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The Master's in Strategic Leadership towards Sustainability (MSLS) offers a transformative learning experience, yet its alumni encounter difficulties in the professional arena that have not been fully explored. This thesis illuminates the difficulties MSLS alumni face in integrating transformative learning outcomes of the program into their professional lives, their coping strategies, and what could support them. The research involved a mixed-methods approach with 34 survey responses and 13 follow-up interviews. The analysis, based on the typology of transformative learning outcomes, revealed that alumni particularly struggle integrating sustainability leadership practices, tools and concepts. Moreover, they have difficulty sustaining their new ways of being and attributes such as enthusiasm, trust and hopefulness. The main impediments to integration are the absence of a shared mental model or language with others and a working culture that inhibits the exploration of new approaches. MSLS alumni tend to address these challenges by surrounding themselves with like-minded people, developing communication strategies, and cultivating personal practices. The findings indicate a need for transition preparation as part of the MSLS program and self-organized support structures that assist alumni in transitioning into the professional world, integrating transformative learning outcomes, and assuming their role as agents for systemic change towards sustainability.

The Master's in Strategic Leadership towards Sustainability (MSLS) offers a transformative learning experience, yet its alumni encounter difficulties in the professional arena that have not been fully explored. This thesis illuminates the difficulties MSLS alumni face in integrating transformative learning outcomes of the program into their professional lives, their coping strategies, and what could support them. The research involved a mixed-methods approach with 34 survey responses and 13 follow-up interviews. The analysis, based on the typology of transformative learning outcomes, revealed that alumni particularly struggle integrating sustainability leadership practices, tools and concepts. Moreover, they have difficulty sustaining their new ways of being and attributes such as enthusiasm, trust and hopefulness. The main impediments to integration are the absence of a shared mental model or language with others and a working culture that inhibits the exploration of new approaches. MSLS alumni tend to address these challenges by surrounding themselves with like-minded people, developing communication strategies, and cultivating personal practices. The findings indicate a need for transition preparation as part of the MSLS program and self-organized support structures that assist alumni in transitioning into the professional world, integrating transformative learning outcomes, and assuming their role as agents for systemic change towards sustainability.

The Master's in Strategic Leadership towards Sustainability (MSLS) offers a transformative learning experience, yet its alumni encounter difficulties in the professional arena that have not been fully explored. This thesis illuminates the difficulties MSLS alumni face in integrating transformative learning outcomes of the program into their professional lives, their coping strategies, and what could support them. The research involved a mixed-methods approach with 34 survey responses and 13 follow-up interviews. The analysis, based on the typology of transformative learning outcomes, revealed that alumni particularly struggle integrating sustainability leadership practices, tools and concepts. Moreover, they have difficulty sustaining their new ways of being and attributes such as enthusiasm, trust and hopefulness. The main impediments to integration are the absence of a shared mental model or language with others and a working culture that inhibits the exploration of new approaches. MSLS alumni tend to address these challenges by surrounding themselves with like-minded people, developing communication strategies, and cultivating personal practices. The findings indicate a need for transition preparation as part of the MSLS program and self-organized support structures that assist alumni in transitioning into the professional world, integrating transformative learning outcomes, and assuming their role as agents for systemic change towards sustainability.

The Master's in Strategic Leadership towards Sustainability (MSLS) offers a transformative learning experience, yet its alumni encounter difficulties in the professional arena that have not been fully explored. This thesis illuminates the difficulties MSLS alumni face in integrating transformative learning outcomes of the program into their professional lives, their coping strategies, and what could support them. The research involved a mixed-methods approach with 34 survey responses and 13 follow-up interviews. The analysis, based on the typology of transformative learning outcomes, revealed that alumni particularly struggle integrating sustainability leadership practices, tools and concepts. Moreover, they have difficulty sustaining their new ways of being and attributes such as enthusiasm, trust and hopefulness. The main impediments to integration are the absence of a shared mental model or language with others and a working culture that inhibits the exploration of new approaches. MSLS alumni tend to address these challenges by surrounding themselves with like-minded people, developing communication strategies, and cultivating personal practices. The findings indicate a need for transition preparation as part of the MSLS program and self-organized support structures that assist alumni in transitioning into the professional world, integrating transformative learning outcomes, and assuming their role as agents for systemic change towards sustainability.

