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An algorithm is presented that has successfully been utilized in practice for several years. It improves data analysis in chromatography. The program runs in an extremely reliable way and evaluates chromatographic raw data with an acceptable error. The algorithm requires a minimum of preliminaries and integrates even unsmoothed noisy data correctly.
Shapes and structures of vortex breakdown phenomena in rotating fluids are visualized. We investigate the flow in a cylindrical container and in a cone between two spherical surfaces. The primary swirling flow is induced by the rotating upper disk in the cylindrical case and by the lower boundary in the spherical case. The upper surface can be fixed with a no slip condition or can be a stress-free surface. Depending on these boundary conditions and on the Reynolds number novel structures of recirculation zones are realized. Experiments are done to visualize the topological structure of the flow and to determine their existence range as function of the geometry and rotation rate. A comparison between the experimental and theoretical approach shows a good agreement in respect to the topological structures of the flows.
Rotating flow systems are often used to study stability phenomena and structure developments. The closed spherical gap problem is generalized into an open flow system by superimposing a mass flux in meridional direction. The basic solutions at low Reynolds numbers are described by analytical methods. The nonlinear supercritical solutions are simulated numerically and realized in experiments. Novel steady and time-dependent modes of flows are obtained. The extensive results concern the stability behaviour, non-uniqueness of supercritical solutions, symmetry behaviour and transitions between steady and time-dependent solutions. The experimental investigations concern the visualization of the various instabilities and the quatitative description of the flow structures including the laminar-turbulent transition. A comparison between theoretical and experimental results shows good agreement within the limit of rotational symmetric solutions from the theory.
In this paper a high-performance thin-layer chromatography (HPTLC) scanner is presented in which a special fibre arrangement is used as HPTLC plate scanning interface. Measurements are taken with a set of 50 fibres at a distance of 400 to 500 μm above the HPTLC plate. Spatial resolutions on the HPTLC plate of better than 160 μm are possible. It takes less than 2 min to scan 450 spectra simultaneously in a range of 198 to 610 nm. The basic improvement of the item is the use of highly transparent glass fibres which provide excellent transmission at 200 nm and the use of a special fibre arrangement for plate illumination and detection.
High performance thin layer chromatography (HPTLC) is a frequently used separation technique which works well for quantification of caffeine and quinine in beverages. Competing separation techniques, e.g. high-performance liquid chromatography (HPLC) or gas chromatography (GC), are not suitable for sugar-containing samples, because these methods need special pretreatment by the analyst. In HPTLC, however, it is possible to separate ‘dirty’ samples without time-consuming pretreatment, because disposable HPTLC plates are used. A convenient method for quantification of caffeine and quinine in beverages, without sample pretreatment, is presented below. The basic theory of in-situ quantification in HPTLC by use of remitted light is introduced and discussed. Several linearization models are discussed.
A home-made diode-array scanner has been used for quantification; this, for the first time, enables simultaneous measurements at different wavelengths. The new scanner also enables fluorescence evaluation without further equipment. Simultaneous recording at different wavelengths improves the accuracy and reliability of HPTLC analysis. These aspects result in substantial improvement of in-situ quantitative densitometric analysis and enable quantification of compounds in beverages.
A new diode-array scanner in combination with a computer-controlled application system meets all the demands of modern HPTLC measurement. Automatic application, simultaneous measurements at different wavelengths, and different linearization models enable appropriate evaluation of all analytical questions. The theory of error propagation recommends quantification at reflectance values smaller than 0.8; this can be verified only by use of diode-array scanning. The same theory also recommends quantification by use of peak height data, because the theory predicts best precision only for peak height evaluation. Diode-array scanning with reflectance monitoring enables appropriate validation in TLC and HPTLC analysis. All these aspects result in substantial improvement of in-situ quantitative densitometric analysis, and simultaneous recording at different wavelengths opens the way for chemometric evaluation, e.g. peak purity monitoring, which improves the accuracy and reliability of HPTLC analysis.
A systematic toxicological analysis procedure using high-performance thin layer chromatography in combination with fibre optical scanning densitometry for identification of drugs in biological samples is presented. Two examples illustrate the practicability of the technique. First, the identification of a multiple intake of analgesics: codeine, propyphenazone, tramadol, flupirtine and lidocaine, and second, the detection of the sedative diphenhydramine. In both cases, authentic urine specimens were used. The identifications were carried out by an automatic measurement and computer-based comparison of in situ UV spectra with data from a compiled library of reference spectra using the cross-correlation function. The technique allowed a parallel recording of chromatograms and in situ UV spectra in the range of 197–612 nm. Unlike the conventional densitometry, a dependency of UV spectra by concentration of substance in a range of 250–1000 ng/spot was not observed.
Ozon-Querempfindlichkeit bei der Immissionsmessung von schwebstaubakkumuliertem Benzo[a]pyren
(2002)
Für die Beschreibung der Belastung der Luft mit polycyclischen aromatischen Kohlenwasserstoffen (PAK) wird vorwiegend die Konzentration eines Vertreters, das auf Schwebstaub akkumulierte Benzo[a]pyren (BaP), analysiert. Hierbei stellt Benzo[a]pyren die Leit komponen te für die Stoffklasse der PAK dar. Auf europäischer Ebene ist vorgesehen, für diesen Luftinhaltsstoff einen Grenzwert als Jahresmittelwert festzulegen. Deshalb wird bei bei der Normungsbehörde CEN zurzeit eine Europäische Norm für diesen Stoff erarbeitet. Aus der Literatur ist bekannt, dass für Benzo[a]pyren eine Querempfindlichkeit gegen Ozon und NO2 besteht. Im Zuge der Neuentwicklung eines Probenahmekopfs (PNK) für PAK-Immissionsmessungen, der durch den Einsatz eines Ozon- Scrubbers eine ozonfreie Immissionsmessung der Benzo[a]pyren-Konzentration ermög licht, wurde in dieser Arbeit die prinzipielle Einsetzbarkeit dieses Probe nahmekopfs geprüft. Zu diesem Zweck wurden Voruntersuchungen und Feldversuche durchgeführt, mit dem Ziel, Kenntnisse über die Ozon-Querempfindlichkeit zu erhalten. Um die Ozon-Querempfindlichkeit bei der Benzo[a]pyren-Bestimmung zu studieren, wurde Ozon in den Ansaugbereich der Probenahme dosiert. Als Ergebnis der Untersuchungen kann festgehalten werden, dass für die Benzo[a]pyren-Immissionsmessung eine deutliche Ozon-Querempfindlichkeit besteht, die unter Einsatz des neuen Ozon- Scrubbers vermieden werden kann.
The aim of this study was to develop a biomechanically validated finite element model to predict the biomechanical behaviour of the human lumbar spine in compression.
For validation of the finite element model, an in vitro study was performed: Twelve human lumbar cadaveric spinal segments (six segments L2/3 and six segments L4/5) were loaded in axial compression using 600 N in the intact state and following surgical treatment using two different internal stabilisation devices. Range of motion was measured and used to calculate stiffness.
A finite element model of a human spinal segment L3/4 was loaded with the same force in intact and surgically altered state, corresponding to the situation of biomechanical in vitro study.
The results of the cadaver biomechanical and finite element analysis were compared. As they were close together, the finite element model was used to predict: (1) load-sharing within human lumbar spine in compression, (2) load-sharing within osteoporotic human lumbar spine in compression and (3) the stabilising potential of the different spinal implants with respect to bone mineral density.
A finite element model as described here may be used to predict the biomechanical behaviour of the spine. Moreover, the influence of different spinal stabilisation systems may be predicted.
The use of a TLC scanner can be regarded as a key step in high performance thin layer chromatography (HPTLC). Densitometric measurements transform the substance distribution on a TLC plate into digital computer data. Systems that allow quantitative measurements have been available for many years for either fluorescence or ultraviolet absorption measurements, while lately the reflection analysis mode for both types is the most common application. New scanning approaches are designed to aid the analyst who has common demands for TLC-densitometry without using special data, such as scanned images. Two examples that have been developed lately in the laboratories of the authors are described in this paper. These approaches were developed on the basis of current needs for analysts who employ TLC as a tool in research, as well as in routine analysis. One approach is aimed to support analysts in economically disadvantaged areas, where cost intensive apparatus is unsuitable but trace analysis by simple means is required. The other system, allows the spectral determination of chromatographic spots on TLC plates covering the ultraviolet and visible range, thus, revealing highly desired information for the analyst.
