Ulm University

The four Zr8O6‐based metal‐organic frameworks (MOFs), porous coordination network (PCN) 221 M, comprising earth‐abundant metalloporphyrin tetracarboxylate (M‐TCPP, M: 2 H, Zn, Ni, and a mixture of 1:1 Zn and Ni), are investigated for light‐driven H2 evolution reaction (HER) in water. Under the irradiation of a 405 nm light emitting diode source and in the presence of triethanolamine (TEOA) as a sacrificial electron donor, the photocatalytic HER activity of PCN 221 varies with the metal center in the porphyrin linker. Among the tested MOFs, the Zn‐porphyrin derivative (PCN 221 Zn) produces H2 at a TON = 4, which is about seven times greater than that of homogeneous Zn‐TCPP (0.6) and superior to its 2 H (2.7), Ni (0.40), and ZnNi (1.6) analogs. Detailed photochemical studies via time‐resolved and steady‐state spectroscopy reveal two distinct charge transfer pathways: Direct H2 evolution from Zn‐TCPP itself, and electron transfer from the Zn‐TCPP photosensitizer to the Zr8O6 SBU catalytic sites. The improved HER performance of PCN 221 Zn is attributed to its favorable features, such as optical absorption, excited‐state properties, and charge separation dynamics, as well as the coordination of TEOA. This study provides fundamental insights into the design of MOF‐based heterogeneous photocatalysts exploiting earth‐abundant metal‐based porphyrin for solar fuel generation.

Object-basd visual attention marks a key process of mammalian perception. By which mechanisms this process is implemented and how it can be interacted with by means of attentional control is not completely understood yet. Incremental binding is a mechanism required in demanding scenarios of object-based attention and is experimentally well investigated. Attention spreads across a representation of the visual object and labels bound elements by constant up-modulation of neural activity. The speed of incremental binding was found to be dependent on the spatial arrangement of distracting elements in the scene and to be scale invariant giving rise to the growth-cone hypothesis. In this work, we propose a neural dynamical model of incremental binding that provides a mechanistic account for these findings. Through simulations, we investigate the model properties and demonstrate how an attentional spreading mechanism tags neurons that participate in the object binding process. They utilize Gestalt properties and eventually show growth-cone characteristics labeling perceptual items by delayed activity enhancement of neuronal firing rates. We discuss the algorithmic process underlying incremental binding and relate it to our model computations. This theoretical investigation encompasses complexity considerations and finds the model to be not only of explanatory value in terms of neurophysiological evidence, but also to be an efficient implementation of incremental binding striving to establish a normative account. By relating the connectivity motifs of the model to neuroanatomical evidence, we suggest thalamo-cortical interactions to be a likely candidate for the flexible and efficient realization suggested by the model. There, pyramidal cells are proposed to serve as the processors of incremental grouping information. Local bottom-up evidence about stimulus features is integrated via basal dendritic sites. It is combined with an apical signal consisting of contextual grouping information which is gated by attentional task-relevance selection mediated via higher-order thalamic representations.

Contact Glow Discharge Electrolysis (CGDE) denotes a plasma inside a vapor layer surrounding a gas-evolving electrode immersed in an aqueous electrolyte and operated at high voltages. We used a high-speed camera to image the formation of the vapor layer as well as its dynamic behavior during continuous CGDE on a Au wire cathode. The plasma ignites with a spark within a large bubble at the tip, which expands along the wire to the top, leaving a stable glow within the vapor layer behind. Using an in-house developed open-source Python-based software we deduced, from a thorough statistical analysis of images taken during continuous CGDE, a vapor layer thickness between 0.1 and 0.4 mm. Furthermore, we provide information on the dynamic behavior of individual discharges through the vapor layer from a series of images. The discharges are confined within the vapor layer and, thus, the extent of the discharges is similar to the vapor layer thickness. We find that the discharges have approximately the shape of oblate spheroids, which appear either as circles or ellipses in the camera images, depending on the orientation of the discharge with respect to the camera. We discuss the relevance of our results for the fundamental understanding of atomic scale surface structural changes and products formed in the solution in the presence of the plasma.

