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Symmetry and its breaking crucially define the chemical properties of molecules and their functionality. Resonant inelastic X-ray scattering is a local electronic structure probe reporting on molecular symmetry and its dynamical breaking within the femtosecond scattering duration. Here, we study pyrimidine, a system from the C-2v point group, in an aqueous solution environment, using scattering though its 2a(2) resonance. Despite the absence of clean parity selection rules for decay transitions from in-plane orbitals, scattering channels including decay from the 7b(2) and 11a(1) orbitals with nitrogen lone pair character are a direct probe for molecular symmetry. Computed spectra of explicitly solvated molecules sampled from a molecular dynamics simulation are combined with the results of a quantum dynamical description of the X-ray scattering process. We observe dominant signatures of core-excited Jahn-Teller induced symmetry breaking for resonant excitation. Solvent contributions are separable by shortening of the effective scattering duration through excitation energy detuning.
Analysis of social media using digital methods is a flourishing approach. However, the relatively easy availability of data collected via platform application programming interfaces has arguably led to the predominance of single-platform research of social media. Such research has also privileged the role of text in social media analysis, as a form of data that is more readily gathered and searchable than images. In this paper, we challenge both of these prevailing forms of social media research by outlining a methodology for visual cross-platform analysis (VCPA), defined as the study of still and moving images across two or more social media platforms. Our argument contains three steps. First, we argue that cross-platform analysis addresses a gap in research methods in that it acknowledges the interplay between a social phenomenon under investigation and the medium within which it is being researched, thus illuminating the different affordances and cultures of web platforms. Second, we build on the literature on multimodal communication and platform vernacular to provide a rationale for incorporating the visual into cross-platform analysis. Third, we reflect on an experimental cross-platform analysis of images within social media posts (n = 471,033) used to communicate climate change to advance different modes of macro- and meso-levels of analysis that are natively visual: image-text networks, image plots and composite images. We conclude by assessing the research pathways opened up by VCPA, delineating potential contributions to empirical research and theory and the potential impact on practitioners of social media communication.
While previous research underscores the role of leaders in stimulating employee voice behaviour, comparatively little is known about what affects leaders' support for such constructive but potentially threatening employee behaviours. We introduce leader member exchange quality (LMX) as a central predictor of leaders' support for employees' ideas for constructive change. Apart from a general benefit of high LMX for leaders' idea support, we propose that high LMX is particularly critical to leaders' idea support if the idea voiced by an employee constitutes a power threat to the leader. We investigate leaders' attribution of prosocial and egoistic employee intentions as mediators of these effects. Hypotheses were tested in a quasi-experimental vignette study (N = 160), in which leaders evaluated a simulated employee idea, and a field study (N = 133), in which leaders evaluated an idea that had been voiced to them at work. Results show an indirect effect of LMX on leaders' idea support via attributed prosocial intentions but not via attributed egoistic intentions, and a buffering effect of high LMX on the negative effect of power threat on leaders' idea support. Results differed across studies with regard to the main effect of LMX on idea support.
Although many studies have shown that victims of child abuse have an increased vulnerability to revictimization in intimate relationships, the underlying mechanisms are not yet sufficiently well understood. Therefore, this study aimed at examining this relationship for both sexual and physical forms of violence as well as investigating the potential mediating role of attitudes toward sexual and physical intimate partner violence (IPV). Also, the potential moderating role of gender was explored. Sexual and physical child abuse and IPV victimization in adulthood as well as attitudes toward the respective form of IPV were assessed among 716 participants (448 female) in an online survey. The path analyses showed that child sexual abuse was positively linked to sexual IPV victimization among both women and men, whereas child physical abuse was positively associated with physical IPV victimization among women only. Furthermore, the relationship between both forms of child abuse and IPV victimization was mediated through more supportive attitudes toward the respective forms of IPV, but only among men. This study provides novel insights regarding the links between sexual and physical child abuse and revictimization in adulthood, suggesting that supporting attitudes toward IPV may be seen as vulnerability factor for revictimization. The moderating role of gender is especially discussed.
