JLUdocsSchriftenrepositoriumhttps://jlupub.ub.uni-giessen.de//handle/jlupub/582024-03-19T06:33:19Z2024-03-19T06:33:19ZNew Ways of Diamondoid Functionalization – A Synthetic Method for the Incorporation of Dispersion Energy Donors into Catalysts and Molecular BalancesOchmann, Lukas Peterhttps://jlupub.ub.uni-giessen.de//handle/jlupub/190822024-03-18T14:15:16Z2023-01-01T00:00:00ZNew Ways of Diamondoid Functionalization – A Synthetic Method for the Incorporation of Dispersion Energy Donors into Catalysts and Molecular Balances
Ochmann, Lukas Peter
This thesis deals with the selective functionalization of diamondoids and their incorporation in existing catalytic systems as well as molecular balances to quantify London dispersion interactions.
In the first part, we present a new substitution reaction based on the Mitsunobu reaction. This sequence works particularly well for lower diamondoids, like adamantane and diamantane, with high yields and good reaction control. Abundant alcohols react to diphenylphosphinite structures. The corresponding diamondoid based trivalent phosphorous compounds are insensitive towards air and moisture and therefore ideal storable precursors. The reaction of the phosphinites with diisopropylazodicarboxylate as activating agent leads to an intermediate betaine structure. The latter collapses upon protonation by a mildly acidic nucleophile, to a carbocation. This cation is trapped by the deprotonated nucleophile leading to the desired target compound. The reaction sequence is universal for all structures that can form a stabilized carbocation intermediate and works well for a broad variety of pronucleophiles. Therefore it offers the possibility of nearly every C−C or C−heteroatom bond formation reaction. Mechanistic studies underline the formation of a carbocation intermediate, which has not been reported in all redox condensation reactions published so far.
The second part of this thesis deals with a new uniform synthesis concept towards all-meta substituted iodobenzenes and anilines. 3,5-Disubstituted catechols serve as starting materials and were synthesized via formylation of the corresponding 2,4-disubstituted phenols and subsequent Dakin reaction. After oxidation of the dihydroxybenzenes, the o quinones react in a [4+2] cycloaddition with an alkyne to a bicyclic 1,2-diketone. Final photodecarbonylation with visible light yield the 1,3,5-trisubstituted scaffold which is further manipulated to the desired targets via known reactions, e.g., Schmidt reaction. The new type of substitution reaction from the first part of this thesis was crucial for the generation of the 3,5-disubstituted diamondoid precursors since the corresponding phenol structure was not available and the sequence described before was not applicable to adamantane and diamantane substituted compounds. This underlines the importance of suitable reaction sequences that also enable the incorporation of diamondoids into existing structures.
We applied our new scalable reaction pathway in the synthesis of chiral BINOL-based phosphoric acid catalysts, substituted with all-meta adamantyl and diamantyl arenes. In a comparative study, this new bulky catalyst performed equally well in comparison to existing catalysts in the reductive amination reaction of acetophenone and delivers enantiomeric excesses of up to 84% without optimization of the reaction conditions.
2023-01-01T00:00:00ZFrom Trialing to Adaptation: Embracing Nuanced Farmers’ Adoption for Agroecological TransitionsOlagoke, AdewoleKassie, MenaleKuyah, ShemNiassy, SaliouNolte, KerstinMartin, Emily A.https://jlupub.ub.uni-giessen.de//handle/jlupub/190932024-03-18T13:30:17Z2023-01-01T00:00:00ZFrom Trialing to Adaptation: Embracing Nuanced Farmers’ Adoption for Agroecological Transitions
Olagoke, Adewole; Kassie, Menale; Kuyah, Shem; Niassy, Saliou; Nolte, Kerstin; Martin, Emily A.