The Master's in Strategic Leadership towards Sustainability (MSLS) offers a transformative learning experience, yet its alumni encounter difficulties in the professional arena that have not been fully explored. This thesis illuminates the difficulties MSLS alumni face in integrating transformative learning outcomes of the program into their professional lives, their coping strategies, and what could support them. The research involved a mixed-methods approach with 34 survey responses and 13 follow-up interviews. The analysis, based on the typology of transformative learning outcomes, revealed that alumni particularly struggle integrating sustainability leadership practices, tools and concepts. Moreover, they have difficulty sustaining their new ways of being and attributes such as enthusiasm, trust and hopefulness. The main impediments to integration are the absence of a shared mental model or language with others and a working culture that inhibits the exploration of new approaches. MSLS alumni tend to address these challenges by surrounding themselves with like-minded people, developing communication strategies, and cultivating personal practices. The findings indicate a need for transition preparation as part of the MSLS program and self-organized support structures that assist alumni in transitioning into the professional world, integrating transformative learning outcomes, and assuming their role as agents for systemic change towards sustainability.

The Master's in Strategic Leadership towards Sustainability (MSLS) offers a transformative learning experience, yet its alumni encounter difficulties in the professional arena that have not been fully explored. This thesis illuminates the difficulties MSLS alumni face in integrating transformative learning outcomes of the program into their professional lives, their coping strategies, and what could support them. The research involved a mixed-methods approach with 34 survey responses and 13 follow-up interviews. The analysis, based on the typology of transformative learning outcomes, revealed that alumni particularly struggle integrating sustainability leadership practices, tools and concepts. Moreover, they have difficulty sustaining their new ways of being and attributes such as enthusiasm, trust and hopefulness. The main impediments to integration are the absence of a shared mental model or language with others and a working culture that inhibits the exploration of new approaches. MSLS alumni tend to address these challenges by surrounding themselves with like-minded people, developing communication strategies, and cultivating personal practices. The findings indicate a need for transition preparation as part of the MSLS program and self-organized support structures that assist alumni in transitioning into the professional world, integrating transformative learning outcomes, and assuming their role as agents for systemic change towards sustainability.

This report is being conducted in collaboration with Koenigsegg Automotive AB, a company founded in 1994 that manufactures mega cars. This study aims to design a license plate holder for their new car Jesko that comes in two models, Absolut and Track. The license plate holder is to be adapted to a specific country and their regulatory framework. The project also involves selecting materials and manufacturing processes in consultation with the industrial partner. The work has been divided into different stages, calculations, CAD modeling, analysis, and selection of materials and manufacturing processes. The CAD modeling is performed using Catia V5, while the analyses are conducted using SimSolid. The methodology used in this project is inspired by the method outlined in the book "Product Design and Development" by Karl T. Ulrich, Steven D. Eppinger, and Maria C. Yang. The method consists of six main steps: planning, research, customer needs, concept generation, concept selection, and detailed design. The result chose six different concepts being developed, analyzed, and compared. After identifying the most suitable concept, it is presented with a detailed product description of its design, materials, and manufacturing methods. This report is being conducted in collaboration with Koenigsegg Automotive AB, a company founded in 1994 that manufactures mega cars. This study aims to design a license plate holder for their new car Jesko that comes in two models, Absolut and Track. The license plate holder is to be adapted to a specific country and their regulatory framework. The project also involves selecting materials and manufacturing processes in consultation with the industrial partner. The work has been divided into different stages, calculations, CAD modeling, analysis, and selection of materials and manufacturing processes. The CAD modeling is performed using Catia V5, while the analyses are conducted using SimSolid. The methodology used in this project is inspired