As research on sexual aggression has been growing, methodological issues in assessing prevalence rates have received increased attention. Building on work by Abbey and colleagues about effects of question format, participants in this study (1,253; 621 female; 632 male) were randomly assigned to one of two versions of the Sexual Aggression and Victimization Scale (SAV-S). In Version 1, the coercive tactic (use/threat of physical force, exploitation of the inability to resist, verbal pressure) was presented first, and sexual acts (sexual touch, attempted and completed sexual intercourse, other sexual acts) were presented as subsequent questions. In Version 2, sexual acts were presented first, and coercive tactics as subsequent questions. No version effects emerged for overall perpetration rates reported by men and women. The overall victimization rate across all items was significantly higher in the tactic-first than in the sexual-act-first conditions for women, but not for men. Classifying participants by their most severe experience of sexual victimization showed that fewer women were in the nonvictim category and more men were in the nonconsensual sexual contact category when the coercive tactic was presented first. Sexual experience background did not moderate the findings. The implications for the measurement of self-reported sexual aggression victimization and perpetration are discussed.
A growing body of research has demonstrated negative effects of sexualization in the media on adolescents' body image, but longitudinal studies and research including interactive and social media are scarce. The current study explored the longitudinal associations of adolescents' use of sexualized video games (SVG) and sexualized Instagram images (SII) with body image concerns. Specifically, our study examined relations between adolescents' SVG and SII use and appearance comparisons, thin- and muscular-ideal internalization, valuing appearance over competence, and body surveillance. A sample of 660 German adolescents (327 female, 333 male;M-age = 15.09 years) participated in two waves with an interval of 6 months. A structural equation model showed that SVG and SII use at Time 1 predicted body surveillance indirectly via valuing appearance over competence at Time 2. Furthermore, SVG and SII use indirectly predicted both thin- and muscular-ideal internalization through appearance comparisons at Time 1. In turn, thin-ideal internalization at Time 1 predicted body surveillance indirectly via valuing appearance over competence at Time 2. The results indicate that sexualization in video games and on Instagram can play an important role in increasing body image concerns among adolescents. We discuss the findings with respect to objectification theory and the predictive value of including appearance comparisons in models explaining the relation between sexualized media and self-objectification.
Magnitude estimation has been studied since the beginnings of scientific psychology and constitutes a fundamental aspect of human behavior. Yet, it has apparently never been noticed that estimates depend on the spatial arrangement used. We tested 167 adults in three experiments to show that the spatial layout of stimuli and responses systematically distorts number estimation, length production, and weight reproduction performance. The direction of distortion depends on the observer's counting habits, but does not seem to reflect the use of spatially associated number concepts. Our results imply that all quantitative estimates are contaminated by a "spell of space" whenever stimuli or responses are spatially distributed.
Alcohol use disorder (AUD) is the most common substance use disorder worldwide. Although dopamine-related findings were often observed in AUD, associated neurobiological mechanisms are still poorly understood. Therefore, in the present study, we investigate D2/3 receptor availability in healthy participants, participants at high risk (HR) to develop addiction (not diagnosed with AUD), and AUD patients in a detoxified stage, applying F-18-fallypride positron emission tomography (F-18-PET). Specifically, D2/3 receptor availability was investigated in (1) 19 low-risk (LR) controls, (2) 19 HR participants, and (3) 20 AUD patients after alcohol detoxification. Quality and severity of addiction were assessed with clinical questionnaires and (neuro)psychological tests. PET data were corrected for age of participants and smoking status. In the dorsal striatum, we observed significant reductions of D2/3 receptor availability in AUD patients compared with LR participants. Further, receptor availability in HR participants was observed to be intermediate between LR and AUD groups (linearly decreasing). Still, in direct comparison, no group difference was observed between LR and HR groups or between HR and AUD groups. Further, the score of the Alcohol Dependence Scale (ADS) was inversely correlated with D2/3 receptor availability in the combined sample. Thus, in line with a dimensional approach, striatal D2/3 receptor availability showed a linear decrease from LR participants to HR participants to AUD patients, which was paralleled by clinical measures. Our study shows that a core neurobiological feature in AUD seems to be detectable in an early, subclinical state, allowing more individualized alcohol prevention programs in the future.
