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Year of publication
Document Type
- Article (reviewed) (673) (remove)
Is part of the Bibliography
- yes (673) (remove)
Keywords
- Dünnschichtchromatographie (17)
- Adsorption (11)
- Metallorganisches Netzwerk (9)
- Ermüdung (8)
- Lithiumbatterie (8)
- Plastizität (8)
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High pressure adsorption phenomena are discussed for different gases on HKUST-1 (Cu3(BTC)2, commercially available product BasoliteTM C300). Sorption isotherms for hydrogen, nitrogen, methane and carbon dioxide on HKUST-1 were measured in the temperature range of 273–343 K and at pressures up to 50 MPa. The calculated surface excess adsorption capacities for all four adsorptive are one of the highest reported in the literature for HKUST-1 samples. All surface excess data were further calculated from the experimental data by using the helium buoyancy correction. A detailed description was given.
Also a procedure to calculate the absolute amount adsorbed from the surface excess amount by using two different models is shown. Using one model, the density and the volume of the adsorbed phase can be calculated. The density of the adsorbed phase ρads corresponds to the liquid density of the adsorptive at its boiling point ρliq,BP. In case of hydrogen no excess maximum was found up to 50 MPa, so that one model could not be applied. Finally, the isosteric heat of adsorption for each gas was calculated by using the Clausius–Clapeyron equation.
In dem abgeschlossenen Vorhaben „Entwicklung von Rechenmodellen zur Lebensdauervorhersage von Motorbauteilen unter thermisch-mechanischer Ermüdungsbeanspruchung“ der Forschungsvereinigung Verbrennungskraftmaschinen e. V. (FVV) wurde am Fraunhofer Institut für Werkstoffmechanik IWM in Freiburg ein Materialmodell zur Lebensdauervorhersage thermomechanisch belasteter Komponenten entwickelt. Das Modell basiert auf einem viskoplastischen Verformungsmodell für Eisengusswerkstoffe und einem mechanismenbasierten Modell für Mikrorisswachstum zur Lebensdauervorhersage.
A survey in 2000 revealed that only about 30% of the prescriptions in the European pediatric population were on the basis of evidence-based medicine (EbM). Less for radiopharmaceuticals and principally for diagnostics, radiologists throughout Europe are referred to the pediatric guidelines of the European Association of Nuclear Medicine (EANM), as none of the frequently used tracers have been evaluated in clinical trials in the different pediatric subgroups. Following a resolution to address the lack of EbM in children, the European Commission published the Pediatric Regulation EC 1901/2006 and its amendment EC 1902/2006, effective from 2007. This regulation foresees the development of evidence-based medicine in the pediatric population. This is effected through a set of principles like the mandatory pediatric investigation plan (PIP) to be included with the market authorization application (MAA), and the pediatric use market authorization (PUMA) for off-patent pharmaceuticals, and to a very small part radiopharmaceuticals with funding possibilities for pediatric-specific research through the 7th Framework Programme (7FP) of the European Union.
Routine nuclear cardiology examinations indicate heart rate, cardiac rhythm, the height of cardiac pulse and respiration rhythm. It would be of interest to study whether these data, especially if the same tests are repeated, can indicate patients’ well being in the future and perhaps patients’ life span, other factors being equal. Related old theories and suggestions are mentioned. Furthermore, some drugs like I-f channel antagonists and stress tests testing cardiac reserves could support such a study.
The Humboldt digital library (HDL) represents an innovative system to access the works and legacy of Alexander von Humboldt in a digital form on the Internet (www.avhumboldt.net). It contributes to the key question about how to present interconnected data in an appropriate form using information technologies. The HDL has been created as a dynamic digital library with the capability of connecting multilingual and multimedia data from diverse online archives. Humboldt’s volumes have become available, but beyond that any relevant information related to the observations of Humboldt, even outside the works can become immediately accessible. This makes it possible to recognize natural changes and compare Humboldt’s descriptions with recent situations. The technology we have developed addresses the issues of sustainability and makes it possible to detect changes in the environment since the time of Humboldt’s observations.
Tonigold, Markus ; Lu, Ying ; Mavrandonakis, Andreas ; Puls, Angela ; Staudt, Reiner ; Möllmer, Jens ; Sauer, Joachim ; Volkmer, Dirk
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.
Lincke, Jörg ; Lässig, Daniel ; Möllmer, Jens ; Reichenbach, Christian ; Puls, Angela ; Möller, Andreas ; Gläser, Roger ; Kalies, Grit ; Staudt, Reiner ; Krautscheid, Harald
Synthesis and crystal structure of a novel copper-based MOF material are presented. The tetragonal crystal structure of [ ∞ 3 ( Cu 4 ( μ 4 -O ) ( μ 2 -OH ) 2 ( Me 2 trz p ba ) 4 ] possesses a calculated solvent-accessible pore volume of 57%. Besides the preparation of single crystals, synthesis routes to microcrystalline materials are reported. While PXRD measurements ensure the phase purity of the as-synthesized material, TD-PXRD measurements and coupled DTA–TG–MS analysis confirm the stability of the network up to 230 °C. The pore volume of the microcrystalline material determined by nitrogen adsorption at 77 K depends on the synthetic conditions applied. After synthesis in DMF/H2O/MeOH the pores are blocked for nitrogen, whereas they are accessible for nitrogen after synthesis in H2O/EtOH and subsequent MeOH Soxhleth extraction. The corresponding experimental pore volume was determined by nitrogen adsorption to be V Pore = 0.58 cm 3 g - 1 . In order to characterize the new material and to show its adsorption potential, comprehensive adsorption studies with different adsorptives such as nitrogen, argon, carbon dioxide, methanol and methane at different temperatures were carried out. Unusual adsorption–desorption isotherms with one or two hysteresis loops are found – a remarkable feature of the new flexible MOF material.