This report is being conducted in collaboration with Koenigsegg Automotive AB, a company founded in 1994 that manufactures mega cars. This study aims to design a license plate holder for their new car Jesko that comes in two models, Absolut and Track. The license plate holder is to be adapted to a specific country and their regulatory framework. The project also involves selecting materials and manufacturing processes in consultation with the industrial partner. The work has been divided into different stages, calculations, CAD modeling, analysis, and selection of materials and manufacturing processes. The CAD modeling is performed using Catia V5, while the analyses are conducted using SimSolid. The methodology used in this project is inspired by the method outlined in the book "Product Design and Development" by Karl T. Ulrich, Steven D. Eppinger, and Maria C. Yang. The method consists of six main steps: planning, research, customer needs, concept generation, concept selection, and detailed design. The result chose six different concepts being developed, analyzed, and compared. After identifying the most suitable concept, it is presented with a detailed product description of its design, materials, and manufacturing methods. This report is being conducted in collaboration with Koenigsegg Automotive AB, a company founded in 1994 that manufactures mega cars. This study aims to design a license plate holder for their new car Jesko that comes in two models, Absolut and Track. The license plate holder is to be adapted to a specific country and their regulatory framework. The project also involves selecting materials and manufacturing processes in consultation with the industrial partner. The work has been divided into different stages, calculations, CAD modeling, analysis, and selection of materials and manufacturing processes. The CAD modeling is performed using Catia V5, while the analyses are conducted using SimSolid. The methodology used in this project is inspired

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

Borries Kukowski,1 Karin Rehberg-Weber,2 Kirsi Taipale,2 Andreas Kowalik,3 Patrick Oschmann4 1Neurologische Gemeinschaftspraxis, Göttingen, Germany; 2Biogen GmbH, Munich, Germany; 3Praxis Dr. Kowalik, Stuttgart, Germany; 4Klinik für Neurologie, Klinikum Bayreuth GmbH, Bayreuth, GermanyCorrespondence: Borries KukowskiNeurologische Gemeinschaftspraxis, Groner-Tor-Straße 3, Göttingen, 37073, GermanyTel +49 551 46069Fax +49 551 55172Email praxis@drkukowski.dePurpose: The purpose of this study was to assess the prevalence of injection site reactions (ISR) and flu-like symptoms (FLS) during treatment with subcutaneous (SC) interferon (IFN) beta therapies and to document measures to mitigate and prevent ISR and FLS.Patients and Methods: The cross-sectional post-authorization safety study PERFECT was conducted from 11/2017 to 7/2019 in neurology practices in Germany. Adult patients with relapsing-remitting multiple sclerosis (MS) receiving SC IFN beta for ≥ 3 months were eligible. The primary endpoints were patient-reported prevalence of ISR and FLS. Additional endpoints reported by patients, MS nurses, and neurologists included type, frequency, duration, time of occurrence, and management of ISR and FLS.Results: In total, 603 patients (median age 45 years [range 36– 53], 74% female) were included in the analysis. Time since MS diagnosis was > 5 years in most patients. The majority had received none (64%) or 1 (22%) prior therapy. Current MS therapy in 36%, 32%, and 30% of patients was IFN beta-1b, IFN beta-1a, and peginterferon beta-1a, respectively. ISR and FLS under current therapy were reported by 84% and 68% of patients, respectively. ISR developed within 5 days after injection (84%) and lasted for 2– 14 days (53%) in most patients. The most frequent patient-reported symptom was erythema (39%). ISR resolved or abated with systemic treatments or topical ointments. Most frequent preventive measures in

Barbara Plagg,1,2 Giuliano Piccoliori,1 Jörg Oschmann,3 Adolf Engl,1 Klaus Eisendle1,4 1Institute of General Practice and Public Health - College of Health Care Professions Claudiana, Bolzano, Italy; 2Free University of Bozen/Bolzano, Bolzano, Italy; 3Institute of Cultural and Social Anthropology, Ludwig Maximilians University, Munich, Germany; 4Central Hospital Bolzano/Bozen, Bolzano, ItalyCorrespondence: Barbara Plagg Email barbara.plagg@unibz.itAbstract: The pandemic due to SARS-CoV-2 tested the resilience of health systems worldwide. The outcome of the pandemic is impacted by health management choices made over the course of the disaster, which in turn are strongly dependent on the underlying healthcare system – as mirrored by the fact that regional pandemic experiences differ considerably: In Italy (a country most impacted by the COVID-19 outbreak), infection and mortality rates vary vastly between regions, with Lombardy – a comparatively well-equipped region with regard to hospitals and centers of scientific excellence – being amongst the worst-affected areas. Within this article, we focus on the challenges within primary health care and hospital organization, cooperation between primary and specialist care, and access to health care services: In Lombardy, neglected primary health care with a comparatively low availability of general practitioners (GPs) per inhabitant, the initial prioritization of hospitals during the pandemic while neglecting primary health care in terms of personal protective equipment (PPE), the lack of testing resources, and a failure to achieve coordinated support contributed to a quick overburdening of hospitals, where the dissolution of traditional departments into “macro-areas” may favor nosocomial infections during an ongoing pandemic. Neither specialized medicine nor privatization, but rather flexible public healthcare services working in consistent cooperation with GPs, show better efficiency in containing viral spread a

