Desorption electrospray ionization and other ambient ionization methods: current progress and preview

Ifa, Demian R.; Wu, Chunping; Ouyang, Zheng; Cooks, R. Graham

doi:10.1039/b925257f

Cited by 354 publications

(310 citation statements)

References 76 publications

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“…Ambient ionization [6][7][8][9][10][11][12][13][14] is a relatively recent approach to MS analysis which avoids chromatography and is characterized by the absence of any requirement for sample preparation. Paper spray ionization [15][16][17][18][19][20] is a particularly simple ambient ionization technique which can be employed to study reactions and identify intermediates as well as to measure trace constituents of complex mixtures. Like other spray ionization methods, paper spray is least successful for non-polar or weakly polar compounds.…”

Section: Introductionmentioning

confidence: 99%

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

Bag

Hendricks

Reynolds

et al. 2015

Analytica Chimica Acta

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Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization.Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, ndodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the arylaldehydeiminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng -5 µg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer.3

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Section: Introductionmentioning

confidence: 99%

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

Bag

Hendricks

Reynolds

et al. 2015

Analytica Chimica Acta

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“…1, 5 of CTH in bulk reaction mixtures (reaction time of a few minutes) (15). Ambient ionization methods (24)(25)(26) such as desorption electrospray ionization (DESI) (27)(28)(29) provide a simpler approach to intercepting reactive species without prior sample preparation (30)(31)(32)(33)(34)(35). We recently demonstrated that DESI can intercept CTH intermediates in solution on the millisecond time scale (36).…”

mentioning

confidence: 99%

Transient Ru-methyl formate intermediates generated with bifunctional transfer hydrogenation catalysts

Perry

Brownell

Chingin

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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Desorption electrospray ionization (DESI) coupled to high-resolution Orbitrap mass spectrometry (MS) was used to study the reactivity of a (β-amino alcohol)(arene)RuCl transfer hydrogenation catalytic precursor in methanol (CH 3 OH). By placing ½ðp-cymeneÞ RuCl 2 2 on a surface and spraying a solution of β-amino alcohol in methanol, two unique transient intermediates having lifetimes in the submillisecond to millisecond range were detected. These intermediates were identified as Ru (II) and Ru (IV) complexes incorporating methyl formate (HCOOCH 3 ). The Ru (IV) intermediate is not observed when the DESI spray solution is sparged with Ar gas, indicating that O 2 dissolved in the solvent is necessary for oxidizing Ru (II) to Ru (IV). These proposed intermediates are supported by high-resolution and high mass accuracy measurements and by comparing experimental to calculated isotope profiles. Additionally, analyzing the bulk reaction mixture using gas chromatography-MS and nuclear magnetic resonance spectroscopy confirms the formation of HCOOCH 3 . These results represent an example that species generated from the (β-amino alcohol)(arene)RuCl (II) catalytic precursor can selectively oxidize CH 3 OH to HCOOCH 3 . This observation leads us to propose a pathway that can compete with the hydrogen transfer catalytic cycle. Although bifunctional hydrogen transfer with Ru catalysts has been well-studied, the ability of DESI to intercept intermediates formed in the first few milliseconds of a chemical reaction allowed identification of previously unrecognized intermediates and reaction pathways in this catalytic system. organometallic catalysis | reaction intermediates | ruthenium | kinetics C atalytic transfer hydrogenation (CTH) is an efficient method for the enantioselective reduction of multiple bonds (e.g., C═O and C═NR) in chemical and pharmaceutical syntheses (1-4). Typically, a hydrogen donor such as isopropanol is used as a convenient reducing agent and is oxidized to its corresponding ketone (5). As a catalytic version of the classical MeerweinPondorf-Verley reduction/Oppenaur oxidation (6-10), CTH provides a mild method for both ketone reduction and alcohol oxidation. Previous studies show that methanol (CH 3 OH) can serve as a hydrogen donor for (arene)Ru complexes ligated by β-amino alcohols (11), but the nature of the oxidized products from CH 3 OH has not been previously characterized (12). Additionally, some Pd and Ru (13, 14) catalysts can oxidize CH 3 OH to methyl formate (HCOOCH 3 ), but selective oxidation to methyl formate has not been observed previously for a transfer hydrogenation catalysis. Fig. 1 shows the mechanism proposed by Kenney, Heck, Walgrove, and Wills (15) for CTH when Fig. 1, 1 is treated with β-amino alcohol ligands in the presence of a base. Ligation of the cymene dimer Fig. 1, 1 with ligand Fig. 1, 2 generates the Ru-Cl catalyst precursor Fig. 1, 3, which undergoes dehydrohalogenation to form the Ru-amide Fig. 1, 4. An outer-sphere concerted hydrogen transfer of α-C─H to Ru and ─O─H t...

