Reliability of stable carbon and oxygen isotope compositions of pedogenic needle fibre calcite as environmental indicators: examples from Western Europe

Stable carbon and oxygen isotope analyses were conducted on pedogenic needle fibre calcite (NFC) from seven sites in areas with roughly similar temperate climates in Western Europe, including the Swiss Jura Mountains, eastern and southern France, northern Wales, and north-eastern Spain. The δ¹³C values (?12.5 to?6.8 ‰ Vienna Pee Dee Belemnite (VPDB)) record the predominant C₃ vegetation cover at the sites. A good correlation was found between mean monthly climatic parameters (air temperature, number of frost days, humidity, and precipitation) and δ¹⁸O values (?7.8 to?3.4‰ VPDB) of all the NFC. Similar seasonal variations of δ¹⁸O values for monthly NFC samples from the Swiss sites and those of mean monthly δ¹⁸O values of local precipitation and meteorological data point out precipitation and preferential growth/or recrystallisation of the pedogenic needle calcite during dry seasons. These covariations indicate the potential of stable isotope compositions of preserved NFC in fossil soil horizons as a promising tool for palaeoenvironmental reconstructions.     

A New Method for the Preparation of Non‐Terminal Alkynes: Application to the Total Syntheses of Tulearin A and C

Lactones are known to react with the reagent generated in situ from CCl₄ and PPh₃ in a Wittig‐type fashion to give gem‐dichloro‐olefin derivatives. Such compounds are now shown to undergo reductive alkylation on treatment with organolithium reagents RLi to furnish acetylene derivatives bearing the substituent R at their termini (R=Me, n‐, sec‐, tert‐alkyl, silyl); the reaction can be catalyzed with either Cu(acac)₂ or Fe(acac)₃/1,2‐diaminobenzene. Two alkynol derivatives prepared in this way from readily accessible lactone precursors served as the key building blocks for the total syntheses of the cytotoxic marine macrolides tulearin A ( 1 ) and C ( 2 ). The assembly of these fragile targets hinged upon ring closing alkyne metathesis (RCAM) followed by a formal trans‐reduction of the resulting cycloalkynes via trans‐hydrosilylation/protodesilylation.     

Effect of monovalent and divalent cations on the photoinactivation of bacteria with meso-substituted cationic porphyrins

It is well established that for successful photoinactivation (PI) of gram-negative bacteria a cationic photosensitizer is required. This requirement suggests a charge-dependent interaction between the photosensitizer and the gram-negative bacterium, which may be influenced by the presence of ions in the suspending medium. The aim of the present study was to investigate the effect of cations Na+ and Ca2+ on the efficacy of the PI of the gram-negative Pseudomonas aeruginosa and the gram-positive Staphylococcus aureus. The bacteria were suspended in buffer containing either meso-tetra(N-methyl-4-pyridyl)-porphyrin or meso-mono-phenyl-tri(N-methyl-4-pyridyl)-porphyrin as photosensitizer and various concentrations of Na+ or Ca2+. The cell suspensions were exposed to a broadband light dose of 9 J/cm2. In buffer without added cations, P. aeruginosa and S. aureus were equally sensitive to PI. Addition of cations strongly decreased the sensitivity of both bacteria to PI, with the PI of P. aeruginosa being much more decreased than that of S. aureus, and Ca2+ being more effective than Na+. The decreased sensitivity was accompanied by a reduced binding of the photosensitizers to the bacteria.     

Enzymatic, spectrophotometric determination of glucose, fructose, sucrose, and inulin/oligofructose in foods

A fast, simple, and accurate method, using only standard laboratory equipment, was developed for the quantification of glucose, fructose, sucrose, and inulin/oligofructose in different food matrixes. Samples were extracted using boiling water and hydrolyzed with sucrase and fructanase. Sugars were determined in the initial extract and in both hydrolysates using an enzymatic, spectrophotometric kit for glucose and fructose determination with hexokinase, glucose-6-phosphate dehydrogenase, and phosphoglucose isomerase. Calculations of sucrose and inulin/oligofructose were based only on fructose measurement. Glucose results of the hydrolysates were not used for inulin/oligofructose calculations because of possible interference. Released glucose by the hydrolysis of maltose or by possible partial hydrolysis of other compounds like maltodextrines, starch, lactose, or maltitol could interfere in the measurement of the sucrase and the fructanase hydrolysates. To validate the method, a wide range of different food matrixes and different amounts of inulin/oligofructose (1-54%) were analyzed. Mean recovery +/- relative standard deviation (RSD) for inulin or oligofructose was 96.0 +/- 5.3%. The RSDr for inulin/oligofructose measured on 35 food samples, analyzed in duplicate, was 5.9%. Accuracy and precision of the method were less for samples with large concentrations of sucrose, maltose, maltodextrines, or starch (ratio to inulin/oligofructose >4 to 1). Precision and accuracy were comparable with those of the ion exchange chromatographic method AOAC 997.08 and the enzymatic, spectrophotometric method AOAC 999.03. In contrast to 999.03, this method allows the accurate quantification of both GFn and Fn forms.     

Two precatalysts for application in propargylic CH activation

The complexes {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ²P,P′}(η⁴‐norbornadiene)rhodium(I) tetrafluoridoborate, [Rh(C₇H₈)(C₃₆H₂₈OP₂)]BF₄, and {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ²P,P′}[η⁴‐(Z,Z)‐cycloocta‐1,5‐diene]rhodium(I) tetrafluoridoborate dichloromethane monosolvate, [Rh(C₈H₁₂)(C₃₆H₂₈OP₂)]BF₄·CH₂Cl₂, are applied as precatalysts in redox‐neutral atomic‐economic propargylic CH activation [Lumbroso et al. (2013). Angew. Chem. Int. Ed. 52 , 1890–1932]. In addition, the catalytically inactive pentacoordinated 18‐electron complex {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ²P,P′}chlorido(η⁴‐norbornadiene)rhodium(I), [RhCl(C₇H₈)(C₃₆H₂₈OP₂)], was synthesized, which can form in the presence of chloride in the reaction system.     

Vortex Generation in a Liquid Metal Duct Flow near a Magnetic Dipole

The generation of vortical structures by a strong magnetic dipole field in a liquid metal duct flow is studied by means of three-dimensional direct numerical simulations. The dipole is considered as the paradigm for a magnetic obstacle which will deviate the streamlines due to Lorentz forces which act on the fluid elements. Our model uses the quasi-static approximation applicable in the limit of small magnetic Reynolds numbers. The analysis covers the stationary flow regime at smaller flow Reynolds numbers Re as well as the fully time-dependent regimes at higher values with a turbulent flow in the wake of the magnetic obstacle. We present a systematic study of these two basic flow regimes on Re and the Hartmann number Ha, a measure of the strength of the magnetic dipole field. Furthermore, three orientations of the dipole are compared, the streamwise, spanwise and wall-normal ones. The most efficient generation of turbulence at a fixed distance above the duct occurs for the spanwise orientation in which we can observe the formation of Hartmann layers at the top plate. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)