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111.
A. Musil E. Gagliardi und K. Reischl 《Fresenius' Journal of Analytical Chemistry》1952,137(1):252-258
Zusammenfassung Die Fällung und Bestimmung von Antimon und Zinn mit dem Sulfidfällungsmittel Thioformamid wird beschrieben und Vor- und Nachteile dieses Reagenses gegenüber Einleiten von H2S-Gas werden aufgezeigt. Antimon läßt sich in orangeroter und schwarzer Modifikation fällen. Am schnellsten erfolgt die Fällung des roten Sulfides, das entweder nach Lösen in Säure maßanalytisch bestimmt wird oder in die schwarze Modifikation übergeführt werden kann. Man kann auch unmittelbar die schwarze Form zur Fällung bringen, die dann nach der Arbeitsvorschrift von Biltz
2 weiterbehandelt wird. Zinn läßt sich aus schwachsaurer Lösung rasch als SnS2 fällen, wobei der Niederschlag schnell absitzt, gut filtriert und gründlich ausgewaschen werden kann. Die zulässigen Säurekonzentrationen werden angegeben, die Fehlergrenzen der Bestimmungen aufgezeigt.Frühere Mitteilungen über die Anwendung von Thioformamid in der quantitativen Analyse vgl. E. Gagliardi und A. Loidl, diese Z. 132, 33, 87, 274 (1951); E. Gagliardi und R. Pietsch, Mh. Chem. (Wien) 82, 432, 656 (1951); vgl. diese Z. 136, 298 (1952). 相似文献
112.
Alessio Fanfani Simone Morosi Luca Ronga Enrico Del Re 《International Journal of Satellite Communications and Networking》2018,36(2):179-193
Reliability and effectiveness are essential features of satellite transceivers for telemetry and telecommand applications. Modem performance has a strong impact on the success of a satellite mission, in particular, during critical scenarios as the early operation phase, the disposal of a satellite at the end of its life, or the deep‐space missions. In these specific mission critical scenarios, fast and correct data reception is even more important than high channel capacity. An unknown and fast variable channel condition, which can be caused by uncertain spacecraft attitude and large Doppler shift with respect to the data rate, requires efficient and innovative receiver architecture. This paper introduces a complete digital implementation of a transceiver for TM/TC application in low Earth orbit mission that is perfectly compliant with aforementioned requirements. Particular attention is dedicated to the definition and selection of the most appropriate frequency recovery technique; 2 open‐loop techniques that are derived from ML optimal estimator are presented and compared. Additionally, the performance of the proposed receiver is extensively studied and compared with an incoherent technique that is based on the double differential PSK modulation and is known to be suitable for sat‐com in critical scenarios. 相似文献
113.
Gagliardi LG Castells CB Ràfols C Rosés M Bosch E 《Journal of separation science》2008,31(6-7):969-980
We propose a general simple equation for accurately predicting the retention factors of ionizable compounds upon simultaneous changes in mobile phase pH and column temperature at a given hydroorganic solvent composition. Only four independent experiments provide the input data: retention factors measured in two pH buffered mobile phases at extreme acidic and basic pH values (e. g., at least +/- 2 pH units far from the analyte pK(a)) and at two column temperatures. The equations, derived from the basic thermodynamics of the acid-base equilibria, additionally require the knowledge of the solute pK(a )and enthalpies of acid-base dissociation of both the solute and the buffer components in the hydroorganic solvent mixture. The performance of the predictive model is corroborated with the comparison between theoretical and experimental retention factors of several weak acids and bases of important pharmacological activity, in mobile phases containing different buffer solutions prepared in 25% w/w ACN in water and at several temperatures. 相似文献
114.
