Low-cost automated capillary electrophoresis instrument assembled from commercially available parts

A CE instrument that can be assembled from commercially available components with minimal construction effort is described. Except for the electronic control circuitry no specially made parts are required. It is based on a flexible design of microfluidic, electropneumatic, and electronic sections and different configurations can easily be implemented. Automated injection into the capillary is performed hydrodynamically by the application of a pressure for a controlled length of time. The performance of the device was tested with a contactless conductivity detector by separating different metal ions. In addition, nine metal cations related to the quality of honey were separated in 2.3 min and four honey samples were analysed quantitatively to demonstrate the applicability of the method.     

A door to model reduction in high-dimensional parameter space

Model reduction techniques such as Proper Generalized Decomposition (PGD) are decision-making tools that are about to revolutionize many domains. Unfortunately, their computation is still problematic for problems involving many parameters, for which one has to face the “curse of dimensionality”. An answer to this challenge is given in solid mechanics by the so-called “parameter-multiscale PGD”, which is based on Saint-Venant's principle. In this article, a model problem composed of up to a thousand parameters is presented, showing that the method is able to overcome the “curse of dimensionality”.     

Radical Cyclisation of α‐Halo Aluminium Acetals: A Mechanistic Study

α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature ¹³C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al₂O₂ ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences.