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The separation of ethane/ethene mixtures (as well as other paraffin/olefin mixtures) is one of the most important but challenging processes in the petrochemical industry. In this work, we report the synthesis of ZIF-318, isostructural to ZIF-8 but built from the mixed linkers of 2-methylimidazole (L1) and 2-trifluoromethylimidazole (L2) (ZIF-318 = [(Zn(L1)(L2)](n)). The synthesis has been optimized to proceed without ZnO-formation. Using only the L2 linker under solvothermal conditions afforded ZnO-embedded in the H-bonded and non-porous coordination polymer ZnO@[Zn-2(L2)(2)(HCOO)(OH)](n). The slight differences in the size of the substituents (-CH3 vs. -CF3) possibly in combination with different electronic inductive effects led to small but significant changes to the pore size and properties respectively, though the effective pore opening (aperture) size of ZIF-318 remained the same in comparison with ZIF-8. ZIF-318 is chemically (boiling water, methanol, benzene, and wide pH range at room temperature for 1 day), thermally (up to 310 degrees C) stable, and more hydrophobic than ZIF-8 which is proven by contact angle measurement. ZIF-318 can be activated for N-2, CO2, CH4, H-2, ethane, ethane, propane, and propene gases sorptions. Consequently, in breakthrough experiments, the ethane/ethene mixtures can be separated.
Regional snow-avalanche detection using object-based image analysis of near-infrared aerial imagery
(2017)
Snow avalanches are destructive mass movements in mountain regions that continue to claim lives and cause infrastructural damage and traffic detours. Given that avalanches often occur in remote and poorly accessible steep terrain, their detection and mapping is extensive and time consuming. Nonetheless, systematic avalanche detection over large areas could help to generate more complete and up-to-date inventories (cadastres) necessary for validating avalanche forecasting and hazard mapping. In this study, we focused on automatically detecting avalanches and classifying them into release zones, tracks, and run-out zones based on 0.25m near-infrared (NIR) ADS80-SH92 aerial imagery using an object-based image analysis (OBIA) approach. Our algorithm takes into account the brightness, the normalised difference vegetation index (NDVI), the normalised difference water index (NDWI), and its standard deviation (SDNDWI) to distinguish avalanches from other land-surface elements. Using normalised parameters allows applying this method across large areas. We trained the method by analysing the properties of snow avalanches at three 4km−2 areas near Davos, Switzerland. We compared the results with manually mapped avalanche polygons and obtained a user's accuracy of >0.9 and a Cohen's kappa of 0.79–0.85. Testing the method for a larger area of 226.3km−2, we estimated producer's and user's accuracies of 0.61 and 0.78, respectively, with a Cohen's kappa of 0.67. Detected avalanches that overlapped with reference data by >80% occurred randomly throughout the testing area, showing that our method avoids overfitting. Our method has potential for large-scale avalanche mapping, although further investigations into other regions are desirable to verify the robustness of our selected thresholds and the transferability of the method.
Four metal organic frameworks with similar topology but different chemical environment inside the pore structure, namely, IFP-1, IFP-3, IFP-5, and IFP-7, have been investigated with respect to the separation potential for olefin paraffin mixtures as well as the influence of the different linkers on adsorption properties using experiments and Monte Carlo simulations. All IFP structures show a higher adsorption of ethane compared to ethene with the exception of IFP-7 which shows no selectivity in breakthrough experiments. For propane/propane separation, all adsorbents show a higher adsorption for the olefin. The experimental results agree quite well with the simulated values except for the IFP-7, which is presumably due to the flexibility of the structure. Moreover, the experimental and simulated isotherms were confirmed with breakthrough experiments that render IFP-1, IFP-3, and IFP-5 as suitable for the purification of ethene from ethane.
