Poly(ethylene glycol)-supported bisoxazolines as ligands for catalytic enantioselective synthesis

Two chiral bisoxazolines (box) supported on a modified poly(ethylene glycol) (PEG) have been prepared by a reaction sequence that involved formation of the properly functionalized box and their attachment to the polymer matrix by means of a spacer and a linker. The solubility properties of PEG allowed use of the supported box as ligands in some catalytic asymmetric transformations carried out under homogeneous conditions and to recover the ligands as if bound to an insoluble support. When the supported box were employed in combination with Cu(II) salts in the Diels-Alder cycloaddition between cyclopentadiene and N-acryloyloxazolidinone, low levels of enantioselectivity were observed (up to 45% ee). Much better results were obtained in the cyclopropanation of styrenes carried out in the presence of CuOTf (up to 93% ee) and in the ene-reaction between alpha-methylstyrene or methylenecyclohexane and ethylglyoxalate (up to 95% ee). One of the ligands, readily recovered by precipitation and filtration, was recycled two times in the ene-reaction with marginal loss in the catalytic activity and very limited erosion of the enantioselectivity.     

Me2Zn mediated, tert-butylhydroperoxide promoted, catalytic enantioselective Reformatsky reaction with aldehydes

A practical and highly enantioselective catalytic Reformatsky reaction with aldehydes using a cheap, commercially available aminoalcohol as ligand is described.     

Comparison of analytical methods: ICP-QMS,ICP-SFMS and FF-ET-AAS for the determination of V,Mn, Ni,Cu, As,Sr, Mo,Cd and Pb in ground natural waters

Three analytical methods, namely, inductively coupled plasma sector field mass spectrometry (ICP-SFMS); inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) and filter-furnace electrothermal atomic-absorption spectroscopy (FF-ET-AAS) for the determination of V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb in ground natural water samples were compared and evaluated for their capacity to provide reliable and precise results. Two certified reference materials (SLEW-3 Estuarine Water; SLRS-4 River Water) were analysed to prove that accurate results could be obtained by using all the listed methods with properly optimised parameters. The limit of detection (LOD) for V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb provided by the ICP-MS methods ranged from 0.001 to 0.05 µg L^?1. Such LOD proved sufficient for the reliable determination of the listed elements in ground natural waters. However, the LOD of the FF-ET-AAS was approximately two orders of magnitude higher than that of ICP-MS, which made it impossible to quantify V, Mn, Ni, Mo and Pb. The effects of the usage of the collision cell mode in ICP-QMS and of the desolvation system Apex for ICP-SFMS to eliminate oxide ions levels were investigated. For all three analytical methods, the influence of the matrix effect on the results of the determination of the investigated elements using matrix model solution, external calibration and standard addition methods was evaluated. A comparison using a paired Student’s t-test between the results obtained by both ICP-MS methods for V, Mn, Ni, Cu, As, Sr, Mo, Cd and Pb concentrations in ground natural waters showed that there was no significant difference on a 95% confidence level. The precision of the results for ICP-SFMS, ICP-QMS and FF-ET-AAS varied between ~0.5 and 11; 2.5 and 12.5; 3 and 13.5%, respectively. Moreover, ICP-SFMS equipped with the desolvation system APEX proved a better choice for As, Cu and Mn analysis due to its better LOD (0.008, 0.03 and 0.02 µg L^?1, respectively) and precision (S_r ≤ 5.0; 7.5; 9.0%, respectively) compared to ICP-QMS and FF-ET-AAS.     

Incompressible Euler Equations and the Effect of Changes at a Distance

Because pressure is determined globally for the incompressible Euler equations, a localized change to the initial velocity will have an immediate effect throughout space. For solutions to be physically meaningful, one would expect such effects to decrease with distance from the localized change, giving the solutions a type of stability. Indeed, this is the case for solutions having spatial decay, as can be easily shown. We consider the more difficult case of solutions lacking spatial decay, and show that such stability still holds, albeit in a somewhat weaker form.     

Investigation of fine scale structure of turbulent and molecular diffusion in coaxial jets of He/CO2 in air by LDA and Rayleigh scattering

This paper revisits the important issue of differential diffusion and provides new experimental results and subsequent analysis that attempts to quantify the relationship between molecular diffusion, turbulent diffusion and their mutual interference in non-reacting axisymmetric coaxial jets of variable Reynolds number. The reported investigation has been focused on the analysis of molecular diffusion of a He/CO₂ mixture in air by combining line imaging of Rayleigh scattering and laser Doppler anemometry (LDA) to determine length scales associated with differential diffusion and turbulent transport. Line imaging Rayleigh scattering was performed applying the index-matching method with a mixture of two gaseous species having scattering cross-sections respectively lower and higher of that of air and the cross-section of the mixture identical to that of the co-flowing air. Any measured variation in scattering intensity is therefore due to differential diffusion between the two species. Instantaneous and ensemble averaged line profiles of Rayleigh scattering intensity are presented and a characteristic length scale associated with differential diffusion is deduced. Autocorrelation analysis is applied to obtain the characteristic scale of differential diffusion fluctuations and the integral length scales of velocity fluctuations, as measured by LDA. Theoretical information from the literature is used in relating these scales to the molecular and turbulent diffusion coefficients, assuming homogeneous and isotropic turbulence, and the ratio of molecular to turbulent diffusivity is estimated as a function of the Reynolds number. The results confirm that the average contribution of molecular diffusion to the effective diffusivity into the air stream progressively reduces when the turbulence level increases. They also suggest that, at higher Re, the differential diffusion remains significant down to the scalar dissipation length scale, and could influence mixing at the molecular level and thus chemical reactions.