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“…[11][12][13][14] Most ambient MS methods were primarily utilized for analysing metabolites and lipids. [15][16][17][18] Protein analysis from dried biological samples such as blood, cell cultures, and tissues was demonstrated by electrospray assisted laser desorption ionization (ELDI) MS. 19 In extracts and crude samples, desorption electrospray ionization (DESI) provided peptide and protein analysis including top down sequencing.…”

Section: 10mentioning

confidence: 99%

Comparative local analysis of metabolites, lipids and proteins in intact fish tissues by LAESI mass spectrometry

Shrestha

Javonillo

Burns

et al. 2013

Analyst

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Direct mass spectrometric analysis of animal tissues is an emerging field enabled by recent developments in ambient ion sources. Label-free in situ analysis of metabolites, lipids, and peptides/proteins from intact tissues in whole fish specimens of different gender and age were performed by laser ablation electrospray ionization (LAESI) mass spectrometry (MS). Hypertrophied glandular tissue (gill gland) of adult male Aphyocharax anisitsi (bloodfin tetra) was compared with gill tissues in females of the same species. Comparison of a large number of sample-specific ions was aided by a multivariate statistical method based on orthogonal projections to latent structures discriminant analysis. More than 200 different ions were detected in the mass spectra corresponding to primary metabolites, hormones, lipids and peptides/proteins. The gill tissues of the sexually mature males exhibited multiply charged ions in the 6+ to 10+ charge states corresponding to a protein with a molecular weight of 11 380 Da. This protein was present only in the mature male gill glands but absent in the corresponding area of the female and immature male specimens. An additional nine proteins were detected by LAESI-MS in both the male and female gill tissues. IntroductionMolecular analysis of proteins, lipids, and metabolites in sh by mass spectrometry (MS) is essential in various aspects of their systems biology, including the understanding of their developmental physiological changes.1,2 Various MS methods are involved in detecting environmental pressures from pharmaceuticals, e.g., antibiotics 3 and contraceptives, 4 to agrochemicals. 5Matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) MS have been established as efficient tools to perform proteomic analysis from sh tissue extracts. 6-8Metabolomics studies of sh tissues frequently utilize extraction protocols followed by gas chromatography (GC) MS or high performance liquid chromatography (HPLC) MS. 9,10Direct MS of tissues by recently developed atmospheric pressure ionization methods offers rapid, label-free analysis with minimal sample preparation.11-14 Most ambient MS methods were primarily utilized for analysing metabolites and lipids. [15][16][17][18] Protein analysis from dried biological samples such as blood, cell cultures, and tissues was demonstrated by electrospray assisted laser desorption ionization (ELDI) MS.19 In extracts and crude samples, desorption electrospray ionization (DESI) provided peptide and protein analysis including top down sequencing.20-22 Sensitive analysis of proteins was performed by extractive electrospray ionization mass spectrometry (EESI) by infusing untreated biological samples into the electrospray plume. 23Laser ablation electrospray ionization (LAESI) MS is an ambient ionization technique that employs mid-infrared (mid-IR) laser pulses to locally ablate the tissue or cell sample and electrospray for the ionization of the ejected material.24 The strong absorption maximum of water at 2.94 mm wavelength enables t...

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Desorption electrospray ionization and other ambient ionization methods: current progress and preview

Cited by 354 publications

References 76 publications

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

Transient Ru-methyl formate intermediates generated with bifunctional transfer hydrogenation catalysts

Comparative local analysis of metabolites, lipids and proteins in intact fish tissues by LAESI mass spectrometry

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