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

Natural hazards cannot be avoided, but their damage to what human beings value, such as life, health, and property, can be limited. Climate change will increase extreme weather events and overall disaster risk, which will particularly affect Least Developed Countries. Mainstreaming Disaster Risk Reduction (DRR) into development planning, the systematic integration of information stemming from risk assessments into all sectors is a recognised means to protect a country’s development gains. But despite acknowledgement and recognition through international agreements, efforts to integrate this information remain limited due to barriers of various types. The present study investigates the barriers and opportunities to mainstream DRR into communal development plans in Burundi focusing on the agricultural and educational sectors. Burundi, a country in East Africa, is frequently affected by different disasters that undermine the country’s ability to sustainably develop its economy and society. This qualitative study used mixed methods but was primarily based on 36 semi-structured interviews. The findings showed that most barriers and opportunities for risk-informed planning are tied to institutional arrangements. These can be clustered in legislation, finance, information, technology, knowledge and expertise as well as socio-political conditions and dynamics that shape disaster risks. The study concludes that to understand barriers to integration, it is essential to consider them as interlinked across different sectors, governance levels and planning phases which are influenced by underlying power dynamics between stakeholders involved. A holistic approach is recommended to address the complex system of institutional barriers and yield opportunities to protect the development process.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.

The main focus of this thesis concerns the development of Pd(II)-catalysed synthetic methodologies for the preparation of biologically active compounds. In the first part (paper I-III), unactivated C–H bonds of a cyclobutane derivative are selectively functionalised using a directing group starting from the feedstock compound verbenone (paper I). In the following part the development of an efficient transamidation protocol for the directing group removal is reported (paper II). Both procedures were then used in conjunction, for the synthesis of diverse C-3 arylated benzofuran-2-carboxylamides, in only 3 steps starting from benzofuran-2-carboxylic acid (paper III). The second part (paper IV-V) aimed to evaluate the catalytic efficiency of the heterogeneous catalyst Pd(II)-AmP-MCF in the intramolecular hydroamination of propargylic carbamates. The catalyst was able to promote the formation of various 1,3-oxazolidin-2-ones in high yields, at room temperature with low palladium loadings (paper IV). This investigation is followed by a mechanistic study of the Pd(II)-AmP-MCF catalyst’s deactivation process during a lactone formation, using X-ray absorption spectroscopy (paper V)., At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.

A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active Pd-II, which results in high efficiency of the heterogeneous catalytic system.

A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active Pd-II, which results in high efficiency of the heterogeneous catalytic system.

A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active Pd-II, which results in high efficiency of the heterogeneous catalytic system.

The main focus of this thesis concerns the development of Pd(II)-catalysed synthetic methodologies for the preparation of biologically active compounds. In the first part (paper I-III), unactivated C–H bonds of a cyclobutane derivative are selectively functionalised using a directing group starting from the feedstock compound verbenone (paper I). In the following part the development of an efficient transamidation protocol for the directing group removal is reported (paper II). Both procedures were then used in conjunction, for the synthesis of diverse C-3 arylated benzofuran-2-carboxylamides, in only 3 steps starting from benzofuran-2-carboxylic acid (paper III). The second part (paper IV-V) aimed to evaluate the catalytic efficiency of the heterogeneous catalyst Pd(II)-AmP-MCF in the intramolecular hydroamination of propargylic carbamates. The catalyst was able to promote the formation of various 1,3-oxazolidin-2-ones in high yields, at room temperature with low palladium loadings (paper IV). This investigation is followed by a mechanistic study of the Pd(II)-AmP-MCF catalyst’s deactivation process during a lactone formation, using X-ray absorption spectroscopy (paper V)., At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.