Background Angioedema (AE) rarely occurs as a potentially life‐threatening adverse drug reaction (ADR) to angiotensin‐converting enzyme inhibitors (ACEi) or angiotensin receptor blockers (ARB). The aim of the present study was to investigate non‐genetic association factors with ACEi‐/ARB‐induced angioedema in the European ADR database EudraVigilance and the database of the vARIANCE study. Methods The cohort of the vARIANCE study comprised 114 patients who suffered from ACEi‐ or ARB‐induced angioedema. In addition, 171 angioedema reports and 4650 reports on other ADRs of ACEi/ARB were identified in the ADR database EudraVigilance with the latter serving as a reference group. Odds ratios were calculated and a logistic regression analysis was performed using angioedema versus reference reports. Results Increased age, smoking, allergies and a history of previous angioedema were identified as associated factors for ACEi‐/ARB‐induced angioedema. In most patients, the swelling affected the face, lips and tongue. In the vARIANCE study, about 70% of angioedema occurred after 1 year of treatment. For one in two patients in the vARIANCE study (84.2% with ACEi treatment) and one in three patients from the EudraVigilance reports (59.6% with ARB treatment), the angioedema resulted in hospitalization. Conclusions We found small to moderate associations with certain individual patient‐related factors in this pharmaco‐epidemiological study. As a future perspective, combining non‐genetic association factors with corresponding genetic data might provide an option to compose stronger and individual risk scores.

Syncytin-1 and Syncytin-2 are envelope glycoproteins encoded by human endogenous retroviruses that have been exapted for the fusion of cytotrophoblast cells into syncytiotrophoblasts during placental development. Pregnancy complications like preeclampsia are associated with altered expression of interferon-stimulated genes, including guanylate-binding protein 5 (GBP5). Here, we show that misdirected antiviral activity of GBP5 impairs processing and activation of Syncytin-1. In contrast, the proteolytic activation of Syncytin-2 is not affected by GBP5, and its fusogenic activity is only modestly reduced. Mechanistic analyses revealed that Syncytin-1 is mainly cleaved by the GBP5 target furin, whereas Syncytin-2 is also efficiently processed by the proprotein convertase subtilisin/kexin type 7 (PCSK7) and thus resistant to GBP5-mediated restriction. Mutational analyses mapped PCSK7 processing of Syncytin-2 to a leucine residue upstream of the polybasic cleavage site. In summary, we identified an innate immune mechanism that impairs the activity of a co-opted endogenous retroviral envelope protein during pregnancy and may potentially contribute to the pathogenesis of pregnancy disorders.

Background The COVID-19 pandemic has posed challenges to healthcare systems worldwide. For healthcare workers (HCW), an increased prevalence of mental distress and the impact of various resources have been identified. Psychotherapists specialise in helping people cope with stressful life events. At the same time, they are susceptible to mental distress, resulting from their work. Data on symptoms of depression and the role of resources during the COVID-19 pandemic are scarce for psychotherapists. Therefore, the present study aimed to evaluate the course of self-reported depression of psychotherapists throughout the COVID-19 pandemic. Additionally, the impact of resources on depression was evaluated. Methods We investigated symptoms of depression using the Patient Health Questionnaire-2 (PHQ-2) at four time points (T1-T4) during the COVID-19 pandemic in Germany. The PHQ-2 scores and resources such as sense of coherence (SOC), general optimism and social support (ESSI-D) of the psychotherapists (N = 1733) were compared with those of a comparison sample of HCW (N = 8470). The impact of resources on PHQ-2 scores was examined using cross-sectional linear modelling and longitudinal linear mixed modelling with interactions and lagged predictors. Results At T1-T4, psychotherapists showed lower mean PHQ-2 scores than the comparison sample (p < 0.001). Among psychotherapists, the PHQ-2 scores increased (T1-T2, and T1-T4, p < 0.050). Cross-sectionally, higher SOC was associated with lower PHQ-2 scores (p < 0.001), with the protective influence weakening over time (p = 0.033). Longitudinal analyses confirmed a protective effect of sense of coherence (stable over time) and general optimism (declining over time) on PHQ-2 scores. An exploratory lagged-predictor analysis suggested that higher social support was associated with lower PHQ-2 scores, whereas higher general optimism was linked to increasing PHQ-2 scores. Conclusions This study revealed lower levels of depression among psychotherapists compared with the comparison sample throughout the pandemic. Concurrently, the resource levels were mostly comparable and stable, with a protective impact of the sense of coherence (stable) and optimism (decreasing) and an association of high social support with low depression throughout the pandemic. Strengthening the sense of coherence and social support should be the focus of professional and policy attention to improve the ability of psychotherapists to cope with future crises.

