Thermogravimetric and kinetic study of a clodronic acid complex formed with sodium

Thermal stability of the clodronic acid complex formed with sodium (Na₂CCl₂(HPO₃)₂ ·4H₂O) was studied using both dynamic and isothermal thermogravimetric analyses as well as mass spectra. The thermal decomposition has two stages: dehydration and loss of two molecules of hydrogen chloride. Using the isothermal TG data the first step was found to be a phase-boundary reaction while the second step obviously cannot be described with just one reaction mechanism. The final residue of the dynamic TG analyses above 810 K was found to be sodium metaphosphate.

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Zusammenfassung Sowohl mittels dynamischer und thermogravimetrischer Untersuchungen als auch and Hand von Massenspektren wurde die thermische Stabilität des mit Natrium gebildeten Säurekomplexes Na₂CCl₂(HPO₃)₂·4H₂O untersucht. Die thermische Zersetzung vollzieht sich in zwei Schritten: Dehydratation und Verlust von zwei Molekülen HCl. Auf Grund der isothermen TG Angaben ist der erste Schritt eine Phasengrenzreaktion, während der zweite Schritt mit einem einzigen Reaktionsmechanismus nicht eindeutig beschrieben werden kann. Das Endprodukt der DTG Analyse oberhalb 810 K erwies sich als Natriummethaphosphat.

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-Na₂CCl₂/HPO_3/2·4H₂O — , - . , , , . , , . 810 .

     

Optimization of capillary electrophoretic-electrospray ionization-mass spectrometric analysis of catecholamines

The capillary electrophoretic-mass spectrometric analysis (CE-MS) of catecholamines was optimized with coaxial sheath flow interface and electrospray ionization (ESI). The parameters studied included the sheath liquid composition and its flow rate, separation conditions in ammonium acetate buffer together with the ESI and cone voltages as mass spectrometric parameters. In addition, the effect of ESI voltage on injection as well as the siphoning effect were considered. The optimized conditions were a sheath liquid composition of methanol-water (80:20 v/v) with 0.5% acetic acid, with a flow rate of 6 microL/min. The capillary electrophoretic separation parameters were optimized with 50 mM ammonium acetate buffer, pH 4.0, to +25 kV separation voltage together with a pressure of 0.1 psi. The most intensive signals were obtained with an ESI voltage of +4.0 kV and a cone voltage of +20 V. The nonactive ESI voltage during injection as well as avoidance of the siphoning effect increased the sensitivity of the MS detection considerably. The use of ammonium hydroxide as the CE capillary conditioning solution instead of sodium hydroxide did not affect the CE-MS performance, but allowed the conditioning of the capillary between analyses to be performed in the MS without contaminating the ion source.     

Strain rate change tests with the Split Hopkinson Bar method

In this paper, methods to produce rapid strain rate changes for strain rate sensitivity measurements in Split Hopkinson Bar arrangements are presented and discussed. Two different cases are considered: a strain rate change test within the high strain rate region in compression, and a tension test incorporating a large strain rate jump directly from the low strain rate region to high strain rates. The former method is based on the loading wave amplitude manipulation, while the latter method is based on the incorporation of a low strain rate loading device into a Tensile Split Hopkinson Bar apparatus.     

Determination of ergot alkaloids from grains with UPLC‐MS/MS

A simple and rapid method for determining six ergot alkaloids and four of their respective epimers was developed for rye and wheat. The analytes were extracted from the sample matrix with ACN/ammonium carbonate solution. The extract was purified with a commercial push‐through SPE column (Mycosep^® 150 Ergot). After concentration and filtration steps, the final separation of the analytes was achieved with ultra‐performance LC‐MS/MS. The chromatographic separation of the ergot alkaloids was achieved in 4.5 min. The method performance proved satisfactory in the preliminary validation. The calculated LOQs were low ranging from 0.01 to 1.0 μg/kg for wheat and from 0.01 to 10.0 μg/kg for rye. At the concentration levels of 10, 50 and 200 μg/kg, the recoveries were between 80 and 120% in most cases and the within‐day repeatability (expressed as RSD) ranged between 1.3 and 13.9%. Despite the cleanup of the samples, some matrix effect was observed in the MS, highlighting the necessity of using matrix‐assisted standards. This is the first article to describe the application of the push‐through columns and ultra‐performance LC in the analysis of ergot alkaloids.     