A Simple and Reliable HPTLC Method for the Quantification of the Intense Sweetener Sucralose®
(2003)
This paper describes a simple and fast thin layer chromatography (TLC) method for the monitoring of the relatively new intense sweetener Sucralose® in various food matrices. The method requires little or no sample preparation to isolate or concentrate the analyte. The Sucralose® extract is separated on amino‐TLC‐plates, and the analyte is derivatized “reagent‐free” by heating the developed plate for 20 min at 190°C. Spots can be measured either in the absorption or fluorescence mode. The method allows the determination of Sucralose® at the levels of interest regarding foreseen European legislation (>50 mg/kg) with excellent repeatability (RSD = 3.4%) and recovery data (95%).
Fluorescence Enhancement of Pyrene Measured by Thin-Layer Chromatography with Diode-Array Detection
(2003)
In-situ densitometry for qualitative or quantitative purposes is a key step in thin-layer chromatography. It offers a simple way of quantifying by measuring the optical density of the separated spots directly on the plate. A new TLC scanner has been developed which is able to measure TLC plates or HPTLC plates, at different wavelengths simultaneously, without destroying the plate surface. The system enables absorbance and fluorescence measurements in one run. Fluorescence measurements are possible without filters or other adjustments.
The measurement of fluorescence from a TLC plate is a versatile means of making TLC analysis more sensitive. Fluorescence measurements with the new scanner are possible without filters or special lamps. Improvement of the signal-to-noise ratio is achieved by wavelength bundling. During plate scanning the scattered light and the fluorescence are both emitted from the surface of the TLC plate and this emitted light provides the desired spectral information from substances on the TLC plate. The measurement of fluorescence spectra and absorbance spectra directly from a TLC plate is based on differential measurement of light emerging from sample-free and sample-containing zones.
The literature recommends dipping TLC plates in viscous liquids to enhance fluorescence. Measurement of the fluorescence and absorbance spectra of pyrene spots reveals the mechanism of enhancement of plate dipping in viscous liquids—blocked contact of the fluorescent molecules with the stationary phase or other sample molecules is responsible for the enhanced fluorescence at lower concentrations.
In conclusion, dipping in TLC analysis is no miracle. It is based on similar mechanisms observable in liquids. The measured TLC spectra are also very similar to liquid spectra and this makes TLC spec-troscopy an important tool in separation analysis.
The free convection in a vertical gap is generalized to realize new analytical solutions of the Boussinesq-equations. The steady and time-dependent solutions for the temperature and velocity distribution are discussed in detail depending on the mass flux in vertical direction. The range of existence for flows with and without back flow is obtained. The transient behaviour of the solutions during the time-dependent development displays interesting physical behaviour.
The structure of the separation bubble that appears in the secondary meridional flow between two coaxially rotating spheres at low and finite Reynolds number (Re) is considered. The low Re analytical study was motivated by recognizing some errors in the analytical work on this problem by Arunachalam and Majhi (1987, Q. Jl Mech. Appl. Math., 40, 47) whilst the finite Re experimental study was motivated by the desire to observe the separation bubble in the laboratory. Though the finite Re experiments were performed in a confined apparatus, they exhibit the qualitative features of the low Re theoretical predictions for the axisymmetric separation bubble that encloses two toroidal vortices symmetrically disposed above and below the mid‐plane of sphere separation, but strong effects of confinement are apparent. The flows observed include (i) a wall‐attached bubble symmetric about the mid‐plane at low Re, (ii) symmetric free‐standing bubbles at moderate Re, and (iii) an asymmetric bubble with flow separating from one sphere and attaching to the support shaft between the spheres at sufficiently high Re.
A new formula is presented for transforming fluorescence measurements in accordance with Kubelka-Munk theory. The fluorescence signals, the absorption signals, and data from a selected reference are combined in one expression. Only diode-array techniques can measure all the required data simultaneously to linearize fluorescence data correctly. To prove the new theory HPTLC quantification of the analgesic flupirtine was performed over the mass range 300 to 5000 ng per spot. The fluorescence calibration curve was linear over the whole range. The transformation of fluorescence measurements into linear mass-dependent data extends the technique of in-situ fluorescence analysis to the high concentration range. It also extends Kubelka-Munk theory from absorption to fluorescence analysis. The results presented also emphasize the importance of Kubelka-Munk theory for in-situ measurements in scattering media, especially in planar chromatography.
In-situ densitometry for qualitative or quantitative purposes is a key step in thin-layer chromatography (TLC). It is a simple means of quantification by measurement of the optical density of the separated spots directly on the plate. A new scanner has been developed which is capable of measuring TLC or HPTLC (high-performance thin-layer chromatography) plates simultaneously at different wavelengths without damaging the plate surface. Fiber optics and special fiber interfaces are used in combination with a diode-array detector. With this new scanner sophisticated plate evaluation is now possible, which enables use of chemometric methods in HPTLC. Different regression models have been introduced which enable appropriate evaluation of all analytical questions. Fluorescent measurements are possible without filters or special lamps and signal-to-noise ratios can be improved by wavelength bundling. Because of the richly structured spectra obtained from PAH, diode-array HPTLC enables quantification of all 16 EPA PAH on one track. Although the separation is incomplete all 16 compounds can be quantified by use of suitable wavelengths. All these aspects are enable substantial improvement of in-situ quantitative densitometric analysis.
Soot particles emitted from a light duty (LD) Volkswagen diesel engine running at different operating points (speed and torque levels) are analyzed for mean size determination using a laser‐based three Wavelength Extinction Method (3‐WEM). For this reason, collected soot samples are suspended using an appropriate sample preparation technique with optimized conditions of sonication as it revealed its effect on the soot mean particle size measured by 3‐WEM.
An online Scanning Mobility Particle Analyzer (SMPS) is also used to measure soot emission at identical engine operating points. Size values obtained from SMPS are lower than those of suspended soot samples obtained from 3‐WEM. The size discrepancies are mainly related to the required sample preparation procedure employed for 3‐WEM measurements. The engine operating points affect, differently, the size measurements obtained from SMPS and 3‐WEM.
Sedimentation Field‐Flow Fractionation (SdFFF) is used for density determination of soot samples based on size measurements of fractions collected at peak maxima of fractograms using the off‐line hyphenation with 3‐WEM. It is assumed that a size dependent separation of soot particles occurred with a uniform particle density over the whole size distribution. An average density value is used for the conversion of soot fractograms to size distributions. Discrepancies are also found with size distribution profiles obtained from SMPS for the same engine operating points, due to the sample preparation procedure employed for SdFFF measurements.
HPTLC on amino plates, with simple heating of the plates for derivatization, has been used for quantification of glucosamine in nutritional supplements. On heating the plate glucosamine reacts to form a compound which strongly absorbs light between 305 and 330 nm, with weak fluorescence. The reaction product can be detected sensitively either by absorption of light or by fluorescence detection. The detection limit in absorption mode is approximately 25 ng per spot. In fluorescence mode a detection limit of 15 ng is achievable. A calibration plot for absorption detection is linear in the range 25 to 4000 ng glucosamine. The derivative formed from glucosamine by heating is stable for months, and the relative standard deviation is 1.64% for 600 ng glucosamine. The amounts of glucosamine found in nutritional supplements were in agreement with the label declarations.
We present an improved quantification method for urethane found in spirits. The quantification is based on a derivatization reaction using cinnamaldehyde in combination with phosphoric acid. Measurements were carried out in the wavelength range from 445 to 460 nm using a diode-TLC device. An LED was used for illumination purposes. It emits very dense light at 365 nm. The quantification range of urethane is in the lower ng range. By applying 20 µL of sprits, the urethane quantification range is from 320 µg/L to 8.1 mg urethane per litre of spirit. The range of linearity covers nearly two magnitudes. The method is cheap, fast and reliable, and is able to monitor all European legislation limits without time-consuming sample pre-treatments.