Background Fragility fractures of the posterior pelvic ring are associated with osteoporosis and are becoming more common with demographic change. Known limitations of conservative therapy include a significant loss of autonomy and high mortality. Surgical stabilisation using percutaneous sacroiliac (SI) or trans-iliac trans-sacral (TITS) screws, has been established to increase mobility, but long-term results have not yet been studied. Materials and Methods 138 patients with percutaneous SI and TITS screw fixation of the posterior pelvic ring in osteoporotic fragility fractures were followed up for more than a year postoperatively in this retrospective study. Thereby, all patients were operated in the conventional supine position in a hybrid operating room consisting of a fixed, robot-assisted 3D flat-panel detector and a navigation system. Results 34 patients were male and 104 female. The mean age was 77.6 ± 9 years. 26 patients were ASA 1 + 2, 93 patients ASA 3 and 19 patients ASA 4. 80 fractures were classified as FFP 2, 23 FFP 3 and 35 FFP 4. Time to surgery was 127.5 ± 113.2 hours. Hospitalisation lasted an average of 15.7 ± 8.5 days. At the time of discharge, 68.8% of the patients had regained their original mobility, while 31.2% remained limited. The home situation remained unchanged in 73.9% of the patients, worsened in 26.1% and improved in 2.8%. 90.6% of the screw fixations showed no signs of loosening. In 9.4%, loosening could not be ruled out radiologically, but a surgical revision was not necessary. The 1-year mortality rate was 10.1%. Conclusion Percutaneous navigated screw fixation of the posterior pelvic ring in fragility fractures is a simple, safe, minimally invasive and precise method with good clinical results in terms of rapid recovery with early mobilization of patients to maintain autonomy and reduce mortality. Further clinical studies with controlled cohorts and a large number of patients with long follow-up periods should be carried out to compare the procedure with other methods. In particular, the question of an additional standardized treatment of the anterior pelvic ring in unstable dislocated fragility fractures should be investigated.

Background Unemployment is a risk factor for the development and perpetuation of psychological distress. Finding support for affected individuals can be particularly challenging, which causes a vicious cycle of psychological distress and unemployment. Objective The aim of this systematic review is to assess and summarize existing evidence regarding interventions that address both mental health and re-employment, emphasizing accessibility through community or social care structures. Methods A systematic literature search using PubMed and EBSCOhost and an additional search using reference list screening were conducted according to the PRISMA (Preferred Reporting Items for Systematic Reviews and Meta-Analyses) guidelines. In order to identify interventions for the mental health and re-employment of individuals experiencing psychological distress and unemployment, an inclusion process according to the PICO (population, intervention, comparison, and outcome) scheme and the study design was applied. Title and abstract screening and full-text screening for eligibility were performed independently by 2 reviewers. Quality assessments using the Cochrane Risk of Bias Tools for randomized and nonrandomized trials were conducted by 2 independent reviewers. Results The initial systematic search yielded 4442 results, and 15 articles were additionally identified via reference list screening. Eventually, 74 articles were subjected to a thorough evaluation process by 2 independent reviewers. The interrater reliability was determined to be good, with a Cohen κ score of 0.770. After a multistep extraction process, 17 studies remained for inclusion, with each focusing on the improvement of mental health, re-employment, or both outcomes. A heterogeneous pattern of results emerged, with most interventions showing improvement in either mental health or re-employment. Most studies were assessed as having a moderate (n=7) or high (n=9) risk of bias. Conclusions The results of the systematic research indicate that low-threshold services in close cooperation with institutions and exchange with other supportive stakeholders should be fostered. Derivable overarching themes and intervention content for integrative support measures can serve as guidelines for future interventions. Trial Registration PROSPERO CRD42022378490; https://www.crd.york.ac.uk/PROSPERO/view/CRD42022378490

Background Metastases are associated with poor survival in head and neck squamous cell carcinoma (HNSCC) patients and tumour-associated macrophages (TAMs) are important drivers in tumour progression and metastasis formation. Small extracellular vesicles (sEVs) are another important factor that contribute to systemic immunosuppression and pre-metastatic niche formation. Here, we investigate the effect of plasma sEVs from HNSCC patients on pre-metastatic niche formation, directly or through modulation of macrophages. Methods Primary macrophages were incubated with sEVs from plasma of HNSCC patients or healthy donors (HD). RNA profiles and inflammatory properties of macrophages were evaluated. Direct and indirect effects of sEVs on chemotaxis, T cell activation, proliferation and epithelial-to-mesenchymal transition (EMT) of tumour cells were investigated. Results sEVs of HNSCC patients and HD induced different RNA profiles in macrophages. sEVs induced apoptosis and inhibition of T cell activation, while tumour cells were attracted by sEV-treated macrophages, but not sEVs directly. Proliferation was inhibited by both, sEVs and supernatant of EV-treated macrophages in HNSCC. Additionally, EMT in tumour cells was reversed by HNSCC sEV-treated macrophages. Conclusion sEVs from plasma of HNSCC patients transformed macrophages into metastasis-promoting TAMs and inhibited anti-tumour T cells, highlighting the potential of sEVs and TAMs as targets for therapeutic approaches.

