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An integrated mass spectrometry platform enables picomole-scale real-time electrosynthetic reaction screening and discovery.

ABSTRACT: The identification of new electrosynthetic pathways enables environmentally friendly synthetic applications. However, the development of miniaturized screening procedures/platforms to expedite the discovery of electrooxidation reactions remains challenging. Herein, we developed an integrated system that serves as a reactor and ion source in a single experimental step using only picomole-scale reactants to monitor electrooxidation in real-time. This reaction screening platform utilizes the intrinsic electrochemical capabilities of nano-electrospray ionization mass spectrometry. We validated the feasibility of this method by reproducing three known electrochemical reactions. We also discovered two new electroorganic reaction pathways: (i) C-N dehydrodimerization of 8-methyl-1,2,3,4-tetrahydroquinoline to construct a novel quinoline skeleton, and (ii) TEMPO-mediated accelerated electrooxidative dehydrogenation of tetrahydroisoquinolines. Moreover, the radical cations and key intermediates captured by this screening platform provided direct evidence for the mechanism of these novel electrochemical reactions.

SUBMITTER: Wan Q

PROVIDER: S-EPMC6050606 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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An integrated mass spectrometry platform enables picomole-scale real-time electrosynthetic reaction screening and discovery.

Wan Qiongqiong Q Chen Suming S Badu-Tawiah Abraham K AK

Chemical science 20180530 26

The identification of new electrosynthetic pathways enables environmentally friendly synthetic applications. However, the development of miniaturized screening procedures/platforms to expedite the discovery of electrooxidation reactions remains challenging. Herein, we developed an integrated system that serves as a reactor and ion source in a single experimental step using only picomole-scale reactants to monitor electrooxidation in real-time. This reaction screening platform utilizes the intrin ...[more]

PMID: 30079181

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Project description:To address the challenges of tracking the multitude of signaling molecules and metabolites that is the basis of biological complexity, we describe a strategy to expand the analytical techniques for dynamic systems biology. Using microfluidics, online desalting, and mass spectrometry technologies, we constructed and validated a platform well suited for sampling the cellular microenvironment with high temporal resolution. Our platform achieves success in: automated cellular stimulation and microenvironment control; reduced non-specific adsorption to polydimethylsiloxane due to surface passivation; real-time online sample collection; near real-time sample preparation for salt removal; and real-time online mass spectrometry. When compared against the benchmark of "in-culture" experiments combined with ultraperformance liquid chromatography-electrospray ionization-ion mobility-mass spectrometry (UPLC-ESI-IM-MS), our platform alleviates the volume challenge issues caused by dilution of autocrine and paracrine signaling and dramatically reduces sample preparation and data collection time, while reducing undesirable external influence from various manual methods of manipulating cells and media (e.g., cell centrifugation). To validate this system biologically, we focused on cellular responses of Jurkat T cells to microenvironmental stimuli. Application of these stimuli, in conjunction with the cell's metabolic processes, results in changes in consumption of nutrients and secretion of biomolecules (collectively, the exometabolome), which enable communication with other cells or tissues and elimination of waste. Naïve and experienced T-cell metabolism of cocaine is used as an exemplary system to confirm the platform's capability, highlight its potential for metabolite discovery applications, and explore immunological memory of T-cell drug exposure. Our platform proved capable of detecting metabolomic variations between naïve and experienced Jurkat T cells and highlights the dynamics of the exometabolome over time. Upregulation of the cocaine metabolite, benzoylecgonine, was noted in experienced T cells, indicating potential cellular memory of cocaine exposure. These metabolomics distinctions were absent from the analogous, traditional "in-culture" UPLC-ESI-IM-MS experiment, further demonstrating this platform's capabilities.

Dataset Information

An integrated mass spectrometry platform enables picomole-scale real-time electrosynthetic reaction screening and discovery.

Publications

An integrated mass spectrometry platform enables picomole-scale real-time electrosynthetic reaction screening and discovery.

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