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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.
Private households constitute a considerable share of Europe's electricity consumption. The current electricity distribution system treats them as effectively passive individual units. In the future, however, users of the electricity grid will be involved more actively in the grid operation and can become part of intelligent networked collaborations. They can then contribute the demand and supply flexibility that they dispose of and, as a result, help to better integrate renewable energy in-feed into the distribution grids.
High-precision signal processing algorithm to evaluate SAW properties as a function of temperature
(2013)
This paper presents a signal processing algorithm which accurately evaluates the SAW properties of a substrate as functions of temperature. The investigated acoustic properties are group velocity, phase velocity, propagation loss, and coupling coefficient. With several measurements carried out at different temperatures, we obtain the temperature dependency of the SAW properties. The analysis algorithm starts by reading the transfer functions of short and long delay lines. The analysis algorithm determines the center frequency of the delay lines and obtains the delay time difference between the short and long delay lines. The extracted parameters are then used to calculate the acoustic properties of the SAW material. To validate the algorithm, its accuracy is studied by determining the error in the calculating delay time difference, center frequency, and group velocity.
Researchers are developing new GNSS receivers and antennas based on an innovative signal-processing scheme to significantly improve GNSS tracking reliability and accuracy under degraded signal conditions. It is based on the principles of synthetic-aperture radar. Like in a multi-antenna phased array receiver, GNSS signals from different spatial locations are combined coherently forming an optimized synthetic antenna-gain pattern. The method is implemented in a real-time PC-based software receiver and works with GPS, GLONASS, and Galileo signals. Multiple frequencies are generally supported. The idea of synthetic-aperture processing is realized as a coherent summation of correlation values of each satellite over the so-called beamforming interval. Each correlation value is multiplied with a phase factor. For example, the phase factor can be chosen to compensate for the relative antenna motion over the beam-forming interval and the resulting sum of the scaled correlation values represents a coherent correlation value maximizing the line of sight signal power.
The paper proposes a system architecture for charging infrastructure that serves the requirements of future fleets of shared-use electric vehicles in urban scenarios. The focus of the development is on the interfaces to central stakeholders such as mobility service providers, distribution network operators and utilities. The main concept of the proposed system is the adherence to a stringent resource-oriented design approach, following the design principles of the Representational State Transfer (REST) architectural software style for distributed systems. This design approach is used from the cloud-based services down to the implementation of the charging infrastructure's control algorithms. Focusing on the resources of the various entities simplifies the implementation of their interactions, compared to the explicit declaration of services that are available. The system design ensures that the charging infrastructure is open to all users and generates a benefit beyond basic charging operations. Integration in emerging smart markets is done via open web-based interfaces. These allow for the generation of an added value of concrete services for shared-use electric mobility. A link to the field of grid operation is proposed using the ISO/IEC 61850 telecontrol standard. The smart meter capabilities of the charging stations can be used to gain additional information on the current state of the distribution grid. As an exemplary service a load management service for a fleet of shared-use electric vehicles is going to be implemented.
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.
Background: Increasing awareness of the importance of evidence-based medicine is demonstrated not only by an increasing number of articles addressing it but also by a specialty-wide evidence-based medicine initiative. The authors critically analyzed the quality of reporting of randomized controlled trials published in this Journal over a 21-year period (1990 to 2010).
Methods: A hand search was conducted, including all issues of Plastic and Reconstructive Surgery from January of 1990 to December of 2010. All randomized controlled trials published during this time period were identified with the Cochrane decision tree for identification of randomized controlled trials. To assess the quality of reporting, a modification of the checklist of the Consolidated Standard of Reporting Trials Statement was used.
Results: Of 7121 original articles published from 1990 to 2010 in the Journal, 159 (2.23 percent) met the Cochrane criteria. A significant increase in the absolute number of randomized controlled trials was seen over the study period (p < 0.0001). The median quality of these trials from 1990 to 2010 was "fair," with a trend toward improved quality of reporting over time (p = 0.127).
Conclusions: A favorable trend is seen with respect to an increased number of published randomized controlled trials in Plastic and Reconstructive Surgery. Adherence to standard reporting guidelines is recommended, however, to further improve the quality of reporting. Consideration may be given to providing information regarding the quality of reporting in addition to the "level of evidence pyramid," thus facilitating critical appraisal.