Effects of the target aspect ratio and intrinsic reactivity onto diffusive search in bounded domains
(2017)
We study the mean first passage time (MFPT) to a reaction event on a specific site in a cylindrical geometry-characteristic, for instance, for bacterial cells, with a concentric inner cylinder representing the nuclear region of the bacterial cell. A similar problem emerges in the description of a diffusive search by a transcription factor protein for a specific binding region on a single strand of DNA. We develop a unified theoretical approach to study the underlying boundary value problem which is based on a self-consistent approximation of the mixed boundary condition. Our approach permits us to derive explicit, novel, closed-form expressions for the MFPT valid for a generic setting with an arbitrary relation between the system parameters. We analyse this general result in the asymptotic limits appropriate for the above-mentioned biophysical problems. Our investigation reveals the crucial role of the target aspect ratio and of the intrinsic reactivity of the binding region, which were disregarded in previous studies. Theoretical predictions are confirmed by numerical simulations.
Methods. We analysed the energy-resolved light curve and the time-resolved X-ray spectra provided by the EPIC cameras on board XMM-Newton. We also analysed the first high-resolution spectrum of this source provided by the Reflection Grating Spectrometer. Results. An X-ray pulse of 9350 +/- 160 s was measured. Comparison with previous measurements confirms the secular spin up of this source. We successfully fit the pulse-phase-resolved spectra with Comptonisation models. These models imply a very small (r similar to 3 km) and hot (kT similar to 2-3 keV) emitting region and therefore point to a hot spot over the neutron star (NS) surface as the most reliable explanation for the X-ray pulse. The long NS spin period, the spin-up rate, and persistent X-ray emission can be explained within the theory of quasi-spherical settling accretion, which may indicate that the magnetic field is in the magnetar range. Thus, 4U0114+65 could be a wind-accreting magnetar. We also observed two episodes of low luminosity. The first was only observed in the low-energy light curve and can be explained as an absorption by a large over-dense structure in the wind of the B1 supergiant donor. The second episode, which was deeper and affected all energies, may be due to temporal cessation of accretion onto one magnetic pole caused by non-spherical matter capture from the structured stellar wind. The light curve displays two types of dips that are clearly seen during the high-flux intervals. The short dips, with durations of tens of seconds, are produced through absorption by wind clumps. The long dips, in turn, seem to be associated with the rarefied interclump medium. From the analysis of the X-ray spectra, we found evidence of emission lines in the X-ray photoionised wind of the B1Ia donor. The Fe K alpha line was found to be highly variable and much weaker than in other X-ray binaries with supergiant donors. The degree of wind clumping, measured through the covering fraction, was found to be much lower than in supergiant donor stars with earlier spectral types. Conclusions. The XMM-Newton spectroscopy provided further support for the magnetar nature of the neutron star in 4U0114+65. The light curve presents dips that can be associated with clumps and the interclump medium in the stellar wind of the mass donor.
On trend detection
(2017)
A main obstacle to trend detection in time series occurs when they are autocorrelated. By reducing the effective sample size of a series, autocorrelation leads to decreased trend significance. Numerous recipes attempt to mitigate the effect of autocorrelation, either by adjusting for the reduced effective sample size or by removing the autocorrelated components of a series. This short note deals with the latter, also called prewhitening (PW). It is known that removal of autocorrelation also removes part of the trend, which may affect the signal-to-noise ratio. Two popular methods have dealt with this problem, the trend-free prewhitening (TFPW) and the iterative prewhitening. Although it is generally accepted that both methods reduce the adverse effects of PW on the trend magnitude, corresponding effects on statistical significance have not been clearly stated for TFPW. Using a Monte Carlo approach, it is demonstrated that both methods entail quite different Type-I error rates. The iterative prewhitening produces rates that are generally close to the nominal significance level. The TFPW, however, shows very high Type-I error rates with increasing autocorrelation. The corresponding rate of false trend detections is unacceptable for applications, so that published trends based on TFPW need to be reassessed.