The interfacial film of physically adsorbed ionic amphiphilic molecules on submicron particles dispersed in water was studied by a combination of surface tension measurements, laser light scattering (LLS) and high-shear experiments in a microchannel. General features in the structure and morphology of the molecular film are identified and understood in the framework of the two-step Langmuir adsorption model deduced from the adsorption isotherm. On the basis of this approach, the phase transitions and structural ordering of the film at the solid-liquid interface are analyzed in detail. A novel methodology based on high-shear aggregation experiments subsequently analyzed by means of LLS is proposed and turns out to be able to provide significant information on the phase transitions and structural arrangements of the adsorbed molecules (in substantial agreement with the adsorption isotherm model) as well as on the resulting interactions. Particularly important for applications is the result that, with no added salt, the films on two particles can adhere/fuse, leading to aggregation as long as an uncovered (hydrophobic) patch is present (unsaturated molecular layers). In the opposite case of fully developed layers, by analyzing the mechanism of shear aggregation of charged particles in the low-salt limit, we show that, when the hydrophobic attraction is absent, short-range hydration repulsive forces dominate over Derjaguin-Landau-Verwey-Overbeek (DLVO) forces and adhesion can never be achieved even upon application of very high collision energies. Consistently, a lower limiting boundary for the hydration interaction is calculated and found to be in agreement with data in the literature. 相似文献
115.
Laser-ablated Th atoms react with molecular hydrogen to give thorium hydrides and their dihydrogen complexes during condensation in excess neon and hydrogen for characterization by matrix infrared spectroscopy. The ThH2, ThH4, and ThH4(H2)x (x = 1-4) product molecules have been identified through isotopic substitution (HD, D2) and comparison to frequencies calculated by density functional theory and the coupled-cluster, singles, doubles (CCSD) method and those observed previously in solid argon. Theoretical calculations show that the Th-H bond in ThH4 is the most polarized of group 4 and uranium metal tetrahydrides, and as a result, a strong attractive "dihydrogen" interaction was found between the oppositely charged hydride and H2 ligands ThH4(H2)x. This bridge-bonded dihydrogen complex structure is different from that recently computed for tungsten and uranium hydride super dihydrogen complexes but is similar to that recently called the "dihydrogen bond" (Crabtree, R. H. Science 1998, 282, 2000). Natural electron configurations show small charge flow from the Th center to the dihydrogen ligands. 相似文献
116.
Ausili A Torrecillas A Aranda F de Godos A Sánchez-Bautista S Corbalán-García S Gómez-Fernández JC 《The journal of physical chemistry. B》2008,112(40):12696-12702
The interaction between oxidized (ubiquinone-10) and reduced (ubiquinol-10) coenzyme Q 10 with dimyristoylphosphatidylcholine has been examined by differential scanning microcalorimetry, X-ray diffraction, infrared spectroscopy, and (2)H NMR. Microcalorimetry experiments showed that ubiquinol-10 perturbed considerably more the phase transition of the phospholipids than ubiquinone-10, both forms giving rise to a shoulder of the main transition peak at lower temperatures. Small angle X-ray diffraction showed an increase in d-spacing suggesting a thicker membrane in the presence of both ubiquinone-10 and ubiquinol-10, below the phase transition and a remarkable broadening of the peaks indicating a loss of the repetitive pattern of the lipid multilamellar vesicles. Infrared spectroscopy showed an increase in wavenumbers of the maximum of the CH 2 stretching vibration at temperatures below the phase transition, in the presence of ubiquinol-10, indicating an increase in the proportion of gauche isomers in the gel phase, whereas this effect was smaller for ubiquinone-10. A very small effect was observed at temperatures above the phase transition. (2)H NMR spectroscopy of perdeuterated DMPC showed only modest changes in the spectra of the phospholipids occasioned by the presence of coenzyme Q 10. These small changes were reflected, in the presence of ubiquinol-10, by a decrease in resolution indicating that the interaction between coenzyme Q and phospholipids changed the motion of the lipids. The change was also visible in the first spectral moment (M1), which is related with membrane order, which was slightly decreased at temperatures below the phase transition especially with ubiquinol-10. A slight decrease in M 1 values was also observed above the phase transition but only for ubiquinol-10. These results can be interpreted to indicate that most ubiquinone-10 molecules are localized in the center of the bilayer, but a considerable proportion of ubiquinol-10 molecules may span the bilayer interacting more extensively with the phospholipid acyl chains. 相似文献
117.
