We have used an infrared laser to ablate materials under ambient conditions that were captured in solvent droplets. The droplets were either deposited on a MALDI target for off-line analysis by MALDI time-of-flight mass spectrometry or flow-injected into a nanoelectrospray source of an ion trap mass spectrometer. An infrared optical parametric oscillator (OPO) laser system at 2.94 μm wavelength and approximately 1 mJ pulse energy was focused onto samples for ablation at atmospheric pressure. The ablated material was captured in a solvent droplet 1-2 mm in diameter that was suspended from a silica capillary a few millimeters above the sample target. Once the sample was transferred to the droplet by ablation, the droplet was deposited on a MALDI target. A saturated matrix solution was added to the deposited sample, or in some cases, the suspended capture droplet contained the matrix. Peptide and protein standards were used to assess the effects of the number of IR laser ablation shots, sample to droplet distance, capture droplet size, droplet solvent, and laser pulse energy. Droplet collected samples were also injected into a nanoelectrospray source of an ion trap mass spectrometer with a 500 nL injection loop. It is estimated that pmol quantities of material were transferred to the droplet with an efficiency of approximately 1%. The direct analysis of biological fluids for off-line MALDI and electrospray was demonstrated with blood, milk, and egg. The implications of this IR ablation sample transfer approach for ambient imaging are discussed.

We have demonstrated an on-line laser ablation sampling system and coupling of the system to liquid chromatography (LC) using an infrared (IR) laser to ablate and transfer materials into a flowing solvent stream. With this approach, samples are deposited on a microscope slide mounted on a translation stage and ablated in transmission geometry using a pulsed mid-IR laser. The ablated material is captured in an exposed flowing solvent stream that carries the ablated material to the electrospray source. Post-ablation separation is accomplished using a capillary column downstream of the capture zone. The performance of the system was assessed using peptide and protein mixtures ablated from the target and analyzed with and without LC separation.

FT-based high performance mass analyzers yield increased resolving power and mass measurement accuracy, yet require increased duration of signal acquisition that can limit many applications. The implementation of stronger magnetic fields, multiple detection electrodes for harmonic signal detection and an array of multiple mass analyzers arranged along the magnetic field axis have been used to decrease required acquisition time. The results presented here show that multiple ICR mass analyzers can also be implemented orthogonal to the central magnetic field axis. The orthogonal ICR cell system presented here consisting of two cells (master and slave cells) was constructed with printed circuit boards and installed within a single superconducting magnet and vacuum system. A master cell was positioned as is normally done with ICR cells, on the central magnetic field axis and a slave cell was located off this central axis, but directly adjacent and alongside the master cell. To achieve ion transfer between cells, ions that were initially trapped in the master cell were drifted across the magnetic field into the slave cell with application of a small DC field applied perpendicularly to the magnetic field axis. A subsequent population of ions was injected and accumulated in the master cell. Simultaneous excitation of cyclotron motion of ions in both cells was carried out, ICR signals from each cell were independently amplified and recorded in parallel. Presented here are the initial results of successful parallel spectral acquisition with this orthogonal dual ICR cell array.

A novel interface for ambient sampling to CE/MS was developed. The interface is generally applicable and has potential utility for mass spectrometry imaging as well as the loading of microfluidic devices from untreated ambient samples.

Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is a powerful instrument for the study of complex biological samples due to its high resolution and mass measurement accuracy. However, the relatively long signal acquisition periods needed to achieve high resolution can serve to limit applications of FTICR-MS. The use of multiple pairs of detector electrodes enables detection of harmonic frequencies present at integer multiples of the fundamental cyclotron frequency, and the obtained resolving power for a given acquisition period increases linearly with the order of harmonic signal. However, harmonic signal detection also increases spectral complexity and presents challenges for interpretation. In the present work, ICR cells with independent dipole and harmonic detection electrodes and preamplifiers are demonstrated. A benefit of this approach is the ability to independently acquire fundamental and multiple harmonic signals in parallel using the same ions under identical conditions, enabling direct comparison of achieved performance as parameters are varied. Spectra from harmonic signals showed generally higher resolving power than spectra acquired with fundamental signals and equal signal duration. In addition, the maximum observed signal to noise (S/N) ratio from harmonic signals exceeded that of fundamental signals by 50 to 100%. Finally, parallel detection of fundamental and harmonic signals enables deconvolution of overlapping harmonic signals since observed fundamental frequencies can be used to unambiguously calculate all possible harmonic frequencies. Thus, the present application of parallel fundamental and harmonic signal acquisition offers a general approach to improve utilization of harmonic signals to yield high-resolution spectra with decreased acquisition time. Graphical Abstract ᅟ.

Fourier transform ion cyclotron resonance mass spectrometry (FTICR−MS) is a powerful instrument for high-resolution analysis of biomolecules. However, relatively long signal acquisition periods are needed to achieve mass spectra with high resolution. The use of multiple detector electrodes for detection of harmonic frequencies has been introduced as one approach to increase scan rate for a given resolving power or to obtain increased resolving power for a given detection period. The achieved resolving power and scan rate increase linearly with the order of detected harmonic signals. In recent years, ICR cell geometries have been investigated to increase the order of the harmonic frequencies and enhance harmonic signal intensities. In this study, we demonstrated PCB-based ICR cell designs with dipole and sixth harmonic detectors for parallel detection of fundamental and harmonic (6f) signals. The sixth harmonic signals from the sixth harmonic detector showed an expected 6 times higher resolving power with (M + 3H) 3+ charge state insulin ions as compared with that from fundamental signals from the dipole detector. Moreover, the insulin isotopic peaks with sixth harmonic frequency signals acquired with the sixth harmonic detector were resolved for a 40 ms data acquisition period but unresolved with the same duration dipole detector signals, corresponding to a 6-fold improvement in achievable spectral acquisition rates for a given resolving power.

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High-pressure gas is produced during the oil production process at offshore plants, and pressure relief devices, such as valves, are widely used to protect related systems from it. The high-pressure gas in the pipes connected to the flare head is burned at the flare stack, or, if it is nontoxic, is vented to the atmosphere. During this process, excessive noise is generated by the pressure relief valves that are used to quickly discharge the high-pressure gas to the atmosphere. This noise sometimes causes severe acoustic-induced vibration in the pipe wall. This study estimated the internal aerodynamic noise due to valve flow in a simple constriction-expansion pipe, by combining the large eddy simulation technique with a wavenumber-frequency analysis, which made it possible to decompose the fluctuating pressure into the incompressible hydrodynamic pressure and compressible acoustic pressure. First, the steady-state flow was numerically simulated, and the result was compared with a quasi-one-dimensional theoretical solution, which confirmed the validity of the current numerical method. Then, an unsteady simulation analysis was performed to predict the fluctuating pressure inside a pipe. Finally, the acoustic pressure modes in a pipe were extracted by applying the wavenumber-frequency transform to the total pressure field. The results showed that the acoustic pressure fluctuations in a pipe could be separated from the incompressible ones. This made it possible to obtain accurate information about the acoustic power, which could be used to assess the likelihood of a piping system failure due to acoustic-induced vibration, along with information about the acoustic power spectrum of each acoustic mode, which could be used to facilitate the systematic mitigation of the potential acoustic-induced vibration in piping systems.