The efficiency of a chromatographic analytical method is determined by the selectivity of the chromatographic separation and the specificity of the detection method. In high-performance thin-layer chromatography (HPTLC) the separated components can be detected and quantified directly on the plate by physical and chemical methods. By coupling high-performance thin-layer chromatography with biological or biochemical inhibition tests it is possible to detect toxic substances in situ.
Hydrogen chloride and sulphur dioxide are gaseous by-products of chloridization processes that employ thionyl chloride. Absorption would be a feasible method to clean the rich gas stream. Two serial connectable absorption columns were equipped with the latest generation of packings to effect product recovery. Therefore, several tests concerning the baffle properties had to be performed. In the first experimental section, the hydraulic parameters pressure drop and hold-up were investigated. The hold up value range of the new baffles Raschig Super Ring (RSR) and Raschig Super Pak (RSP) was clearly below that of the former installed packing, Raschig Ring (RR). However, due to the low maximal flow rate, the range of stagnation and flooding could not be measured. The maximal measured pressure drop value was, for RR, only 0.3 mbar/m, which is very low compared to the measurement error. Batch experiments, where the waste gases were produced by reaction of thionyl chloride in water, showed that for the steady state determination of the separation steps it is advisable to use just one column in simplex mode with a defined gas supply by a gas cylinder. The HTU determination for RSR and a HCl/H2O system delivered a value of HTUHCl,OG = 0.14 ± 0.01 m with a variation coefficient of 24.2%.
Flows in nature and technology are often associated with specific structures and pattern. This paper deals with the development and behaviour of such flow pattern. Flow structures are important for the mass, momentum and energy transport. The behaviour of different flow pattern is used by engineers to obtain an efficient mass and energy consumption. Mechanical power is transmitted via the momentum of rotating machine parts. Therefore the physical and mathematical knowledge of these basic concepts is important. Theoretical and experimental investigations of principle experiments are described in the following. We start with the classical problem of the flow between two concentric cylinders where the inner cylinder rotates. Periodic instabilities occur which are called Taylor vortices. The analogy between the cylindrical gap flow, the heat transfer in a horizontal fluid layer exposed to the gravity field and the boundary layer flow along concave boundaries concerning their stability behaviour is addressed. The vortex breakdown phenomenon in a cylinder with rotating cover is also described. A generalization to spherical sectors leads then to investigations with different boundary conditions. The spherical gap flow exhibits interesting phenomena concerning the nonlinear character of the Navier-Stokes equations. Multiple solutions in the nonlinear regime give rise to different routes during the laminar-turbulent transition. The interaction of two rotating spheres results in flow structures with separation and stagnation lines. Experimental results are confirmed by numerical simulations.
We report improved separation of the highly toxic contact herbicides paraquat, diquat, difenzoquat, mepiquat, and chloromequat by HPTLC. Quantification was based on a new derivatization reaction using sodium tetraphenylborate. Measurements were in the wavelength range from 440 to 480 nm or from 440 to 590 nm. An LED emitting very intense light at 365 nm was used for excitation. The quantification limits of paraquat and diquat in water, using improved solid-phase extraction, was in the low ng L −1 range. The linear range covered more than two orders of magnitude. Recovery was investigated for all the compounds, and was insufficient, ranging from 11 to 92%, but the method is inexpensive, rapid, and works reliably.
A diode array HPTLC method for dequalinium chloride in pharmaceutical preparations is presented. For separation a Nano TLC silica gel plate (Merck) is used with the mobile phase methanol-7.8% aqueous NH(4)(+)CH(3)COO(-) (17:3, v/v) over a distance of 6 cm. Dequalinium chloride shows an R(F) value of 0.58. Pure dequalinium chloride is measured in the wavelength range from 200 to 500 nm and shows several by-products, contour plot visualized in absorption, fluorescence and using the Kubelka-Munk transformation. Scanning of a single track in absorption and fluorescence measuring 600 spectra in the range from 200 to 1100 nm takes 30s. As a sample pre-treatment of an ointment it is simply dissolved in methanol and can be quantified in absorption from 315 to 340 nm. The same separation can also be quantified using fluorescence spectrometry in the range from 355 to 370 nm. A new staining method for dequalinium chloride, using sodium tetraphenyl borate/HCl in water allows a fluorescence quantification in the range from 445 to 485 nm. The linearity range of absorption and fluorescence measurements is from 10 to 2000 ng. Sugar-containing preparations like liquids or lozenges with a reduced sample pre-treatment can be reliably quantified only in fluorescence. The total for the quantification of an ointment sample (measuring four standards and five samples), including all sample pre-treatment steps takes less than 45 min!
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.
The engineering company Evomotiv GmbH and the University of Applied Sciences Offenburg have developed a drive concept for light city scooters since 2008. The electrical drive train's goal is the series production of the highly-integrated, non-transmission and non-ferrous wheel-hub motor. The German Federal Ministry of Economy and Technology (BMWi) supports this project. The concept of this wheel-hub motor was awarded with the Bosch-Innovation prize in 2006. In 2011 Evomotiv will test the first prototypes with its cooperation partners on the track.
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.
Regarding the importance of adsorptive removal of carbon monoxide from hydrogen-rich mixtures for novel applications (e.g. fuel cells), this work provides a series of experimental data on adsorption isotherms and breakthrough curves of carbon monoxide. Three recently developed 5A zeolites and one commercial activated carbon were used as adsorbents. Isotherms were measured gravimetrically at temperatures of 278–313 K and pressures up to 0.85 MPa. Breakthrough curves of CO were obtained from dynamic column measurements at temperatures of 298–301 K, pressures ranging from 0.1 MPa to ca. 6 MPa and concentrations of CO in H2/CO mixtures of 5–17.5 mol%. A simple mathematical model was developed to simulate breakthrough curves on adsorbent beds using measured and calculated data as inputs. The number of parameters and the use of correlations to evaluate them were restricted in order to focus the importance of measured values. For the given assumptions and simplifications, the results show that the model predictions agree satisfactorily with the experimental data at the different operating conditions applied.
This work provides a series of methane adsorption isotherms and breakthrough curves on one 5A zeolite and one activated carbon. Breakthrough curves of CH4 were obtained from dynamic column measurements at different temperature and pressure conditions for concentrations of 4.4 – 17.3 mol.‐% in H2/CH4 mixtures. A simple model was developed to simulate the curves using measured and calculated data inputs. The results show that the model predictions agree very well with the experiments.
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.
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.
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.
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.
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.
The newly synthesized Zn4O-based MOF 3∞[Zn4(μ4-O){(Metrz-pba)2mPh}3]·8 DMF (1·8 DMF) of rare tungsten carbide (acs) topology exhibits a porosity of 43% and remarkably high thermal stability up to 430 °C. Single crystal X-ray structure analyses could be performed using as-synthesized as well as desolvated crystals. Besides the solvothermal synthesis of single crystals a scalable synthesis of microcrystalline material of the MOF is reported. Combined TG-MS and solid state NMR measurements reveal the presence of mobile DMF molecules in the pore system of the framework. Adsorption measurements confirm that the pore structure is fully accessible for nitrogen molecules at 77 K. The adsorptive pore volume of 0.41 cm3 g−1 correlates well with the pore volume of 0.43 cm3 g−1 estimated from the single crystal structure.
Cost effectiveness of preventive screening programmes for type 2 diabetes mellitus in Germany
(2010)
As in several other industrialized countries, Germany’s statutory health insurance (SHI) is facing rising healthcare costs as well as the challenges caused by a double-aging society. The early detection and prevention of chronic diseases is considered a possible way to reduce the impact of these developments. However, controversy surrounds the costs and effects in terms of medical and financial outcomes of such programmes.
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.
