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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.