Asymmetric Hydrogenation of Unfunctionalized Tetrasubstituted Acyclic Olefins

Asymmetric hydrogenation has evolved as one of the most powerful tools to construct stereocenters. However, the asymmetric hydrogenation of unfunctionalized tetrasubstituted acyclic olefins remains the pinnacle of asymmetric synthesis and an unsolved challenge. We report herein the discovery of an iridium catalyst for the first, generally applicable, highly enantio‐ and diastereoselective hydrogenation of such olefins and the mechanistic insights of the reaction. The power of this chemistry is demonstrated by the successful hydrogenation of a wide variety of electronically and sterically diverse olefins in excellent yield and high enantio‐ and diastereoselectivity.     

Parahydrogen‐Induced Radio Amplification by Stimulated Emission of Radiation

Radio amplification by stimulated emission of radiation (RASER) was recently discovered in a low‐field NMR spectrometer incorporating a highly specialized radio‐frequency resonator, where a high degree of proton‐spin polarization was achieved by reversible parahydrogen exchange. RASER activity, which results from the coherent coupling between the nuclear spins and the inductive detector, can overcome the limits of frequency resolution in NMR. Here we show that this phenomenon is not limited to low magnetic fields or the use of resonators with high‐quality factors. We use a commercial bench‐top 1.4 T NMR spectrometer in conjunction with pairwise parahydrogen addition producing proton‐hyperpolarized molecules in the Earth's magnetic field (ALTADENA condition) or in a high magnetic field (PASADENA condition) to induce RASER without any radio‐frequency excitation pulses. The results demonstrate that RASER activity can be observed on virtually any NMR spectrometer and measures most of the important NMR parameters with high precision.     

Formation of H3+ in Collisions of H2+ with H2 Studied in a Guided Ion Beam Instrument

In order to study collisions between ions and neutrals, a new Guided Ion Beam (GIB) apparatus, called NOVion, has been assembled and tested. The primary purpose of this instrument is to measure absolute cross sections at energies relevant for technical or inter- and circumstellar plasmas. New and improved results are presented for forming H₃⁺ in collisions of H₂⁺ with H₂. Between 0.1 eV and 2 eV, our measured effective cross sections are in good overall agreement with most previous measurements. However, at higher energies, our results do not show the steep decline, recommended in the standard literature. After critical evaluation of all experimental and theoretical data, a new analytical function is proposed, describing properly the dependence of the title reaction on the collision energy up to 10 eV.     

Vakuum-UV-Oxidation als Methode zur Abwasserbehandlung

The development of a novel generation of excimer UV lamps enables versatile applications of quasi-monochromatic UV radiation. For example, xenon-excimer flow-through photoreactors may be used for wastewater treatment. The vacuum-UV radiation (λ = 172 nm) initiates water cleavage with formation of H atoms and oxidizing hydroxyl radicals. The latter are responsible for the photomineralization of organic substrates. An automated model reactor demonstrates the basic concepts of this advanced oxidation process.     

K-line X-ray fluorescence from highly charged iron ions under dense astrophysical plasma conditions

In the present work, we report an investigation of plasma environment effects on the atomic parameters associated with the K-vacancy states in highly charged iron ions within the astrophysical context of accretion disks around black holes. More particularly, the sensitivity of K-line X-ray fluorescence parameters (wavelengths, radiative transition probabilities, and Auger rates) in Fe XVII–Fe XXV ions has been estimated for plasma conditions characterized by an electron temperature ranging from 10⁵ to 10⁷ K and an electron density ranging from 10¹⁸ to 10²² cm⁻³. In order to do this, relativistic multiconfiguration Dirac-Fock atomic structure calculations have been carried out by considering a time averaged Debye-Hückel potential for both the electron–nucleus and electron–electron interactions.     

Quantification of veterinary antibiotics (sulfonamides and trimethoprim) in animal manure by liquid chromatography-mass spectrometry

A fast and cost effective method was developed to extract and quantify residues of veterinary antimicrobial agents (antibiotics) in animal manure by liquid-liquid extraction and liquid chromatography-mass spectrometry. The compounds investigated include six sulfonamides, one metabolite, and trimethoprim. The method was performed without sample clean up. Recoveries from spiked manure slurry samples (spike level = 1 mg/kg) were as follows: sulfaguanidine (52%), sulfadiazine (47%), sulfathiazole (64%), sulfamethazine (89%), its metabolite N4-acetyl-sulfamethazine (88%), sulfamethoxazole (84%), sulfadimethoxine (51%), and trimethoprim (64%). Relative standard deviations of the recoveries were less than 5% within the same day and less than 20% between days. The limit of quantification was below 0.1 mg/kg liquid manure slurry for all compounds and calibration curves obtained from extracts of spiked samples were linear up to a level of 5 mg/kg liquid manure, except for trimethoprim (0.01-0.5 mg/kg). Analysis of six grab samples taken in Switzerland from manure pits on farms where medicinal feed had been applied revealed total sulfonamide concentrations of up to 20 mg/kg liquid manure.     

Post-polymerization modification of aromatic polyimides via Diels-Alder cycloaddition

We report a facile post-polymerization modification route to functionalized aromatic polyimides via Diels-Alder cycloaddition. Aromatic polyimides are important, versatile high-performance polymers; however, their structural diversity is restricted by the requirements of the step-growth polymerization. We prepared polyimides with alkynes in their main-chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution-processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels-Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high-performance polymers with value-added functionality and thus considerable potential in a wide range of advanced materials.