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Mass-selected IR plus UV/VUV spectroscopy and mass spectrometry have been coupled into a powerful technique to investigate chemical, physical, structural, and electronic properties of radicals, molecules, and clusters. Advantages of the use of vacuum ultraviolet (VUV) radiation to create ions for mass spectrometry are its application to nearly all compounds with ionization potentials below the energy of a single VUV photon, its circumventing the requirement of UV chromophore group, its inability to ionize background gases, and its greatly reduced fragmenting capabilities. In this review, mass-selected IR plus VUV (118 nm) spectroscopy is introduced first in a general manner. Selected application examples of this spectroscopy are presented, which include the detections and structural analysis of radicals, molecules, and molecular clusters in a supersonic jet., (© 2013 Wiley Periodicals, Inc.)

In present study, photoionization and dissociation of acetic acid dimers have been studied with the synchrotron vacuum ultraviolet photoionization mass spectrometry and theoretical calculations. Besides the intense signal corresponding to protonated cluster ions (CH3COOH)n·H+, the feature related to the fragment ions (CH3COOH)H+·COO (105 amu) via β-carbon-carbon bond cleavage is observed. By scanning photoionization efficiency spectra, appearance energies of the fragments (CH3COOH)·H+ and (CH3COOH)H+·COO are obtained. With the aid of theoretical calculations, seven fragmentation channels of acetic acid dimer cations were discussed, where five cation isomers of acetic acid dimer are involved. While four of them are found to generate the protonated species, only one of them can dissociate into a C-C bond cleavage product (CH3COOH)H+·COO. After surmounting the methyl hydrogen-transfer barrier 10.84 ± 0.05 eV, the opening of dissociative channel to produce ions (CH3COOH)+ becomes the most competitive path. When photon energy increases to 12.4 eV, we also found dimer cations can be fragmented and generate new cations (CH3COOH)·CH3CO+. Kinetics, thermodynamics, and entropy factors for these competitive dissociation pathways are discussed. The present report provides a clear picture of the photoionization and dissociation processes of the acetic acid dimer in the range of the photon energy 9-15 eV. [ABSTRACT FROM AUTHOR]

The nanomaterials function as the substrate to trap analytes, absorb energy from the laser irradiation and transfer energy to the analytes to facilitate the laser desorption process. In this work, the signal intensity and reproducibility of analytes with nanomaterials as matrices were explored by laser desorption postionization mass spectrometry (LDPI-MS). Herein, the desorbed neutral species were further ionized by vacuum ultraviolet (VUV, 118 nm) and analyzed by mass spectrometer. Compared with other nanomaterial matrices such as graphene and carbon nanotubes (CNTs), boron nitride nanotubes (BNNTs) exhibited much higher desorption efficiency under infrared (IR) light and produced no background signal in the whole mass range by LDPI-MS. Additionally, this method was successfully and firstly exploited to in situ detection and imaging for drugs of low concentration in intact tissues, which proved the utility, facility and convenience of this method applied in drug discovery and biomedical research. [ABSTRACT FROM AUTHOR]

Mass spectrometry imaging (MSI) is an innovative and powerful tool in biomedical research. It is well-known that folic acid (FA) has a high affinity for folic acid receptor (FR), which is overexpressing in epithelial cancer. Herein, we propose a novel method to diagnose cancer through direct mapping of the label-free FA spatial distribution in tissue sections by state-of-the-art laser desorption postionization-mass spectrometry imaging (LDPI-MSI). Compared with other tumor imaging methods, such as fluorescence imaging, photoacoustic imaging (PAI), magnetic resonance imaging (MRI), and micro-SPECT/CT, complicated synthesis and labeling processes are not required. The LDPI-MSI was performed on 30 μm thick sections from a murine model of breast cancer (inoculation of 4T1 cells) that were predosed with 20 mg/kg of FA. The image obtained from the characteristic mass spectrometric signature of FA at m/z 265 illustrated that FA was concentrated primarily in tumor tissue and displayed somewhat lower retention in adjacent normal controls. The results suggest that the proposed method could be used potentially in cancer diagnosis. [ABSTRACT FROM AUTHOR]

