan, and the need to implement a holistic volcano risk reduction strategy.
Weniger anzeigenStock market participation among working household heads jumped upwards in 2020 - in Germany by about 25 %. A major cause is the required use of work from home (WfH). We show this by adding WfH to a large set of explanatory variables. Moreover, we implement an instrumental variables estimation based on industry-specific levels of WfH-capacity. The transmission channels seem to work via increased available time and time flexibility. Moreover, we show that WfH makes the stock market accessible to a broader population, including lower income groups, which may contribute to lower income and wealth inequality in the future.
Weniger anzeigenGlycoproteins cover the surface of enveloped viruses such as herpes simplex virus 1 (HSV-1). Whilst essential for cellular attachment and entry, they also are excellent targets for host immune responses. This dichotomy culminates in an evolutionary struggle in which receptor recognition and immune escape are intricately balanced. Herpesviruses feature a variety of different glycoproteins with diverse molecular functions. Here, we describe the rapid evolution of HSV-1 towards syncytial plaque phenotypes in Vero cell culture, as well as anti-gD antibody resistance in human foreskin fibroblast cells. Using a mild hypermutator virus to accelerate experimental evolution, we identified multiple genetic variants leading to syncytial plaques. Strikingly, these variants differentially affect interactions within viral populations. Whilst gK mutants engage in collective syncytia formation upon entry, accelerate superinfection exclusion and maintain fitness advantages at high multiplicities of infection, gB and gD mutants do not. Furthermore, we find gE mutants which lead to mouse anti-gD antibody resistance and cross protect wt virus in mixed populations. Our findings suggest complex social interactions within herpesvirus populations and illustrate the evolutionary plasticity and diverse function of their glycoproteins.
Weniger anzeigenIn this functional magnetic resonance imaging study, we investigated whether language production and understanding recruit similar phoneme-specific networks. We did so by comparing the brain’s response to different phoneme categories in minimal pairs: Bilabial-initial words (eg “monkey”) were contrasted to alveolar-initial words (eg “donkey”) in 37 participants performing both language production and comprehension tasks. Individual-specific region-of-interest analyses showed that the same sensorimotor networks were activated across the language modalities. In motor regions, word production and comprehension elicited the same phoneme-specific topographical activity patterns, with stronger haemodynamic activations for alveolar-initial words in the tongue cortex and stronger activations for bilabial-initial words in the lip cortex. In the posterior and middle superior temporal cortex, production and comprehension likewise resulted in similar activity patterns, with enhanced activations to alveolar- compared to bilabial-initial words. These results disagree with the classical asymmetry between language production and understanding in neurobiological models of language, and instead advocate for a cortical organization where phonology is carried by similar topographical activations in motor cortex and distributed activations in temporal cortex across the language modalities.
Weniger anzeigenThis study investigates the expression of predicative possession in Argentinian Spanish, focusing on the alternation between two constructions: tener (‘have’) + NP and estar con (‘be with’) + NP. Building on previous research, we explore the factors that determine speakers’ choices between these constructions, particularly the influence of temporal context and the presence of adverbs. Using a forced-choice experimental design, participants were presented with vignettes varying in temporal duration (durative vs. non-durative) and adverbial modification (extending, limiting, or none). Results show a strong overall preference for the tener + NP construction, particularly in durative contexts. However, the estar con + NP construction is more likely to be selected in non-durative contexts, especially when a limiting adverb is present. These findings suggest that the distinction between the two constructions is not purely semantic but also pragmatically modulated by temporal and contextual factors. We argue that this pattern reflects a subset-superset relationship between the two constructions, where tener + NP can cover a broader temporal scope than estar con + NP. This overlap mirrors cross-linguistic findings on possessive constructions and aspectual distinctions, with implications for understanding grammaticalization processes in Romance languages.