Zusammenfassung Prädiktion und Prävention des Typ-1-Diabetes bilden den Rahmen für die Diskussion, ob ein Antikörperscreening Teil der Regelversorgung werden sollte. Der Inselautoantikörpertest charakterisiert nicht die Stoffwechselsituation, sondern ist eine Momentaufnahme von Autoimmunität und ermöglicht eine Prognose des künftigen Typ-1-Diabetes-Risikos. Für Personen mit positivem Test bietet er jedoch keine verlässliche, individuelle Vorhersage, wann die Erkrankung auftreten wird. Eine medikamentöse Therapie zur Prävention des Typ-1-Diabetes ist aktuell noch nicht verfügbar. Somit konfrontiert ein positiver Test Betroffene mit einer Krankheitsprognose, ohne dass ein sinnvolles Therapieangebot existiert. Die psychologische Belastung des Tests kann daher erheblich sein. Weitere klinische Studien sind erforderlich, um Nutzen und Risiken des Inselautoantikörpertests zu untersuchen.

Solid-state quantum systems that utilize optical and spin degrees of freedom in a spin–photon interface have found widespread application in emerging quantum technologies. Recently, molecular qubits have gained center stage as precisely tunable entities that present a compelling alternative to well-established, yet structurally less flexible point defects in solid-state systems. In this work, we disclose ground-state triplet (GST) carbenes embedded in a molecular matrix as organic qubits comprising two unpaired electrons in close proximity that can be optically initialed and read out. In-situ photoactivation enables the precise allo- cation of the carbene position and tuning of its density in the crystalline matrix and lays the ground for optically detected magnetic resonance (ODMR) with high fluorescence contrast of more than 40%, as well as record- high spin coherence times for a molecular spin–photon interface of T2 = 157(4) μs at a temperature of around 5 K. In addition, we show how state-of-the-art quantum chemical calcu- lations including multiscale geometry predictions and complete active space self-consistent field (CASSCF) computations offer comprehensive insight into fundamental spin characteristics. With that, for the first time a series of attractive properties could be united in a single solid-state qubit material: Exclusive usage of light elements (C,H,O,N), optical spin-selective excitations and relaxation pathways, and large zero-field splitting (ZFS) parameters on the order of a few GHz resulting in protection against decoherence sources at low magnetic fields. In this study, we take first steps into a hitherto dormant playground for the design and fabrication of molecular solid-state color centers made of purely organic compounds.

Excited state properties such as excitation energy, accessibility of the respective excited state either by direct or indirect population transfer, and its lifetime govern the application of these excited states in light‐driven reactions, for example, photocatalysis using transition metal complexes. Compared with triplet metal‐to‐ligand charge transfer (³MLCT) states, charge‐separated (³CS) excited states involving organic moieties, such as triplet intra‐ligand or ligand‐to‐ligand charge transfer (³ILCT and ³LLCT) states, tend to possess longer‐lived excited states due to the weak spin‐orbit coupling with the closed‐shell ground state. Thus, the combination of inorganic and organic chromophores enables isolating the triplet states onto the organic chromophore. In this study, we aim to elucidate the excited‐state relaxation processes in a Ru(II)‐terpyridyl donor–acceptor–donor system (RuCl) in a joint spectroscopic‐theoretical approach combining steady‐state and time‐resolved spectroscopy as well as quantum chemical simulations and dissipative quantum dynamics. The electron transfer (ET) processes involving the low‐lying ³MLCT, ³ILCT, and ³LLCT excited states were investigated experimentally and computationally within a semiclassical Marcus picture. Finally, dissipative quantum dynamical simulations—capable of describing incomplete ET processes involving all three states—enabled us to unravel the competitive relaxation channels at short and long timescales among the strongly coupled ³MLCT‐³ILCT states and weakly coupled ³MLCT‐³LLCT and ³ILCT‐³LLCT states.