There is an increasing demand by an ever-growing number of mobile customers for transfer of rich media content. This requires very high bandwidth which either cannot be provided by the current cellular systems or puts pressure on the wireless networks, affecting customer service quality. This study introduces COARSE – a novel cluster-based quality-oriented adaptive radio resource allocation scheme, which dynamically and adaptively manages the radio resources in a cluster-based two-hop multi-cellular network, having a frequency reuse of one. COARSE is a cross-layer approach across physical layer, link layer and the application layer. COARSE gathers data delivery-related information from both physical and link layers and uses it to adjust bandwidth resources among the video streaming end-users. Extensive analysis and simulations show that COARSE enables a controlled trade-off between the physical layer data rate per user and the number of users communicating using a given resource. Significantly, COARSE provides 25–75% improvement in the computed user-perceived video quality compared with that obtained from an equivalent single-hop network.
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.
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.
Multi-phase management is crucial for performance and durability of electrochemical cells such as batteries and fuel cells. In this paper we present a generic framework for describing the two-dimensional spatiotemporal evolution of gaseous, liquid and solid phases, as well as their interdependence with interfacial (electro-)chemistry and microstructure in a continuum description. The modeling domain consists of up to seven layers (current collectors, channels, electrodes, separator/membrane), each of which can consist of an arbitrary number of bulk phases (gas, liquid, solid) and connecting interfaces (two-phase or multi-phase boundaries). Bulk and interfacial chemistry is described using global or elementary kinetic reactions. Multi-phase management is coupled to chemistry and to mass and charge transport within bulk phases. The functionality and flexibility of this framework is demonstrated using four application areas in the context of post-lithium-ion batteries and fuel cells, that is, lithium-sulfur (Li-S) cells, lithium-oxygen (Li-O) cells, solid oxide fuel cells (SOFC) and polymer electrolyte membrane fuel cells (PEFC). The results are compared to models available in literature and properties of the generic framework are discussed.
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.
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.
The study from Mehrazin et al. in HJNM 2011; 14(3): 243-50 on the neuropsychology, morphological computerized tomography (CT) and functional neuroimaging with 99mTc-labelled ethylene cystein-ate dimer single-photon emission tomography (SPET) in mild trau-matic brain injury (MTBI) is an interesting new approach to a disease condition which is often neglected or denied. Related to the above, we may note that the French composer Maurice Ravel (1875-1937), who suffered from Pick ́s disease with primary progressive apha-sia, had a taxi accident in 1932, with a mild concussion, perhaps an MTBI. Apart from the dysphasia and beginning apraxia, which Rav-el had already 5 years prior to the taxi accident, these symptoms exacerbated-the dysphasia became a progressive aphasia-and he developed additional severe deficits in concentration and atten-tion after the accident. It has also been suspected that this accident may have triggered Ravel ́s agraphia the unability to write down any new composition beyond the date of the taxi accident, a condi-tion that Ravel himself described as unacceptable and which made him feel very sad as his mind was full of ideas. Due to the deterio-ration of his health, which can also be seen in his appearance on late photographs, Ravel consulted the famous neurosurgeon Prof. Clovis Vincent. Vincent, who suspected a hydrocephalus, opened Ravel ́s skull on December 19, 1937, showing a normal brain. Soon after surgery Ravel died. In conclusion, a SPET/CT approach com-bined with a brain perfusion analysis using statistical parametric mapping might be the recommendable approach today for mild traumatic brain injury.
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.
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.
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.
The suffix-free-prefix-free hash function construction and its indifferentiability security analysis
(2012)
In this paper, we observe that in the seminal work on indifferentiability analysis of iterated hash functions by Coron et al. and in subsequent works, the initial value (IV) of hash functions is fixed. In addition, these indifferentiability results do not depend on the Merkle–Damgård (MD) strengthening in the padding functionality of the hash functions. We propose a generic n-bit-iterated hash function framework based on an n-bit compression function called suffix-free-prefix-free (SFPF) that works for arbitrary IVs and does not possess MD strengthening. We formally prove that SFPF is indifferentiable from a random oracle (RO) when the compression function is viewed as a fixed input-length random oracle (FIL-RO). We show that some hash function constructions proposed in the literature fit in the SFPF framework while others that do not fit in this framework are not indifferentiable from a RO. We also show that the SFPF hash function framework with the provision of MD strengthening generalizes any n-bit-iterated hash function based on an n-bit compression function and with an n-bit chaining value that is proven indifferentiable from a RO.
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.
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.
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.
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.
A survey in 2000 revealed that only about 30% of the prescriptions in the European pediatric population were on the basis of evidence-based medicine (EbM). Less for radiopharmaceuticals and principally for diagnostics, radiologists throughout Europe are referred to the pediatric guidelines of the European Association of Nuclear Medicine (EANM), as none of the frequently used tracers have been evaluated in clinical trials in the different pediatric subgroups. Following a resolution to address the lack of EbM in children, the European Commission published the Pediatric Regulation EC 1901/2006 and its amendment EC 1902/2006, effective from 2007. This regulation foresees the development of evidence-based medicine in the pediatric population. This is effected through a set of principles like the mandatory pediatric investigation plan (PIP) to be included with the market authorization application (MAA), and the pediatric use market authorization (PUMA) for off-patent pharmaceuticals, and to a very small part radiopharmaceuticals with funding possibilities for pediatric-specific research through the 7th Framework Programme (7FP) of the European Union.
Routine nuclear cardiology examinations indicate heart rate, cardiac rhythm, the height of cardiac pulse and respiration rhythm. It would be of interest to study whether these data, especially if the same tests are repeated, can indicate patients’ well being in the future and perhaps patients’ life span, other factors being equal. Related old theories and suggestions are mentioned. Furthermore, some drugs like I-f channel antagonists and stress tests testing cardiac reserves could support such a study.
The Humboldt digital library (HDL) represents an innovative system to access the works and legacy of Alexander von Humboldt in a digital form on the Internet (www.avhumboldt.net). It contributes to the key question about how to present interconnected data in an appropriate form using information technologies. The HDL has been created as a dynamic digital library with the capability of connecting multilingual and multimedia data from diverse online archives. Humboldt’s volumes have become available, but beyond that any relevant information related to the observations of Humboldt, even outside the works can become immediately accessible. This makes it possible to recognize natural changes and compare Humboldt’s descriptions with recent situations. The technology we have developed addresses the issues of sustainability and makes it possible to detect changes in the environment since the time of Humboldt’s observations.
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.
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.
Uptakes of 9.2 mmol g−1 (40.5 wt %) for CO2 at 273 K/0.1 MPa and 15.23 mmol g−1 (3.07 wt %) for H2 at 77 K/0.1 MPa are among the highest reported for metal–organic frameworks (MOFs) and are found for a novel, highly microporous copper‐based MOF (see picture; Cu turquoise, O red, N blue). Thermal analyses show a stability of the flexible framework up to 250 °C.
Metal–organic frameworks (MOFs) as highly porous materials have gained increasing interest because of their distinct adsorption properties.1–3 They exhibit a high potential for applications in gas separation and storage,4 as sensors5 as well as in heterogeneous catalysis.6 In the last few years, the H2 storage capacity of MOFs has been considerably increased. Mesoporous MOFs show high adsorption capacities for CH4, CO2, and H2 at high pressures.2, 3, 7–10 To increase the uptake of H2 and CO2 by physisorption at ambient pressure, adsorbents with small micropores as well as high specific surface areas and micropore volumes are required.11, 12 Such microporous materials seem to be more appropriate for gas‐mixture separation by physisorption than mesoporous materials. For gas separation in MOFs the interactions between the fluid adsorptive and “open metal sites” (coordinatively unsaturated binding sites) or the ligands are regarded as important.13 Industrial processes, such as natural‐gas purification or biogas upgrading, can be improved with those materials during a vapor‐pressure swing adsorption cycle (VPSA cycle) or a temperature swing adsorption cycle (TSA cycle).14 The microporous MOF series CPO‐27‐M (M=Mg, Co, Ni, Zn), for example, shows very high CO2 uptakes at low pressures (<0.1 MPa).15, 16 Concerning H2 adsorption, the microporous MOF PCN‐12 offers with 3.05 wt % the highest uptake at ambient pressure and 77 K reported to date.17
Herein, we present a novel microporous copper‐based MOF equation image[Cu(Me‐4py‐trz‐ia)] (1; Me‐4py‐trz‐ia2−=5‐(3‐methyl‐5‐(pyridin‐4‐yl)‐4H‐1,2,4‐triazol‐4‐yl)isophthalate) with extraordinarily high CO2 and H2 uptakes at ambient pressure, the H2 uptake being similar to that in PCN‐12. The ligand Me‐4py‐trz‐ia2−, which can be obtained from cheap starting materials by a three‐step synthesis in good yield, combines carboxylate, triazole, and pyridine functions and is adopted from a recently presented series of linkers,18 for which up to now only a few coordination polymers are known.