Weniger anzeigenThe Hadamard test is one of the pillars on which quantum algorithm development rests and, at the same time, is naturally suited for the intermediate regime between the current era of noisy quantum devices and complete fault tolerance. Its applications use measurements of the auxiliary qubit to extract information but disregard the system register completely. Concomitantly, but independently of this development, advances in quantum learning theory have enabled the efficient representation of quantum states via classical shadows. This Letter shows that, strikingly, putting both lines of thought into a new context results in substantial improvements to the Hadamard test on a single auxiliary readout qubit, by suitably exploiting classical shadows on the remaining 𝑛 -qubit work register. We argue that this combination inherits the best of both worlds and discuss statistical phase estimation as a vignette application. At the same time, the framework is more general and applicable to a wide range of other algorithms. There, we can use the Hadamard test to estimate energies on the auxiliary qubit, while classical shadows on the system register provide access to additional features such as (i) the fidelity of the initial state with certain pure quantum states, (ii) the initial state’s energy, and (iii) how pure and how close the initial state is to an eigenstate of the Hamiltonian. Finally, we also discuss how anticontrolled unitaries can further augment this framework and explain how this Letter settles the exploitation of the Hadamard test for intermediate applications.
Weniger anzeigenNew designs for molecular switches are essential for driving the development of nanoelectronics. The effect of quantum interference in cross-conjugated structures such as anthracene have already been thoroughly explored. A similar structural motif can be found in diboracenes, whose unsubstituted variants could only be synthesized recently. In this contribution, we explore the potential of these structures to produce similar quantum interference effects varying with substitution and how these could be used to produce a spin-filtering device. We investigate the eletronic properties of diboracenes through density functional theory and the global and local transport properties at the quasi-stationary limit using nonequilibrium Green’s function methods. Our findings show how the current may be tuned through the substituent and that larger unsubstituted diboracenes favor a triplet ground state with a destructive quantum interference effect for one of the spin channels.
Weniger anzeigenThe coefficients of elastic and dissipative operators in a linear hyperbolic SPDE are jointly estimated using multiple spatially localised measurements. As the resolution level of the observations tends to zero, we establish the asymptotic normality of an augmented maximum likelihood estimator. The rate of convergence for the dissipative coefficients matches rates in related parabolic problems, whereas the rate for the elastic parameters also depends on the magnitude of the damping. The analysis of the observed Fisher information matrix relies upon the asymptotic behaviour of rescaled M, N-functions generalising the operator cosine and sine families appearing in the undamped wave equation. In contrast to the energetically stable undamped wave equation, the M, N-functions emerging within the covariance structure of the local measurements have additional smoothing properties similar to the heat kernel, and their asymptotic behaviour is analysed using functional calculus.
Weniger anzeigenObjective
Chronic stress is a risk factor for developing stress-induced mental disorders like major depression and post-traumatic stress disorder. Low-grade inflammatory processes seem to mediate this association. The sphingolipid metabolism with its most important lipid messengers ceramide and sphingosine-1-phosphate (S1P) was shown to play an important role in the pathophysiology of affective disorders and inflammation.
Method
We conducted an exploratory trial to investigate the effect of intensive psychosomatic - psychotherapeutic treatment of stress-induced disorders on the biological level. Before and after eight weeks of treatment, blood plasma of 67 patients was analyzed for sphingolipid levels and their metabolizing enzymes. Symptom severity of depression (PHQ-9), anxiety (GAD-7), and somatization (PHQ-15) was assessed in parallel.
Results
During psychosomatic - psychotherapeutic treatment, symptom severity of depression, anxiety, and somatization decreased significantly. Levels of the stress molecule cortisol decreased upon treatment. Enzymatic activities of secreted acid sphingomyelinase (S-ASM) and neutral sphingomyelinase (NSM) increased significantly upon treatment, as well as of neutral ceramidase (NC). Regarding the lipid level, the molar ratio of ceramide species Cer16:0 and Cer18:0 decreased upon treatment, whereas sphingosine and S1P levels increased.
Conclusions
Psychosomatic – psychotherapeutic treatment was associated with a reduction in specific ceramide ratios and an increase in sphingosine and S1P levels potentially resulting from increased activity of sphingolipid metabolizing enzymes. Stress-induced mental disorders might be associated with disturbed sphingolipid levels that seem to be balanced during psychosomatic treatment. This study offers a further piece of evidence that the sphingolipid metabolism could be involved in the pathophysiology of stress-induced disorders, and its analysis could be helpful for treatment monitoring.