Lässig, Daniel ; Lincke, Jörg ; Möllmer, Jens ; Reichenbach, Christian ; Möller, Andreas ; Gläser, Roger ; Kalies, Grit ; Cychosz, Katie A. ; Thommes, Matthias ; Staudt, Reiner ; Krautscheid, Harald
Uptakes of 9.2 mmol g−1 (40.5 wt %) for CO2 at 273 K/0.1 MPa and 15.23 mmol g−1 (3.07 wt %) for H2 at 77 K/0.1 MPa are among the highest reported for metal–organic frameworks (MOFs) and are found for a novel, highly microporous copper‐based MOF (see picture; Cu turquoise, O red, N blue). Thermal analyses show a stability of the flexible framework up to 250 °C.
Metal–organic frameworks (MOFs) as highly porous materials have gained increasing interest because of their distinct adsorption properties.1–3 They exhibit a high potential for applications in gas separation and storage,4 as sensors5 as well as in heterogeneous catalysis.6 In the last few years, the H2 storage capacity of MOFs has been considerably increased. Mesoporous MOFs show high adsorption capacities for CH4, CO2, and H2 at high pressures.2, 3, 7–10 To increase the uptake of H2 and CO2 by physisorption at ambient pressure, adsorbents with small micropores as well as high specific surface areas and micropore volumes are required.11, 12 Such microporous materials seem to be more appropriate for gas‐mixture separation by physisorption than mesoporous materials. For gas separation in MOFs the interactions between the fluid adsorptive and “open metal sites” (coordinatively unsaturated binding sites) or the ligands are regarded as important.13 Industrial processes, such as natural‐gas purification or biogas upgrading, can be improved with those materials during a vapor‐pressure swing adsorption cycle (VPSA cycle) or a temperature swing adsorption cycle (TSA cycle).14 The microporous MOF series CPO‐27‐M (M=Mg, Co, Ni, Zn), for example, shows very high CO2 uptakes at low pressures (<0.1 MPa).15, 16 Concerning H2 adsorption, the microporous MOF PCN‐12 offers with 3.05 wt % the highest uptake at ambient pressure and 77 K reported to date.17
Herein, we present a novel microporous copper‐based MOF equation image[Cu(Me‐4py‐trz‐ia)] (1; Me‐4py‐trz‐ia2−=5‐(3‐methyl‐5‐(pyridin‐4‐yl)‐4H‐1,2,4‐triazol‐4‐yl)isophthalate) with extraordinarily high CO2 and H2 uptakes at ambient pressure, the H2 uptake being similar to that in PCN‐12. The ligand Me‐4py‐trz‐ia2−, which can be obtained from cheap starting materials by a three‐step synthesis in good yield, combines carboxylate, triazole, and pyridine functions and is adopted from a recently presented series of linkers,18 for which up to now only a few coordination polymers are known.
The present study describes medium-chain-length polyhydroxyalkanoates (mcl-PHAs) production by the Pseudomonas Gl01 strain isolated from mixed microbial communities utilized for PHAs synthesis. A two-step fedbatch fermentation was conducted with glucose and waste rapeseed oil as the main carbon source for obtaining cell growth and mcl-PHAs accumulation, respectively. The results show that the Pseudomonas Gl01 strain is capable of growing and accumulating mcl-PHAs using a waste oily carbon source. The biomass value reached 3.0 g/l of CDW with 20% of PHAs content within 48 h of cultivation. The polymer was purified from lyophilized cells and analyzed by gas chromatography (GC). The results revealed that the monomeric composition of the obtained polyesters depended on the available substrate. When glucose was used in the growth phase, 3-hydroxyundecanoate and 3- hydroxydodecanoate were found in the polymer composition, whereas in the PHAs-accumulating stage, the Pseudomonas Gl01 strain synthesized mcl-PHAs consisting mainly of 3- hydroxyoctanoate and 3-hydroxydecanoate. The transcriptional analysis using reverse-transcription real-time PCR reaction revealed that the phaC1 gene could be transcribed simultaneously to the phaZ gene.
An analytical and numerical study of the wobbling dynamics of friction disks is presented. Of particular interest is the excitation mechanism taking into account two contrarian effects both originating in dry friction: the circulatory terms describing the energy input due to the sliding contacts and the friction induced damping which stabilizes the system. Balance of these terms determines the instability domain in the parameter space. It is shown that there is a slip threshold so that, if the slip is under this limit, the system remains stable. If the slip is larger than this limit, then the criterion of stability is determined by the relation between the friction coefficient and the internal damping. The limit cycle appearing in the unstable domain is also investigated. It is shown that the limit cycle can be described as a kind of a regular reverse precession of the wobbling disc. Its amplitude is limited by the geometric nonlinearity and partial contact loss. Analytic results are compared with numeric simulations.