Quantitative evaluation of transient valence orbital occupations in a 3d transition metal complex as seen from the metal and ligand perspective

It is demonstrated for the case of photo excited ferrocyanide how time resolved soft X ray absorption spectroscopy in transmission geometry at the ligand K edge and metal L3 edge provides quantitatively equivalent valence electronic structure information, where signatures of photo oxidation are assessed locally at the metal as well as the ligand. This allows for a direct and independent quantification of the number of photo oxidized molecules at two soft X ray absorption edges highlighting the sensitivity of X ray absorption spectroscopy to the valence orbital occupation of 3d transition metal complexes throughout the soft X ray rang

The democratic origins of the term "group analysis": Karl Mannheim's "third way" for psychoanalysis and social science.

It is well known that Foulkes acknowledged Karl Mannheim as the first to use the term ‘group analysis’. However, Mannheim’s work is otherwise not well known. This article examines the foundations of Mannheim’s sociological interest in groups using the Frankfurt School (1929–1933) as a start point through to the brief correspondence of 1945 between Mannheim and Foulkes (previously unpublished). It is argued that there is close conjunction between Mannheim’s and Foulkes’s revision of clinical psychoanalysis along sociological lines. Current renderings of the Frankfurt School tradition pay almost exclusive attention to the American connection (Herbert Marcuse, Eric Fromm, Theodor Adorno and Max Horkheimer) overlooking the contribution of the English connection through the work of Mannheim and Foulkes

Probing Solute Solvent Interactions of Transition Metal Complexes Using L Edge Absorption Spectroscopy

In order to tailor solution phase chemical reactions involving transition metal complexes, it is critical to understand how their valence electronic charge distributions are affected by the solution environment. Here, solute amp; 8722;solvent interactions of a solvatochromic mixed ligand iron complex were investigated using X ray absorption spectroscopy at the transition metal L2,3 edge. Due to the selectivity of the corresponding core excitations to the iron 3d orbitals, the method grants direct access to the valence electronic structure around the iron center and its response to interactions with the solvent environment. A linear increase of the total L2,3 edge absorption cross section as a function of the solvent Lewis acidity is revealed. The effect is caused by relative changes in different metal amp; 8722;ligand bonding channels, which preserve local charge densities while increasing the density of unoccupied states around the iron center. These conclusions are corroborated by a combination of molecular dynamics and spectrum simulations based on time dependent density functional theory. The simulations reproduce the spectral trends observed in the X ray but also optical absorption experiments. Our results underscore the importance of solute amp; 8722;solvent interactions when aiming for an accurate description of the valence electronic structure of solvated transition metal complexes and demonstrate how L2,3 edge absorption spectroscopy can aid in understanding the impact of the solution environment on intramolecular covalency and the electronic charge distributio

Metal water covalency in the photo aquated ferrocyanide complex as seen by multi edge picosecond X ray absorption

In this work, we investigate the photo aquation reaction of the ferrocyanide anion with multi edge picosecond soft X ray spectroscopy. Combining the information of the iron L edge with nitrogen and oxygen K edges, we carry out a complete characterization of the bonding channels in the [Fe CN 5 H2O ]3 amp; 8722; photo product. We observe clear spectral signatures of covalent bonding between water and the metal, reflecting the mixing of the Fe dz2 orbital with the 3a1 and 4a1 orbitals of H2O. Additional fingerprints related to the symmetry reduction and the resulting loss in orbital degeneracy are also reported. The implications of the elucidated fingerprints in the context of future ultra fast experiments are also discusse

A de novo paradigm for male infertility

Genetics of Male Infertility Initiative (GEMINI) consortium: Donald F. Conrad, Liina Nagirnaja, Kenneth I. Aston, Douglas T. Carrell, James M. Hotaling, Timothy G. Jenkins, Rob McLachlan, Moira K. O’Bryan, Peter N. Schlegel, Michael L. Eisenberg, Jay I. Sandlow, Emily S. Jungheim, Kenan R. Omurtag, Alexandra M. Lopes, Susana Seixas, Filipa Carvalho, Susana Fernandes, Alberto Barros, João Gonçalves, Iris Caetano, Graça Pinto, Sónia Correia, Maris Laan, Margus Punab, Ewa Rajpert-De Meyts, Niels Jørgensen, Kristian Almstrup, Csilla G. Krausz & Keith A. Jarvi.De novo mutations are known to play a prominent role in sporadic disorders with reduced fitness. We hypothesize that de novo mutations play an important role in severe male infertility and explain a portion of the genetic causes of this understudied disorder. To test this hypothesis, we utilize trio-based exome sequencing in a cohort of 185 infertile males and their unaffected parents. Following a systematic analysis, 29 of 145 rare (MAF < 0.1%) protein-altering de novo mutations are classified as possibly causative of the male infertility phenotype. We observed a significant enrichment of loss-of-function de novo mutations in loss-of-function-intolerant genes (p-value = 1.00 × 10−5) in infertile men compared to controls. Additionally, we detected a significant increase in predicted pathogenic de novo missense mutations affecting missense-intolerant genes (p-value = 5.01 × 10−4) in contrast to predicted benign de novo mutations. One gene we identify, RBM5, is an essential regulator of male germ cell pre-mRNA splicing and has been previously implicated in male infertility in mice. In a follow-up study, 6 rare pathogenic missense mutations affecting this gene are observed in a cohort of 2,506 infertile patients, whilst we find no such mutations in a cohort of 5,784 fertile men (p-value = 0.03). Our results provide evidence for the role of de novo mutations in severe male infertility and point to new candidate genes affecting fertility.This project was funded by The Netherlands Organization for Scientific Research (918-15-667) to J.A.V. as well as an Investigator Award in Science from the Wellcome Trust (209451) to J.A.V. a grant from the Catherine van Tussenbroek Foundation to M.S.O. a grant from MERCK to R.S. a UUKi Rutherford Fund Fellowship awarded to B.J.H. and the German Research Foundation Clinical Research Unit “Male Germ Cells” (DFG, CRU326) to C.F. and F.T. This project was also supported in part by funding from the Australian National Health and Medical Research Council (APP1120356) to M.K.O.B., by grants from the National Institutes of Health of the United States of America (R01HD078641 to D.F.C. and K.I.A., P50HD096723 to D.F.C.) and from the Biotechnology and Biological Sciences Research Council (BB/S008039/1) to D.J.E.info:eu-repo/semantics/publishedVersio

National identity predicts public health support during a global pandemic

Changing collective behaviour and supporting non-pharmaceutical interventions is an important component in mitigating virus transmission during a pandemic. In a large international collaboration (Study 1, N = 49,968 across 67 countries), we investigated self-reported factors associated with public health behaviours (e.g., spatial distancing and stricter hygiene) and endorsed public policy interventions (e.g., closing bars and restaurants) during the early stage of the COVID-19 pandemic (April-May 2020). Respondents who reported identifying more strongly with their nation consistently reported greater engagement in public health behaviours and support for public health policies. Results were similar for representative and non-representative national samples. Study 2 (N = 42 countries) conceptually replicated the central finding using aggregate indices of national identity (obtained using the World Values Survey) and a measure of actual behaviour change during the pandemic (obtained from Google mobility reports). Higher levels of national identification prior to the pandemic predicted lower mobility during the early stage of the pandemic (r = −0.40). We discuss the potential implications of links between national identity, leadership, and public health for managing COVID-19 and future pandemics.publishedVersio