500 Naturwissenschaften und Mathematik
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AbstractThe triplet‐sensitized (by the solvent acetone) as well as the direct (λex=300–320 nm) photochemical decarboxylation of N‐phthaloylated γ‐aminobutyric acid (GABA) derivatives are versatile and high‐yielding routes to benzopyrrolizidines via intramolecular electron transfer initiated decarboxylation followed by radical coupling. The ß‐mono‐ and ß,ß'‐disubstituted N‐phthaloyl GABA derivatives 7 a–7 g, respectively, were applied as substrates. Decarboxylative photocyclization yielded hydroxy benzopyrrolizidines 8 a–8 g in high chemical yields and with moderate diastereoselectivities from the ß‐monosubstituted substrates. The analogous α‐substituted GABA derivatives 11 a–11 c were also applied as potential substrates for memory of chirality effects. The reaction quantum yields of the photodecarboxylation reactions for the parent GABA derivative 13 and for the new substrates 7 h and 11 a were determined by the quantum yield determination system (QYDS) and showed a remarkable concentration dependency indicating aggregation at higher substrate concentrations. Inhibition studies on the atherogenic human serine hydrolase cholesterol esterase showed derivatives 8 a and 8 d to exhibit a hyperbolic mode of inhibition with moderate IC50 values of about 60–80 μM.
The aldol reaction of bio acetone in presence of a strongly basic ion exchange resin was carried out with and without the addition of water in a temperature range between − 30 °C and 45 °C. The conversion, selectivity and service time of the ion exchange resins were investigated in a stirred batch reactor and a continuous fixed bed reactor. For the batch experiments, both conversion and selectivity increased with decreasing temperature. Furthermore, the addition of water to the reaction medium has a positive effect on selectivity and catalyst service time of the resins. For the continuous flow experiments carried out in a fixed bed reactor, the selectivity towards diacetone alcohol is higher than in a batch reactor. This high selectivity is favored by a short contact time which inhibits as expected most of the consecutive reactions.
Agroforestry coffee cultivation represents a promising sustainable agricultural practice in the Cerro de Kuskawás Natural Reserve (CKNR). This study evaluates the impacts of agroforestry systems on the sustainability of smallholder farms, considering economic, environmental, social, and governance dimensions. Data were collected from 15 smallholder farms participating in agroforestry initiatives supported by private sector interventions, specifically through an outgrowers scheme. The research utilized a mixed-method approach, incorporating questionnaires based on the FAO’s TAPE tool and interviews, to assess changes in income stability, biodiversity, gender equity, and land tenure security.
The findings reveal that agroforestry coffee cultivation significantly enhances sustainability across multiple dimensions. Economically, it provides increased income stability and diversification, as smallholders benefit from both the higher market value of sustainably produced coffee and additional revenue from integrated crops like fruits and timber. Environmentally, agroforestry systems improve soil health, enhance biodiversity, and reduce the need for chemical inputs, contributing to a more resilient and sustainable agricultural ecosystem. Socially, the inclusion of women in these agroforestry initiatives has led to improved gender equity and greater empowerment for female smallholders.
However, the study also highlights key challenges, including the high initial costs of transitioning to agroforestry, the dependency on external support from private sector entities, and limited autonomy for smallholders due to centralized control structures. The results suggest that while agroforestry systems have the potential to significantly contribute to sustainable development in the CKNR, achieving long-term sustainability will require addressing these challenges through cooperative models and local governance structures. This study provides valuable insights into the role of agroforestry coffee cultivation in promoting sustainability.
Hydroperoxide lyases (HPLs) catalyze the splitting of 13S-hydroperoxyoctadecadienoic acid (13S-HPODE) into the green note flavor hexanal and 12-oxo-9(Z)-dodecenoic acid, which is not yet used industrially. Here, HPL from Carica papaya (HPLCP) was cloned and functionally expressed in Escherichia coli to investigate synthesis of 12-oxo-9(Z)-dodecenoic acid in detail. To improve the low catalytic activity of full-length HPLCP, the hydrophobic, non-conserved N-terminal sequence was deleted. This enhanced enzyme activity from initial 10 to 40 U/l. With optimization of solubilization buffer, expression media enzyme activity was increased to 2700 U/l. The tetrameric enzyme was produced in a 1.5 l fermenter and enriched by affinity chromatography. The enzyme preparation possesses a slightly acidic pH optimum and a catalytic efficiency (kcat/KM) of 2.73 × 106 s−1·M−1 towards 13S-HPODE. Interestingly, HPLCP-N could be applied for the synthesis of 12-oxo-9(Z)-dodecenoic acid, and 1 mM of 13S-HPODE was transformed in just 10 s with a yield of 90%. At protein concentrations of 10 mg/ml, the slow formation of the 10(E)-isomer traumatin was observed, pointing to a non-enzymatic isomerization process. Bearing this in mind, a one-pot enzyme cascade starting from safflower oil was developed with consecutive addition of Pseudomonas fluorescens lipase, Glycine max lipoxygenase (LOX-1), and HPLCP-N. A yield of 43% was obtained upon fast extraction of the reaction mixtures after 1 min of HPLCP-N reaction. This work provides first insights into an enzyme cascade synthesis of 12-oxo-9(Z)-dodecenoic acid, which may serve as a bifunctional precursor for bio-based polymer synthesis.