Heteromeric HSFA2/HSFA3 complexes drive transcriptional memory after heat stress in Arabidopsis
(2021)
Adaptive plasticity in stress responses is a key element of plant survival strategies. For instance, moderate heat stress (HS) primes a plant to acquire thermotolerance, which allows subsequent survival of more severe HS conditions. Acquired thermotolerance is actively maintained over several days (HS memory) and involves the sustained induction of memory-related genes. Here we show that FORGETTER3/ HEAT SHOCK TRANSCRIPTION FACTOR A3 (FGT3/HSFA3) is specifically required for physiological HS memory and maintaining high memory-gene expression during the days following a HS exposure. HSFA3 mediates HS memory by direct transcriptional activation of memory-related genes after return to normal growth temperatures. HSFA3 binds HSFA2, and in vivo both proteins form heteromeric complexes with additional HSFs. Our results indicate that only complexes containing both HSFA2 and HSFA3 efficiently promote transcriptional memory by positively influencing histone H3 lysine 4 (H3K4) hyper-methylation. In summary, our work defines the major HSF complex controlling transcriptional memory and elucidates the in vivo dynamics of HSF complexes during somatic stress memory. Moderate heat stress primes plants to acquire tolerance to subsequent, more severe heat stress. Here the authors show that the HSFA3 transcription factor forms a heteromeric complex with HSFA2 to sustain activated transcription of genes required for acquired thermotolerance by promoting H3K4 hyper-methylation.
The transversal hypergraph problem asks to enumerate the minimal hitting sets of a hypergraph. If the solutions have bounded size, Eiter and Gottlob [SICOMP'95] gave an algorithm running in output-polynomial time, but whose space requirement also scales with the output. We improve this to polynomial delay and space. Central to our approach is the extension problem, deciding for a set X of vertices whether it is contained in any minimal hitting set. We show that this is one of the first natural problems to be W[3]-complete. We give an algorithm for the extension problem running in time O(m(vertical bar X vertical bar+1) n) and prove a SETH-lower bound showing that this is close to optimal. We apply our enumeration method to the discovery problem of minimal unique column combinations from data profiling. Our empirical evaluation suggests that the algorithm outperforms its worst-case guarantees on hypergraphs stemming from real-world databases.
The Devonian Las Chacras-Potrerillos batholith comprises six nested monzonitic to granitic intrusions with metaluminous to weakly peraluminous composition and a Sr-Nd isotopic signature indicating a dominantly juvenile mantle-derived source. The chemically most evolved units in the southern batholith contain a large number of intra-granitic, pod-shaped tourmaline-bearing pegmatites. This study uses in situ chemical and boron isotopic analyses of tourmaline from nine of these pegmatites to discuss their relationship to the respective host intrusions and the implications of their B-isotope composition for the source and evolution of the magmas. The tourmalines reveal a diversity in element composition (e.g., FeO, MgO, TiO2, CaO, MnO, F) which distinguishes individual pegmatites from one another. However, all have a narrow 5 11 B range of -13.7 to -10.5%0 (n = 100) which indicates a relatively uniform magmatic system and similar temperature conditions during tourmaline crystallization. The average delta(11) B value of -11.7%0 is typical for S-type granites and is within the range reported for peraluminous granites. pegmatites, and metamorphic units of the Ordovician basement into which the Las Chacras-Potrerillos batholith intruded. The B-isotope evidence argues for a crustal boron source like that of the Ordovician basement, in contrast to the metaluminous to weakly peraluminous composition and juvenile initial Sr and Nd isotope ratios of the Las Chacras-Potrerillos batholith magmas. We propose that the boron was not derived from the magma source region but was incorporated from dehydration melting of elastic metasedimentary rocks higher up in the crustal column.
The Altiplano-Puna Plateau holds several shallow lakes, which are very sensitive to climate changes. This work is focused on a high-altitude lake system called Lagunas de Vilama (LVS), located in a complex climatic transition area with scarcity of continuous and homogeneous instrumental records. The objective of this study is to determine the regional spatial-temporal variability of precipitation and evaluate the seasonal and interannual lake responses. We use a lake-surfaces record derived from Landsat images to investigate links with regional precipitations and different climatic forcings. The results reveal that austral summer and autumn precipitations control the variability of the annual lake-surfaces. Also, we found intra-annual and interannual lags in the lake responses to precipitations, and identified several wet and dry stages. Our results show negative trends in precipitations and lake-surfaces, whose were strengthened by a shift to a warm phase of the Atlantic Multidecadal Oscillation in the 1990s. The El Nino Southern Oscillation, Pacific Decadal Oscillation, and Southern Annular Mode also exert a strong influence in the region. This study demonstrates that the variability of LVS lakes is strongly related to the South American Monsoon System dynamics and large-scale climate fordngs from the Pacific and Atlantic Oceans. This work provides novel indices which demonstrated to be good indicators of regional hydroclimatological variability for this region of South America.