In this work the adsorption of CO2 and CH4 on a series of isoreticular microporous metal–organic frameworks based on 2-substituted imidazolate-4-amide-5-imidates, IFP-1–IFP-6 (IFP = Imidazolate Framework Potsdam), is studied firstly by pure gas adsorption at 273 K. All experimental isotherms can be nicely described by using the Tòth isotherm model and show the preferred adsorption of CO2 over CH4. At low pressures the Tòth isotherm equation exhibits a Henry region, wherefore Henry's law constants for CO2 and CH4 uptake could be determined and ideal selectivity αCO2/CH4 has been calculated. Secondly, selectivities were calculated from mixture data by using nearly equimolar binary mixtures of both gases by a volumetric–chromatographic method to examine the IFPs. Results showed the reliability of the selectivity calculation. Values of αCO2/CH4 around 7.5 for IFP-5 indicate that this material shows much better selectivities than IFP-1, IFP-2, IFP-3, IFP-4 and IFP-6 with slightly lower selectivity αCO2/CH4 = 4–6. The preferred adsorption of CO2 over CH4 especially of IFP-5 and IFP-4 makes these materials suitable for gas separation application.
As a basis for the evaluation of hydrogen storage by physisorption, adsorption isotherms of H2 were experimentally determined for several porous materials at 77 K and 298 K at pressures up to 15 MPa. Activated carbons and MOFs were studied as the most promising materials for this purpose. A noble focus was given on how to determine whether a material is feasible for hydrogen storage or not, dealing with an assessment method and the pitfalls and problems of determining the viability. For a quantitative evaluation of the feasibility of sorptive hydrogen storage in a general analysis, it is suggested to compare the stored amount in a theoretical tank filled with adsorbents to the amount of hydrogen stored in the same tank without adsorbents. According to our results, an “ideal” sorbent for hydrogen storage at 77 K is calculated to exhibit a specific surface area of >2580 m2 g−1 and a micropore volume of >1.58 cm3 g−1.
An isomorphous series of 10 microporous copper-based metal–organic frameworks (MOFs) with the general formulas ∞3[{Cu3(μ3-OH)(X)}4{Cu2(H2O)2}3(H-R-trz-ia)12] (R = H, CH3, Ph; X2– = SO42–, SeO42–, 2 NO32– (1–8)) and ∞3[{Cu3(μ3-OH)(X)}8{Cu2(H2O)2}6(H-3py-trz-ia)24Cu6]X3 (R = 3py; X2– = SO42–, SeO42– (9, 10)) is presented together with the closely related compounds ∞3[Cu6(μ4-O)(μ3-OH)2(H-Metrz-ia)4][Cu(H2O)6](NO3)2·10H2O (11) and ∞3[Cu2(H-3py-trz-ia)2(H2O)3] (12Cu), which are obtained under similar reaction conditions. The porosity of the series of cubic MOFs with twf-d topology reaches up to 66%. While the diameters of the spherical pores remain unaffected, adsorption measurements show that the pore volume can be fine-tuned by the substituents of the triazolyl isophthalate ligand and choice of the respective copper salt, that is, copper sulfate, selenate, or nitrate.
In this paper, the multiaxial formulation of a mechanism-based model for fatigue life prediction is presented whichcan be applied to low-cycle fatigue (LCF) and thermomechanical fatigue (TMF) problems in which high-cycle fa-tigue loadings are superimposed. The model assumes that crack growth is the lifetime limiting mechanism and thatthe crack advance in a loading cycleda/dNcorrelates with the cyclic crack-tip opening displacement ΔCTOD.The multiaxial formulation makes use of fracture mechanics solutions and thus, does not need additional modelparameters quantifying the effect of the multiaxiality. Furthermore, the model includes contributions of HCF on ΔCTODand assesses the effect of the direction of the HCF loadings with respect to LCF or TMF loadings inthe life prediction. The model is implemented into the finite-element program ABAQUS. It is applied to predictthe fatigue life of a thermomechanically loaded notched specimen that should represent the situation between theinlet and outlet bore holes of cylinder heads. A good correlation of the predicted and the measured fatigue lives isobtained.
Limits of quantification of some neonicotinoid insecticides measured by thin-layer chromatography
(2012)
A simple method to quantify the neonicotinoid insecticides nitenpyram, thiamethoxam, acetamiprid, imidacloprid, thiacloprid and clothianidin directly on an HPTLC-plate is presented. As stationary phase silica gel 60 RP-18WF254 s plates were used and a mixture of methyl-t-butyl ether, 2-butanone, NH3 (25%) (5 + 2+0.1, v/v) was used as solvent. All neonicotinoid insecticides show light absorptions below 300 nm. The calculated limits of quantification (LOQ) by UV-detection are in the range from 12 ng to 26 ng on plate depending on the different insecticides.Nitenpyram can be stained using fast blue salt B, forming red zones. The observed LOQ is 25 ng on plate. Acetamiprid can be specifically stained using phenylglyoxylic acid forming a yellow/green fluorescent compound. The LOQ is 52 ng per spot.The compounds thiamethoxam, acetamiprid, thiacloprid and clothianidin can be transformed into blue fluorescing zones, using a relatively new staining solution. This consists of tetraphenylborate and HCl. This is the first publication mentioning that neonicotinoids undergo this reaction. The calculated limits of quantification are in the range from 10 ng to 27 ng on plate.A simple pre-treatment procedure using an acetonitrile extraction and a Chromabond SiOH clean up procedure leads to overall LOQs for bee samples of 48 to 108 µg/Kg. The method can be used to measure neonicotinoid contaminations of bees.
Pure gas adsorption isotherms of CH4 and N2 and their binary mixtures were measured at 273 K, 298 K and 323 K and up to 2 MPa on two different microporous metal–organic frameworks (MOFs), i.e. the commercially available Basolite® A100 and the recently reported copper-based triazolyl benzoate MOF 3∞[Cu(Me-4py-trz-ia)] (1). The Tòth isotherm model and the vacancy solution model were used to describe the experimentally determined isotherms and proved to be well suited for this purpose. While 1 shows a more homogeneous surface with a nearly constant isosteric heat of adsorption of 18–18.5 kJ mol−1 for CH4 and 12–15 kJ mol−1 for N2, the isosteric heat of adsorption at zero coverage for Basolite® A100 is 19 kJ mol−1 for CH4 and 16.2 kJ mol−1 for N2, decreasing significantly with increasing loading. Binary adsorption isotherms were measured gravimetrically to determine the total adsorbed mass of CH4 and N2. The van Ness method was successfully applied to calculate partial loadings from gravimetrically measured binary adsorption isotherms. Further studies by volumetric–chromatographic experiments support the good correlation between experimental data and predictions by the vacancy solution model (VSM-Wilson) and the ideal adsorbed solution theory (IAST) from pure gas isotherms. The experimental selectivities were determined to be αCH4/N2 = 4.0–5.0 for 1, slightly higher than for Basolite® A100 with αCH4/N2 = 3.4–4.5. These values are in good agreement with predictions for ideal selectivities based on Henry's law constants. From the experimental selectivities the potential of both MOFs in gas separation of CH4 from N2 can be derived.
The CO2 uptake on nanoscale AlO(OH) hollow spheres (260 mg g−1) as a new material is comparable to that on many metal–organic frameworks although their specific surface area is much lower (530 m2 g¬1versus 1500–6000 m2g¬1). Suited temperature–pressure cycles allow for reversible storage and separation of CO2 while the CO2 uptake is 4.3-times higher as compared to N2.
Improved separation of highly toxic contact herbicides paraquat (1,1′-dimethyl-4-4′-bipyridinium), diquat (6,7-dihydrodipyridol[ 1,2-a:2′,1′-c]pyrazine-5,8-di-ium), difenzoquat (1,2-dimethyl-3,5-diphenyl-1H-pyrazolium-methyl sulfate), mepiquat (1,1-dimethyl-piperidinium), and chloromequat (2-chloroethyltrimethylammonium) were presented by high-performance thin-layer chromatography (HPTLC). The quantification is based on a derivatization reaction, using sodium tetraphenylborate. Measurements were made in the wavelength range from 500 to 535 nm, using a light-emitting diode (LED) for excitation purposes, which emits very dense light at 365 nm. For calculations, a new theory of standard addition method was used, thus leading to a minimal error if exactly the same amount of sample content is added as a standard. The method provides a fast and inexpensive approach to quantification of the five most important quats used for plant protection purposes. The method works reliably because it takes into account losses during pre-treatment procedure. The method meets the European legislation limits for paraquat and diquat in drinking water according to United States Environmental Protection Agency (US EPA) method 549.2 which are 680 ng L−1 for paraquat and 720 ng L−1 for diquat. The method of standard addition in planar chromatography can be beneficially used to reduce systematic errors. Although recovery rates of 33.7% to 65.2% are observed, calculated contents according to the method of standard addition lie between 69% and 127% of the theoretical amounts.