A growing body of research indicates that problematic social media use can have detrimental effects on adolescents' mental health and well-being. This systematic review aims to synthesize evidence on longitudinal risk factors contributing to the development of problematic social media use in adolescents, defined as the use of social media impacting physical or mental well-being. The review was conducted following PRISMA guidelines. A comprehensive literature search was performed on PubMed, PsycINFO, and Embase databases, including articles published from 2010 onwards. Out of 1,729 screened articles, 23 were included. Findings on risk factors related to individuals and their social environment were categorized into nine groups: motivations for use, parenting factors, adverse childhood experiences, peer factors, emotions, self-regulation, personality, mental health, and the impact of the COVID-19 pandemic. Peer factors (e.g., poor social relationships, social comparison, fear of missing out, negative peer pressure, exposure to relational aggression), negative emotions, personality traits (e.g., sensation seeking), and poor mental health emerged as the most common risk factors. Due to methodological limitations in the studies included, further research is necessary. It is essential to use clinical samples, objective measures, and consistent conceptualizations to contribute to a better understanding of problematic social media use as well as its mechanisms and effects.

Background Pathways between social isolation (SI), loneliness and health are unclear. Aims To analyze the relationship between SI and loneliness with biomarkers of inflammation, cardiac and immune function, functional parameters, and mortality. Methods SI (Lubben Social Network Scale) from family, friends, and overall as well as loneliness (single direct question) were assessed at baseline in a population-based cohort study of 1459 community-dwelling adults aged 65 + in Germany. Serum biomarkers and functional parameters measured at baseline and at three-year follow-up included high-sensitivity C reactive protein (hs-CRP), growth differentiation factor-15 (GDF-15), N-terminal pro-brain natriuretic peptide (NT-proBNP), high-sensitivity troponin I (hs-cTnI), high-sensitivity troponin T (hs-cTnT), gait speed, and hand grip strength. We used linear and Cox regression analyses adjusted for age and sex (model 1) and established confounders (model 2). Results High SI from friends was associated with small but significant adverse associations with some biomarkers (hs-CRP, GDF-15, hs-cTnT) at follow-up (model 1). High SI from family associated with NT-proBNP (model 2), high SI and moderate to severe loneliness with lower gait speed. Loneliness was linked to hs-CRP at baseline, but SI was a stronger predictor of biomarker levels. High SI overall (Hazard ratio 1.39, 95% CI 1.15; 1.67, model 2) was associated with increased 10-year mortality. Discussion Mainly SI from friends is linked to unfavorable biomarker profiles with small associations. Overall SI was negatively associated with functional parameters and positively with mortality. Conclusions Further research should confirm our findings using, e.g. a multidimensional assessment of loneliness.

Negatively charged nitrogen‐vacancy (NV⁻) centers in diamond are appealing for quantum sensing applications due to their environmental sensitivity and long coherence times. Precise and scalable shallow color center creation is essential yet challenging for technological quantum applications. This is due to the involvement of several lengthy processes, such as ion implantation and thermal annealing of the samples. The latter process can be addressed by application of an alternative activation technique that bypasses the high‐temperature annealing. For this, nitrogen‐implanted regions on a diamond substrate are exposed to continuous‐wave 405 nm laser radiation. The illumination leads to local activation of NV⁻ centers with photoluminescence yield saturation for regions activated with laser power at around 800 µW. For low implantation doses, single NV⁻ centers are created with corresponding mean T2 coherence time value around 71 µs. The NV⁻ creation yield for the lower implantation doses match conventional creation methods, while higher doses show reduced yield values. However, the coherent properties are comparable to NV⁻ centers within annealed samples. This shows that the activated NV⁻ centers are well‐suited for advanced applications in quantum sensing and related technologies.

Background The diagnosis of personality disorders (PD) in adolescence still poses a challenge. Early diagnosis and targeted intervention are called for, since patients with PD present with severe consequences in terms of psychosocial functioning and personal suffering including higher suicide risk. New guidelines advise semi-structured interviews for the dimensional assessment of personality functioning. Methods We included 136 patients aged 13 to 17.9 years with a categorical PD diagnosis and 35 healthy control (HC) adolescents to assess the applicability of the Structured Interview for Personality Organization (STIPO) for adolescents and evaluate its validity by correlating the six outcome domains (identity, object relations, defenses, aggression, moral values, reality testing) and the overall severity level to several validated instruments. Furthermore, we assessed personality traits, internalizing and externalizing behavior and depressive symptoms. Results All STIPO domains differed significantly between patients and HC (p < 0.001). Outcome measures correlated significantly with validated self-rating questionnaires. STIPO severity levels correlated significantly with psychopathology. Personality traits “dissocial behavior” and “emotional dysregulation” correlated positively with all STIPO domains and the overall level of personality organization (PO). Conclusions Results indicate that the STIPO is a reliable and valid instrument for the assessment of PD in adolescents. It comprises the core elements of personality functioning, as requested in Criterion A in the AMPD of the DSM-5 and ICD-11 and could be useful for treatment planning, evaluation of the course of treatment as well as for prognostic considerations.