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1.
  • Gil, R. L., et al. (author)
  • Addressing the Detection of Ammonium Ion in Environmental Water Samples via Tandem Potentiometry-Ion Chromatography
  • 2022
  • In: ACS Measurement Science Au. - : American Chemical Society (ACS). - 2694-250X. ; 2:3, s. 199-207
  • Journal article (peer-reviewed)abstract
    • An analytical methodology for detecting ammonium ion (NH4+) in environmental water through potentiometry-ion chromatography (IC) in tandem is presented here. A multielectrode flow cell is implemented as a potentiometric detector after chromatographic separation of cations in the sample. The electrodes are fabricated via miniaturized all-solid-state configuration, using a nonactin-based plasticized polymeric membrane as the sensing element. The overall analytical setup is based on an injection valve, column, traditional conductometric detector, and new potentiometric detector (in that order), permitting the characterization of the analytical performance of the potentiometric detector while validating the results. The limit of detection was found to be ca. 3 × 10-7 M NH4+ concentration after linearization of the potentiometric response, and intra- and interelectrode variations of <10% were observed. Importantly, interference from other cations was suppressed in the tandem potentiometry-IC, and thus, the NH4+ content in fresh- and seawater samples from different locations was successfully analyzed. This analytical technology demonstrated a great potential for the reliable monitoring of NH4+ at micromolar levels, in contrast to the conductivity detector and previously reported NH4+ potentiometric sensors functioning in batch mode or even coupled with IC. Additionally, the suitability of the potentiometric cell for selective multi-ion analysis in the same sample, i.e., Na+, NH4+, and K+ in water, has been proven.
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2.
  • Pachulicz, River J., et al. (author)
  • Structural Analysis and Identity Confirmation of Anthocyanins in Brassica oleracea Extracts by Direct Injection Ion Mobility-Mass Spectrometry
  • 2023
  • In: ACS Measurement Science Au. - : American Chemical Society (ACS). - 2694-250X. ; 3:3, s. 200-207
  • Journal article (peer-reviewed)abstract
    • Anthocyanins are a subclass of plant-derived flavonoids that demonstrate immense structural heterogeneity which is challenging to capture in complex extracts by traditional liquid chromatography-mass spectrometry (MS)-based approaches. Here, we investigate direct injection ion mobility-MS as a rapid analytical tool to characterize anthocyanin structural features in red cabbage (Brassica oleracea) extracts. Within a 1.5 min sample run time, we observe localization of structurally similar anthocyanins and their isobars into discrete drift time regions based upon their degree of chemical modifications. Furthermore, drift time-aligned fragmentation enables simultaneous collection of MS, MS/MS, and collisional cross-section data for individual anthocyanin species down to a low picomole scale to generate structural identifiers for rapid identity confirmation. We finally identify anthocyanins in three other Brassica oleracea extracts based on red cabbage anthocyanin identifiers to demonstrate our high-throughput approach. Direct injection ion mobility-MS therefore provides wholistic structural information on structurally similar, and even isobaric, anthocyanins in complex plant extracts, which can inform the nutritional value of a plant and bolster drug discovery pipelines.
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3.
  • Zheng, Ying-Ning, et al. (author)
  • Dynamic Visualization and Quantification of Single Vesicle Opening and Content by Coupling Vesicle Impact Electrochemical Cytometry with Confocal Microscopy.
  • 2021
  • In: ACS measurement science Au. - : American Chemical Society (ACS). - 2694-250X. ; 1:3, s. 131-138
  • Journal article (peer-reviewed)abstract
    • In this work, we introduce a novel method for visualization and quantitative measurement of the vesicle opening process by correlation of vesicle impact electrochemical cytometry (VIEC) with confocal microscopy. We have used a fluorophore conjugated to lipids to label the vesicle membrane and manipulate the membrane properties, which appears to make the membrane more susceptible to electroporation. The neurotransmitters inside the vesicles were visualized by use of a fluorescence false neurotransmitter 511 (FFN 511) through accumulation inside the vesicle via the neuronal vesicular monoamine transporter 2 (VMAT 2). Optical and electrochemical measurements of single vesicle electroporation were carried out using an in-house, disk-shaped, gold-modified ITO (Au/ITO) microelectrode device (5 nm thick, 33 μm diameter), which simultaneously acted as an electrode surface for VIEC and an optically transparent surface for confocal microscopy. As a result, the processes of adsorption, electroporation, and opening of single vesicles followed by neurotransmitter release on the Au/ITO surface have been simultaneously visualized and measured. Three opening patterns of single isolated vesicles were frequently observed. Comparing the vesicle opening patterns with their corresponding VIEC spikes, we propose that the behavior of the vesicular membrane on the electrode surface, including the adsorption time, residence time before vesicle opening, and the retention time after vesicle opening, are closely related to the vesicle content and size. Large vesicles with high content tend to adsorb to the electrode faster with higher frequency, followed by a shorter residence time before releasing their content, and their membrane remains on the electrode surface longer compared to the small vesicles with low content. With this approach, we start to unravel the vesicle opening process and to examine the fundamentals of exocytosis, supporting the proposed mechanism of partial or subquantal release in exocytosis.
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