Im Eurocode 3 wird im Gegensatz zu DIN 18800 die Bemessung von Verbindungen nicht in der Grundnorm DIN EN 1993‐1‐1, sondern in anderen Normenteilen geregelt. Dieser Beitrag behandelt die Bemessung geschweißter Verbindungen nach DIN EN 1993‐1‐8, die auch Hohlprofile, aber weder dünnwandige Bauteile noch Stähle höherer Festigkeit als S460 einschließt, vergleicht diese Bemessung mit der nach DIN 18800‐1, erläutert sie an Beispielen und hebt die wesentlichen Änderungen hervor. Da diese Änderungen auch die im Vergleich zu DIN 18800 viel stärkere Verknüpfung der in der Tragwerksplanung ansetzbaren Beanspruchbarkeiten mit dem Aufwand der Prüfung und Qualitätsüberwachung bei der Herstellung betreffen, werden abschließend wichtige Regelungen der DIN EN 1090‐2 zur Ausführung und Prüfung von Schweißnähten beschrieben, die auch der Tragwerksplaner kennen muss.
Die Zuverlässigkeit und Betriebssicherheit von Feldgeräten ist für den sicheren und wirtschaftlichen Betrieb prozesstechnischer Anlagen unerlässlich. Ein entscheidender Faktor ist die Widerstandskraft der Geräte gegen die herrschenden Umgebungsbedingungen. Durch Korrosionsschäden hervorgerufene Anlagenstillstände zeigen, dass diesem Thema nicht immer die notwendige Aufmerksamkeit gewidmet wird, obwohl die korrosionsbedingten wirtschaftlichen Schäden immens sind. Wie man mit dem Thema Korrosionsschutz ernsthaft umgehen kann, zeigt dieser Beitrag am Beispiel elektrischer Stellantriebe.
Der Endkundenvertrieb ist für die Bewahrung und Weiterentwicklung des Kundenstamms eines Energieversorgers essenziell. Doch um knappe Mittel im Vertrieb möglichst wirkungsvoll einsetzen zu können, wird Wissen darüber benötigt, wie sich die durchschnittlich erzielbaren Strompreise und die zu erwartende Kundenbindungsdauer zwischen verschiedenen Vertriebskanälen unterscheiden. Leitet man anhand dieser Informationen den Wert eines Kunden je Vertriebskanal ab, lässt sich treffsicherer über einzusetzende Marketing-Budgets entscheiden.
Der Einbau von Smart Metern und deren intelligente Vernetzung in Richtung eines Smart Grid wird Stromverbrauchsmuster bis in die Haushalte hinein verändern. Über die technisch geprägte Diskussion um die Komponenten dafür darf deshalb keinesfalls die Einbeziehung der Gesellschaft in den anstehenden Wandel vergessen werden. Transparenz bei den Kosten, die Förderung von Vertrauen insbesondere in die Datenschutzstandards und eine verständliche Aufklärungsarbeit sind Schlüssel für den notwendigen Dialog zwischen Energieversorgern, Politik und Bürgern.
A series of isostructural 3D coordination polymers (3)∞[M(tdc)(bpy)] (M(2+) = Zn(2+), Cd(2+), Co(2+), Fe(2+); tdc(2-) = 2,5-thiophenedicarboxylate; bpy = 4,4'-bipyridine) was synthesized and characterized by X-ray diffraction, thermal analysis, and gas adsorption measurements. The materials show high thermal stability up to approximately 400 °C and a solvent induced phase transition. Single crystal X-ray structure determination was successfully performed for all compounds after the phase transition. In the zinc-based coordination polymer, various amounts of a second type of metal ions such as Co(2+) or Fe(2+) could be incorporated. Furthermore, the catalytic behavior of the homo- and heteronuclear 3D coordination polymers in an oxidation model reaction was investigated.
Gas adsorption studies of CO2 and N2 in spatially aligned double-walled carbon nanotube arrays
(2013)
Gas adsorption studies (CO2 and N2) over a wide pressure range on vertically, highly aligned dense double-walled carbon nanotube arrays of high purity and high specific surface area are reported. At high pressures, the adsorption capacity of these materials was found to be comparable to those of metal organic frameworks and mesoporous molecular sieves. These highly aligned CNT arrays were chemically modified by treating with oxygen plasma and structurally modified by decreasing the diameter of individual carbon nanotubes. Oxygen plasma treatment led to grafting of a large number of C–O functional groups onto the CNT surface, which further increased the gas adsorption capacity. It was found that gas adsorption is dependent on tube diameter and increases with decrease of the individual CNT diameter in the CNT bundles. As results of our studies we have found that at lower pressure regimes, plasma functionalized carbon nanotubes exhibit better adsorption characteristics whereas at higher pressures, lower diameter carbon nanotube structures exhibited better gas adsorption characteristics.
Mit längerfristigen Nutzerbefragungen in zwei unmittelbar benachbarten Bürogebäuden in Freiburg wurden das Temperaturempfinden der Nutzer und deren Zufriedenheit mit dem thermischen Raumkomfort zweimal täglich erfasst. Ein Bürogebäude wird im Sommer mit einem maschinellen Nachtlüftungskonzept konditioniert und das zweite verfügt über eine Betonkerntemperierung und eine Zu‐ und Abluftanlage. Auf Basis der vorhandenen Daten aus der Erhebung wurde mit Hilfe von Regressionsanalysen ein Modell zur Vorhersage der Komforttemperatur berechnet und mit den Modellen in DIN EN 15251 verglichen.
In this paper, an unconditionally stable algorithm for the numerical integration and finite-element implementation of a class of pressure dependent plasticity models with nonlinear isotropic and kinematic hardening is presented. Existing algorithms are improved in the sense that the number of equations to be solved iteratively is significantly reduced. This is achieved by exploitation of the structure of Armstrong-Frederik-type kinematic hardening laws. The consistent material tangent is derived analytically and compared to the numerically computed tangent in order to validate the implementation. The performance of the new algorithm is compared to an existing one that does not consider the possibility of reducing the number of unknowns to be iterated. The algorithm is used to implement a time and temperature dependent cast iron plasticity model, which is based on the pressure dependent Gurson model, in the finite-element program ABAQUS. The implementation is applied to compute stresses and strains in a large-scale finite-element model of a three cylinder engine block. This computation proofs the applicability of the algorithm in industrial practice that is of interest in applied sciences.
Unter dem europäischen Programm Intelligent Energy for Europe (IEE) fanden sich acht europäische Partner zusammen, um im Rahmen des Projektes ThermCo Lüftungs‐ und Kühlenergiekonzepte für Nichtwohngebäude mit niedrigem Energieeinsatz im Hinblick auf die Energieeffizienz und den thermischen Raumkomfort zu bewerten (siehe Teil 1 dieser Veröffentlichung in Bauphysik 34 (2012), Heft 6. Mit Hilfe einer Simulationsstudie für ein typisches Bürogebäude wird das Potenzial unterschiedlicher Lüftungs‐ und Kühlstrategien unter Berücksichtigung von Energieeffizienz und Raumkomfort für verschiedene europäische Klimazonen bewertet. Die Ergebnisse weisen eine hohe Wirksamkeit von Nachtlüftungskonzepten im nord‐europäischen Sommerklima mit verhältnismäßig niedrigen Außentemperaturen nach. Im mitteleuropäischen Sommerklima bietet das Erdreich ein ausreichend niedriges Temperaturniveau für den effizienten Einsatz von wassergeführten Flächentemperiersystemen. Im südeuropäischen Sommerklima kann eine aktive Kühlung über Luft die hohen und schnell fluktuierenden Kühllasten effizient abführen.
