Study of gas-phase molecular recognition using Fourier transform ion cyclotron resonance mass spectrometry (FTICR/MS).

The application of Fourier transform ion cyclotron resonance (FTICR) mass spectrometry to the quantitative study of molecular recognition in the gas phase is reviewed. Because most quantitative measurements are dependent on accurate determination of the pressure of a neutral reagent, methods for accurate pressure measurement in FTICR, including gauge calibration using a reaction with known rate constants (the traditional method), exothermic proton transfer rate measurement (often the best method when accurate neutral pressures in the trapping cell are desired), and linewidth measurement (a little-used, but generally applicable method) are discussed. The use of rate constant measurements in molecular recognition is illustrated with examples employing natural abundance isotopic labeling to study self-exchange and 2 : 1 ligand:metal complex formation kinetics in crown ether-alkali cation systems. Self-exchange rates do not correlate with alkali cation/crown cavity size relationships, whereas 2 : 1 complex formation kinetics correlate strongly with size relationships. The use of exchange equilibrium constant measurements to characterize molecular recognition is illustrated by alkali cation exchanges between 18-crown-6 and the isomers of dicyclohexano-18-crown-6. These experiments show that the alkyl-substituted ligand binds alkali cations better than unsubstituted 18-crown-6 in the gas phase, in accordance with expectations based on the higher polarizability of the alkyl-substituted ligand. Further, the metal binding thermochemistry differs for the two dicyclohexano-18-crown-6 isomers, with the bowl-shaped cis-syn-cis isomer binding all the alkali cations more strongly than the cis-anti-cis isomer. The measurement of entropies and enthalpies associated with one of the most subtle forms of molecular recognition, enantiomeric discrimination, is illustrated by studies of the discrimination between enantiomers of chiral amines by dimethyldiketopyridino-18-crown-6. This chiral ligand binds chiral primary ammonium cations that have the opposite absolute configuration at their stereocenter more strongly than the enantiomer with the same absolute configuration. Gas-phase studies show that this enantiomeric discrimination is enthalpic in origin, likely related to more favorable pi-pi stacking for the preferred enantiomer. Entropy disfavors binding of the preferred enantiomer.

Gas-Phase studies of valinomycin-alkali metal cation complexes: attachment rates and cation affinities.

Reactions of laser-desorbed Na(+), K(+), Rb(+), and Cs(+) with thermally vaporized valinomycin generate metal-ligand complexes in a Fourier transform ion cyclotron resonance trapping cell, proving that complexes can form via gas-phase ion-molecule reactions. Although desorption of intact pre-formed complexes cannot be ruled out, this route appears minor. Relative rate constants for the complexation reactions show strong dependence on the charge densities of the cations. Competition experiments between valinomycin and the synthetic ionophores 18-crown-6 (18C6) and [2.2.2]-cryptand ([2.2.2]) show that valinomycin has a higher intrinsic alkali metal cation affinity than either 18C6 or [2.2.2], in contrast to the complex formation constants observed in methanol, where K+ affinities are in the order [2.2.2] > 18C6 > valinomycin.

Outbreak of Legionnaires' disease at University Hospital, Nottingham. Epidemiology, microbiology and control.

Twelve patients in a large teaching hospital contracted Legionnaires' disease over a period of 11 months. The source was a domestic hot water system in one of the hospital blocks, which was run at a temperature of 43 degrees C. Five different subtypes of Legionella pneumophila serogroup 1 have been isolated from water in different parts of the hospital, over a period of time. Only one subtype, Benidorm RFLP 14, was implicated in disease. Circumstantial evidence suggested that the outbreak may have been due to recent colonization of the hot water system with a virulent strain of Legionella pneumophila. The outbreak was controlled by raising the hot water temperature to 60 degrees C, but careful surveillance uncovered two further cases in the following 30 months. Persistent low numbers of Legionella pneumophila were isolated from the domestic hot water of wards where Legionnaires' disease had been contracted, until an electrolytic unit was installed releasing silver and copper ions into this supply.

Letters.

WHO HAS UPDATE ON RESEARCH EDUCATING DOCTORS A NATIONAL RESOURCE? A HOLISTIC APPROACH MORE SAMPLES NEEDED A USEFUL RESOURCE THE APPLIANCE OF SCIENCE WILL THE PRICE BE RIGHT? COMMUNITY NEEDS DISPARITY IN CARE BACK TO BASICS INFECTION MATTERS PREACHING TO THE CONVERTED? SUPPORT FOR STAFF A NURSE-LED DISCIPLINE INNOVATION NEEDED PRESCRIBING IMPLICATIONS.