The Arnoldi process can be applied to inexpensively approximate matrix functions of the form f (A)v and matrix functionals of the form v*(f (A))*g(A)v, where A is a large square non-Hermitian matrix, v is a vector, and the superscript * denotes transposition and complex conjugation. Here f and g are analytic functions that are defined in suitable regions in the complex plane. This paper reviews available approximation methods and describes new ones that provide higher accuracy for essentially the same computational effort by exploiting available, but generally not used, moment information. Numerical experiments show that in some cases the modifications of the Arnoldi decompositions proposed can improve the accuracy of v*(f (A))*g(A)v about as much as performing an additional step of the Arnoldi process.
Background and aims:
The objective of the present work was to determine to what extent sleep quality may mediate the association between chronodisruption (CD) and metabolic syndrome (MS), and between CD and body composition (BC).
Methodology:
Cross-sectional study which included 300 adult health workers, 150 of whom were night shift workers and thereby exposed to CD. Diagnosis of MS was made based on Adult Treatment Panel III criteria. Sleep quality was measured using the Pittsburgh Sleep Quality Index. Body mass index (BMI), fat mass percentage, and visceral fat percentage were measured as indicators of body composition (BC). Data were analyzed using logistic, linear regression and structural equation models.
Results:
The odds of health workers exposed to CD to suffer MS was 22.13 (IC95 8.68-66.07) when the model was adjusted for age, gender, physical activity and energy consumption. CD was also significantly associated with an increase in fat mass and visceral fat percentages, but not to BMI. Surprisingly, there was not enough evidence supporting the hypothesis that sleep quality contributes to the association between CD and MS or between CD and BC.
Conclusions:
Sleep quality does not mediate the negative effects of CD on MS nor on BC.
Based on suggested interactions of potential tipping elements in the Earth's climate and in ecological systems, tipping cascades as possible dynamics are increasingly discussed and studied. The activation of such tipping cascades would impose a considerable risk for human societies and biosphere integrity. However, there are ambiguities in the description of tipping cascades within the literature so far. Here we illustrate how different patterns of multiple tipping dynamics emerge from a very simple coupling of two previously studied idealized tipping elements. In particular, we distinguish between a two phase cascade, a domino cascade and a joint cascade. A mitigation of an unfolding two phase cascade may be possible and common early warning indicators are sensitive to upcoming critical transitions to a certain degree. In contrast, a domino cascade may hardly be stopped once initiated and critical slowing down-based indicators fail to indicate tipping of the following element. These different potentials for intervention and anticipation across the distinct patterns of multiple tipping dynamics should be seen as a call to be more precise in future analyses of cascading dynamics arising from tipping element interactions in the Earth system.
The synthesis and the crystal structure of the double cluster compound [Nb6Cl14(MeCN)(4)][Nb6Cl14(pyz)(4)]middot6CH(3)CN are described. The synthesis is based on a partial ligand exchange reaction, which proceeds upon dissolving [Nb6Cl14(pyz)(4)]middot2CH(2)Cl(2) in acetonitrile. The compound is built up of two discrete neutral cluster units, which consist of octahedra of Nb-6 atoms coordinated by 12 edge-bridging chlorido and two terminal chlorido ligands, and four acetonitrile ligands on one and four pyrazine ligands on the other cluster unit. Co-crystallized acetonitrile molecules are also present. The single-crystal structure determination has revealed a cluster arrangement in which the [Nb6Cl14(pyz)(4)] units are connected by (halogen) lone-pair-(pyrazine) pi interactions. These lead to chains of [Nb6Cl14(pyz)(4)] clusters. These chains are further connected to cluster layers by (nitrile-halogen) dipole-dipole interactions, in which the [Nb6Cl14(MeCN)(4)] and co-crystallized MeCN molecules are also involved. These cluster layers are arranged parallel to the crystallographic {011} plane.