Weniger anzeigenA series of bidentate quinoline/quinoxaline-NHC ligands were coordinated to an iron(II) metal centre with the aim of taking advantage of the combined effect of NHC σ-donor and quinoline/quinoxaline π-acceptors on the excited-state stabilization of the resulting Fe(II) complexes. Excitation of these complexes at 530 nm promoted excited state formation with lifetimes of up to 74 ps. A detailed study combining spectroelectrochemistry, UV/VIS transient absorption spectroscopy as well as steady-state and time-resolved luminescence concludes that these long-lived triplet states display spectroscopic properties compatible with both MC and MLCT character, with a degree of mixing that depends on the precise ligand structure.
Weniger anzeigenData show that the presence of women in quantum science is affected by a number of detriments and their percentage decreases even further for higher positions. Beyond data, from our shared personal experiences as female tenured quantum physics professors, we believe that the current model of scientific leadership, funding, and authority fails to represent many of us. Women for quantum calls for a joint effort and aims with this initiative to contribute to such a transformation. It is time for a real change that calls for a different kind of force and for the participation of everyone.
Weniger anzeigenBiodiversity knowledge, from genes to ecosystems, is crucial for addressing the biodiversity crisis. However, even in well-explored countries like Germany, much biodiversity remains unknown. Therefore, several research institutions are joining forces to conduct a comprehensive biodiversity inventory, combining broad taxonomic expertise with advanced technologies. By consolidating data across many organismic groups, the Unknown Germany initiative will significantly enhance conservation strategies and may serve as a model for similar efforts worldwide.
Weniger anzeigenAdverse alcohol consumption is a major public health concern, which might have been further increased by the COVID-19 pandemic. In this study we investigated the impact of a lockdown stage on the association between alcohol consumption, loneliness, and COVID-19-related worries. We used smartphone-based Ecological Momentary Assessment (EMA) conducted during the COVID-19 pandemic in Germany. We recruited 280 participants from the general population, who experienced at least mild loneliness and distress due to the COVID-19 pandemic. We assessed daily alcohol intake, loneliness, and COVID-19-related worries every evening for 7 consecutive days across a no-lockdown [8th August 2020–1st November 2020] and lockdown stage [2nd November 2020–11th March 2021]. We did not find that a lockdown stage, compared to a no-lockdown stage, is associated with increased alcohol consumption. We found that loneliness, previous day drinking, and COVID-19-related worries were not associated with increased, but with decreased alcohol consumption. Moreover, COVID-19-related worries were more negatively associated with alcohol consumption during a no-lockdown stage compared to a lockdown stage. We found that the effect of COVID-19 related worries on alcohol consumption is mediated by loneliness. Our study suggests that heightened levels of worry can decrease alcohol intake. This association can be explained by loneliness: individuals who worry more are lonelier and thus less likely to engage in social drinking. However, during a lockdown stage, the negative association between worrying and drinking diminishes.
Weniger anzeigenThe KCNQ1 + KCNE1 potassium channel complex produces the slow delayed rectifier current (IKs) critical for cardiac repolarization. Loss-of-function mutations in KCNQ1 and KCNE1 cause long QT syndrome (LQTS) types 1 and 5 (LQT1/LQT5), accounting for over one-third of clinical LQTS cases. Despite prior structural work on KCNQ1 and KCNQ1 + KCNE3, the structural basis of KCNQ1 + KCNE1 remains unresolved. Using cryo-electron microscopy and electrophysiology, we determined high-resolution (2.5–3.4 Å) structures of human KCNQ1APO, and KCNQ1 + KCNE1 in both closed and open states. KCNE1 occupies a pivotal position at the interface of three KCNQ1 subunits, inducing six helix-to-loop transitions in KCNQ1 transmembrane segments. Three of them occur at both ends of the S4–S5 linker, maintaining a loop conformation during IKs gating, while the other three, in S6 and helix A, undergo dynamic helix-loop transitions during IKs gating. These structural rearrangements: (1) stabilize the closed pore and the conformation of the intermediate state voltage-sensing domain, thereby determining channel gating, ion permeation, and single-channel conductance; (2) enable a dual-PIP2 modulation mechanism, where one PIP2 occupies the canonical site, while the second PIP2 bridges the S4–S5 linker, KCNE1, and the adjacent S6’, stabilizing channel opening; (3) create a fenestration capable of binding compounds specific for KCNQ1 + KCNE1 (e.g., AC-1). Together, these findings reveal a previously unrecognized large-scale secondary structural transition during ion channel gating that fine-tunes IKs function and provides a foundation for developing targeted LQTS therapy.
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