Vaporization of Intact Neutral Biomolecules Using Laser-Based Thermal Desorption

Dauletyarov, Yerbolat; Wang, Siwen; Horke, Daniel A.

doi:10.1021/jasms.3c00194

Cited by 3 publications

(3 citation statements)

References 34 publications

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“…This confirms our molecular assignment and highlights the relative softness of the fs-MPI process. 34 Pyridone is known to form very stable dimers, and these were also present in our mass spectrum. Even under supersonic expansion conditions optimized to minimize dimer formation, we observed a signal in the dimer channel with an intensity of around 5% that of the monomer, as shown in the inset of Figure 2 .…”

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confidence: 62%

“…In panel (b) we show a reference mass spectrum from NIST obtained using electron impact ionization, which exhibits identical fragmentation channels, with an overall larger degree of fragmentation. This confirms our molecular assignment and highlights the relative softness of the fs-MPI process . Pyridone is known to form very stable dimers, and these were also present in our mass spectrum.…”

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confidence: 99%

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Preparation of Tautomer-Pure Molecular Beams by Electrostatic Deflection

Abma,

Parkes,

Horke

2024

J. Phys. Chem. Lett.

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Tautomers are ubiquitous throughout chemistry and typically considered inseparable in solution. Yet (bio)chemical activity is highly tautomer-specific, with common examples being the amino and nucleic acids. While tautomers exist in an equilibrium in solution, in the cold environment of a molecular beam the barrier to tautomerization is typically much too high for interconversion, and tautomers can be considered separate species.Here we demonstrate the first separation of tautomers within a molecular beam and the production of tautomerically pure gas-phase samples. We show this for the 2-pyridone/2hydroxypyridine system, an important structural motif in both uracil and cytosine. Spatial separation of the tautomers is achieved via electrostatic deflection in strong inhomogeneous fields. We furthermore collect tautomer-resolved photoelectron spectra using femtosecond multiphoton ionization. This paves the way for studying the structure−function−dynamic relationship on the level of individual tautomers, using approaches that typically lack the resolution to do so, such as ultrafast dynamics experiments.

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confidence: 62%

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confidence: 99%

Preparation of Tautomer-Pure Molecular Beams by Electrostatic Deflection

Abma,

Parkes,

Horke

2024

J. Phys. Chem. Lett.

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“…The combined approach of LBTD with fs-MPI is clearly a very powerful approach of introducing intact biomolecules into the gas phase at high densities. It also has the potential for vaporizing significantly larger and more fragile systems intact, as has recently been demonstrated [ 37 ]. The continuous nature of the source allows the combination with high repetition-rate lasers for high throughput experiments with the overall repetition rate, and hence, throughput limited by the ion time-of-flight.…”

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confidence: 99%

High-Throughput UV Photoionization and Fragmentation of Neutral Biomolecules as a Structural Fingerprint

Wang¹,

Dauletyarov²,

Horke³

2023

Molecules

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We present UV photofragmentation studies of the structural isomers paracetamol, 3-Pyridinepropionic acid (3-PPIA) and (R)-(-)-2-Phenylglycine. In particular, we utilized a new laser-based thermal desorption source in combination with femtosecond multiphoton ionization at 343 nm and 257 nm. The continuous nature of our molecule source, combined with the 50 kHz repetition rate of the laser, allowed us to perform these experiments at high throughput. In particular, we present detailed laser intensity dependence studies at both wavelengths, producing 2D mass spectra with highly differential information about the underlying fragmentation processes. We show that UV photofragmentation produces highly isomer-specific mass spectra, and assign all major fragmentation pathways observed. The intensity-dependence measurements, furthermore, allowed us to evaluate the appearance intensities for each fragmentation channel, which helped to distinguish competing from consecutive fragmentation pathways.

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Design and characterization of an optical-fiber-coupled laser-induced desorption source for gas-phase dynamics experiments

Milešević,

Popat,

Gellersen

et al. 2023

Review of Scientific Instruments

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Preparation of neutral non-volatile molecules intact in the gas phase for mass spectrometry or chemical dynamics experiments remains a challenge for many classes of molecules. Here, we report the design and characterization of a fiber-coupled laser-based thermal desorption source capable of preparing intact neutral molecules at high molecular densities in the gas phase for use in velocity-map imaging experiments. Within this source, the sample is deposited onto a thin tantalum foil. Irradiation of the foil from the reverse side by a focused laser beam leads to highly localized heating of the sample, resulting in desorption of a plume of molecules into the gas phase. The fiber-coupled design simplifies the alignment of the desorption laser beam, and the ability to rotate the foil relative to the fixed laser beam allows the sample to be continually refreshed under vacuum. We use 118 nm photoionization of three test molecules—uracil, adenine, and phenylalanine—to characterize the source and to demonstrate various aspects of its performance. These include the dependence of the velocity-map imaging performance on the size of the interaction region and the dependence of the laser-induced desorption source emission on desorption laser power and heating time. Signal levels recorded in these measurements are comparable to those we typically obtain in similar experiments using a pulsed supersonic molecular beam, and we, therefore, believe that the source has considerable potential for use in a wide range of chemical dynamics and other experiments.

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Vaporization of Intact Neutral Biomolecules Using Laser-Based Thermal Desorption

Cited by 3 publications

References 34 publications

Preparation of Tautomer-Pure Molecular Beams by Electrostatic Deflection

Preparation of Tautomer-Pure Molecular Beams by Electrostatic Deflection

High-Throughput UV Photoionization and Fragmentation of Neutral Biomolecules as a Structural Fingerprint

Design and characterization of an optical-fiber-coupled laser-induced desorption source for gas-phase dynamics experiments

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