We report on the first multi-colour precision light curve of the bright Wolf-Rayet binary gamma(2) Velorum, obtained over six months with the nanosatellites in the BRITE-Constellation fleet. In parallel, we obtained 488 high-resolution optical spectra of the system. In this first report on the data sets, we revise the spectroscopic orbit and report on the bulk properties of the colliding winds. We find a dependence of both the light curve and excess emission properties that scales with the inverse of the binary separation. When analysing the spectroscopic properties in combination with the photometry, we find that the phase dependence is caused only by excess emission in the lines, and not from a changing continuum. We also detect a narrow, high-velocity absorption component from the He perpendicular to lambda 5876 transition, which appears twice in the orbit. We calculate smoothed-particle hydrodynamical simulations of the colliding winds and can accurately associate the absorption from He perpendicular to to the leading and trailing arms of the wind shock cone passing tangentially through our line of sight. The simulations also explain the general strength and kinematics of the emission excess observed in wind lines such as C III lambda 5696 of the system. These results represent the first in a series of investigations into the winds and properties of gamma(2) Velorum through multi-technique and multi-wavelength observational campaigns.
We present the Pristine survey, a new narrow-band photometric survey focused on the metallicity-sensitive Ca H&K lines and conducted in the Northern hemisphere with the wide-field imager MegaCam on the Canada-France-Hawaii Telescope. This paper reviews our overall survey strategy and discusses the data processing and metallicity calibration. Additionally we review the application of these data to the main aims of the survey, which are to gather a large sample of the most metal-poor stars in the Galaxy, to further characterize the faintest Milky Way satellites, and to map the (metal-poor) substructure in the Galactic halo. The current Pristine footprint comprises over 1000 deg(2) in the Galactic halo ranging from b similar to 30 degrees to similar to 78 degrees and covers many known stellar substructures. We demonstrate that, for Sloan Digital Sky Survey (SDSS) stellar objects, we can calibrate the photometry at the 0.02-mag level. The comparison with existing spectroscopic metallicities from SDSS/Sloan Extension for Galactic Understanding and Exploration (SEGUE) and Large Sky Area Multi-Object Fiber Spectroscopic Telescope shows that, when combined with SDSS broad-band g and i photometry, we can use the CaHK photometry to infer photometric metallicities with an accuracy of similar to 0.2 dex from [Fe/H] = -0.5 down to the extremely metal-poor regime ([Fe/H] < -3.0). After the removal of various contaminants, we can efficiently select metal-poor stars and build a very complete sample with high purity. The success rate of uncovering [Fe/H](SEGUE) < -3.0 stars among [Fe/H](Pristine) < -3.0 selected stars is 24 per cent, and 85 per cent of the remaining candidates are still very metal poor ([Fe/H]<-2.0). We further demonstrate that Pristine is well suited to identify the very rare and pristine Galactic stars with [Fe/H] < -4.0, which can teach us valuable lessons about the early Universe.
Investigations on the post mortal formation of fluorescent zinc protoporphyrin (ZnPP) IX in pork meat are currently in focus of meat science research. The role of myoglobin degradation in this context appears to be one of the most diversely discussed issues. To address this question meat-extracts of longissimus lumborum (LL) muscle (0.8 mg/mL) were incubated at 30 degrees C for up to 72 h and investigated by HPSEC-UV-fluorescence, SDS-PAGE and MALDI-TOF-MS. Between 0 and 72 h of incubation the fluorescence intensity (lambda(ex)./(em). = 420/590 nm) of the meat-extracts rose significantly (p < 0.001) from 10.9 +/- 0.8 to 34.8 +/- 0.3 (rel. units) while the staining intensity of the SDS-PAGE of myoglobin non-significantly (p > 0.4) changed from 6.2 +/- 0.5 x 105 to 5.0 +/- 0.3 x 105 (rel. units). The results indicate that ZnPP is formed by a Fe(II)-Zn(II)-substitution in myoglobin heme where an accompanying myoglobin degradation is not necessarily obligatory. (C) 2017 Elsevier Ltd. All rights reserved.
We introduce an abstract concept of quantum field theory on categories fibered in groupoids over the category of spacetimes. This provides us with a general and flexible framework to study quantum field theories defined on spacetimes with extra geometric structures such as bundles, connections and spin structures. Using right Kan extensions, we can assign to any such theory an ordinary quantum field theory defined on the category of spacetimes and we shall clarify under which conditions it satisfies the axioms of locally covariant quantum field theory. The same constructions can be performed in a homotopy theoretic framework by using homotopy right Kan extensions, which allows us to obtain first toy-models of homotopical quantum field theories resembling some aspects of gauge theories.