Biobased polymers derived from plant oils are sustainable alternatives to petro based polymers. In recent years, multienzyme cascades have been developed for the synthesis of biobased ω-aminocarboxylic acids, which serve as building blocks for polyamides. In this work, we have developed a novel enzyme cascade for the synthesis of 12-aminododeceneoic acid, a precursor for nylon-12, starting from linoleic acid. Seven bacterial ω-transaminases (ω-TAs) were cloned, expressed in Escherichia coli and successfully purified by affinity chromatography. Activity towards the oxylipin pathway intermediates hexanal and 12-oxododecenoic acid in their 9(Z) and 10(E) isoforms was demonstrated for all seven transaminases in a coupled photometric enzyme assay. The highest specific activities were obtained with ω-TA from Aquitalea denitrificans (TRAD), with 0.62 U mg−1 for 12-oxo-9(Z)-dodecenoic acid, 0.52 U mg−1 for 12-oxo-10(E)-dodecenoic acid and 1.17 U mg−1 for hexanal. A one-pot enzyme cascade was established with TRAD and papaya hydroperoxide lyase (HPLCP-N), reaching conversions of 59% according to LC-ELSD quantification. Starting from linoleic acid, up to 12% conversion to 12-aminododecenoic acid was achieved with a 3-enzyme cascade comprising soybean lipoxygenase (LOX-1), HPLCP-N and TRAD. Higher product concentrations were achieved by the consecutive addition of enzymes compared to simultaneous addition at the beginning.
Der Beitrag stellt zwei Best Practices im Chatbot Coaching vor. Der erste Teil gibt Einblicke in die Entwicklung des StudiCoachBots der TH Köln, der Reflexionsprozesse bei Studierenden zu Prüfungsangst anregt. Er fasst zentrale Forschungsergebnisse zur Beziehungsgestaltung zusammen, die Hinweise auf beziehungsbildende Faktoren im Chatbot Coaching geben (technische Funktionalität, Disclosure-Verhalten, Interaktionsmethode). Der zweite Teil stellt das Startup evoach vor – eine Coaching Plattform, die hybrides Coaching mit maßgeschneiderten Chatbots anbietet – und beschreibt anhand konkreter Anwendungsfälle, wie Chatbots in Kombination mit persönlichem Coaching den Coachingprozess bereichern.
Chatbots gelten als eine maßgebliche technologische Innovation der letzten Jahre, die als digitales Selbst-Coachingtool zunehmend den Coachingbereich erfasst. Der Beitrag gibt einen Überblick über aktuelle Entwicklungslinien von digitalen Coaching-Begleitern und Assistenten. Es werden Einsatzfelder in Unternehmen, Organisationen und Hochschulen skizziert sowie Potenziale und Herausforderungen von Coaching-Chatbots benannt. Die Konzeption und Entwicklung von Chatbots werden als interdisziplinärer, co-kreativer und iterativer Prozess vorgestellt. Der Beitrag schließt mit einem Ausblick auf die Zukunft von Chatbots im Coaching.
The use of two-component transposon plasmid vector systems, namely, a transposase construct and a donor vector carrying the gene of interest (GOI) can accelerate the development of recombinant cell lines. However, the undesired stable transfection of the transposase construct and the sustained expression of the enzyme can cause genetic instability due to the re-mobilization of the previously transposed donor vectors. Using a Sleeping Beauty -derived vector system, we established three recombinant cell pools and demonstrate stable integration of the transposase construct and sustained expression of the transposase over a period of 48 days. To provide an alternative approach, transcripts of the transposase gene were generated in vitro and co-transfected with donor vector plasmid at different ratios and mediating high GOI copy number integrations and expression levels. We anticipate that the use of transposase mRNA will foster further improvements in future cell line development processes.
Exposure is an essential component of risk models and describes elements that are endangered by a hazard and susceptible to damage. The associated vulnerability characterizes the likelihood of experiencing damage (which can translate into losses) at a certain level of hazard intensity. Frequently, the compilation of exposure information is the costliest component (in terms of time and labor) of risk assessment procedures. Existing models often describe exposure in an aggregated manner, e.g., by relying on statistical/census data for given administrative entities. Nowadays, earth observation techniques allow the collection of spatially continuous information for large geographic areas while enabling a high geometric and temporal resolution. Consequently, we exploit measurements from the earth observation missions TanDEM-X and Sentinel-2, which collect data on a global scale, to characterize the built environment in terms of constituting morphologic properties, namely built-up density and height. Subsequently, we use this information to constrain existing exposure data in a spatial disaggregation approach. Thereby, we establish dasymetric methods for disaggregation. The results are presented for the city of Santiago de Chile, which is prone to natural hazards such as earthquakes. We present loss estimations due to seismic ground shaking and corresponding sensitivity as a function of the resolution properties of the exposure data used in the model. The experimental results underline the benefits of deploying modern earth observation technologies for refined exposure mapping and related earthquake loss estimation with enhanced accuracy properties.
This contribution provides a detailed comparison of the impact of various rheological models on the filling phase of injection molding simulations in order to enhance the accuracy of flow predictions and improve material processing. The challenge of accurately modeling polymer melt flow behavior under different temperature and shear rate conditions is crucial for optimizing injection molding processes. Therefore, the study examines commonly used rheological models, including Power-Law, Second-Order, Herschel-Bulkley, Carreau and Cross models. Using experimental data for validation, the accuracy of each model in predicting the flow front and viscosity distribution for a quadratic molded part with a PA66 polymer is evaluated. The Carreau-WLF Winter model showed the highest accuracy, with the lowest RMSE values, closely followed by the Carreau model. The Second-Order model exhibited significant deviations in the edge region from experimental results, indicating its limitations. Results indicate that models incorporating both shear rate and temperature dependencies, such as Carreau-WLF Winter, provide superior predictions compared to those including only shear rate dependence. These findings suggest that selecting appropriate rheological models can significantly enhance the predictive capability of injection molding simulations, leading to better process optimization and higher quality in manufactured parts. The study emphasizes the significance of comprehensive rheological analysis and identifies potential avenues for future research and industrial applications in polymer processing.