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In recent years, dynamic chromatography and stopped-flow chromatographic techniques have become versatile tools for the determination of enantiomerization and isomerization barriers. Increasing demands for the stereochemical safety of chiral drugs contributed to the rapid development of new techniques. New computer-aided evaluation systems allow the on-line determination of interconversion barriers from the experimental chromatograms. Both dynamic chromatography and stopped-flow chromatography have been applied to the entire range of chromatographic methods (GC, SFC, HPLC, CE).

A unified equation to evaluate elution profiles of reversible as well as irreversible (pseudo-) first-order reactions in dynamic chromatography and on-column reaction chromatography has been derived. Rate constants k1 and k(-1) and Gibbs activation energies are directly obtained from the chromatographic parameters (retention times tR(A) and tR(B) of the interconverting or reacting species A and B, the peak widths at half-height wA and wB, and the relative plateau height h(p)), the initial amounts A0 and B0 of the reacting species, and the equilibrium constant K(A/B). The calculation of rate constants requires only a few iterative steps without the need of performing a computationally extensive simulation of elution profiles. The unified equation was validated by comparison with a data set of 125,000 simulated elution profiles to confirm the quality of this equation by statistical means and to predict the minimal experimental requirements. Surprisingly, the recovery rate from a defined data set is on average 35% higher using the unified equation compared to the evaluation by iterative computer simulation.

In chemistry and biology, chirality, or handedness, refers to molecules that exist in two spatial configurations that are incongruent mirror images of one another. Almost all biologically active molecules are chiral, and the correct determination of their absolute configuration is essential for the understanding and the development of processes involving chiral molecules. Anomalous x-ray diffraction and vibrational optical activity measurements are broadly used to determine absolute configurations of solid or liquid samples. Determining absolute configurations of chiral molecules in the gas phase is still a formidable challenge. Here we demonstrate the determination of the absolute configuration of isotopically labeled (R,R)-2,3-dideuterooxirane by foil-induced Coulomb explosion imaging of individual molecules. Our technique provides unambiguous and direct access to the absolute configuration of small gas-phase species, including ions and molecular fragments.

Tröger's base 1 (2,8-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine) undergoes enantiomerization in the gas and liquid phases. By enantioselective stopped-flow multidimensional gas chromatography, Eyring activation parameters of the enantiomerization barrier have been determined in the inert mobile gas phase (helium):  ΔG ⧧ gas(298.15 K) = 112.8 ± 0.5 kJ mol-1; ΔH ⧧ gas = 62.7 ± 0.3 kJ mol-1; ΔS ⧧ gas = −168 ± 6 J (K mol)-1. An enantiomerization pathway proceeding via a degenerated retro-hetero-Diels−Alder ring opening or formation of a zwitterionic structure of 1 is proposed. By enantioselective dynamic gas chromatography, Eyring activation parameters have also been determined via computer-aided simulation of experimental interconversion peak profiles in the chiral stationary liquid phase:  ΔG ⧧ liq(298.15 K) = 117.8 ± 0.5 kJ mol-1; ΔH ⧧ liq = 48.9 kJ mol-1; ΔS ⧧ liq = −231 ± 8 J (K mol)-1. Surprisingly, in the presence of the chiral stationary phase (CSP) Chirasil-β-Dex, required for enantiomer separation of 1, the enantiomerization barrier is higher than in the gas phase. The concept of the retention increment R‘ has been applied to distinguish the enantiomerization barrier of 1 in the dissolved and complexed state of the stationary phase.

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Formaldehyde is an important precursor to numerous industrial processes and is produced in multimillion ton scale every year by catalytic oxidation of methanol in an energetically unfavorable and atom-inefficient industrial process. In this work, we present a highly selective one-step synthesis of a formaldehyde derivative starting from carbon dioxide and hydrogen gas utilizing a homogeneous ruthenium catalyst. Here, formaldehyde is obtained as dimethoxymethane, its dimethyl acetal, by selective reduction of carbon dioxide at moderate temperatures (90 °C) and partial pressures (90 bar H2/20 bar CO2) in the presence of methanol. Besides the desired product, only methyl formate is formed, which can be transformed to dimethoxymethane in a consecutive catalytic step. By comprehensive screening of the catalytic system, maximum turnover numbers of 786 for dimethoxymethane and 1290 for methyl formate were achieved with remarkable selectivities of over 90% for dimethoxymethane.

Reactive superhydrophobic surfaces are highly promising for biotechnological, analytical, sensor, or diagnostic applications but are difficult to realize due to their chemical inertness. In this communication, we report on a photoactive, inscribable, nonwettable, and transparent surface (PAINTS), prepared by polycondensation of trichlorovinylsilane to form thin transparent reactive porous nanofilament on a solid substrate. The PAINTS shows superhydrophobicity and can be conveniently functionalized with the photoclick thiol-ene reaction. In addition, we show for the first time that the PAINTS bearing vinyl groups can be easily modified with disulfides under UV irradiation. The effect of superhydrophobicity of PAINTS on the formation of high-resolution surface patterns has been investigated. The developed reactive superhydrophobic coating can find applications for surface biofunctionalization using abundant thiol or disulfide bearing biomolecules, such as peptides, proteins, or antibodies.