Herein, we present a short and highly modular synthetic route that involves 8-aminoquinoline directed C–H arylation and transamidation chemistry, and which enables access to a wide range of elaborate benzofuran-2-carboxamides. For the directed C–H arylation reactions, Pd catalysis was used to install a wide range of aryl and heteroaryl substituents at the C3 position of the benzofuran scaffold in high efficiency. Directing group cleavage and further diversification of the C3-arylated benzofuran products were then achieved in a single synthetic operation through the utilization of a one-pot, two-step transamidation procedure, which proceeded via the intermediate N-acyl-Boc-carbamates. Given the high efficiency and modularity of this synthetic strategy, it constitutes a very attractive method for generating structurally diverse collections of benzofuran derivatives for small molecule screening campaigns.

Background:Vast increases in life expectancy over the last century have led to shifts in population demographics and the emergence of a largely aged population, globally. This has led to a need to understand neurobiological changes associated with healthy aging. Studies on age-related changes in functional connectivity networks have largely been cross-sectional and focused on the default mode network (DMN). The current study investigated longitudinal changes in functional connectivity in multiple resting-state networks over 4 years of aging in cognitively normal older adults. Methods:Resting-state functional magnetic resonance imaging scans from older adults (n = 16) who maintained cognitive normal status over 4 years were retrieved at baseline and follow-up from the Alzheimer's Disease Neuroimaging Initiative database. A seed-based approach was executed in Functional MRI of the Brain Software Library (FSL) to examine significant changes in functional connectivity within the DMN, frontoparietal network (FPN), and salience network (SN) within subjects over time. Results:Results indicated significantly (p < 0.05, corrected) reduced functional connectivity in the FPN and SN, but not in the DMN at year 4 compared with baseline in older adults who were cognitively stable. Conclusions:The current study highlights the importance of a longitudinal approach for understanding changes in functional connectivity. The findings also underscore the need to examine multiple networks within the same participants, given that changes were apparent in the FPN and SN but not in the DMN. Future studies should also examine changes in internetwork connectivity as well as shifts in structural connectivity over time.

The main focus of this thesis concerns the development of Pd(II)-catalysed synthetic methodologies for the preparation of biologically active compounds. In the first part (paper I-III), unactivated C–H bonds of a cyclobutane derivative are selectively functionalised using a directing group starting from the feedstock compound verbenone (paper I). In the following part the development of an efficient transamidation protocol for the directing group removal is reported (paper II). Both procedures were then used in conjunction, for the synthesis of diverse C-3 arylated benzofuran-2-carboxylamides, in only 3 steps starting from benzofuran-2-carboxylic acid (paper III). The second part (paper IV-V) aimed to evaluate the catalytic efficiency of the heterogeneous catalyst Pd(II)-AmP-MCF in the intramolecular hydroamination of propargylic carbamates. The catalyst was able to promote the formation of various 1,3-oxazolidin-2-ones in high yields, at room temperature with low palladium loadings (paper IV). This investigation is followed by a mechanistic study of the Pd(II)-AmP-MCF catalyst’s deactivation process during a lactone formation, using X-ray absorption spectroscopy (paper V)., At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.

Background:Vast increases in life expectancy over the last century have led to shifts in population demographics and the emergence of a largely aged population, globally. This has led to a need to understand neurobiological changes associated with healthy aging. Studies on age-related changes in functional connectivity networks have largely been cross-sectional and focused on the default mode network (DMN). The current study investigated longitudinal changes in functional connectivity in multiple resting-state networks over 4 years of aging in cognitively normal older adults. Methods:Resting-state functional magnetic resonance imaging scans from older adults (n = 16) who maintained cognitive normal status over 4 years were retrieved at baseline and follow-up from the Alzheimer's Disease Neuroimaging Initiative database. A seed-based approach was executed in Functional MRI of the Brain Software Library (FSL) to examine significant changes in functional connectivity within the DMN, frontoparietal network (FPN), and salience network (SN) within subjects over time. Results:Results indicated significantly (p < 0.05, corrected) reduced functional connectivity in the FPN and SN, but not in the DMN at year 4 compared with baseline in older adults who were cognitively stable. Conclusions:The current study highlights the importance of a longitudinal approach for understanding changes in functional connectivity. The findings also underscore the need to examine multiple networks within the same participants, given that changes were apparent in the FPN and SN but not in the DMN. Future studies should also examine changes in internetwork connectivity as well as shifts in structural connectivity over time.

