Beyond the flask: Reactions on the fly in ambient mass spectrometry

Espy, Ryan D.; Wleklinski, Michael; Yan, Xingru; Cooks, R. Graham

doi:10.1016/j.trac.2014.02.008

Cited by 72 publications

(77 citation statements)

References 104 publications

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“…[4] Although beyond the scope of this Minireview,w ec ite af ew examples.A na symmetric palladiumcatalyzed conjugate addition reaction of arylboronic acids to enone substrates has been investigated mechanistically by DESI-MS,t hus leading to the identification of intermediates along the catalytic cycle and allowing differentiation the substrate reactivity. [62] In polymer growth studies,D ESI-MS was used for real-time monitoring of the homogeneously catalyzed polymerization of ethylene.…”

Section: Discussionmentioning

confidence: 99%

“…[4,38] Moreover,t he electrospray microdroplet might serve as ac onfined space where acid-catalyzed reactions can occur more easily.…”

Section: Mapping Routes Of Multicomponent Reactionsmentioning

confidence: 99%

“…[2][3][4] In this context "soft" electrospray ionization can be considered am onitoring interface for ions and ionizable species existing in solution, thus conveying them into the gas phase for observation.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

2016

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Just as periscopes allow a submarine to visually search for objects above the surface of the sea, in a reversed periscope fashion electrospray mass spectrometry (ESI-MS) can analyze the compounds at the gas phase/liquid phase interface for chemical entities which may exist in solution. The challenge is the identification and structural characterization of key elusive reaction intermediates in chemical transformations, intermediates which are able to explain how chemical processes occur. This Minireview summarizes recent selected publications on the use of ESI-MS techniques for studying solution intermediates of homogeneous chemical reactions.

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Section: Discussionmentioning

confidence: 99%

“…[4,38] Moreover,t he electrospray microdroplet might serve as ac onfined space where acid-catalyzed reactions can occur more easily.…”

Section: Mapping Routes Of Multicomponent Reactionsmentioning

confidence: 99%

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Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

2016

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“…An example is the insitu derivatization of cholesterol with betaine aldehyde during desorption electrospray ionization 17 . The derivatization of ketones and aldehydes by Schiff-base formation improves the detection limits of these important molecules 18 . Another example of enhanced derivatization using spray-based methods has recently been presented by Wu et al 19 , where a derivatization reagent was deposited onto a tissue sample by electrospray before imaging by matrix assisted laser desorption ionization.…”

Section: Introductionmentioning

confidence: 99%

Molecular labels for analysis of amines and diols by spray based ionization-mass spectrometry

Ayrton

Cooks

Pugia

2016

Analyst

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A family of imidazolium and pyridinium salts was synthesized for the purpose of labeling amines and 1,2-diols for highly sensitivite analysis by mass spectrometry. The chosen mass labels are shown to serve as effective reporters when bound to particles functionalized with amines or 1,2-diols and the binding is reversible. The straightforward synthetic route allows analogous internal standards to be generated quickly. Solvents amenable to electrospray ionization facilitate the rapid liberation of imidazolium and pyridinium mass labels from particles by hydrolysis in aqueous acid, while the acetal bond remains stable in anhydrous or buffered aqueous solution. Detection of the labels is demonstrated at 1 nM and quantitation of mass labels released from particles is also demonstrated.

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“…A recent advance developed by Zare and co-workers involves using DESI to capture short-lived solution-phase reaction intermediates (<1 ms) [17][18][19][20][21][22][23] at ambient conditions, while minimizing sample preparation times, carry over effects, and experimental complexity compared with ESI configurations. This elegant discovery has opened the possibility for the development of new types of ambient ionization sources and applications for characterizing fast solution-phase processes [4,[24][25][26][27][28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Multistage Reactive Transmission-Mode Desorption Electrospray Ionization Mass Spectrometry

Peters

Comi

Perry

2015

J. Am. Soc. Mass Spectrom.

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Abstract. Elucidating reaction mechanisms is important for advancing many areas of science such as catalyst development. It is often difficult to probe fast reactions at ambient conditions with high temporal resolution. In addition, systems involving reagents that cross-react require analytical methods that can minimize interaction time and specify their order of introduction into the reacting system. Here, we explore the utility of transmission mode desorption electrospray ionization (TM-DESI) for reaction monitoring by directing a microdroplet spray towards a series of meshes with micrometer-sized openings coated with reagents, an approach we call multistage reactive TM-DESI (TM n -DESI, where n refers to the number of meshes; n=2 in this report). Various stages of the reaction are initiated at each mesh surface, generating intermediates and products in microdroplet reaction vessels traveling towards the mass spectrometer. Using this method, we investigated the reactivity of iron porphyrin catalytic hydroxylation of propranolol and other substrates. Our experimental results indicate that TM n -DESI provides the ability to spatially separate reagents and control their order of introduction into the reacting system, thereby minimizing unwanted reactions that lead to catalyst deactivation and degradation products. In addition, comparison with DESI-MS analyses (the Zare and Latour laboratories published results suggesting accessible reaction times <1 ms) of the reduction of dichlorophenolindophenol by L-ascorbic acid suggest that TM 1 -DESI can access reaction times less than 1 ms. Multiple meshes allow sequential stages of desorption/ionization per MS scan, increasing the number of analytes and reactions that can be characterized in a single experiment.

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Beyond the flask: Reactions on the fly in ambient mass spectrometry

Cited by 72 publications

References 104 publications

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

Molecular labels for analysis of amines and diols by spray based ionization-mass spectrometry

Multistage Reactive Transmission-Mode Desorption Electrospray Ionization Mass Spectrometry

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