The present study describes medium-chain-length polyhydroxyalkanoates (mcl-PHAs) production by the Pseudomonas Gl01 strain isolated from mixed microbial communities utilized for PHAs synthesis. A two-step fedbatch fermentation was conducted with glucose and waste rapeseed oil as the main carbon source for obtaining cell growth and mcl-PHAs accumulation, respectively. The results show that the Pseudomonas Gl01 strain is capable of growing and accumulating mcl-PHAs using a waste oily carbon source. The biomass value reached 3.0 g/l of CDW with 20% of PHAs content within 48 h of cultivation. The polymer was purified from lyophilized cells and analyzed by gas chromatography (GC). The results revealed that the monomeric composition of the obtained polyesters depended on the available substrate. When glucose was used in the growth phase, 3-hydroxyundecanoate and 3- hydroxydodecanoate were found in the polymer composition, whereas in the PHAs-accumulating stage, the Pseudomonas Gl01 strain synthesized mcl-PHAs consisting mainly of 3- hydroxyoctanoate and 3-hydroxydecanoate. The transcriptional analysis using reverse-transcription real-time PCR reaction revealed that the phaC1 gene could be transcribed simultaneously to the phaZ gene.
An analytical and numerical study of the wobbling dynamics of friction disks is presented. Of particular interest is the excitation mechanism taking into account two contrarian effects both originating in dry friction: the circulatory terms describing the energy input due to the sliding contacts and the friction induced damping which stabilizes the system. Balance of these terms determines the instability domain in the parameter space. It is shown that there is a slip threshold so that, if the slip is under this limit, the system remains stable. If the slip is larger than this limit, then the criterion of stability is determined by the relation between the friction coefficient and the internal damping. The limit cycle appearing in the unstable domain is also investigated. It is shown that the limit cycle can be described as a kind of a regular reverse precession of the wobbling disc. Its amplitude is limited by the geometric nonlinearity and partial contact loss. Analytic results are compared with numeric simulations.
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.
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.
The separation of nitrogen and methane from hydrogen-rich mixtures is systematically investigated on a recently developed binder-free zeolite 5A. For this adsorbent, the present work provides a series of experimental data on adsorption isotherms and breakthrough curves of nitrogen and methane, as well as their mixtures in hydrogen. Isotherms were measured at temperatures of 283–313 K and pressures of up to 1.0 MPa. Breakthrough curves of CH4, N2, and CH4/N2 in H2 were obtained at temperatures of 300–305 K and pressures ranging from 0.1 to 6.05 MPa with different feed concentrations. An LDF-based model was developed to predict breakthrough curves using measured and calculated data as inputs. The number of parameters and the use of correlations were restricted to focus on the importance of measured values. For the given assumptions, the results show that the model predictions agree satisfactorily with the experiments under the different operating conditions applied.
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 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.
We present a novel fabrication route yielding Raney-platinum film electrodes intended as glucose oxidation anodes for potentially implantable fuel cells. Fabrication roots on thermal alloying of an extractable metal with bulk platinum at 200 °C for 48 h. In contrast to earlier works using carcinogenic nickel, we employ zinc as potentially biocompatible alloying partner. Microstructure analysis indicates that after removal of extractable zinc the porous Raney-platinum film (roughness factor ∼2700) consists predominantly of the Pt3Zn phase. Release of zinc during electrode operation can be expected to have no significant effect on physiological normal levels in blood and serum, which promises good biocompatibility. In contrast to previous anodes based on hydrogel-bound catalyst particles the novel anodes exhibit excellent resistance against hydrolytic and oxidative attack. Furthermore, they exhibit significantly lower polarization with up to approximately 100 mV more negative electrode potentials in the current density range relevant for fuel cell operation. The anodes’ amenability to surface modification with protective polymers is demonstrated by the exemplary application of an approximately 300 nm thin Nafion coating. This had only a marginal effect on the anode long-term stability and amino acid tolerance. While in physiological glucose solution after approximately 100 h of operation gradually increasing performance degradation occurs, rapid electrode polarization within 24 h is observed in artificial tissue fluid. Optimization approaches may include catalyst enhancement by adatom surface modification and the application of specifically designed protective polymers with controlled charge and mesh size.
