Neutral p-cymene ruthenium complexes with P-stereogenic monophosphines. New catalytic precursors in enantioselective transfer hydrogenation and cyclopropanation

A family of eight neutral, pseudotetrahedral piano-stool ruthenium complexes C, of the type [RuCl₂(p-cymene)(PArPhR)] (Ar = 1-naphthyl, 9-phenanthryl and 2-biphenylyl; R = Me, i-Pr, OMe, –CH₂SiMe₃ and –CH₂SiPh₃) have been prepared and characterised, including the X-ray crystal structure for C6 (Ar = 2-biphenylyl; R = i-Pr). These complexes catalyse the asymmetric hydrogen transfer reaction of acetophenone in refluxing 2-propanol in the presence of potassium tert-butoxyde, reaching full conversions and up to 45% ee after 24 h towards the S enantiomer of 1-phenylethanol. Cationic complexes formed upon treatment of C with one equivalent of AgSbF₆ or (Et₃O)PF₆ are active in the cyclopropanation reaction of styrene and α-methylstyrene by ethyl diazoacetate. Low to moderate conversions (up to 58%), diastereoselectivities (up to 40% de), and moderate enantioselectivities (up to 69% ee) have been found. For both reactions, bulky complexes and C6 in particular lead to the best results.     

The movement of a forager: strategies for the efficient use of resources

We study a simple model of a foraging animal that modifies the substrate on which itmoves. This substrate provides its only resource, and the forager manages it by taking alimited portion at each visited site. The resource recovers its value after the visitfollowing a relaxation law. We study different scenarios to analyze the efficiency of themanaging strategy, corresponding to control the bite size. We observe the non trivialemergence of a home range, that is visited in a periodic way. The duration of thecorresponding cycles and the transient until it emerges is affected by the bite size. Ourresults show that the most efficient use of the resource, measured as the balance betweengathering and traveled distance, corresponds to foragers that take larger portions butwithout exhausting the resource. We also analyze the use of space determining the numberof attractors of the dynamics, and we observe that it depends on the bite size and therecovery time of the resource.     

XANES speciation of mercury in three mining districts – Almadén,Asturias (Spain), Idria (Slovenia)

The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found.     

Scaffold Effects on Osteogenic Differentiation of Equine Mesenchymal Stem Cells: An In Vitro Comparative Study

The in vitro viability, osteogenic differentiation, and mineralization of four different equine mesenchymal stem cells (MSCs) from bone marrow, periosteum, muscle, and adipose tissue are compared, when they are cultured with different collagen‐based scaffolds or with fibrin glue. The results indicate that bone marrow cells are the best source of MSCs for osteogenic differentiation, and that an electrochemically aggregated collagen gives the highest cell viability and best osteogenic differentiation among the four kinds of scaffolds studied.

     

Effervescence-assisted carbon nanotubes dispersion for the micro-solid-phase extraction of triazine herbicides from environmental waters

Extraction techniques are surface-dependent processes since their kinetic directly depends on the contact area between the sample and the extractant phase. The dispersion of the extractant (liquid or solid) increases this area improving the extraction efficiency. In this article, the dispersion of a nanostructured sorbent at the very low milligram level is achieved by effervescence thanks to the in situ generation of carbon dioxide. For this purpose, a special tablet containing the effervescence precursors (sodium carbonate as carbon dioxide source and sodium dihydrogen phosphate as proton donor) and the sorbent [multiwalled carbon nanotubes (MWCNTs)] is prepared. All the microextraction steps take place in a glass beaker containing 100 mL of the sample. After the extraction, the MWCNTs, enriched with the extracted analytes, are recovered by vacuum filtration. Methanol was selected to elute the retained analytes. The extraction mode is optimized and characterized using the determination of nine herbicides in water samples as model analytical problem. The absolute recoveries of the analytes were in the range 48–76 %, while relative recoveries were close to 100 % in all cases. These values permit the determination of these analytes at the low microgram per liter range with good precision (relative standard deviations lower than 9.3 %) using ultra performance liquid chromatography (UPLC) combined with ultraviolet detection (UV).     

Critical evaluation of the potential of radiofrequency pulsed glow discharge–time-of-flight mass spectrometry for depth-profile analysis of innovative materials

The combination of radiofrequency pulsed glow discharge (RF-PGD) analytical plasmas with time-of-flight mass spectrometry (TOFMS) has promoted the applicability of this ion source to direct analysis of innovative materials. In this sense, this emerging technique enables multi-elemental depth profiling with high depth resolution and sensitivity, and simultaneous production of elemental, structural, and molecular information. The analytical potential and trends of this technique are critically presented, including comparison with other complementary and well-established techniques (e.g. SIMS, GD–OES, etc.). An overview of recent applications of RF-PGD–TOFMS is given, including analysis of nano-structured materials, coated-glasses, photovoltaic materials, and polymer coatings     

A Synthesis of Fused Butenoudes

It has been shown that tert-butyldimethylsilylated (Z) 2-carboethoxymethylene cycloalkanols are readily desilylated with concomitant cyclization to give the corresponding butenolides. The (E) isomers are desilylated, but not cyclized under these conditions.