Reactions of cationic iron clusters with ammonia, models of nitrogen hydrogenation and dehydrogenation

The gas phase reactivities of small cationic iron clusters, Fen+ (n = 1-20), towards ammonia were investigated using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Sequential addition of ammonia molecules to the clusters was observed to be the dominating process for n > 4. In the case of n = 4 we observed addition of ammonia accompanied by dehydrogenation. This reaction was modelled using hybrid density functional theory. Clusters with n < 4 do not react with ammonia. Clusters Fen+ (n = 1-20) react with neither N2 nor H2 at around 10(-8) mbar. When dinitrogen was seeded into the expanding helium, mixed clusters of the type FenNm+ were observed. These ions react with H2, either by addition, or by substitution of N2. The clusters with m = 1 were isolated in separate experiments and reacted with H2, which showed that mixed clusters with n = 5-13 add up to 5 molecules of dihydrogen in successive slow reactions.     

NANOPARTICLE DESIGN AND HANDLING--CHALLENGES FOR ENGINEERS AND PARTICLE TECHNOLOGISTS

In this paper, the opportunities and challenges which future applications based on nanoparticles offer to engineers are described. New high-added value products induce us to rethink ways to control nanoparticle design and handling. Several challenges are described and typical solutions are given: (1) finding relevant engineering tasks outside traditional process industry; (2) the importance of mixing reactants; (3) obtaining monodisperse particles; (4) gaining efficient control via electric forces and (5) developing multi-step processes which allow more control over particle properties.     

Energetics and mechanisms for the unimolecular dissociation of protonated trioses and relationship to proton-mediated formaldehyde polymerization to carbohydrates in interstellar environments

We report the unimolecular decomposition of protonated glyceraldehyde, [HOCH(2)CH(OH)CHO]H(+), and protonated dihydroxyacetone, [HOCH(2)C(O)CH(2)OH]H(+). On the basis of mass spectrometric experiments and computational quantum chemistry, we have found that these isomeric ions interconvert freely at energies below that required for their unimolecular decompositions. The losses of formaldehyde and water (the latter also followed by CO loss) are the dominating processes, with formaldehyde loss having the lower energetic threshold. The reverse of the formaldehyde loss, namely, the addition of formaldehyde to protonated glycolaldehyde, appears to be an inefficient reaction at low temperature and pressure in the gas phase, leading to dissociation products. The relevance of these findings to interstellar chemistry and prebiotic chemistry is discussed, and it is concluded that the suggestion made in the literature that successive addition of formaldehyde by proton-assisted reactions should account for interstellar carbohydrates most likely is incorrect.     

Parallel electromembrane extraction in a multiwell plate

This paper describes the concept of parallel electromembrane extraction (Pa-EME) with flat membranes in a multiwell format for the first time. The setup is based on a multiwell plate and provided simultaneous and selective isolation, cleanup, and enrichment of several human plasma samples as well as LC-MS-compatible extracts within 8 min of extraction. Undiluted human plasma samples spiked with four antidepressant drugs were added to separate wells in the donor plate. Subsequently, the samples were extracted with Pa-EME. The four drugs migrated electrokinetically from undiluted human plasma through a flat polypropylene membrane impregnated with 2-nitrophenyl octyl ether, and were isolated into formic acid. Extraction time, extraction voltage, agitation rate, sample volume, and acceptor solution volume were all optimized with an experimental design. The optimal conditions were as follows: The agitation rate was 1,040 rpm, and an extraction voltage of 200 V was applied. The sample volume and acceptor solution volume was 240 and 70 μL, respectively. The extraction was continued for 8 min. Eventually, the extracts were analyzed by LC-MS/MS. The combination of Pa-EME with LC-MS/MS provided quantitation limits below the therapeutic level and reported relative standard deviations in the range 5–13 %. Linear calibration curves were obtained for all analytes, and the correlation coefficients were above 0.9974 in the range 1–400 ng mL^?1. The drug concentrations from two subjects treated with quetiapine and sertraline were successfully determined with Pa-EME combined with LC-MS/MS. Post-column infusion experiments demonstrated that Pa-EME provided extracts free from interfering matrix components.     

Eine einfache Methode zur Berechnung des Viskosit?tsgrades von Mineral?lmischungen

Ohne Zusammenfassung