The main focus of this thesis concerns the development of Pd(II)-catalysed synthetic methodologies for the preparation of biologically active compounds. In the first part (paper I-III), unactivated C–H bonds of a cyclobutane derivative are selectively functionalised using a directing group starting from the feedstock compound verbenone (paper I). In the following part the development of an efficient transamidation protocol for the directing group removal is reported (paper II). Both procedures were then used in conjunction, for the synthesis of diverse C-3 arylated benzofuran-2-carboxylamides, in only 3 steps starting from benzofuran-2-carboxylic acid (paper III). The second part (paper IV-V) aimed to evaluate the catalytic efficiency of the heterogeneous catalyst Pd(II)-AmP-MCF in the intramolecular hydroamination of propargylic carbamates. The catalyst was able to promote the formation of various 1,3-oxazolidin-2-ones in high yields, at room temperature with low palladium loadings (paper IV). This investigation is followed by a mechanistic study of the Pd(II)-AmP-MCF catalyst’s deactivation process during a lactone formation, using X-ray absorption spectroscopy (paper V)., At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.

A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active Pd-II, which results in high efficiency of the heterogeneous catalytic system.

The main focus of this thesis concerns the development of Pd(II)-catalysed synthetic methodologies for the preparation of biologically active compounds. In the first part (paper I-III), unactivated C–H bonds of a cyclobutane derivative are selectively functionalised using a directing group starting from the feedstock compound verbenone (paper I). In the following part the development of an efficient transamidation protocol for the directing group removal is reported (paper II). Both procedures were then used in conjunction, for the synthesis of diverse C-3 arylated benzofuran-2-carboxylamides, in only 3 steps starting from benzofuran-2-carboxylic acid (paper III). The second part (paper IV-V) aimed to evaluate the catalytic efficiency of the heterogeneous catalyst Pd(II)-AmP-MCF in the intramolecular hydroamination of propargylic carbamates. The catalyst was able to promote the formation of various 1,3-oxazolidin-2-ones in high yields, at room temperature with low palladium loadings (paper IV). This investigation is followed by a mechanistic study of the Pd(II)-AmP-MCF catalyst’s deactivation process during a lactone formation, using X-ray absorption spectroscopy (paper V)., At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.

The main focus of this thesis concerns the development of Pd(II)-catalysed synthetic methodologies for the preparation of biologically active compounds. In the first part (paper I-III), unactivated C–H bonds of a cyclobutane derivative are selectively functionalised using a directing group starting from the feedstock compound verbenone (paper I). In the following part the development of an efficient transamidation protocol for the directing group removal is reported (paper II). Both procedures were then used in conjunction, for the synthesis of diverse C-3 arylated benzofuran-2-carboxylamides, in only 3 steps starting from benzofuran-2-carboxylic acid (paper III). The second part (paper IV-V) aimed to evaluate the catalytic efficiency of the heterogeneous catalyst Pd(II)-AmP-MCF in the intramolecular hydroamination of propargylic carbamates. The catalyst was able to promote the formation of various 1,3-oxazolidin-2-ones in high yields, at room temperature with low palladium loadings (paper IV). This investigation is followed by a mechanistic study of the Pd(II)-AmP-MCF catalyst’s deactivation process during a lactone formation, using X-ray absorption spectroscopy (paper V)., At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.

A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active Pd-II, which results in high efficiency of the heterogeneous catalytic system.

A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active Pd-II, which results in high efficiency of the heterogeneous catalytic system.

