Relativistic Energy-consistent Pseudopotentials for f-Elements

In this thesis relativistic energy-consistent pseudopotentials (PPs) for f-elements have been adjusted. The PP approach restricts the explicit calculations to the chemically relevant valence electron system and implicitly includes relativistic effects by means of a simple parameterization. Thus, it is a commonly used approximation to study molecules containing f-elements, where the large number of electrons and the significant relativistic effects are the main obstacles. Even difficulties due to open shells can be avoided, if these are included in the core, as it is the case for f-in-core PPs. However, if the f shell is not treated explicitly, one PP for each oxidation state has to be adjusted. This thesis completes the already existing quasirelativistic f-in-core PPs, i.e. 5f-in-core PPs for di- (Pu-No), tetra- (Th-Cf), penta- (Pa-Am), and hexavalent (U-Am) actinides and 4f-in-core PPs for tetravalent (Ce-Nd, Tb, Dy) lanthanides are presented. Corresponding molecular basis sets of polarized valence double- to quadruple-zeta quality have been derived. Smaller basis sets suitable for crystal calculations form subsets of these basis sets. Furthermore, core-polarization potentials for di-, tri-, and tetravalent actinides have been adjusted to account for the neglect of static and dynamic core-polarization. Atomic test calculations on actinide ionization potentials as well as molecular test calculations on actinide and lanthanide fluorides using the Hartree-Fock and coupled cluster method show satisfactory agreement with calculations using f-in-valence PPs and experimental data, respectively, except for plutonium difluoride and neptunium, plutonium, and americium hexafluoride. While for plutonium difluoride the large deviations are due to the fact that for plutonium the divalent oxidation state is not stable, in the hexavalent case the 5f-in-core approximation seems to reach its limitations except for uranium. Moreover, the 5f-in-core PPs are successfully applied to actinocenes, actinyl ions, and uranyl(VI) complexes. Thus, the f-in-core PPs should be an efficient computational tool for those compounds, where the f orbitals do not participate significantly in chemical bonding. In addition to the quasirelativistic f-in-core PPs, the recently adjusted 5f-in-valence uranium PP including scalar-relativistic effects as well as spin-orbit coupling have been tested by calculating the fine-structure splittings of U5+ and U4+. These test calculations gave reliable results and thus confirm earlier benchmark calculations on uranium monohydride

Influence of Increasing Nutrient Availability on Fern and Lycophyte Diversity

Increased nutrient supply can have drastic effects on natural ecosystems, especially in naturally nutrient-poor ones such as most tropical rainforests. Many studies have focused on the reaction of trees to fertilization, but little is known about herbaceous plants. Ferns are a particularly common group in tropical forests, spanning all vegetation types and zones. Here, we assess how seven years of moderate addition of nitrogen (N), phosphorus (P), and N+P along an elevational gradient (1000–3000 m) have impacted richness and composition of fern and lycophyte assemblages in tropical montane rain forests growing on naturally nutrient deficient soils in the Ecuadorian Andes. We found that fertilization does not affect overall species richness, but that there were strong differences in species abundances (∼60% of species), both negative and positive, that were apparently related to the systematic affiliations and ecological properties of the affected species. These diverse responses of ferns to fertilization provide insight into the sensitivity and complexity of the relationships of nutrient availability and community composition in tropical forests

Templated Total Synthesis of Cu(I)‐Methanobactin OB3b **

Abstract Methanobactin OB3b (Mbn‐OB3b) is a unique natural product with stunning affinity for copper ions ( K a ≈Cu(I) 10 34 ). Here, we report the first total synthesis of Cu(I)‐bound methanobactin OB3b featuring as key transformations a cyclodehydration‐thioacylation sequence, to generate the conjugated heterocyclic systems, and a copper‐templated cyclization, to complete the caged structure of the very sensitive target compound

Introgressive hybridisation between domestic pigs (<i>Sus scrofa domesticus</i>) and endemic Corsican wild boars (<i>S. s. meridionalis</i>):Effects of human-mediated interventions

Owing to the intensified domestication process with artificial trait selection, introgressive hybridisation between domestic and wild species poses a management problem. Traditional free-range livestock husbandry, as practiced in Corsica and Sardinia, is known to facilitate hybridisation between wild boars and domestic pigs (Sus scrofa). Here, we assessed the genetic distinctness and genome-wide domestic pig ancestry levels of the Corsican wild boar subspecies S. s. meridionalis, with reference to its Sardinian conspecifics, employing a genome-wide single nucleotide polymorphism (SNP) assay and mitochondrial control region (mtCR) haplotypes. We also assessed the reliance of morphological criteria and the melanocortin-1 receptor (MC1R) coat colour gene to identify individuals with domestic introgression. While Corsican wild boars showed closest affinity to Sardinian and Italian wild boars compared to other European populations based on principal component analysis, the observation of previously undescribed mtCR haplotypes and high levels of nuclear divergence (Weir's θ > 0.14) highlighted the genetic distinctness of Corsican S. s. meridionalis. Across three complementary analyses of mixed ancestry (i.e., STRUCTURE, PCADMIX, and ELAI), proportions of domestic pig ancestry were estimated at 9.5% in Corsican wild boars, which was significantly higher than in wild boars in Sardinia, where free-range pig keeping was banned in 2012. Comparison of morphologically pure- and hybrid-looking Corsican wild boars suggested a weak correlation between morphological criteria and genome-wide domestic pig ancestry. The study highlights the usefulness of molecular markers to assess the direct impacts of management practices on gene flow between domestic and wild species