We report the fabrication and characterization of glucose-tolerant Raney-platinum cathodes for oxygen reduction in potentially implantable glucose fuel. Fabricated by extraction of aluminum from 1 μm thin platinum–aluminum bi-layers annealed at 300 °C, the novel cathodes show excellent resistance against hydrolytic and oxidative attack. This renders them superior over previous cathodes fabricated from hydrogel-bound catalyst particles. Annealing times of 60, 120, and 240 min result in approximately 400–550 nm thin porous films (roughness factors ∼100–150), which contain platinum and aluminum in a ratio of ∼9:1. Aluminum release during electrode operation can be expected to have no significant effect on physiological normal levels, which promises good biocompatibility. Annealing time has a distinct influence on the density of trenches formed in the cathode. Higher trench densities lead to lower electrode potentials in the presence of glucose. This suggests that glucose sensitivity is governed by mixed potential formation resulting from oxygen depletion within the trenches. During performance characterization the diffusion resistance to be expected from tissue capsule formation upon electrode implantation was taken into account by placing a membrane in front of the cathode. Despite the resulting limited oxygen supply, cathodes prepared by annealing for 60 min show more positive electrode potentials than previous cathodes fabricated from hydrogel-bound activated carbon. Compared to operation in phosphate buffered saline containing 3.0 mM glucose, a potential loss of approximately 120 mV occurs in artificial tissue fluid. This can be reduced to approximately 90 mV with a protective Nafion layer that is easily electro-coated onto the Raney-platinum film.
Thin-layer chromatography is a rapid and reliable working method for quantification of mycotoxins which is suitable for checking EC legislation aflatoxin limits for dried figs without an RP-18 pre-column cleaning step. We describe normal-phase chromatography on silica gel plates with 2.4:0.05:0.1:0.05 ( v/v ) methyl t -butyl ether-water-methanol-cyclohexane as mobile phase and reversed-phase chromatography on RP-18 plates with methanol-4% aqueous ZnSO 4 solution-ethyl methyl ketone 15:15:3 ( v/v ) as mobile phase. Sample pretreatment was by modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) extraction with tetrahydrofuran or acetone. NaCl was used as QuEChERS salt. Response was a linear function of amount chromatographed in the ranges 3 to 100 pg per zone for aflatoxins B 2 and G 2 , 10 to 350 pg per zone for the aflatoxins B 1 and G 1 , and 0.25 to 2.5 ng per zone for ochratoxin A. Quantification limits for the aflatoxins were between 13 and 35 pg per zone (equivalent to 1.5 and 2.4 ppb, taking the pre-treatment procedure into account). Ochratoxin A was detectable with a limit of quantification of 970 pg per zone, corresponding to 56 ppb in the sample. Normal phase and RP-18 separations work rapidly, reliably, and at low cost. They are also suitable for checking the content of the mycotoxins patulin, penicillic acid, zearalenone, and deoxynivalenol.
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%.
There are some existing Java benchmarks, application benchmarks as well as micro benchmarks or mixture both of them,such as: Java Grande, Spec98, CaffeMark, HBech, etc. But none of them deal with behaviors of multi tasks operating systems. As a result, the achieved outputs are not satisfied for performance evaluation engineers. Behaviors of multi tasks operating systems are based on a schedule management which is employed in these systems. Different processes can have different priority to share the same resources. The time is measured by estimating from applications started to it is finished does not reflect the real time value which the system need for running those programs. New approach to this problem should be done. Having said that, in this paper we present a new Java benchmark, named FHOJ benchmark, which directly deals with multi tasks behaviors of a system. Our study shows that in some cases, results from FHOJ benchmark are far more reliable in comparison with some existing Java benchmarks.
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!
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.
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.
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.
A theoretical description is given for the propagation of surface acoustic wave pulses in anisotropic elastic media subject to the influence of nonlinearity. On the basis of nonlinear elasticity theory, an evolution equation is presented for the surface slope or the longitudinal surface velocity associated with an acoustic pulse. It contains a non-local nonlinearity, characterized by a kernel that strongly varies from one propagation geometry to another due to the anisotropy of the substrate. It governs pulse shape evolution in homogeneous halfspaces and the shapes of solitary surface pulses that exist in coated substrates. The theory describing nonlinear Rayleigh-type surface acoustic waves is extended in a straightforward way to surface waves that are localized at a one-dimensional acoustic waveguide like elastic wedges.
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.
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.
This paper presents a multicarrier code-division multiple-access (CDMA) system architecture that is based on complete complementary orthogonal spreading codes. The architecture has several advantages as compared to conventional CDMA systems. Specifically, it offers multiple-access interference-free operation in additive white Gaussian noise channels, reduces cochannel interference significantly, and has the potential of higher capacity and spectral efficiency than conventional CDMA systems. This is accomplished by using an ldquooffset stackedrdquo spreading modulation technique. To maintain good performance in the presence of fading, the offset stacked modulator is followed by a quadrature-amplitude modulation map, which is designed to optimize performance in a fading environment. This new modulation scheme also simplifies the rate-matching algorithms that are relevant for multimedia services and Internet Protocol-based applications.