- The visible-light photocatalyticE/Zisomerization of olefins can be mediated by a wide spectrum of triplet sensitizers (photocatalysts). However, the search for the most efficient photocatalysts through screenings in photo batch reactors is material and time consuming. Capillary and microchip flow reactors can accelerate this screening process. Combined with a fast analytical technique for isomer differentiation, these reactors can enable high-throughput analyses. Ion mobility (IM) spectrometry is a cost-effective technique that allows simple isomer separation and detection on the millisecond timescale. This work introduces a hyphenation method consisting of a microchip reactor and an infrared matrix-assisted laser desorption ionization (IR-MALDI) ion mobility spectrometer that has the potential for high-throughput analysis. The photocatalyzedE/Zisomerization of ethyl-3-(pyridine-3-yl)but-2-enoate (E-1) as a model substrate was chosen to demonstrate the capability of this device. Classic organic triplet sensitizers as well as Ru-, Ir-,The visible-light photocatalyticE/Zisomerization of olefins can be mediated by a wide spectrum of triplet sensitizers (photocatalysts). However, the search for the most efficient photocatalysts through screenings in photo batch reactors is material and time consuming. Capillary and microchip flow reactors can accelerate this screening process. Combined with a fast analytical technique for isomer differentiation, these reactors can enable high-throughput analyses. Ion mobility (IM) spectrometry is a cost-effective technique that allows simple isomer separation and detection on the millisecond timescale. This work introduces a hyphenation method consisting of a microchip reactor and an infrared matrix-assisted laser desorption ionization (IR-MALDI) ion mobility spectrometer that has the potential for high-throughput analysis. The photocatalyzedE/Zisomerization of ethyl-3-(pyridine-3-yl)but-2-enoate (E-1) as a model substrate was chosen to demonstrate the capability of this device. Classic organic triplet sensitizers as well as Ru-, Ir-, and Cu-based complexes were tested as catalysts. The ionization efficiency of theZ-isomer is much higher at atmospheric pressure which is due to a higher proton affinity. In order to suppress proton transfer reactions by limiting the number of collisions, an IM spectrometer working at reduced pressure (max. 100 mbar) was employed. This design reduced charge transfer reactions and allowed the quantitative determination of the reaction yield in real time. Among 14 catalysts tested, four catalysts could be determined as efficient sensitizers for theE/Zisomerization of ethyl cinnamate derivativeE-1. Conversion rates of up to 80% were achieved in irradiation time sequences of 10 up to 180 s. With respect to current studies found in the literature, this reduces the acquisition times from several hours to only a few minutes per scan.…
MetadatenAuthor details: | Chris PrüfertORCiDGND, Raphael David Urban, Tillmann Georg FischerORCiD, José Andrés VillatoroORCiDGND, Daniel RiebeORCiDGND, Toralf BeitzORCiD, Detlev BelderORCiDGND, Kirsten ZeitlerORCiD, Hans-Gerd LöhmannsröbenORCiDGND |
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DOI: | https://doi.org/10.1007/s00216-020-02923-y |
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ISSN: | 1618-2642 |
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ISSN: | 1618-2650 |
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Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/32918557 |
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Title of parent work (English): | Analytical and bioanalytical chemistry : a merger of Fresenius' journal of analytical chemistry, Analusis and Quimica analitica |
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Publisher: | Springer |
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Place of publishing: | Heidelberg |
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Publication type: | Article |
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Language: | English |
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Date of first publication: | 2020/09/12 |
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Publication year: | 2020 |
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Release date: | 2023/03/22 |
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Tag: | IR-MALDI; Olefin isomerization; ion mobility spectrometry; microchip; photocatalysis; photochemistry; reaction monitoring |
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Volume: | 412 |
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Issue: | 28 |
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Number of pages: | 13 |
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First page: | 7899 |
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Last Page: | 7911 |
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Funding institution: | Projekt DEAL; Deutsche Forschungsgemeinschaft (DFG, German Research; Foundation)German Research Foundation (DFG) [275653032 (FOR 2177)] |
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Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
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DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
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Peer review: | Referiert |
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Publishing method: | Open Access / Hybrid Open-Access |
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License (German): | CC-BY - Namensnennung 4.0 International |
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