We present a video-densitometric quantification method in combination with diode-array quantification for the methyl-, ethyl-, propyl-, and butylparaben in cosmetics. These parabens were separated on cyanopropyl bonded plates using water-acetonitrile-dioxane-ethanol-NH3 (25%) (8:2:1:1:0.05, v/v) as mobile phase. The quantification is based on UV-measurements at 255 nm and a bioeffectively-linked analysis using Vibrio fischeri bacteria. Within 5 min, a Tidas S 700 diode-array scanner (J&M, Aalen, Germany) scans 8 tracks and thus measures in total 5600 spectra in the wavelengths range from 190 to 1000 nm. The quantification range for all these parabens is from 20 to 400 ng per band, measured at 255 nm. In the V. fischeri assay a CCD-camera registers the white light of the light-emitting bacteria within 10 min. All parabens effectively suppress the bacterial light emission which can be used for quantifying within a linear range from 100 to 400 ng. Measurements were carried out using a 16-bit MicroChemi chemiluminescence system (biostep GmbH, Jahnsdorf, Germany), using a CCD camera with 4.19 megapixels. The range of linearity is achieved because the extended Kubelka-Munk expression was used for data transformation. The separation method is inexpensive, fast, and reliable.
Die Analyse von Engpässen im Güterverkehr ist eine wichtige Voraussetzung, um zukünftige Heraus-forderungen der Infrastrukturplanung und Logistik bewältigen zu können. Im Rahmen des EU-Projekts Code24 sollen Strategien für die Behandlung zukünftiger Herausforderungen im Schienengüterverkehr im wichtigsten europäischen Güterverkehrskorridor Rotterdam-Genua entwickelt werden. Hierfür sind Infor-mationen über Zugzahlen und die Kapazitätsauslastung auf einzelnen Streckenabschnitten eine wichtige Voraussetzung.
Raman spectra from three different binary gasoline-ethanol blends (with ratios 95:5, 90:10, and 85:15) have been obtained by using a low-cost, frequency precise Fourier-transform Raman spectrometer (FT-Raman) prototype. The spectral information is presented in the range of 0 to 3500 cm-1 with a resolution of 1.66 cm-1, which is greater than the required for most liquid and solid chemical samples. This set-up delivers spectral information about the sample with a reduced spectral deviation compared to theoretical values (less than 0.4 cm-1 without compensation for instrumental response). The robust and highly fexible FT-Raman prototype presented for the spectral analysis, consisting mainly of a Michelson interferometer and a self-designed photon counter, is able to deliver high resolution and frequency precise Raman spectra from the gasoline-ethanol blends comparable to the obtained by using commercial devices. This FT-Raman set-up does not need additional complex hardware or software control and relies on re-sampling and interpolation algorithms. The qualitative spectral information obtained has been used to calculate the proportion of gasoline and ethanol present in the used chemical samples without using extra calibrations methods or chemical markers.
We present a two dimensional (2D) planar chromatographic separation of estrogenic active compounds on RP-18 (Merck, 1.05559) and silica gel (Merck, 1.05721) phase. A mixture of 13 substances was separated using a solvent mix consisting of methanol–acetonitrile–water (2 + 2 + 1, v/v/v) on RP-18 phase in the first direction and cyclohexane–butylacetate–methanol (8 + 6 + 1, v/v/v) in the second direction on silica gel plate. Both developments were carried out over a distance of 70 mm. We used the grafted method to combine both plates in a 2D-separation. This 2D-separation method can be used to quantify 17α-ethinylestradiol (EE2) in an effect-directed analysis using the yeast strain Saccharomyces cerevisiae BJ3505. The test strain (according to McDonnell) contains the estrogen receptor. Its activation by estrogen active compounds is measured by inducting the reporter gene lacZ that encodes the enzyme ß-galactosidase. This enzyme activity is determined on plate by using the fluorescent substrate MUG (4-methylumbelliferyl ß-D-galactopyranoside).
Pure component sorption isotherms of n-butane, isobutane, 1-butene and isobutene on the metal–organic framework (MOF) 3∞[Cu4(μ4-O)(μ2-OH)2(Me2trz-pba)4] at various temperatures between 283 K and 343 K and pressures up to 300 kPa are presented. The isotherms show a stepwise pore filling which is typical for structurally flexible materials with broad adsorption–desorption hysteresis loops. Gate opening pressures in their endemic characteristic depend on the used hydrocarbon gases. From all investigated gases only the isotherms of 1-butene present a second step at a relative pressure above p/p0 = 0.55. As a consequence, only 1-butene can fully open the framework resulting in a pore volume of 0.54 cm3 g−1. This result is in good agreement with the value of 0.59 cm3 g−1 calculated based on single crystal structure data. The isosteric heat of adsorption was calculated from the experimental isotherms for all C4-isomers. At low loadings the isosteric heat is in a narrow region between 41 and 49 kJ mol−1. Moreover, in situ XRD measurements at different relative hydrocarbon pressures were performed at 298 K for the C4-isomers. The differences in the pressure-depending powder diffraction patterns indicate phase transitions as a result of adsorption. Similar diffraction patterns were observed for all C4-hydrocarbons, except 1-butene, where the second step at higher relative pressure (p/p0 > 0.55) is accompanied by an additional phase transition. This powder pattern resembles that of the as-synthesized MOF material containing solvent molecules in the pore system. The resulting structural changes of the material during guest and pressure induced external stimuli are evidenced by the new coupled XRD adsorption equipment.
Aqueous lithium–oxygen batteries are promising candidates for electric energy storage. In this paper we present and discuss a multiphase continuum model of an aqueous lithium–oxygen single cell including reactions and transport in a porous gas diffusion electrode (GDE). The model is parameterized using in-house half-cell experiments and available literature data on aqueous electrolytes. We validate our transport model with cyclic voltammetry and electrochemical impedance spectroscopy measurements over a wide range of temperatures (25, 40, 55 °C) and electrolyte concentrations (0.1–2 M). We observe very good agreement between simulations and measurements during oxygen reduction conditions. A sensitivity analysis of the validated model demonstrates the influence of the porous structure on GDE performance and gives directions for the future development of electrodes.
In 35 deutschen und 7 europäischen Büro- und Verwaltungsgebäuden wurden auf Basis von Monitoringkampagnen über mehrere Betriebsjahre Raum- und Außentemperaturwerte in zeitlich hoher Auflösung erfasst und der thermische Raumkomfort im Sommer standardisiert nach der Komfortnorm DIN EN 15251:2007-08 detailliert ausgewertet. Ergänzt wird die Auswertung um Kurzzeitmesskampagnen über zwei sehr warme Wochen im Sommer in unsanierten bzw. teilsanierten Bürogebäuden, errichtet im Zeitraum von 1960 bis 1975. Die untersuchten Gebäude mit ihrem jeweiligen Kühlkonzept lassen sich in sechs Kategorien einteilen: ohne Kühlung, passive, luftgeführte und wassergeführte Kühlung sowie Mixed-mode-Kühlung und Vollklimatisierung. Im Quervergleich aller Gebäude werden die Kühlkonzepte gleichermaßen nach dem thermischen Raumkomfort und thermischen Kühlenergiebezug bewertet. Detaillierte Komfortuntersuchungen nach der Europäischen Komfortnorm DIN EN 15251:2007-08 geben Hinweise auf die Wirksamkeit der eingesetzten Kühltechnologien in den jeweiligen Klimazonen. Daraus lassen sich Handlungsempfehlungen für die Planungspraxis und den Gebäudebetrieb ableiten.