Radical prostatectomy in kidney transplant recipients : a multicenter experience

Background and objective: Kidney transplant recipients (KTRs) have an increased risk of developing genitourinary cancers, including prostate cancer (PCa), which is expected to become more prevalent due to an aging KTR population. Thus, knowledge of surgical outcomes, including treatment of PCa, within this unique cohort is required. Methods: Data of 62 KTRs undergoing radical prostatectomy (RP) between 2006 and 2023 at nine urologic transplant centers were analyzed. Complications were assessed using the Clavien-Dindo classification. Perioperative outcomes were evaluated, and a follow-up was conducted. Overall survival (OS), biochemical recurrence–free survival (BRFS), and death-censored graft survival were determined via the Kaplan-Meier method and log-rank testing. Key findings and limitations: Overall, 50 open radical retropubic RPs and 12 robot-assisted RPs (RARPs) were included. The intraoperative blood loss was lower after RARP, but operative time was longer. Of the patients, 50% experienced no postoperative complication, and grade ≥3 complications were observed in 14.5%. There was no graft loss related to RP. A histopathologic analysis revealed pN1 in 8.1% and positive surgical margins in 25.8% of the cases. At a median follow-up of 48.5 mo, the median OS was 128 (95% confidence interval [CI] 71.2–184.8) mo, BRFS was 106 (95% CI 55.8; 156.2) mo, and graft survival was 127 (95% CI 66.7–187.3) mo. Limitations include the retrospective design, and variations between groups and centers. Conclusions and clinical implications: Our findings support RP as a feasible and safe treatment option for localized PCa in KTRs with acceptable oncologic outcome. Special care is required in screening and awareness for the risk of understaging. Patient summary: This study analyzed the safety and effectiveness of two prostate cancer surgery methods—open and robot-assisted surgery—in the special group of kidney transplant recipients. Both surgical methods were performed safely with acceptable oncologic outcomes; however, sample size was too small to draw definite conclusions between the two operative methods

Predicting Antidepressant Effects of Ketamine: the Role of the Pregenual Anterior Cingulate Cortex as a Multimodal Neuroimaging Biomarker

Background: Growing evidence underscores the utility of ketamine as an effective and rapid-acting treatment option for major depressive disorder (MDD). However, clinical outcomes vary between patients. Predicting successful response may enable personalized treatment decisions and increase clinical efficacy. Methods: We here explored the potential of pregenual anterior cingulate cortex (pgACC) activity to predict antidepressant effects of ketamine in relation to ketamine-induced changes in glutamatergic metabolism. Prior to a single i.v. infusion of ketamine, 24 patients with MDD underwent functional magnetic resonance imaging during an emotional picture-viewing task and magnetic resonance spectroscopy. Changes in depressive symptoms were evaluated using the Beck Depression Inventory measured 24 hours pre- and post-intervention. A subsample of 17 patients underwent a follow-up magnetic resonance spectroscopy scan. Results: Antidepressant efficacy of ketamine was predicted by pgACC activity during emotional stimulation. In addition, pgACC activity was associated with glutamate increase 24 hours after the ketamine infusion, which was in turn related to better clinical outcome. Conclusions: Our results add to the growing literature implicating a key role of the pgACC in mediating antidepressant effects and highlighting its potential as a multimodal neuroimaging biomarker of early treatment response to ketamine. Keywords: antidepressant effects; ketamine; multimodal neuroimaging biomarker; pgACC; pregenual anterior cingulate cortex

Dilemma diagnosis between pulmonary embolism and amniotic fluid embolism during first stage of labor : a case report

We report the sudden onset of dyspnea and loss of consciousness and fetal bradycardia in a middle-aged obese nulliparous woman at 39 weeks of gestation during first stage of labor leading to the decision for emergency cesarean section. Still during surgery, the mother underwent cardiac arrest. Transesophageal echocardiography during resuscitation showed right ventricular failure leading to the diagnosis of pulmonary embolism. Return of spontaneous circulation was achieved after emergency administration of thrombolysis with alteplase and cardiopulmonary resuscitation after 40 min. Severe bleeding, coagulopathy and persistent right ventricular failure resulted in persistent hemodynamic instability leading to supracervical hysterectomy and veno-arterial extracorporal life support. Both mother and baby survived without hypoxic brain injury

Interdisziplinäre Studienprojekte gestalten: Aus der Praxis für die Praxis

In dem Praxisband werden Konzepte und praktische Umsetzung von fachbereichsübergreifenden Studienprojekten dokumentiert. Grundlage ist das Know-how aus über 30 interdisziplinären Projekten für 10 000 Studierende an der Technischen Universität Darmstadt. Die Publikation wendet sich an Lehrende, Hochschuldidaktiker sowie Lehr- und Studiengangentwickler. Das Autorenteam führt in das didaktische Konzept ein und erläutert die Gestaltung interdisziplinärer Wochen-, Semester- und Kleingruppenprojekte. Schwerpunkte der weiteren Kapitel sind die Qualifizierung von Studienprojekt-Tutoren sowie der strukturelle Rahmen für die flächendeckende Einführung von interdisziplinären Studienprojekten. Zahlreiche Übersichten, Checklisten, Beispiele und Vorlagen erleichtern die Umsetzung in die Praxis.The practical handbook documents concepts and practical implementation of interdepartmental study projects. It is based on know-how from more than 30 interdisciplinary projects for 10,000 students at Technische Universität Darmstadt. The publication is intended for teaching staff, university educationalists, as well as course developers. The team of authors gives an introduction to the didactic concept and explains the design of interdisciplinary weekly and semesterly projects and projects in small groups. Other chapters focus on qualification of study project tutors, as well as structural frameworks for comprehensive introduction of interdisciplinary study projects. Practical implementation is facilitated by numerous overviews, checklists, examples and models