Synthesis, complexation behavior and application of a new diphosphite ligand in rhodium-catalyzed hydroformylation

Oxidative coupling of 3-(3-tert-butyl-4-hydroxyphenyl)propionic acid methyl ester (2) gave dimethyl 3,3′-(5,5′-di-tert-butyl-6,6′-dihydroxybiphenyl-3,3′-diyl)-dipropionate (1c), which upon phosphorylation/transesterification with a phosphochloridite derived from (R)-binaphthol, formed the new unsymmetrical binaphthol-bridged diphosphite 4. A rhodium catalyst based on 4 as ligand gave predominantly iso-selectivity in the hydroformylation of selected styrenes but opposite regioselectivity with 2,6-disubstituted derivatives. New chelate metal complexes (acac)RhL, PdCl₂L and PtCl₂L have been synthesized by reacting 4 with (acac)Rh(CO)₂, PdCl₂(MeCN)₂ and PtCl₂(COD), respectively. The structure of obtained compounds is determined based on ¹H, ¹³C, ³¹P and ¹⁹⁵Pt NMR spectroscopy and mass spectrometry data.     

On the influence of basis sets and quantum chemical methods on the prediction accuracy of COSMO-RS

This paper examines how the accuracy of activity coefficients at infinite dilution calculated from the conductor-like screening model for real solvents (COSMO-RS) depends on the basis set and the quantum chemical method used. Activity coefficients at various temperatures serve as experimental parameters for optimising the COSMO-RS parameters. A modification of the electrostatic misfit term of the energy function of COSMO-RS is presented that leads to a slightly higher accuracy. COSMO-RS parameter sets for nine different systematically varied basis sets using the density functional theory with the BP86 functional show that at least a valence double-zeta basis set is necessary for good accuracy. Larger basis sets show no advantages. Investigations of eight different quantum chemical calculation methods using a valence triple-zeta basis set are documented. Hartree-Fock and local density approximations give relatively poor results. The gradient-corrected density functionals investigated and the B3LYP hybrid functional show practically identical accuracy. The most accurate parameterisation was obtained with MP2.     

Limit theorems for a recursive maximum process with location-dependent periodic intensity-parameter

We investigate the recursive sequence Z _n : =  max {Z _n − 1,λ(Z _n − 1)X _n } where X _n is a sequence of iid random variables with exponential distributions and λ is a periodic positive bounded measurable function. We prove that the Césaro mean of the sequence λ(Z _n ) converges toward the essential minimum of λ. Subsequently we apply this result and obtain a limit theorem for the distributions of the sequence Z _n . The resulting limit is a Gumbel distribution.     

A cylindrical liquid-core waveguide

A novel concept for a liquid-core lightguide in cylindrical symmetry is presented. For a concrete 17 cm long device using water as a core and the transparent fluorinated polymer Teflon as a cladding layer, the coupling efficiency and guiding properties are investigated theoretically and compared with experimental results. The guide is found to exhibit low losses. A possible application of this type of guide is investigated by replacing the optical cell of a standard UV/VIS spectrometer by the cylindrical liquid-core waveguide. An increasing sensitivity for especially low concentrations of a polluting dye by a factor of about 15 is observed. Concentrations as low as a few parts per billion of the pollutant can be detected with a good signal-to-noise ratio.     

A Functional Non-Central Limit Theorem for Jump-Diffusions with Periodic Coefficients Driven by Stable Lévy-Noise

We prove a functional non-central limit theorem for jump-diffusions with periodic coefficients driven by stable Lévy-processes with stability index α>1. The limit process turns out to be an α-stable Lévy process with an averaged jump-measure. Unlike in the situation where the diffusion is driven by Brownian motion, there is no drift related enhancement of diffusivity.     

A simple method for labelling proteins with211At via diazotized aromatic diamine

A simple and rapid method for labelling proteins with²¹¹At by means of a 1,4-diaminobenzene link is described. 1,4-diaminobenzene is transformed into the diazonium salt and subsequently reactions of both²¹¹At and proteins with the diazonium salt take place simultaneously. For possibly high yields of astatized protein an appropriate temperature of 273 K was found. The results demonstrate the difference between the reaction mechanisms of iodine and astatine with proteins.