323 research outputs found
Small-Size Resonant Photoacoustic Cell of Inclined Geometry for Gas Detection
A photoacoustic cell intended for laser detection of trace gases is
represented. The cell is adapted so as to enhance the gas-detection performance
and, simultaneously, to reduce the cell size. The cell design provides an
efficient cancellation of the window background (a parasite response due to
absorption of laser beam in the cell windows) and acoustic isolation from the
environment for an acoustic resonance of the cell. The useful photoacoustic
response from a detected gas, window background and noise are analyzed in
demonstration experiments as functions of the modulation frequency for a
prototype cell with the internal volume ~ 0.5 cm^3. The minimal detectable
absorption for the prototype is estimated to be ~ 1.2 10^{-8} cm^{-1} W
Hz^{-1/2}.Comment: 11 pages, 5 figure
High resolution temperature and density profiles during the energy quench of density limit disruptions in Rijnhuizen tokamak project
Measurements of the electron temperature, Te, and density, ne, during the energy quench of a major disruption showed that the onset of Te erosion in the neighborhood of the m/n = 2/1 O point at the low field side (LFS) accelerates the well-known m/n = 1/1 erosion of the core temperature. During this phase Te(r) is only partially flat in the region between the q = 2 and the q = 1 surfaces and ne(r) decreases in the core and increases inside the m/n = 2/1 island. Immediately after the flattening of Te(r) a large peak in Te and to a lesser extent in ne has been observed. This peak is radially localized at the q = 2 radius at the LFS, is very short lived and is poloidally asymmetric. Te profiles measured by the heterodyne radiometer and the Thomson scattering agree very well up to the time Te(r) flattens but afterwards can be a factor of two different
Secondary structure of Ac-Ala-LysH polyalanine peptides (=5,10,15) in vacuo: Helical or not?
The polyalanine-based peptide series Ac-Ala_n-LysH+ (n=5-20) is a prime
example that a secondary structure motif which is well-known from the solution
phase (here: helices) can be formed in vacuo. We here revisit this conclusion
for n=5,10,15, using density-functional theory (van der Waals corrected
generalized gradient approximation), and gas-phase infrared vibrational
spectroscopy. For the longer molecules (n=10,15) \alpha-helical models provide
good qualitative agreement (theory vs. experiment) already in the harmonic
approximation. For n=5, the lowest energy conformer is not a simple helix, but
competes closely with \alpha-helical motifs at 300K. Close agreement between
infrared spectra from experiment and ab initio molecular dynamics (including
anharmonic effects) supports our findings.Comment: 4 pages, 4 figures, Submitted to JPC Letter
Probing the competition among different coordination motifs in metal-ciprofloxacin complexes through IRMPD spectroscopy and DFT calculations
The vibrational spectra of ciprofloxacin complexes with monovalent (Li+, Na+, K+, Ag+) and polyvalent (Mg2+, Al3+) metal ions are recorded in the range 1000-1900 cm(-1) by means of infrared multiple-photon dissociation (IRMPD) spectroscopy. The IRMPD spectra are analyzed and interpreted in the light of density functional theory (DFT)-based quantum chemical calculations in order to identify the possible structures present under our experimental conditions. For each metal-ciprofloxacin complex, four isomers are predicted, considering different chelation patterns. A good agreement is found between the measured IRMPD spectrum and the calculated absorption spectrum of the most stable isomer for each complex. Metal ion size and charge are found to drive the competition among the different coordination motifs: small size and high charge density metal ions prefer to coordinate the quinolone between the two carbonyl oxygen atoms, whereas large-size metal ions prefer the carboxylate group as a coordination site. In the latter case, an intramolecular hydrogen bond compensates the weaker interaction established by these cations. The role of the metal cation on the stabilization of ionic and nonionic structures of ciprofloxacin is also investigated. It is found that large-size metal ions preferentially stabilize charge separated motifs and that the increase of metal ion charge has a stabilizing effect on the zwitterionic form of ciprofloxacin
BREAKDOWN PRODUCTS OF GASEOUS POLYCYCLIC AROMATIC HYDROCARBONS INVESTIGATED WITH INFRARED ION SPECTROSCOPY
Action spectroscopy of gas-phase carboxylate anions by multiple photon IR electron detachment/attachment
We report on a form of gas-phase anion action spectroscopy based on infrared
multiple photon electron detachment and subsequent capture of the free
electrons by a neutral electron scavenger in a Fourier Transform Ion Cyclotron
Resonance (FTICR) mass spectrometer. This method allows one to obtain
background-free spectra of strongly bound anions, for which no dissociation
channels are observed. The first gas-phase spectra of acetate and propionate
are presented using SF6 as electron scavenger and a free electron laser as
source of intense and tunable infrared radiation. To validate the method, we
compare infrared spectra obtained through multiple photon electron
detachment/attachment and multiple photon dissociation for the benzoate anion.
In addition, different electron acceptors are used, comparing both associative
and dissociative electron capture. The relative energies of dissociation (by
CO2 loss) and electron detachment are investigated for all three anions by DFT
and CCSD(T) methods. DFT calculations are also employed to predict vibrational
frequencies, which provide a good fit to the infrared spectra observed. The
frequencies of the symmetric and antisymmetric carboxylate stretching modes for
the aliphatic carboxylates are compared to those previously observed in
condensed-phase IR spectra and to those reported for gas-phase benzoate,
showing a strong influence of the solution environment and a slight substituent
effect on the antisymmetric stretch.Comment: Revised version, Submitted to J Phys Chem
Separation and identification of structural isomers by quadrupole collision-induced dissociation-hydrogen/deuterium exchange-infrared multiphoton dissociation (QCID-HDX-IRMPD)
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