FiD: a software for ab initio structural identification of product ions from tandem mass spectrometric data

We present FiD (Fragment iDentificator), a software tool for the structural identification of product ions produced with tandem mass spectrometric measurement of low molecular weight organic compounds. Tandem mass spectrometry (MS/MS) has proven to be an indispensable tool in modern, cell-wide metabolomics and fluxomics studies. In such studies, the structural information of the MS(n) product ions is usually needed in the downstream analysis of the measurement data. The manual identification of the structures of MS(n) product ions is, however, a nontrivial task requiring expertise, and calls for computer assistance. Commercial software tools, such as Mass Frontier and ACD/MS Fragmenter, rely on fragmentation rule databases for the identification of MS(n) product ions. FiD, on the other hand, conducts a combinatorial search over all possible fragmentation paths and outputs a ranked list of alternative structures. This gives the user an advantage in situations where the MS/MS data of compounds with less well-known fragmentation mechanisms are processed. FiD software implements two fragmentation models, the single-step model that ignores intermediate fragmentation states and the multi-step model, which allows for complex fragmentation pathways. The software works for MS/MS data produced both in positive- and negative-ion modes. The software has an easy-to-use graphical interface with built-in visualization capabilities for structures of product ions and fragmentation pathways. In our experiments involving amino acids and sugar-phosphates, often found, e.g., in the central carbon metabolism of yeasts, FiD software correctly predicted the structures of product ions on average in 85% of the cases. The FiD software is free for academic use and is available for download from www.cs.helsinki.fi/group/sysfys/software/fragid. Copyright (c) 2008 John Wiley & Sons, Ltd.     

In Situ Observation of C−C Coupling and Step Poisoning During the Growth of Hydrocarbon Chains on Ni(111)

The synthesis of high-value fuels and plastics starting from small hydrocarbon molecules plays a central role in the current transition towards renewable energy. However, the detailed mechanisms driving the growth of hydrocarbon chains remain to a large extent unknown. Here we investigated the formation of hydrocarbon chains resulting from acetylene polymerization on a Ni(111) model catalyst surface. Exploiting X-ray photoelectron spectroscopy up to near-ambient pressures, the intermediate species and reaction products have been identified. Complementary in situ scanning tunneling microscopy observations shed light onto the C−C coupling mechanism. While the step edges of the metal catalyst are commonly assumed to be the active sites for the C−C coupling, we showed that the polymerization occurs instead on the flat terraces of the metallic surface.     

Dynamic systems view of learning a three‐tiered theory in physics: robust learning outcomes as attractors

The process of learning scientific knowledge from the dynamic systems viewpoint is studied in terms probabilistic learning model (PLM), where learning accrues from foraging in the epistemic landscape. The PLM leads to the formation of attractor‐type regions of preferred models in an epistemic landscape. The attractor‐type states correspond to robust learning outcomes which are more probable than others. These can be assigned either to the high confidence in model selection or to the dynamic evolution of a learner's proficiency, which depends on the learning history. The results suggest that robust learning states are essentially context dependent, and that learning is a continuous development between these context dependent states. © 2016 Wiley Periodicals, Inc. Complexity 21: 259–267, 2016     

High Strain Rate Torsion Properties of Ultrafine-Grained Aluminum

Mechanical properties of most metallic materials can be improved by reducing their grain size. One of the methods used to reduce the grain size even to the nanometer level is the severe plastic deformation processing. Equal Channel Angular Pressing (ECAP) is one of the most promising severe plastic deformation processes for the nanocrystallization of ductile metals. Nanocrystalline and ultrafine grained metals usually have significantly higher strength properties but lower tensile ductility compared to the coarse grained metals. In this work, the torsion properties of ECAP processed ultrafine grained pure 1070 aluminum were studied in a wide range of strain rates using both servohydraulic materials testing machines and Hopkinson Split Bar techniques. The material exhibits extremely high ductility in torsion and the specimens did not fail even after 300% of strain. Pronounced yield point behavior was observed at strain rates 500 s⁻¹ and higher, whereas at lower strain rates the yielding was continuous. The material showed slight strain softening at the strain rate of 10⁻⁴ s⁻¹, almost ideally plastic behavior at strain rates between 10⁻³ s⁻¹ and 500 s⁻¹, and slight but increasing strain hardening at strain rates higher than that. The tests were monitored using digital cameras, and the strain distributions on the surface of the specimens were calculated using digital image correlation. The strain in the specimen localized very rapidly after yielding at all strain rates, and the localization lead to the development of a shear band. At high strain rates the shear band developed faster than at low strain rates.