Björn Hansmann

Universitätsmedizin Göttingen, Göttingen, Lower Saxony, Germany

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Publications (4)42.42 Total impact

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    ABSTRACT: Recent work has focused on the damaging effects of free radicals on biological molecules. This study investigates the kinetics of the attack of OH radicals on L-alanine ethyl ester in the gas phase in cold beams of Laval nozzle expansions. Experiments and high-level theory are used to understand the preferred site of attack by the OH radical. Optimizations of L-alanine and L-alanine ethyl ester show that the essential transition state features for hydrogen abstraction off the C(alpha), C(beta), and N are similar. The energetics show that for L-alanine, the C(alpha)-site, C(beta)-site, and N-site transition states are all below the reactants level. For L-alanine ethyl ester, however, the energetics for hydrogen abstraction off the C(alpha) and N are the preferred site of reaction. These findings are supported by the observed negative temperature dependence of the rate constants of OH with alanine ethyl ester in Laval nozzle expansion experiments. More importantly, both the experiments and theory show that L-alanine ethyl ester provides a good model for gas phase studies of the amino acids such as L-alanine.
    The Journal of Physical Chemistry A 08/2009; 113(26):7570-5. DOI:10.1021/jp9015596 · 2.69 Impact Factor
  • Björn Hansmann · Bernd Abel ·
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    ABSTRACT: New developments and recent applications of pulsed and miniaturised Laval nozzle technology allowing many gas-phase molecular processes to be studied at very low temperatures are highlighted. In the present Minireview we focus on molecular energy transfer and reactions of molecular radicals (e.g. OH) with neutral molecules. We show that with the combination of pulsed laser photolysis and sensitive laser-induced fluorescence detection a large number of fast reactions of radicals with more or less complex neutral molecules can be measured in Laval nozzle expansions nowadays. It is also demonstrated that collisional energy transfer of neutral molecules can be measured via kinetically controlled selective fluorescence (KCSF) excitation down to 58 Kelvin. Finally, we show that even the primary steps in the oxidation of biomolecules or biomolecular building blocks initiated by OH radicals can be followed at low temperatures. The temperature dependence of the measured rate constants is the key for an understanding of the underlying molecular mechanisms and the Laval nozzle expansion provides a unique environment for these measurements. The experimental finding that many reactions between radicals and neutral species can be rapid at low temperatures are discussed in terms of pre-reactive complexes formed in the overall complex forming bimolecular reactions.
    ChemPhysChem 02/2007; 8(3):343-56. DOI:10.1002/cphc.200600646 · 3.42 Impact Factor
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    ABSTRACT: There has been considerable speculation about the role of water and water complexes in chemical gas-phase reactions, including the conjecture that water may act as a molecular catalyst through its ability to form hydrogen bonds. Here, we present kinetic studies in which the effect of water on the rate of the reaction between hydroxyl radicals and acetaldehyde has been measured directly in Laval nozzle expansions at low temperatures. An increasing enhancement of the reaction rate by added water was found with decreasing temperatures between 300 and 60 kelvin. Quantum chemical calculations and statistical rate theory support our conclusions that this observation is due to the reduction of an intrinsic reaction barrier caused by specific water aggregation. The results suggest that even single water molecules can act as catalysts in radical-molecule reactions.
    Science 02/2007; 315(5811):497-501. DOI:10.1126/science.1134494 · 33.61 Impact Factor
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    ABSTRACT: The kinetics of the reactions of OH radicals with propene and isoprene in N-2 have been studied in the temperature range of 58-300 K in a Laval nozzle expansion. Laser-induced fluorescence of the OH radical that is formed in the photolysis of H2O2 at 193 nm has been detected. The determined rate constants (2 x 10(-11) to 2 x 10(-11) cm(3) molecule(-1) s(-1)) for the OH radicals reacting with excess propene and isoprene (2-methyl- 1,3-butadiene) have been found to increase when the temperature is decreased. The room temperature rate constants are in agreement with the literature data. Below 120 K, a saturation of the rate constant for the case of propene and a turnover to a formally positive temperature dependence for isoprene have been observed. The observed negative temperature dependence and the course of the temperature dependence at very low temperatures for both reactions are discussed within the framework of the loose transition-state theory and a simple two-transition-state model.
    The Journal of Physical Chemistry A 09/2004; 108(37):7527-7534. DOI:10.1021/jp031228m · 2.69 Impact Factor