This paper reports on the evolution of cracks in the cylinder heads of a large V8 Diesel engine during cyclic engine tests. The observations are compared with the predictions of a lifetime model for combined thermo-mechanical (TMF) and high cycle fatigue (HCF) loading, which is based on a fracture mechanics analysis of microcrack growth in viscoplastic solids and assumes that the crack advance per cycle is proportional to the cyclic crack tip opening displacement. Since the material of the cylinder heads, the cast iron EN-GJV450, exhibits the typical features of cast iron, namely pressure dependence of the yield stress, dilatancy and tension-compression asymmetry, the Gurson model is applied and combined with the viscoplastic Chaboche model. This constitutive model together with the lifetime model is implemented into a finite element code as a user defined material routine. Published model parameters for the considered cast iron are used to carry out the simulation of the engine test. This simulation comprises a CFD analysis to determine the heat transfer coefficients, a thermal analysis of the load cycle and the mechanical analysis. The thermal analysis reproduces the temperatures at various measuring points sufficiently accurately. Finally, the mechanical analysis predicts the location and orientation of the cracks in the valve bridges correctly in all cases. However, the lifetime predictions are rather conservative compared to the tests (by a factor of 1 to 5 in lifetime). This is discussed and explained by the fact that the cracks were detected in the tests only when they had already spread over a substantial fraction of the valve bridge width. To describe this situation a long-crack analysis would be necessary, which is not yet included in the applied lifetime model.
Packed beds serve as thermal energy storages (TES) and heat exchangers (HEX) in different technological applications. In this paper, a general heterogeneous model of heat transfer in packed beds is developed. It is implemented by lumped element formulation in object-oriented modeling language Modelica and is successful validated with data sets taken from two different experiments reported in literature.
The main advantages of the introduced model are the general, theory-based approach and the lumped element formulation in Modelica. The first point mentioned above should allow to simulate a packed bed TES/HEX without the necessity applying measured data for model calibration or to apply specific heat transfer correlations with restricted application. The second point establishes the possibility to integrate the TES/HEX model within plant models of larger scale without increasing the simulation time drastically.
We tested the MOF framework Cu-BTC for natural gas (NG) storage. Adsorption isotherms of C1–C4 alkanes were simulated applying the Grand Canonical ensemble and the Monte Carlo algorithm in a classical molecular mechanics approach. Experimental monocomponent isotherm of the alkanes was used to validate the force field. We performed multicomponent adsorptions calculations for three different quaternary mixtures of C1–C4 alkanes, matching typical NG streams composition, and predicted theoretical storage capacities, efficiency and accumulation of the NG within that composition. Despite being one of the frameworks with greatest storage capacity of methane, we found that Cu-BTC presented great sensitivity to the variation of the heavier alkanes in NG composition. When we increase the percentage of butane from 0.1% to 0.7% in the mixture, the mass of components retained in the discharge pressure (1 bar) increases from 35 to 60%. We also perform siting and interaction energy investigations and compare the NG storage performance of the Cu-BTC with that of activated carbons. To our knowledge, this is the first study regarding the efficiency of the NG storage in Cu-BTC.
Adsorption of N2 and CO2 on Activated Carbon, AlO(OH) Nanoparticles, and AlO(OH) Hollow Spheres
(2015)
Adsorption behaviors of nitrogen and CO2 on Norit R1 Extra and AlO(OH) nanoparticles and hollow spheres were measured under different temperature and pressure conditions using a magnetic suspension balance. Independent from the substrate investigated, all isotherms increase at lower pressure, reach a maximum, and then decrease with increasing pressure. In addition, selected experimental data were correlated with different model approaches and compared with reliable literature data. In case of CO2 on AlO(OH), capillary condensation was observed at two defined temperatures. The results suggest that the conversion of the liquid into a supercritical adsorbate phase does not take place suddenly.
Phosphate-based inorganic–organic hybrid nanoparticles (IOH-NPs) with the general composition [M]2+[Rfunction(O)PO3]2– (M = ZrO, Mg2O; R = functional organic group) show multipurpose and multifunctional properties. If [Rfunction(O)PO3]2– is a fluorescent dye anion ([RdyeOPO3]2–), the IOH-NPs show blue, green, red, and near-infrared fluorescence. This is shown for [ZrO]2+[PUP]2–, [ZrO]2+[MFP]2–, [ZrO]2+[RRP]2–, and [ZrO]2+[DUT]2– (PUP = phenylumbelliferon phosphate, MFP = methylfluorescein phosphate, RRP = resorufin phosphate, DUT = Dyomics-647 uridine triphosphate). With pharmaceutical agents as functional anions ([RdrugOPO3]2–), drug transport and release of anti-inflammatory ([ZrO]2+[BMP]2–) and antitumor agents ([ZrO]2+[FdUMP]2–) with an up to 80% load of active drug is possible (BMP = betamethason phosphate, FdUMP = 5′-fluoro-2′-deoxyuridine 5′-monophosphate). A combination of fluorescent dye and drug anions is possible as well and shown for [ZrO]2+[BMP]2–0.996[DUT]2–0.004. Merging of functional anions, in general, results in [ZrO]2+([RdrugOPO3]1–x[RdyeOPO3]x)2– nanoparticles and is highly relevant for theranostics. Amine-based functional anions in [MgO]2+[RaminePO3]2– IOH-NPs, finally, show CO2 sorption (up to 180 mg g–1) and can be used for CO2/N2 separation (selectivity up to α = 23). This includes aminomethyl phosphonate [AMP]2–, 1-aminoethyl phosphonate [1AEP]2–, 2-aminoethyl phosphonate [2AEP]2–, aminopropyl phosphonate [APP]2–, and aminobutyl phosphonate [ABP]2–. All [M]2+[Rfunction(O)PO3]2– IOH-NPs are prepared via noncomplex synthesis in water, which facilitates practical handling and which is optimal for biomedical application. In sum, all IOH-NPs have very similar chemical compositions but can address a variety of different functions, including fluorescence, drug delivery, and CO2 sorption.
The durability of polymer electrolyte membrane fuel cells (PEMFC) is governed by a nonlinear coupling between system demand, component behavior, and physicochemical degradation mechanisms, occurring on timescales from the sub-second to the thousand-hour. We present a simulation methodology for assessing performance and durability of a PEMFC under automotive driving cycles. The simulation framework consists of (a) a fuel cell car model converting velocity to cell power demand, (b) a 2D multiphysics cell model, (c) a flexible degradation library template that can accommodate physically-based component-wise degradation mechanisms, and (d) a time-upscaling methodology for extrapolating degradation during a representative load cycle to multiple cycles. The computational framework describes three different time scales, (1) sub-second timescale of electrochemistry, (2) minute-timescale of driving cycles, and (3) thousand-hour-timescale of cell ageing. We demonstrate an exemplary PEMFC durability analysis due to membrane degradation under a highly transient loading of the New European Driving Cycle (NEDC).
Seven cell design concepts for aqueous (alkaline) lithium–oxygen batteries are investigated using a multi-physics continuum model for predicting cell behavior and performance in terms of the specific energy and specific power. Two different silver-based cathode designs (a gas diffusion electrode and a flooded cathode) and three different separator designs (a porous separator, a stirred separator chamber, and a redox-flow separator) are compared. Cathode and separator thicknesses are varied over a wide range (50 μm–20 mm) in order to identify optimum configurations. All designs show a considerable capacity-rate effect due to spatiotemporally inhomogeneous precipitation of solid discharge product LiOH·H2O. In addition, a cell design with flooded cathode and redox-flow separator including oxygen uptake within the external tank is suggested. For this design, the model predicts specific power up to 33 W/kg and specific energy up to 570 Wh/kg (gravimetric values of discharged cell including all cell components and catholyte except housing and piping).
The energy system of the future will transform from the current centralised fossil based to a decentralised, clean, highly efficient, and intelligent network. This transformation will require innovative technologies and ideas like trigeneration and the crowd energy concept to pave the way ahead. Even though trigeneration systems are extremely energy efficient and can play a vital role in the energy system, turning around their deployment is hindered by various barriers. These barriers are theoretically analysed in a multiperspective approach and the role decentralised trigeneration systems can play in the crowd energy concept is highlighted. It is derived from an initial literature research that a multiperspective (technological, energy-economic, and user) analysis is necessary for realising the potential of trigeneration systems in a decentralised grid. And to experimentally quantify these issues we are setting up a microscale trigeneration lab at our institute and the motivation for this lab is also briefly introduced.
