Simulation of Cement/Clay Interactions: Feedback on the Increasing Complexity of Modelling Strategies

During the last decade, numerous studies have focused on long-term predictive reactive transport modelling of cement/clay interactions. These simulations have been performed using modelling strategies of growing complexity, e.g. (i) taking more minerals into account, (ii) considering the effect of dissolution/precipitation kinetics versus thermodynamic equilibrium, (iii) refining the spatial discretisation of the models, etc. The present study reviews these simulations in order to identify the main factors affecting numerical results (e.g. mass transport, mesh, selected phases). Simulations are reproduced here with a consistent set of data and input parameters arranged with increasing order of complexity. Only such a standardised approach can allow a proper comparison of numerical results. Modelled reaction pathways (i.e. mineralogical transformations) appear to be independent from the chosen modelling assumptions. Irrespective of the simulated case or the underlying hypotheses, the geochemical transformations remain located very close to the cement/clay interface.     

Development of Dissolution DNP-MR Substrates for Metabolic Research

Dissolution dynamic nuclear polarization (DNP) provides a broadly applicable and rather simple means of developing probes for the real-time molecular imaging of cellular functions in vivo. The development of novel dissolution DNP substrate formulations is only rewarding for substrates that yield detectable metabolism within few minutes. In addition, in vivo preparations usually require amorphous samples at molar substrate concentrations for an efficient and reproducible DNP step with sufficient material. The composition ranges of novel substrate preparations need to be established experimentally owing to the solute’s impact on vitrification behavior. Here, we describe simple rationales employed in the development of novel substrate preparations for dissolution DNP-magnetic resonance. Solution state substrate polarizations between 10 and 40?% have been obtained for ~40 metabolic substrates in highly concentrated preparations that yield physiologically tolerable solutions with sufficient T ₁ for in vivo nuclear magnetic resonance. Substrate metabolism is observed for novel in vivo substrates such as 3-hydroxybutyrate and aspartate.     

Hyperpolarizability effects in a Sr optical lattice clock

We report the observation of a higher-order frequency shift due to the trapping field in a (87)Sr optical lattice clock. We show that, at the magic wavelength of the lattice, where the first-order term cancels, the higher-order shift will not constitute a limitation to the fractional accuracy of the clock at a level of 10(-18). This result is achieved by operating the clock at very high trapping intensity up to 400 kW/cm(2) and by a specific study of the effect of the two two-photon transitions near the magic wavelength.     

Prediction of human dietary δ15N intake from standardised food records: validity and precision of single meal and 24-h diet data

Natural stable isotope ratios (δ¹⁵N) of humans can be used for nutritional analyses and dietary reconstruction of modern and historic individuals and populations. Information about an individual’s metabolic state can be obtained by comparison of tissue and dietary δ¹⁵N. Different methods have been used to estimate dietary δ¹⁵N in the past; however, the validity of such predictions has not been compared to experimental values. For a total of 56 meals and 21 samples of 24-h diets, predicted and experimental δ¹⁵N values were compared. The δ¹⁵N values were predicted from self-recorded food intake and compared with experimental δ¹⁵N values. Predicted and experimental δ¹⁵N values were in good agreement for meals and preparations (r?=?0.89, p?r?=?0.76, p?δ¹⁵N was mainly determined by the amount of fish, whereas the contribution of meat to dietary δ¹⁵N values was less pronounced. Prediction of human dietary δ¹⁵N values using standardised food records and representative δ¹⁵N data sets yields reliable data for dietary δ¹⁵N intake. A differentiated analysis of the primary protein sources is necessary when relating the proportion of animal-derived protein in the diet by δ¹⁵N analysis.     

Mercury speciation analysis in human hair by species-specific isotope-dilution using GC–ICP–MS

We optimized a mercury (Hg) speciation extraction method for human hair in combination with species-specific isotope-dilution analysis by gas chromatography–inductively coupled plasma–mass spectrometry (GC–ICP–MS). The method was validated on human hair reference material RM (IAEA-086), which is recommended for analysis of monomethylmercury (MMHg) and inorganic mercury (IHg). Three reagents, hydrochloric acid (HCl), nitric acid (HNO₃), and tetramethylammonium hydroxide (TMAH), and three extraction procedures, at ambient temperature for 12 h, microwave-assisted at 75 °C for 6 min, and oven heated at 80 °C for 2 h were tested. Extraction efficiency, recovery, and potential species transformations were evaluated for each method. The most efficient procedures, with recovery of ~90 % for each species with limited demethylation (<5 %) and methylation (0 %), were HNO₃ digestion, irrespective of temperature, and microwave-assisted TMAH extraction. Acidic extraction with HCl induces significant demethylation, with production of artifacts. To correct for potential demethylation artifacts we recommend spiking with isotopically enriched standards before the extraction step.     

Metallorganische Lewis-säuren: XXI. Tetracarbonyl(η4 -tetramethylcyclobutadien)mangan(I)-tetrafluoroborat

Pentacarbonyltetrafluoroboratomanganese(I), (OC)₅MnFBF₃, reacts with 2-butyne at 15°C in dichloromethane to give tetracarbonyl(η⁴-tetramethylcyclobutadiene)manganese(I) tetrafluoroborate, [(OC)₄Mn(C₄Me₄)]⁺ BF₄^?     

New chromogenic reagents for labelling amino groups in peptides. Chromatographic and preparatives aspects

Summary A new type of chromogenic reagent for labelling the amino groups of peptides or amino acids, 5-substituted 2,4-dinitrofluorobenzenes, is presented. These reagents are characterized by a polarity determined by the function included in the substituent in the 5-position and by the nature of this substituent. Preparation and chromatographic behaviour of these reagents, of eventual by-products of reactions and of some N-(2,4-dinitro-5-diethylaminophenyl)-peptides or amino acids are described.Proportions in solvent mixtures are v/v except otherwise indicated. Abbreviations: lit=literature, TLC=thin-layer chromatography, TLE=TL electrophoresis, see also: Figs. 2, 3, 5.