2023-01-01T00:00:00ZFrom Project interventions to Transformative Impacts: Charting Paths for Sustained Adoption of Agri-Food InnovationsOlagoke, AdewoleKassie, Menalehttps://jlupub.ub.uni-giessen.de//handle/jlupub/190942024-03-18T13:30:16Z2023-01-01T00:00:00ZFrom Project interventions to Transformative Impacts: Charting Paths for Sustained Adoption of Agri-Food Innovations
Olagoke, Adewole; Kassie, Menale
Sustainable agriculture and resilient food systems require farmers to adopt agri-food innovations. Many development initiatives have promoted promising innovations, but achieving sustained adoption is challenging. Project interventions often witness fleeting uptake, with many farmers reverting to traditional practices when project cycles are over. This "project syndrome" phenomenon is a well-known issue in agricultural development, where farmers' adoption behavior is driven largely by project incentives rather than a genuine acceptance based on the potential benefits of the innovations, which hinders widespread impacts and a desirable systemic change. It calls for a shift from a project-centric approach to a more transformative one that prioritizes farmers' buy-in, stakeholder engagement, and co-execution of innovation processes and outcomes. This interactive dialogue session brings together a diverse group of stakeholders, including researchers, practitioners, donors, policymakers, agro-dealers, and farmers, to discuss and chart the paths for sustained adoption of agri-food innovations. We will explore the incidence, underlying causes, and consequences of project syndrome and identify strategies to encourage organic and transformative adoption of Agri-Food innovations. The session will begin with a keynote presentation, setting the stage for subsequent interactions. Then, a panel discussion featuring experts from different regions with first-hand experience, insights, and recommendations to facilitate sustained adoption will follow. Among other relevant topics, the panel will provide perspectives on farmer-centered design and co-creation, local capacity-building, market incentives and value chains, and policy and governance frameworks. Participants will have the opportunity to ask questions to the panel, share ideas and experiences, and co-create strategies necessary to achieve sustained adoption of agri-food innovations, leading to a lasting impact on the lives of farmers and their communities. Overall, this dialogue session provides a valuable platform for advancing the discourse on the sustained adoption of agri-food innovations and for catalyzing collective action towards transformative change.
2023-01-01T00:00:00ZPulmonary Artery Hypertension Incidence in the Postoperative Course in Lung Cancer Surgery and the Influence of Pulmonary Artery Hypertension on the Postoperative Course and Long-term SurvivalAlkoudmani, Ibrahimhttps://jlupub.ub.uni-giessen.de//handle/jlupub/190912024-03-15T10:45:14Z2023-01-01T00:00:00ZPulmonary Artery Hypertension Incidence in the Postoperative Course in Lung Cancer Surgery and the Influence of Pulmonary Artery Hypertension on the Postoperative Course and Long-term Survival
Alkoudmani, Ibrahim
Objectives: Pulmonary artery hypertension (PAH) is one of the serious complications of advanced lung cancer, as well as lung cancer surgical therapy. PAH is also related to high morbidity and mortality in postoperative lung cancer survivors. This study aims to determine the postoperative incidence of PAH in lung cancer surgery in stage II & III lung cancer patients, and the influence of PAH on the postoperative course and long-term survival.
Methods: A retrospective cohort study included 241 lung cancer patients who underwent curative resection for non-small cell lung cancer NSCLC (stage II, III) at Giessen Lung Cancer Centre in Hessen Germany between 2010 and 2019. Pulmonary artery diameter/Aorta diameter (PA/A) ratio derived from chest computed tomography (CT) scan was used as a predictor for pulmonary hypertension before and after lung surgery. Techniques, complications, Long-term survival and outcomes were analyzed using IBM SSPS.
Results: Mean PA & A diameters and PA/A ratio were 27.2 mm, 34.1 mm and 0.81 respectively. Postoperative PAH incidence at 6, 12, 18 months was 5.9%, 9.4%, and 15% respectively. Complications after lung resection occurred in 117 (48.5%) patients; respiratory complications were the most common. However, patients with postoperative atrial fibrillation were at a high risk to develop PAH in each follow-up (p<0.01), mostly at 18 months (odds ratio, 9.9; 95% CI, 2.5 to 295; p= 0.006). Mean hospitalization period in patients with postoperative PAH at 6, 12, 18 months was 12.6, 14.8, and 12.6 days respectively, mean survival years for those patients was (2.6 ± 2.79), (3.2 ± 3.05), (4.3 ± 2.94) respectively (p>0.05). Mortality was related to pulmonary comorbidities with a detected 118-fold risk for those patients (p=0.02), complicated cases were also at a higher risk for death compared to patients without postoperative complications (non-adjusted hazard ratio, 2.1; 95% CI, 1.2 to 3.5; p=0.006). Pulmonary artery hypertension as a predictor of death was of weak sensitivity and specificity (< 70%).
Conclusion: Pulmonary artery hypertension is one of the possible lung cancer comorbidities. However, new onset PAH after lung resection is often detected, with tendency to occur late. Therefore, investigations for increased pulmonary artery pressure should -at least- continue for 18 months after surgery. Atrial fibrillation in particular should arise suspicion for PAH.
