New data on the mobility of Pt emitted from catalytic converters

The mobility and speciation of Pt was investigated in dust deposited in highway tunnels and in gully sediments. For this, a sequential extraction technique was used in combination with a microwave digestion procedure, followed by detection of Pt with high resolution ICP-MS. A digestion procedure using HNO₃/HCl/H₂O₂ was developed and its efficiency tested for environmental materials. Total Pt contents ranged from approximately 100 to 300 g/kg. The high share of chemically mobile Pt in the tunnel dust (up to about 40%) indicates that Pt is predominantly emitted in a mobile form from the converter. The absence of a mobile fraction in the gully sediment is explained by the elution of Pt by run-off. Except for the mobile and easily mobilised fractions none of the other fractions of the sequential extraction contains Pt, neither in the dust samples nor in the gully sediment.     

Lagrangian tracers on a surface flow: the role of time correlations

Finite time correlations of the velocity in a surface flow are found to be important for the formation of clusters of Lagrangian tracers. The degree of clustering characterized by the Lyapunov spectrum of the flow is numerically shown to be in qualitative agreement with the predictions for the white-in-time compressible Kraichnan flow, but to deviate quantitatively. For intermediate values of compressibility the clustering is surprisingly weakened by time correlations.     

The effect of sodium dodecyl sulfate and Pluronic F127 on the electrophoretic separation of protein and polypeptide test mixtures at acid pH

Using a test mixture consisting of standard proteins (cytochrome c, chymotrypsinogen A, hen egg albumin, bovine serum albumin, aldolase, catalase and ferritin) and synthetic polypeptides (polylysine, polyaspartic, polyglutamic acid and polyproline) it was revealed that using sodium dodecyl sulfate (SDS) as background electrolyte modifier at acid pH (2.5) allows selective separation of highly positively charged polypeptides (polylysine) provided that their relative molecular mass is sufficiently low (3300 Da). The altered elution sequence of standard proteins as compared to a separation done without SDS may help their identification. Addition of Pluronic F127 offers clear-cut separations of standard proteins up to a relative molecular mass of 5 x 10(4) Da and allows to reveal protein/polypeptide microheterogeneity where applicable. None of the systems tested is suitable for the separation of acidic polypeptides and polyproline.     

The cost of deterministic,adaptive, automatic algorithms: Cones,not balls

Automatic numerical algorithms attempt to provide approximate solutions that differ from exact solutions by no more than a user-specified error tolerance. The computational cost is often determined adaptively by the algorithm based on the function values sampled. While adaptive, automatic algorithms are widely used in practice, most lack guarantees, i.e., conditions on input functions that ensure that the error tolerance is met.     

Expedient Synthesis of 1,2‐Thiaborines by Means of Sulfur Insertion into Boroles

The propensity of boroles to undergo ring expansion reactions has been exploited as a route to generate 1,2‐thiaborines, molecules that can be viewed as hybrid inorganic/organic analogues of benzene. Computational studies as well as structural data indicate that the species reported here have a high degree of aromatic character.     

Point vortex dynamics: recent results and open problems

he concept of point vortex motion, a classical model in the theory of two-dimensional, incompressible fluid mechanics, was introduced by Helmholtz in 1858. Exploration of the solutions to these equations has made fitful progress since that time as the point vortex model has been brought to bear on various physical situations: atomic structure, large scale weather patterns, “vortex street” wakes, vortex lattices in superfluids and superconductors, etc. The point vortex equations also provide an interesting example of transition to chaotic behavior. We give a brief historical introduction to these topics and develop two of them in particular to the point of current understanding: (i) Steadily moving configurations of point vortices; and (ii) Collision dynamics of vortex pairs.     

Iridium‐Catalyzed Silylation of Five‐Membered Heteroarenes: High Sterically Derived Selectivity from a Pyridyl‐Imidazoline Ligand

The steric effects of substituents on five‐membered rings are less pronounced than those on six‐membered rings because of the difference in bond angles. Thus, the regioselectivities of reactions of five‐membered heteroarenes that occur with selectivities dictated by steric effects, such as the borylation of C?H bonds, have been poor in many cases. We report that the silylation of five‐membered‐ring heteroarenes occurs with high sterically derived regioselectivity when catalyzed by the combination of [Ir(cod)(OMe)]₂ (cod=1,5‐cyclooctadiene) and a phenanthroline ligand or a new pyridyl‐imidazoline ligand that further increases the regioselectivity. The silylation reactions with these catalysts produce high yields of heteroarylsilanes from functionalization at the most sterically accessible C?H bonds of these rings under conditions that the borylation of C?H bonds with previously reported catalysts formed mixtures of products or products that are unstable. The heteroarylsilane products undergo cross‐coupling reactions and substitution reactions with ipso selectivity to generate heteroarenes that bear halogen, aryl, and perfluoroalkyl substituents.     

Switchable‐hydrophilicity solvent liquid‐liquid microextraction versus dispersive liquid‐liquid microextraction prior to HPLC‐UV for the determination and isolation of piperine from Piper nigrum L

Switchable‐hydrophilicity solvent liquid‐liquid microextraction and dispersive liquid‐liquid microextraction were compared for the extraction of piperine from Piper nigrum L. prior to its analysis by using high‐performance liquid chromatography with UV detection. Under optimum conditions, limits of detection and quantitation were found as 0.2–0.6 and 0.7–2.0 μg/mg with the two methods, respectively. Calibration graphs showed good linearity with coefficients of determination (R²) higher than 0.9962 and percentage relative standard deviations lower than 6.8%. Both methods were efficiently used for the extraction of piperine from black and white pepper samples from different origins and percentage relative recoveries ranged between 90.0 and 106.0%. The results showed that switchable‐hydrophilicity solvent liquid‐liquid microextraction is a better alternative to dispersive liquid‐liquid microextraction for the routine analysis of piperine in food samples. A novel scaled‐up dispersive liquid‐liquid microextraction method was also proposed for the isolation of piperine providing a yield of 102.9 ± 4.9% and purity higher than 98.0% as revealed by NMR spectroscopy.     

Quantum effects of periodic orbits for the kicked top

We analyze traces of powers of the time evolution operator of a periodically kicked top. Semiclassically, such traces are related to periodic orbits of the classical map. We derive the semiclassical traces in a coherent state basis and show how the periodic orbits can be recovered via a Fourier transform. A breakdown of the stationary phase approximation is detected. The quasi energy spectrum remains elusive due to lack of knowledge of sufficiently many periodic orbits. Divergencies of periodic orbit formulas are avoided by appealing to the finiteness of the quantum mechanical Hilbert space. The traces also enter the coefficients of the characteristic polynominal of the Floquet operator. Statistical properties of these coefficients give rise to a new criterion for the distinction of chaos and regular motion.