The mechanism of the (bispidine)copper(II)-catalyzed aziridination of styrene: a combined experimental and theoretical study

Experimental and DFT-based computational results on the aziridination mechanism and the catalytic activity of (bispidine)copper(I) and -copper(II) complexes are reported and discussed (bispidine=tetra- or pentadentate 3,7-diazabicyclo[3.1.1]nonane derivative with two or three aromatic N donors in addition to the two tertiary amines). There is a correlation between the redox potential of the copper(II/I) couple and the activity of the catalyst. The most active catalyst studied, which has the most positive redox potential among all (bispidine)copper(II) complexes, performs 180 turnovers in 30 min. A detailed hybrid density functional theory (DFT) study provides insight into the structure, spin state, and stability of reactive intermediates and transition states, the oxidation state of the copper center, and the denticity of the nitrene source. Among the possible pathways for the formation of the aziridine product, the stepwise formation of the two N-C bonds is shown to be preferred, which also follows from experimental results. Although the triplet state of the catalytically active copper nitrene is lowest in energy, the two possible spin states of the radical intermediate are practically degenerate, and there is a spin crossover at this stage because the triplet energy barrier to the singlet product is exceedingly high.     

Separation of very hydrophobic analytes by micellar electrokinetic chromatography. I. Optimization of the composition of the sample solution for the determination of the aromatic ingredients of sassafras and other essential oils of forensic interest

A micellar electrokinetic chromatographic method using UV and (UV)LIF detection in-line was developed for the determination of aromatic constituents, mainly allylbenzenes in essential oils. The method optimization included the optimization of the composition of the separation electrolyte using ACN and urea to reduce retention factors and CaCl(2) to widen the migration time window. In addition, it was necessary to optimize the composition of the sample solution which included the addition of a neutral surfactant at high concentration. With the optimized method, the determination of minor constituents in essential oils was possible despite of the presence of a structurally related compound being in a molar ratio excess of 1000:1. The use of UV and LIF-detection in-line enabled the direct comparison of the two detection traces using an electrophoretic mobility x-axis instead of the normal time-based scale. This simplifies the assignment of signals and enhances repeatability. The method developed was successfully applied to the determination of minor and major constituents in herbal essential oils, some of them being forensically relevant as sources of precursors for synthetic drugs.     

Enantioselective synthesis of (+)(R)- and (-)(S)-nicotine based on Ir-catalysed allylic amination

The synthesis of nicotine with enantiomeric excess of >99% ee was accomplished by asymmetric Ir-catalysed allylic amination followed by ring closing metathesis and racemization-free double bond reduction.     

Carbocycles via enantioselective inter- and intramolecular iridium-catalysed allylic alkylations

Carbocycles with > 90% ee were prepared via Ir-catalysed asymmetric allylic alkylation/ring closing metathesis sequences or enantioselective Ir-catalysed intramolecular allylic alkylations.     

Advancements in capacitance-to-digital converter-based C4D technology for detection in capillary electrophoresis using amplified excitation voltages and comparison to classical and open-source C4Ds

This work introduces new hardware configurations for a capacitively coupled contactless conductivity detector (C⁴D) based on capacitance-to-digital conversion (CDC) technology for CE. The aim was to improve sensitivity, handling, price, and portability of CDC-based C⁴D detectors (CDCD) to reach LODs similar to classic C⁴Ds with more sophisticated electric circuits. To achieve this, a systematic study on the CDCDs was carried out including a direct comparison to already established C⁴D setups. Instrumental setups differing in electrode lengths, measurement modes, and amplification of excitation voltages were investigated to achieve LODs for alkali metal ions of 4 to 12 μM, similar to LODs obtained by classic C⁴D setups. Lowest LODs were achieved for a setup with two 10 mm electrodes at a distance of 0.2 mm and an excitation voltage of 24 V. The detection head was exceptionally lightweight with only 2.6 g and covered only 20 mm of the capillary on total. This allowed the use of multiple detectors along the separation path to enable spatial tracking of analytes during separation. The entirely battery-powered detector assembly weighs less than 200 g, and the data are transmitted wirelessly for possible portable applications. The freely accessible hardware and software were optimized for fully automated measurements with real time data plotting and allowed handling multidetector setups. The new developments were applied to quantify the potassium salt of glyphosate in its herbicide formulation.     

Mechanochemically Initiated Achmatowicz Rearrangement

The Achmatowicz rearrangement converts furfuryl alcohols, obtainable from renewable carbohydrates, into 6-hydroxy-2H-pyrane-3(6H)-ones, which are versatile intermediates for organic synthesis. We describe here the first examples of a solvent-free mechanochemical Achmatowicz rearrangement. Furfuryl alcohols were prepared from furfurals using mechanochemically initiated reductions and Reformatsky reactions. Mechanochemical reaction conditions for the Achmatowicz rearrangement of the obtained furfuryl alcohols were optimized and applied to a series of derivatives, yielding the corresponding rearrangement products in yields of 39 to 95%.     

A model for predicting the shear bearing capacity of FRP-strengthened beams

The shear failure of reinforced concrete beams needs more attention than the bending failure since no or only small warning precedes the failure. For this reason, it is of utmost importance to understand the shear bearing capacity and also to be able to undertake significant rehabilitation work if necessary. In this paper, a design model for the shear strengthening of concrete beams by using fiber-reinforced polymers (FRP) is presented, and the limitations of the truss model analogy are highlighted. The fracture mechanics approach is used in analyzing the bond behavior between the FRP composites and concrete. The fracture energy of concrete and the axial rigidity of the FRP are considered to be the most important parameters. The effective strain in the FRP when the debonding occurs is determined. The limitations of the anchorage length over the cross section are analyzed. A simple iterative design method for the shear debonding is finally proposed. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 44, No. 3, pp. 357–372, May–June, 2008.     

Radiatively induced flavour violation in the general two-Higgs doublet model with Yukawa alignment

The most general two-Higgs doublet model contains new sources of flavour violation that are usually in conflict with the experimental constraints. One possibility to suppress the exotic contribution to the flavour changing neutral currents consists on imposing the alignment of the Yukawa couplings. This condition presumably holds at a high-energy scale and is spoiled by the radiative corrections. We compute in this Letter the size of the radiatively induced flavour violating Higgs couplings at the electroweak scale. These also yield the absolute lower bound on the size of the exotic contributions to the flavour changing neutral currents in any two-Higgs doublet model, barring cancellations and the existence of discrete symmetries. We show that these contributions are well below the experimental bounds in large regions of the parameter space.