2023-01-01T00:00:00ZQuantifying ecological structure and ecosystem services in farmlandPoppenborg Martin, Emilyhttps://jlupub.ub.uni-giessen.de//handle/jlupub/190872024-03-14T14:15:15Z2023-03-01T00:00:00ZQuantifying ecological structure and ecosystem services in farmland
Poppenborg Martin, Emily
In this talk, I will describe how we can assess and support the management of ecosystem services in crops through targeted increases in arthropod functional biodiversity. Various management practices can be implemented to increase biodiversity on farms, but how well do these translate into increased or more stable ecosystem services, are there tradeoffs, and what are the consequences for yields? Management of individual fields, but also the structure and composition of whole landscapes have an impact on arthropod communities and associated services. However, patterns are highly variable between studies, geographical regions, organism groups and crops. I outline elements of consensus that have recently emerged for the quantification of ecological structures in farmed landscapes and highlight gaps in our understanding of how to predict their impact on ecosystem service provision and stability across space and time.
2023-03-01T00:00:00ZThe upscaling and out-scaling of ecological intensification: how smallholder farms can inform the science of managing biocontrol at scaleMartin, Emily A.Librán Embid, FelipeOlagoke, Adewolehttps://jlupub.ub.uni-giessen.de//handle/jlupub/190862024-03-14T11:45:14Z2023-01-01T00:00:00ZThe upscaling and out-scaling of ecological intensification: how smallholder farms can inform the science of managing biocontrol at scale
Martin, Emily A.; Librán Embid, Felipe; Olagoke, Adewole
Current objectives to harness agroecological functioning to improve the biological control of crop pests are conditional on a range of ecological, social, economic and cultural mechanisms that may hinder or support the success of such endeavours. Against the backdrop of ongoing work focused on the push-pull technology, a mixed cropping strategy aiming to increase biocontrol in smallholder farms of Sub-Saharan Africa, we review some key challenges and knowledge gaps associated with enhancing and managing biocontrol practices on farms. While major knowledge gaps exist with regard to ecological processes affecting biocontrol success at small to large scales, these can quickly be trumped in terms of capacity for implementation by non-ecological factors such as the structure of social systems and the existence and effectiveness of training networks. We argue that it is our responsibility to formulate questions for biocontrol research that lead to effective, adaptable and resilient solutions for the real-world contexts in which they should be implemented. Consequently, research aiming to understand ecological processes for improved biocontrol must be increasingly transdisciplinary and leave a wide margin for flexible application of ecologically-driven principles.
2023-01-01T00:00:00ZHarnessing the push-pull technology for biodiverse agroecosystems in East Africa: the UPSCALE projectPoppenborg Martin, Emilyhttps://jlupub.ub.uni-giessen.de//handle/jlupub/190852024-03-14T14:14:18Z2022-01-01T00:00:00ZHarnessing the push-pull technology for biodiverse agroecosystems in East Africa: the UPSCALE project
Poppenborg Martin, Emily
The push-pull technology is a mixed cropping system practiced in smallholder tropical cereal farming in areas of East and Central Africa. Push-pull systems harness the chemical interactions of companion plants and insects to provide highly effective pest protection and yield enhancement of crops. In this talk I will present the EU Horizon 2020 project UPSCALE which is working to upscale the push-pull technology for sustainable agricultural intensification in East Africa and beyond. Major focal points of the project include investigation of how landscape-level factors influence the effectiveness of push-pull systems, how increases in the landscape-level amount of push-pull cropping influences arthropod communities within and outside crops, and how transdisciplinarity can help to address key bottlenecks for the implementation of push-pull practices at scale. From this I will discuss and highlight key knowledge and practice gaps for the broader expansion of biodiversity-enhancing intensification practices in tropical agroecosystems.
2022-01-01T00:00:00ZInvestigation of All-Solid-State batteries' Transition towards Large-Scale Processing with Emphasis on In Situ Gas AnalysisTeo, Jun Haohttps://jlupub.ub.uni-giessen.de//handle/jlupub/190882024-03-14T09:00:19Z2022-01-01T00:00:00ZInvestigation of All-Solid-State batteries' Transition towards Large-Scale Processing with Emphasis on In Situ Gas Analysis
Teo, Jun Hao
With liquid-based lithium-ion batteries approaching both its theoretical and practical limits, the progress in all-solid-state batteries (SSBs) offer an exciting improvement and future for energy storage systems. The exponential progress of SSBs on the laboratory/research-scale in the last decade has led to promising results and is currently on the cusp of large-scale implementation. The transition from lab-scale to industrial-scale is not trivial and require the considerations of several intertwined factors, for example safety, processability, performance, etc.…. In the present work, the use of industrial relevant materials are crucial for a seamless transition from liquid- to solid-based lithium ion batteries. The cathode active material (CAM) is a layered lithium transition metal oxides Li1+x(Ni1–y–zCoyMnz)1–xO2 (NCM or NMC). For the solid electrolyte (SE), sulfides (thiophosphate) are a popular choice largely due to both its processability and mechanical properties. The present work will address key questions on the safety aspect, specifically the gas evolution during cell operation using in situ gas analysis. Additionally, questions regarding the processability and performance will be addressed using a number of analysis techniques with in situ gas analysis in tandem.
The first section will introduce the motivations and principles behind a lithium-ion battery and elaborate upon the active materials used for our study on SSBs. In the second section, the customized cell setup used for in situ gas analysis for SSBs will be elaborated. Additionally, we will provide an in-depth insight into the gassing technique used in this study (Differential electrochemical mass spectrometry, DEMS). The third section will elaborate upon the large-scale processing technique employed in our lab to produce sheet-based electrodes. The process of selection and optimization along every stage of the fabrication process will be described in detail. Lastly, in the fourth section (results and discussion), a compilation of the various publications can be found.
The first publication will demonstrate the capabilities of the customized cell to investigate gas evolution in SSBs. This study was used to establish a baseline for future gassing studies on SSBs, thus the comparison between conventional liquid-based lithium-ion batteries (LIBs) and two sulfide-based SSBs (𝛽-Li3PS4 and Li6PS5Cl). The measurements first illustrate the differences in the type and amount of gas evolved between LIBs and SSBs, with LIBs mostly outgassing the SSBs except for two exceptions, namely O2 and SO2. The observation of toxic SO2 gas brings to attention the hazards of using sulfide SEs in SSBs. Additionally, the main contribution of CO2 gas evolution in SSBs was clarified to be a result of electrochemical decomposition of the coating (impurity) layer. This led to the further use of in situ gassing studies for the evaluation of coating chemistries in future publications.
The second publication will display the transition toward large-scale processing techniques for SSBs. First, the individual processing steps (mixing, casting, drying) were optimized for the preparation of mechanically stable, homogeneous electrode sheets (section 3). The electrode sheets exhibited highly competitive performance versus those prepared using conventional powder-based processing. The second publication highlights a design-of-experiments (DoE)-guided approach to evaluate the influence of polymeric binder and carbon additives on the overall cell performance. The results were primarily supported by in situ gas analysis, which showed that certain polymeric functional group and/or chains/units potentially interact with the surrounding electrode components and lead to an increased degradation during cell operation.
In the third publication, the dependence of cell performance on (chemo)mechanical effects was investigated. The combination of slurry-based processing and glassy SE was shown to improve the (chemo)mechanical properties of a cell, which allowed the cell components to maintain tight contact between each other while at the same time mitigating volume changes.
The results demonstrate that the CAM/SE interface should not only function as a self-limiting interface, preventing further (electro)chemical reactions, but also possess the necessary mechanical strength needed to maintain intimate contact after prolonged cycling.
2022-01-01T00:00:00ZUpscaling push-pull technology for sustainable agricultural intensification in East AfricaPoppenborg Martin, EmilyLibrán Embid, FelipeOlagoke, Adewolehttps://jlupub.ub.uni-giessen.de//handle/jlupub/190832024-03-18T12:59:27Z2021-01-01T00:00:00ZUpscaling push-pull technology for sustainable agricultural intensification in East Africa
Poppenborg Martin, Emily; Librán Embid, Felipe; Olagoke, Adewole
The UPSCALE project aims to achieve food security in sub-Saharan Africa by using nature-based solutions inspired by push-pull technology to close the yield gap in smallholder agriculture.
2021-01-01T00:00:00ZDemokratie Leben Lernen 2.0: Politische Sozialisation zu Beginn der Sekundarstufe I - Erste ErgebnisseGerezgiher, MicalKamper, Patriciahttps://jlupub.ub.uni-giessen.de//handle/jlupub/190782024-03-13T14:30:16Z2023-01-01T00:00:00ZDemokratie Leben Lernen 2.0: Politische Sozialisation zu Beginn der Sekundarstufe I - Erste Ergebnisse
Gerezgiher, Mical; Kamper, Patricia
2023-01-01T00:00:00Z