In the present study, in vitro toxicity as well as biopersistence and photopersistence of four artificial sweeteners (acesulfame, cyclamate, saccharine, and sucralose) and five antibiotics (levofloxacin, lincomycin, linezolid, marbofloxacin, and sarafloxacin) and of their phototransformation products (PTPs) were investigated. Furthermore, antibiotic activity was evaluated after UV irradiation and after exposure to inocula of a sewage treatment plant. The study reveals that most of the tested compounds and their PTPs were neither readily nor inherently biodegradable in the Organisation for Economic Co-operation and Development (OECD)-biodegradability tests. The study further demonstrates that PTPs are formed upon irradiation with an Hg lamp (UV light) and, to a lesser extent, upon irradiation with a Xe lamp (mimics sunlight). Comparing the nonirradiated with the corresponding irradiated solutions, a higher chronic toxicity against bacteria was found for the irradiated solutions of linezolid. Neither cytotoxicity nor genotoxicity was found in human cervical (HeLa) and liver (Hep-G2) cells for any of the investigated compounds or their PTPs. Antimicrobial activity of the tested fluoroquinolones was reduced after UV treatment, but it was not reduced after a 28-day exposure to inocula of a sewage treatment plant. This comparative study shows that PTPs can be formed as a result of UV treatment. The study further demonstrated that UV irradiation can be effective in reducing the antimicrobial activity of antibiotics, and consequently may help to reduce antimicrobial resistance in wastewaters. Nevertheless, the study also highlights that some PTPs may exhibit a higher ecotoxicity than the respective parent compounds. Consequently, UV treatment does not transform all micropollutants into harmless compounds and may not be a large-scale effluent treatment option.
An Extraction Method for 17α-Ethinylestradiol from Water using a new kind of monolithic Stir-bar
(2015)
We present a 3D simulation approach utilising the diffuse interface representation of the phase-field method combined with a heat transfer equation to analyse the thermal conductivity in air-filled aluminium foams with complex cellular structures of different porosity. Algorithmic methods are introduced to create synthetic open-cell foam structures and to compute the thermal conductivity by means of phase-field modelling. A material law for the effective thermal conductivity is derived by determining the appropriate exponent depending on the relative density in the system. The results are compared with the thermal conductivity in massive aluminium and in pure air.
A 2D-separation of 16 polyaromatic hydrocarbons (PAHs) according to the Environmental Protecting Agency (EPA) standard was introduced. Separation took place on a TLC RP-18 plate (Merck, 1.05559). In the first direction, the plate was developed twice using n-pentane at −20°C as the mobile phase. The mixture acetonitrile-methanol-acetone-water (12:8:3:3, v/v) was used for developing the plate in the second direction. Both developments were carried out over a distance of 43 mm. Further on in this publication, a specific and very sensitive indication method for benzo[a]pyrene and perylene was presented. The method can detect these hazardous compounds even in complicated PAH mixtures. These compounds can be quantified by a simple chemiluminescent reaction with a limit of detection (LOD) of 48 pg per band for perylene and 95 pg per band for benzo[a]pyrene. Although these compounds were separated from all other PAHs in the standard, a separation of both compounds was not possible from one another. The method is suitable for tracing benzo[a]pyrene and/or perylene. The proposed chemiluminescence screening test on PAHs is extremely sensitive but may indicate a false positive result for benzo[a]pyrene.
Since 2003, most European countries established heat health warning systems to alert the population to heat load. Heat health warning systems are based on predicted meteorological conditions outdoors. But the majority of the European population spends a substantial amount of time indoors, and indoor thermal conditions can differ substantially from outdoor conditions. The German Meteorological Service (Deutscher Wetterdienst, DWD) extended the existing heat health warning system (HHWS) with a thermal building simulation model to consider heat load indoors. In this study, the thermal building simulation model is used to simulate a standardized building representing a modern nursing home, because elderly and sick people are most sensitive to heat stress. Different types of natural ventilation were simulated. Based on current and future test reference years, changes in the future heat load indoors were analyzed. Results show differences between the various ventilation options and the possibility to minimize the thermal heat stress during summer by using an appropriate ventilation method. Nighttime ventilation for indoor thermal comfort is most important. A fully opened window at nighttime and the 2-h ventilation in the morning and evening are more sufficient to avoid heat stress than a tilted window at nighttime and the 1-h ventilation in the morning and the evening. Especially the ventilation in the morning seems to be effective to keep the heat load indoors low. Comparing the results for the current and the future test reference years, an increase of heat stress on all ventilation types can be recognized.
Photovoltaics Energy Prediction Under Complex Conditions for a Predictive Energy Management System
(2015)
Systemic Constellations are a phenomenological approach to resolving personal, professional and organizational issues. They offer a way of mapping a present reality, working at the source of the hidden dynamics and moving to a resolution. This systemic approach often delivers surprising and unexpected insights while also offering the possibility to analyze and solve organizational problems. Rational analysis provides the whole picture of the problem which often turns out to be too complex for a decision making. Systemic constellations can help to simplify and clarify the situation and inform what has to happen next [8], [17]. The outcomes of systemic constellations as an additional resource for solving comprehensive technical problems have not yet been sufficiently investigated. In structural constellation work dealing with technical problems, the individuals who are involved in the problem situation are used to represent different system components, substances or fields. A moderator voices the feedback from the representatives concerning their feelings or intuitive movements, and points to possible solutions. For example, a moderator places the representatives somewhere in the room, develops a three-dimensional picture of the constellation of the analyzed situation and tries to expose the factors empowering or blocking the way towards constructive solutions [13]. This paper explores the theoretical background and practical outcomes of the systemic constellation method for technical problem solving. It presents some case study work which has been conducted in recent years, and then discusses its findings and implications. The research outlined in this paper demonstrates that the noteworthy contribution of structural constellation work for problem solving is typically the result of a combination of functional analysis and the feeling-as-information principle. The constellation work helps, at first, to reveal the subjective experiences, such as feelings, moods, emotions, and bodily sensations, and then to accept them as a source of objective information relevant to the decision making process. In accordance with the latest research [19], the use of feelings as a source of information follows the same principles as the use of any other information. This paper provides the structures of some standard templates and types of constellation work for technical problems, and discusses the preconditions for their application.
Demand Side Management for Thermally Activated Building Systems based on Multiple Linear Regression
(2015)
In this paper, the initial multiaxial yield behavior of three different gray cast iron materials with lamellar shaped graphite inclusions is numerically investigated by means of the finite-element method. Therefore, volume elements including the real microstructure of the materials are loaded bi- and triaxially beyond macroscopic yield. The shape of the obtained yield surfaces are compared to the surfaces of four continuum models which, amongst others, are proposed in literature to describe the inelastic behavior of gray cast iron with lamellar shaped graphite inclusions. It is found that the presented continuum models and the macroscopic yield surfaces obtained with microstructure-based finite-element models deviate. Furthermore, the initial inelastic flow direction is computed at the onset of macroscopic yielding. The analysis show that the inelastic flow is normal to the yield surface.
In this paper fatigue crack closure under in-phase and out-of-phase thermomechanical fatigue (TMF) loading is studied using a temperature dependent strip yield model. It is shown that fatigue crack closure is strongly influenced by the phase relation between mechanical loading and temperature, if the temperature difference goes along with a temperature dependence of the yield stress. In order to demonstrate the effect of the temperature dependent yield stress, the influence of in-phase and out-of-phase TMF loading is studied for a polycrystalline nickel-base superalloy. By using a mechanism based lifetime model, implications for fatigue lives are demonstrated.
In this paper, the correlation of the cyclic J-integral, ΔJ, and the cyclic crack-tip opening displacement, ΔCTOD, is studied in the presence of crack closure to assess the question if ΔJ describes the crack-tip opening displacement in this case. To this end, a method is developed to evaluate ΔJ numerically within finite-element calculations. The method is validated for an elastic–plastic material that exhibits Masing behavior. Different strain ranges and strain ratios are considered under fully plastic cyclic conditions including crack closure. It is shown that the cyclic J-integral is the parameter to determine the cyclic crack-tip opening displacement even in cases where crack closure is present.