Luigi Ambrosio Alessio Figalli 《Calculus of Variations and Partial Differential Equations》2008,31(4):497-509
In this paper we improve the regularity in time of the gradient of the pressure field arising in Brenier’s variational weak
solutions (Comm Pure Appl Math 52:411–452, 1999) to incompressible Euler equations. This improvement is necessary to obtain
that the pressure field is not only a measure, but a function in . In turn, this is a fundamental ingredient in the analysis made by Ambrosio and Figalli (2007, preprint) of the necessary
and sufficient optimality conditions for the variational problem by Brenier (J Am Mat Soc 2:225–255, 1989; Comm Pure Appl
Math 52:411–452, 1999). 相似文献
118.
Alessio P Ferreira DM Job AE Aroca RF Riul A Constantino CJ Gonzalez ER 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):4729-4737
The synthesis of a poly(azo)urethane by fixing CO(2) in bis-epoxide followed by a polymerization reaction with an azodiamine is presented. Since isocyanate is not used in the process, it is termed "clean method" and the polymers obtained are named "NIPUs" (non-isocyanate polyurethanes). Langmuir films were formed at the air-water interface and were characterized by surface pressure vs mean molecular area per mer unit (Pi-A) isotherms. The Langmuir monolayers were further studied by running stability tests and cycles of compression/expansion (possible hysteresis) and by varying the compression speed of the monolayer formation, the subphase temperature, and the solvents used to prepare the spreading polymer solutions. The Langmuir-Blodgett (LB) technique was used to fabricate ultrathin films of a particular polymer (PAzoU). It is possible to grow homogeneous LB films of up to 15 layers as monitored using UV-vis absorption spectroscopy. Higher number of layers can be deposited when PAzoU is mixed with stearic acid, producing mixed LB films. Fourier transform infrared (FTIR) absorption spectroscopy and Raman scattering showed that the materials do not interact chemically in the mixed LB films. The atomic force microscopy (AFM) and micro-Raman technique (optical microscopy coupled to Raman spectrograph) revealed that mixed LB films present a phase separation distinguishable at micrometer or nanometer scale. Finally, mixed and neat LB films were successfully characterized using impedance spectroscopy at different temperatures, a property that may lead to future application as temperature sensors. Principal component analysis (PCA) was used to correlate the data. 相似文献
119.
Matxain JM Rezabal E Lopez X Ugalde JM Gagliardi L 《The Journal of chemical physics》2008,128(19):194315
A large set of electronic states of scandium dimer has been calculated using high-level theoretical methods such as quantum diffusion Monte Carlo (DMC), complete active space perturbation theory as implemented in GAMESS-US, coupled-cluster singles, doubles, and triples, and density functional theory (DFT). The 3 Sigma u and 5 Sigma u states are calculated to be close in energy in all cases, but whereas DFT predicts the 5 Sigma u state to be the ground state by 0.08 eV, DMC and CASPT2 calculations predict the 3 Sigma u to be more stable by 0.17 and 0.16 eV, respectively. The experimental data available are in agreement with the calculated frequencies and dissociation energies of both states, and therefore we conclude that the correct ground state of scandium dimer is the 3 Sigma u state, which breaks with the assumption of a 5 Sigma u ground state for scandium dimer, believed throughout the past decades. 相似文献
120.
Alexander Turkin Lei Zhang Alessio Marcozzi Walter F. Mangel Andreas Herrmann Antoine M. van Oijen 《Chemical science》2016,7(2):916-920
Numerous biological processes involve association of a protein with its binding partner, an event that is preceded by a diffusion-mediated search bringing the two partners together. Often hindered by crowding in biologically relevant environments, three-dimensional diffusion can be slow and result in long bimolecular association times. Similarly, the initial association step between two binding partners often represents a rate-limiting step in biotechnologically relevant reactions. We demonstrate the practical use of an 11-a.a. DNA-interacting peptide derived from adenovirus to reduce the dimensionality of diffusional search processes and speed up associations between biological macromolecules. We functionalize binding partners with the peptide and demonstrate that the ability of the peptide to one-dimensionally diffuse along DNA results in a 20-fold reduction in reaction time. We also show that modifying PCR primers with the peptide sled enables significant acceleration of standard PCR reactions. 相似文献