Localization and quantification of the target drug in tissues is a key indicator of efficacy in drug discovery. In contrast to established methods that require matrices and complex sample pretreatment steps, matrix-free and low cost in situ analysis of small molecule drugs by mass spectrometry (MS) remains challenging. Here, we present a novel approach, laser desorption postionization (LDPI), which is coupled to a linear time-of-flight (TOF) MS and used to image the distribution of acriflavine (ACF) directly from a histological section of mouse kidney without any matrix or sample pretreatment. The identification of the mass peaks assigned to ACF was further confirmed by DESI-MS/MS. Moreover, the matrix effect from the tissue section was explored, showing minimal desorption and ionization suppression in the LDPI-MS process. LDPI-MS imaging (LDPI-MSI) was performed on 30 μm kidney sections from mice 15 min postdose that were dosed with 30 mg kg−1 of ACF by monitoring the fragment ion at m/z 209. The LDPI-MS image revealed a global view of the distribution of ACF in the kidney compartments (pelvis, medulla, and cortex). Estimated concentrations of ACF residue in mouse kidney were obtained by LDPI-MSI and LC-MS/MS and a 12.1% difference in measured tissue concentration was found. These results suggest that the use of LDPI-MS in small molecule drug localization and quantification directly from biological tissue at the same time is favorable. [ABSTRACT FROM AUTHOR]

Highlights: [•] Medicinal chemicals (taking the methylene blue (MB) as the example) in situ in intact tissues has been observed by laser desorption postionization mass spectrometry with 10.5eV vacuum ultraviolet single photon ionization. [•] The experiment shows the optimal delay time between the desorption laser and ionization laser was 18–35μs. [•] The detections of amino acids fragments and other biological species in the tissue do not interfere with the signal of MB detected in the MB-dosed tissue. [ABSTRACT FROM AUTHOR]

Site-selective ionization of ethanol dimer and the subsequent fragmentation were studied by synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry. With photoionization efficiency spectra measurements and theoretical calculations, the detailed mechanisms of the ionization-dissociation processes of ethanol dimer under VUV irradiation were explored. In 9.49-10.89 eV photon energy range, it was found that the ejection of the highest occupied molecular orbital (HOMO) electron from hydrogen bond donor induces a rapid barrierless proton-transfer process followed by two competitive dissociation channels, generating (C2H5OH)·H+ and CH2O·(C2H5OH)H+, respectively. The latter comes from a carbon-carbon bond cleavage in the donor. While the photon energy is 10.9-11.58 eV, the electron of HOMO-1 of the hydrogen bond acceptor, is removed. Besides the dissociation channel to produce C2H5OH and C2H5OH+, a new channel to generate (C2H5OH)·CH2OH+ is opened, where the cleavage of the carbon-carbon bond occurs in the acceptor. When the photon energy increases to 11.58 eV, the electron from HOMO-2 is ejected. [ABSTRACT FROM AUTHOR]

Acrylonitrile (AN), one of the most abundant nitriles in space, is considered to closely relate to the formation of interstellar prebiotic nitrogen-containing aromatics. Herein, we measured the vibrational spectra of acrylonitrile cluster cations (AN) 2,3 + in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet (VUV) photoionization and time-of-flight mass spectroscopy. Interestingly, the observed IR spectra demonstrate that a new molecular ion [ CH 2 = CHC = N − C (H) 2 C (H) C ≡ N ] + , is generated from the dimer and trimer of AN upon VUV single-photo ionization. Calculation results reveal that the new molecular cations can be generated through a relative low energy barrier after ionization of the neutral (AN) 2. However, the reaction pathways are barrierless for the trimer, in which the third solvent AN acts as a catalyst. The mechanisms of those reactions also have been discussed in detail. This study contributes to a deeper understanding of ion-molecule reaction in gas-phase and the quest for the formation of prebiotic N -containing molecules in the outer space. Image 1 • IR-VUV spectroscopy of neutral and cationic (AN) 2 , 3 have been obtained. • It is found that the neutral (AN) 2 , 3 with cyclic structures are stabilized by dipole-dipole and H-bonded interactions. • A new molecular cations with the N-C covalent bond can be generated through a relative low energy barrier after ionization of the neutral (AN) 2. However, the reaction pathways are barrierless for the trimer. • The study contributes to a deeper understanding of ion-molecule reaction in gas-phase and the quest for the formation of prebiotic N-containing molecules in the outer space. [ABSTRACT FROM AUTHOR]