With the aim to understand prolonged and repeated marine anoxia after the Triassic-Jurassic massextinction event, a continuously cored, 338 metre thick succession of Rhaetian to Toarcian sediments was retrieved close to the village of Schandelah near Braunschweig (Lower Saxony, northern Germany). Here, preliminary biostratigraphical, lithological, sedimentological, geochemical, and geophysical borehole data are presented and discussed. Based on the presence of ammonites, ostracods, benthic foraminifers, calcareous nannofossils, and palynomorphs, all major Late Triassic and Early Jurassic stage boundaries and many of the standard Lower Jurassic ammonite zones could be defined. The deltaic Rhaetian sand- and siltstone succession (Exter Fm) contains evidence for seismic activity probably related to large-scale geodynamic processes. The Hettangian (Lias Alpha) is represented by a thick heterolithic succession composed of shallow marine sandy and silty beds with intercalated organic-rich shale, representing deposition on a shoreface with frequent storm activity. Progressive deepening during the Sinemurian to Toarcian resulted in repeated deposition of laminated organic-rich facies. Periods of relative sea-level fall likely occurred during the Late Hettangian, the Late Sinemurian, and Early Pliensbachian, where a series of hardgrounds occur indicating erosion on the sea floor followed by sea level rise leading to omission, and increased reworking. One of the most conspicuous features of the Lower Jurassic in the Schandelah-1 core is the presence of abundant authigenic carbonates (glendonites, concretions, beef-calcite) within the Upper Pliensbachian with partly very negative C-isotope values (down to -37%o V-PDB) suggesting the anaerobic oxidation of methane. A high-resolution organic carbon isotope record based on 485 analyses shows two major negative carbon isotope excursions (CIEs) within the lowermost Hettangian and Lower Toarcian, respectively. Both excursions coi

Tertiary alcohols are known to be challenging substrates for applications in asymmetric synthesis due to their complexity and steric hinderance. The occurrence of tertiary alcohols and their esters in nature indicates the presence of natural biocatalytic synthetic routes for their preparation. Lipase A from Candida antarctica (CalA) is a hydrolase that has previously been shown to catalyze the transesterification of racemic 2-phenylbut-3-yn-2-ol at a low rate. In this work, the activity of that enzyme was improved by protein engineering through a semi-rational design strategy. An enzyme library was created and screened for transesterification activity towards racemic 2-phenylbut-3-yn-2-ol in an organic solvent. One successful enzyme variant (L367G) showed a tenfold increased reaction rate compared to the wild-type enzyme, while maintaining a high enantioselectivity., QC 20190610

The highly active ruthenium-based water oxidation catalyst [Ru-X(mcbp)(OHn)(py)(2)] [mcbp(2-)=2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine; n=2, 1, and 0 for X=II, III, and IV, respectively], can be generated in a mixture of Ru-III and Ru-IV states from either [Ru-II(mcbp)(py)(2)] or [Ru-III(Hmcbp)(py)(2)](2+) precursors. The precursor complexes are isolated and characterized by single-crystal X-ray analysis, NMR, UV/Vis, EPR, and FTIR spectroscopy, ESI-HRMS, and elemental analysis, and their redox properties are studied in detail by electrochemical and spectroscopic methods. Unlike the parent catalyst [Ru(tda) (py)(2)] (tda(2-)=[2,2:6,2-terpyridine]-6,6-dicarboxylate), for which full transformation into the catalytically active species [Ru-IV(tda)(O)(py)(2)] could not be carried out, stoichiometric generation of the catalytically active Ru-aqua complex [Ru-X(mcbp)(OHn)(py)(2)] from the Ru-II precursor was achieved under mild conditions (pH7.0) and short reaction times. The redox properties of the catalyst were studied and its activity for electrocatalytic water oxidation was evaluated, reaching a maximum turnover frequency (TOFmax) of around 40000s(-1) at pH9.0 (from foot-of-the-wave analysis), which is comparable to the activity of the state-of-the-art catalyst [Ru-IV(tda)(O)(py)(2)]., QC 20190806

Herein, we present an operationally simple protocol for the cycloisomerization of propargylic carbamates in which a heterogeneous catalyst consisting of Pd species immobilized on amino-functionalized siliceous mesocellular foam (Pd-II-AmP-MCF) is used. This Pd nanocatalyst displayed high efficiency at low catalyst loading and reaction temperatures, which allowed for the efficient and mild synthesis of a wide range of 1,3-oxazolidin-2-one derivatives and related compounds. Moreover, it proved possible to re-use the Pd nanocatalyst for several reactions, although a gradual decrease in activity was observed in the subsequent cycles.

