Energy-resolved competitive collision-induced dissociation is used to investigate the proton-bound heterodimer anions of a series of carboxylic acids (formic, acetic, and benzoic acid) and nitrous acid with their conjugate bases. The dissociation reactions of the complexes [CH3COO.H.OOCH]-, [CH3COO.H.ONO]-, [HCOO.H. ONO]-, [C6H5COO.H.OOCH]-, and [C6H5COO.H.ONO]- are investigated using a guided ion beam tandem mass spectrometer. Cross sections of the two dissociation channels are measured as a function of the collision energy between the complex ions and xenon target gas. Apparent relative gas-phase acidities are found by modeling the cross sections near the dissociation thresholds using statistical rate theory. Internal inconsistencies are found in the resulting relative acidities. These deviations apparently result from the formation of higher-energy conformers of the acids within the complex ions induced by double hydrogen bonding, which impedes the kinetics of dissociation to ground-state product acid conformations.
Beams of hyperthermal K atoms cross beams of the oriented haloforms CF(3)H, CCl(3)H, and CBr(3)H, and transfer of an electron mainly produces K(+) and the X(-) halide ion which are detected in coincidence. As expected, the steric asymmetry of CCl(3)H and CBr(3)H is very small and the halogen end is more reactive. However, even though there are three potentially reactive centers on each molecule, the F(-) ion yield in CF(3)H is strongly dependent on orientation. At energies close to the threshold for ion-pair formation ( approximately 5.5 eV), H-end attack is more reactive to form F(-). As the energy is increased, the more productive end switches, and F-end attack dominates the reactivity. In CF(3)H near threshold the electron is apparently transferred to the sigma(CH) antibonding orbital, and small signals are observed from electrons and CF(3)(-) ions, indicating "activation" of this orbital. In CCl(3)H and CBr(3)H the steric asymmetry is very small, and signals from free electrons and CX(3)(-) ions are barely detectable, indicating that the sigma(CH) antibonding orbital is not activated. The electron is apparently transferred to the sigma(CX) orbital which is believed to be the LUMO. At very low energies the proximity of the incipient ions probably determines whether salt molecules or ions are formed.
This proof-of-concept study used solid-phase microextraction fibers (SPME) to collect headspace vapors from a methicillin sensitive Staphylococcus aureus (MSSA) and a methicillin-resistant Staphylococcus aureus (MRSA) strain grown in vitro in liquid growth medium. The collected molecules were separated and identified using gas chromatography and mass spectrometry (GC/MS). Preliminary results distinguished these two strains and provide a foundation for a biomarker library that could one day serve as a diagnostic tool for identifying specific bacterial infections.
Rubidium atoms are accelerated in a high-temperature expansion of hydrogen to produce beams with energies high enough to observe collisional ionization with a cross beam. The speed of the atoms is directly measured by time-of-flight techniques, and the positive and negative ions produced are detected in separate mass spectrometers and detected in coincidence. Chloroperfluoroethane produces C(2)F(5)(-) and Cl(-) ions, whereas iodoperfluoroethane produces I(-), C(2)F(5)(-), and C(2)F(5)I(-) ions. When the measured speed distributions are used, the signal versus energy may be deconvolved to yield thresholds and electron affinities (EAs). The EA for C(2)F(5)I is measured to be 0.96 +/- 0.1 eV. Anomalously high EA values result for C(2)F(5) apparently because C(2)F(5)(-) is produced by parts per million concentrations of Rb(2).
We propose a mesoscopic particle-exchange heat engine realized via coupled quantum dots. The engine is able to extract work from a bosonic reservoir and can be used as a refrigerator. The electric current is derived from a master-equation method and is readdressed under a thermodynamic context. The quantum-mechanical result is found to be consistent with thermodynamic analysis.
Molecular and fragment negative ions are produced from the collisions between rubidium atoms and several kinds of halogenated unsaturated organic molecules in crossed supersonic beams. Their apparent electron affinities and the bond dissociation energies are measured.
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