We report here the construction and characterization of a high-power laser-induced acoustic desorption (LIAD) probe designed for Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometers to facilitate analysis of non-volatile, thermally labile compounds. This "next generation" LIAD probe offers significant improvements in sensitivity and desorption efficiency for analytes with larger molecular weights via the use of higher laser irradiances. Unlike the previous probes which utilized a power limiting optical fiber to transmit the laser pulses through the probe, this probe employs a set of mirrors and a focusing lens. At the end of the probe, the energy from the laser pulses propagates through a thin metal foil as an acoustic wave, resulting in desorption of neutral molecules from the opposite side of the foil. Following desorption, the molecules can be ionized by electron impact or chemical ionization. Almost an order of magnitude greater power density (up to 5.0 × 10 9 W/cm 2 ) is achievable on the backside of the foil with the high-power LIAD probe compared to the earlier LIAD probes (maximum power density ~9.0 × 10 8 W/cm 2 ). The use of higher laser irradiances is demonstrated not to cause fragmentation of the analyte. The use of higher laser irradiances increases sensitivity since it results in the evaporation of a greater number of molecules per laser pulse. Measurement of the average velocities of LIAD evaporated molecules demonstrates that higher laser irradiances do not correlate with higher velocities of the gaseous analyte molecules.
We report here the first application of laser desorption (LD) in transmission geometry (backside irradiation of the sample through a transparent support) inside a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). A probe-mounted fiber optic assembly was used to simplify the implementation of this LD technique. This setup requires little or no instrument modifications, has minimum maintenance requirements, and is relatively inexpensive to build. The performance of the probe was tested by determining the molecular weight of a commercial polystyrene standard from its matrix-assisted laser desorption/ionization (MALDI) spectrum. The measured average molecular weight is comparable to that obtained for the same sample by MALDI in the conventional top-illumination arrangement (reflection geometry) and by the manufacturer of the sample by gel permeation chromatography. The average velocities measured for ions evaporated by transmission mode LD of several neat samples are about half the velocity of those obtained by using the reflection geometry. Therefore, transmission mode irradiation of the sample holds promise to desorb ions that are easier to trap in an ICR cell. An oscillating capillary nebulizer was adapted for the deposition of analytes to improve sampling reproducibility.
A pulsed-leak valve that allows the introduction of a prolonged, flat, and controllable pulse of gas is described. Test results from the valve that utilized a Fourier transform ion cyclotron resonance mass spectrometer with Ar and C2H6 as the sample gases indicate that the valve functions as expected and yields basically rectangular pressure profiles in the cell region. The rise and fall times are similar to those of just the stand-alone pulsed valve and are believed to be determined mainly by the design of the vacuum system, rather than the design of the pulsed-leak valve. Kinetic data for the reaction of Nb(+) with C2H6, acquired with the use of the pulsed-leak valve to introduce the C2H6 gas, demonstrates the practical application of this valve for kinetic and other analogous studies. Use of the pulsed-leak valve greatly reduces the loss of the reactant ion signal during the cooling period.
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