Purpose UK guidelines recommend dietary saturated fatty acids (SFAs) should not exceed 10% total energy (%TE) for cardiovascular disease prevention, with benefits observed when SFAs are replaced with unsaturated fatty acids (UFAs). This study aimed to assess the efficacy of a dietary exchange model using commercially available foods to replace SFAs with UFAs. Methods Healthy men (n = 109, age 48, SD 11 year) recruited to the Reading, Imperial, Surrey, Saturated fat Cholesterol Intervention-1 (RISSCI-1) study (ClinicalTrials.Gov n degrees NCT03270527) followed two sequential 4-week isoenergetic moderate-fat (34%TE) diets: high-SFA (18%TE SFAs, 16%TE UFAs) and low-SFA (10%TE SFAs, 24%TE UFAs). Dietary intakes were assessed using 4-day weighed diet diaries. Nutrient intakes were analysed using paired t-tests, fasting plasma phospholipid fatty acid (PL-FA) profiles and dietary patterns were analysed using orthogonal partial least square discriminant analyses. Results Participants exchanged 10.2%TE (SD 4.1) SFAs for 9.7%TE (SD 3.9) UFAs between the high and low-SFA diets, reaching target intakes with minimal effect on other nutrients or energy intakes. Analyses of dietary patterns confirmed successful incorporation of recommended foods from commercially available sources (e.g. dairy products, snacks, oils, and fats), without affecting participants' overall dietary intakes. Analyses of plasma PL-FAs indicated good compliance to the dietary intervention and foods of varying SFA content. Conclusions RISSCI-1 dietary exchange model successfully replaced dietary SFAs with UFAs in free-living healthy men using commercially available foods, and without altering their dietary patterns. Further intervention studies are required to confirm utility and feasibility of such food-based dietary fat replacement models at a population level.
This paper studies cosmic-ray (CR) transport in magnetohydrodynamic (MHD) turbulence. CR transport is strongly dependent on the properties of the magnetic turbulence.
We perform test particle simulations to study the interactions of CR with both total MHD turbulence and decomposed MHD modes.
The spatial diffusion coefficients and the pitch angle scattering diffusion coefficients are calculated from the test particle trajectories in turbulence.
Our results confirm that the fast modes dominate the CR propagation, whereas Alfven and slow modes are much less efficient and have shown similar pitch-angle scattering rates.
We investigate the cross field transport on large and small scales. On large/global scales, normal diffusion is observed and the diffusion coefficient is suppressed by M-A(zeta) compared to the parallel diffusion coefficients, with zeta closer to 4 in Alfven modes than that in total turbulence, as theoretically expected.
For the CR transport on scales smaller than the turbulence injection scale, both the local and global magnetic reference frames are adopted. Superdiffusion is observed on such small scales in all the cases. Particularly, CR transport in Alfven modes show clear Richardson diffusion in the local reference frame. The diffusion transitions smoothly from the Richardson's one with index 1.5 to normal diffusion as the particle mean free path decreases from lambda(parallel to) >> L to lambda(parallel to) << L, where L is the injection/coherence length of turbulence.
Our results have broad applications to CRs in various astrophysical environments.
Active matter broadly covers the dynamics of self-propelled particles.
While the onset of collective behavior in homogenous active systems is relatively well understood, the effect of inhomogeneities such as obstacles and traps lacks overall clarity.
Here, we study how interacting, self-propelled particles become trapped and released from a trap.
We have found that captured particles aggregate into an orbiting condensate with a crystalline structure. As more particles are added, the trapped condensates escape as a whole.
Our results shed light on the effects of confinement and quenched disorder in active matter.
Quantification of reaction fluxes of metabolic networks can help us understand how the integration of different metabolic pathways determines cellular functions. Yet, intracellular fluxes cannot be measured directly but are estimated with metabolic flux analysis (MFA), which relies on the patterns of isotope labeling of metabolites in the network. The application of MFA also requires a stoichiometric model with atom mappings that are currently not available for the majority of large-scale metabolic network models, particularly of plants. While automated approaches such as the Reaction Decoder Toolkit (RDT) can produce atom mappings for individual reactions, tracing the flow of individual atoms of the entire reactions across a metabolic model remains challenging. Here we establish an automated workflow to obtain reliable atom mappings for large-scale metabolic models by refining the outcome of RDT, and apply the workflow to metabolic models of Arabidopsis thaliana. We demonstrate the accuracy of RDT through a comparative analysis with atom mappings from a large database of biochemical reactions, MetaCyc. We further show the utility of our automated workflow by simulating N-15 isotope enrichment and identifying nitrogen (N)-containing metabolites which show enrichment patterns that are informative for flux estimation in future N-15-MFA studies of A. thaliana. The automated workflow established in this study can be readily expanded to other species for which metabolic models have been established and the resulting atom mappings will facilitate MFA and graph-theoretic structural analyses with large-scale metabolic networks.