This work demonstrates how a series of complex, chiral cyclobutane derivatives can be accessed in four steps from the terpene verbenone through the application of a directed C-H functionalization approach. The developed synthetic route involved an 8-aminoquinoline-directed C(sp(3))-H arylation as the key step, and this reaction could be carried out with a wide range of aryl and heteroaryl iodides to furnish a variety of cyclobutane products with three contiguous stereocenters. Moreover, it was shown that the 8-aminoquinoline auxiliary could be effectively removed from the cyclobutane derivatives using an ozonolysis-based cleavage method.

The highly active ruthenium-based water oxidation catalyst [Ru-X(mcbp)(OHn)(py)(2)] [mcbp(2-)=2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine; n=2, 1, and 0 for X=II, III, and IV, respectively], can be generated in a mixture of Ru-III and Ru-IV states from either [Ru-II(mcbp)(py)(2)] or [Ru-III(Hmcbp)(py)(2)](2+) precursors. The precursor complexes are isolated and characterized by single-crystal X-ray analysis, NMR, UV/Vis, EPR, and FTIR spectroscopy, ESI-HRMS, and elemental analysis, and their redox properties are studied in detail by electrochemical and spectroscopic methods. Unlike the parent catalyst [Ru(tda) (py)(2)] (tda(2-)=[2,2:6,2-terpyridine]-6,6-dicarboxylate), for which full transformation into the catalytically active species [Ru-IV(tda)(O)(py)(2)] could not be carried out, stoichiometric generation of the catalytically active Ru-aqua complex [Ru-X(mcbp)(OHn)(py)(2)] from the Ru-II precursor was achieved under mild conditions (pH7.0) and short reaction times. The redox properties of the catalyst were studied and its activity for electrocatalytic water oxidation was evaluated, reaching a maximum turnover frequency (TOFmax) of around 40000s(-1) at pH9.0 (from foot-of-the-wave analysis), which is comparable to the activity of the state-of-the-art catalyst [Ru-IV(tda)(O)(py)(2)].

Tertiary alcohols are known to be challenging substrates for applications in asymmetric synthesis due to their complexity and steric hinderance. The occurrence of tertiary alcohols and their esters in nature indicates the presence of natural biocatalytic synthetic routes for their preparation. Lipase A from Candida antarctica (CalA) is a hydrolase that has previously been shown to catalyze the transesterification of racemic 2-phenylbut-3-yn-2-ol at a low rate. In this work, the activity of that enzyme was improved by protein engineering through a semi-rational design strategy. An enzyme library was created and screened for transesterification activity towards racemic 2-phenylbut-3-yn-2-ol in an organic solvent. One successful enzyme variant (L367G) showed a tenfold increased reaction rate compared to the wild-type enzyme, while maintaining a high enantioselectivity.

Today’s turbulent economic environment confronts the European tooling industry with new challenges: strategic differentiation via cost-leadership has not worked out for European toolmakers over the last years. Other industries have shown a promising approach for creating competitive advantages over competitors and higher profitability by enhancing the existing range of products with customer-specific services. An intelligent bundling of individual services with the core product leads to so-called hybrid products or product-service-systems. These systems not only ensure the proper functioning of the product but also increase efficiency and effectiveness of the customer's processes. Even though, the concept of product-service-systems is well known, few concepts exist, which build a holistic focus on products and services from a developers point of view. In order to apply the idea of moving into the service business to the tooling industry we set up a study on product-service systems in the tooling industry. As other European manufacturers as well, players in the tooling industry face an increasing market pressure from international competitors. One solution to remain competitive is to focus on delivering knowledge intensive products and services This research paper's goal is to develop an empirically based portfolio for future product-service systems and is embedded in a larger European study. The overall study is funded by the seventh framework program of the EU and has the goal to integrate the customer and developer perspectives in developing product-service-systems. This paper concentrates on the customer perspective of developing product-service systems. The first step of our study was to develop a questionnaire together with toolmakers covering topics like general customer needs, existing and desired services, the production process itself as well as the distribution of cost in the maintenance process. Conducting the survey using mailings and an internet based p