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Crystal structures of two metal–organic frameworks (MFU‐1 and MFU‐2) are presented, both of which contain redox‐active CoII centres coordinated by linear 1,4‐bis[(3,5‐dimethyl)pyrazol‐4‐yl] ligands. In contrast to many MOFs reported previously, these compounds show excellent stability against hydrolytic decomposition. Catalytic turnover is achieved in oxidation reactions by employing tert‐butyl hydroperoxide and the solid catalysts are easily recovered from the reaction mixture. Whereas heterogeneous catalysis is unambiguously demonstrated for MFU‐1, MFU‐2 shows catalytic activity due to slow metal leaching, emphasising the need for a deeper understanding of structure–reactivity relationships in the future design of redox‐active metal–organic frameworks. Mechanistic details for oxidation reactions employing tert‐butyl hydroperoxide are studied by UV/Vis and IR spectroscopy and XRPD measurements. The catalytic process accompanying changes of redox states and structural changes were investigated by means of cobalt K‐edge X‐ray absorption spectroscopy. To probe the putative binding modes of molecular oxygen, the isosteric heats of adsorption of O2 were determined and compared with models from DFT calculations. The stabilities of the frameworks in an oxygen atmosphere as a reactive gas were examined by temperature‐programmed oxidation (TPO). Solution impregnation of MFU‐1 with a co‐catalyst (N‐hydroxyphthalimide) led to NHPI@MFU‐1, which oxidised a range of organic substrates under ambient conditions by employing molecular oxygen from air. The catalytic reaction involved a biomimetic reaction cascade based on free radicals. The concept of an entatic state of the cobalt centres is proposed and its relevance for sustained catalytic activity is briefly discussed.
Einblick in die deutsche TGA-Landschaft. Energietechniker der Hochschule Offenbach auf Exkursion
(2011)
We present a video-densitometric quantification method for the pain killer known as diclofenac and ibuprofen. These non-steroidal anti-inflammatory drugs were separated on cyanopropyl bonded plates using CH2Cl2, methanol, cyclohexane (95 + 5 + 40, v/v) as mobile phase. The quantification is based on a bio-effective-linked analysis using Vibrio fisheri bacteria. Within 10 min a CCD-camera registered the white light of the light-emitting bacteria. Diclofenac and ibuprofen effectively suppressed the bacterial light emission which can be used for quantification within a linear range of 10 to 2000 ng. The detection limit for ibuprofen is 20 ng and the limit of quantification 26 ng per zone. Measurements were carried out using a 16-bit ST-1603ME CCD camera with 1.56 megapixels (from Santa Barbara Instrument Group, Inc., Santa Barbara, USA). The range of linearity covers more than two magnitudes because the extended Kubelka-Munk expression is used for data transformation. The separation method is inexpensive, fast, and reliable.
Die Ziele des Projekts waren die Einführung der Zellseparations-Technik „Feldfluss-Fraktionierung“ (FFF) zur Analyse und Fraktionierung von Hefezellen zur Weinherstellung, sowie deren Weiterentwicklung und Optimierung für den Praxiseinsatz, insbesondere Auswahl einer einfachen FFF-Variante, Vereinfachung und Kostenoptimierung, um ein für Weinbaubetriebe erschwingliches FFF-Gerät anbieten zu können. Des Weiteren sollten FFF-Techniken als online Überwachung während des Wein-Fermentationsprozesses untersucht werden. Zur Qualitätsüberwachung war es wünschenswert unerwünschte Veränderungen während des Fermentationsprozesses frühzeitig erkennen zu können, um dann zur Qualitätsoptimierung gezielte Maßnahmen gegen unerwünschte Veränderungen vornehmen zu können. Das Projekt war auch dafür gedacht als Modell-Charakter bzw. als Pilotprojekt für andere auf dem Gärungswege durch Mikroorganismen hergestellte Produkte im Lebensmittel- oder biotechnologischen Bereich zu dienen.
The German Weather Service (DWD) releases a heat warning, when the weather forecast provides a warm, humid, sunny, and windless weather condition during the next days. The heat stress is calculated by the so called Klima-Michel model. If the apparent air temperature exceeds ca. 32°C / 38°C, there is a strong / extreme heat stress. The smallest forecast area is each administrative district. As people (and especially the vulnerable population) stay most of the time indoors, the heat health warning system was extended by the prediction of heat stress in typical rooms. Therewith it is feasible to forecast the heat stress using a combination of the outdoor and indoor heat stress. The prediction for the indoor heat stress is based on the same weather forecast like the Heat Health Warning Systems (HHWS).and calculates the heat stress by the PMV-model (predicted mean vote). Based on a sophisticated data analysis and simulation study, realistic but summer-critical living situations were defined and implemented in the building simulation program ESP-r. As the simulation runs especially for extreme weather conditions, a simplified building model cannot be used. Standardized input/output routines and an adaptive handover of start values provide for short run times for each forecast area. Good building designs and urban planning provide effective measures to reduce heat stress in cities. However, we have to also pay attention to the present building stock under climate change and a higher heat-wave risk. The extended German HHWS provide information for the emergency services to support the social assistants during heat waves.
This study presents some results from a monitoring project with night ventilation and earthto-air heat exchanger. Both techniques refer to air-based low-energy cooling. As these technologies are limited to specific boundary conditions (e.g. moderate summer climate, low temperatures during night, or low ground temperatures, respectively), water-based low-energy cooling may be preferred in many projects. A comparison of the night-ventilated building with a ground-cooled building shows major differences in both concepts.