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Rational design and evaluation of the sensing mechanism of a europium(III)-based luminescent turn-ON chemosensor for citrate.

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Title: Rational design and evaluation of the sensing mechanism of a europium(III)-based luminescent turn-ON chemosensor for citrate.
Authors: Shaw, Ashwini Kumari1 (AUTHOR), Shukla, Nitin1 (AUTHOR), Patra, Ashis K.1 (AUTHOR) akpatra@iitk.ac.in
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 4/28/2026, Vol. 55 Issue 16, p6545-6557. 13p.
Subjects: Luminescent probes, Time-resolved spectroscopy, Ligands (Chemistry), Biomarkers, Chemical detectors
Abstract: Citrate plays a multifaceted and crucial role as a key intermediate in the Krebs cycle (citric acid cycle or TCA cycle), the central metabolic pathway for energy production or a source of ATP in aerobic organisms. Besides a metabolic regulator, dysregulation of citrate levels is intricately linked to the pathology of multiple diseases, including metabolism in cancer cells. Abnormal citrate concentrations have been associated with kidney stones, inflammation, metabolic disorders, cancers, non-alcoholic fatty liver diseases, neurological disorders, etc., highlighting its diagnostic and prognostic value. Therefore, the selective recognition and monitoring of changes in the citrate levels in physiological conditions is useful for advancing our understanding of these diseases, enabling early diagnosis and guiding effective therapeutic strategies. Developing a selective receptor for citrate is challenging due to its structural resemblance to competing biological anions (PO43−, NO3−, tartrate, HCO3−, etc.) and its lower levels than other common anions in biological media. The uniquely attractive optical properties of luminescent Ln(III) probes, narrow emission bands, photobleaching resistance, photostability, especially the long luminescence lifetime, and the hard oxophilic nature of tripositive Ln(III) ions make them ideal for time-gated luminescence measurements for trinegative hard [citrate]3− ions with an enhanced S/N ratio and minimized scattering and autofluorescence from the media. We report here the rationale and fundamental design principles for an emissive Eu(III) probe, [Eu(EDTA3AQ)(H2O)3]Cl (Eu.1), containing EDTA3AQ2− as an EDTA-bisamide framework linked to two 3-aminoquinolines as antennae for the selective sensing of [citrate]3− as an important regulatory metabolite at physiological pH using highly sensitive and selective time-resolved luminescence (TRL) from Eu.1. The facile displacement of three labile inner-sphere H2O molecules and coordinative unsaturation at the Eu(III) centre in Eu.1 satisfying the steric demand for preferential 1 : 1 binding of [citrate]3− at Eu(III) are found to be important design criteria, which were comprehensively studied using various solution-based spectroscopic studies and DFT. The [ EuL -citrate] complexation, solution speciation, effects of variation of the coordination number of Eu(III), and the change in hydration numbers (q) were studied and validated to gain an insightful correlation of the rationale of Eu.1 probe design based on the luminescence sensing mechanism of Eu.1 for citrate. The strong electrostatic binding of [citrate]3−via displacing H2O molecules in the 1st-sphere in Eu.1 suppresses the nonradiative vibrational energy transfer (VET), resulting in enhanced TRL from the f–f transitions, and thus acts as a reversible, selective and sensitive turn-ON sensor at the ppb level of citrate using both the TRL intensity and lifetime-based modalities. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Rational design and evaluation of the sensing mechanism of a europium(III)-based luminescent turn-ON chemosensor for citrate.
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  Data: Citrate plays a multifaceted and crucial role as a key intermediate in the Krebs cycle (citric acid cycle or TCA cycle), the central metabolic pathway for energy production or a source of ATP in aerobic organisms. Besides a metabolic regulator, dysregulation of citrate levels is intricately linked to the pathology of multiple diseases, including metabolism in cancer cells. Abnormal citrate concentrations have been associated with kidney stones, inflammation, metabolic disorders, cancers, non-alcoholic fatty liver diseases, neurological disorders, etc., highlighting its diagnostic and prognostic value. Therefore, the selective recognition and monitoring of changes in the citrate levels in physiological conditions is useful for advancing our understanding of these diseases, enabling early diagnosis and guiding effective therapeutic strategies. Developing a selective receptor for citrate is challenging due to its structural resemblance to competing biological anions (PO43−, NO3−, tartrate, HCO3−, etc.) and its lower levels than other common anions in biological media. The uniquely attractive optical properties of luminescent Ln(III) probes, narrow emission bands, photobleaching resistance, photostability, especially the long luminescence lifetime, and the hard oxophilic nature of tripositive Ln(III) ions make them ideal for time-gated luminescence measurements for trinegative hard [citrate]3− ions with an enhanced S/N ratio and minimized scattering and autofluorescence from the media. We report here the rationale and fundamental design principles for an emissive Eu(III) probe, [Eu(EDTA3AQ)(H2O)3]Cl (Eu.1), containing EDTA3AQ2− as an EDTA-bisamide framework linked to two 3-aminoquinolines as antennae for the selective sensing of [citrate]3− as an important regulatory metabolite at physiological pH using highly sensitive and selective time-resolved luminescence (TRL) from Eu.1. The facile displacement of three labile inner-sphere H2O molecules and coordinative unsaturation at the Eu(III) centre in Eu.1 satisfying the steric demand for preferential 1 : 1 binding of [citrate]3− at Eu(III) are found to be important design criteria, which were comprehensively studied using various solution-based spectroscopic studies and DFT. The [ EuL -citrate] complexation, solution speciation, effects of variation of the coordination number of Eu(III), and the change in hydration numbers (q) were studied and validated to gain an insightful correlation of the rationale of Eu.1 probe design based on the luminescence sensing mechanism of Eu.1 for citrate. The strong electrostatic binding of [citrate]3−via displacing H2O molecules in the 1st-sphere in Eu.1 suppresses the nonradiative vibrational energy transfer (VET), resulting in enhanced TRL from the f–f transitions, and thus acts as a reversible, selective and sensitive turn-ON sensor at the ppb level of citrate using both the TRL intensity and lifetime-based modalities. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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      – Type: doi
        Value: 10.1039/d5dt02901e
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      – Code: eng
        Text: English
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        PageCount: 13
        StartPage: 6545
    Subjects:
      – SubjectFull: Luminescent probes
        Type: general
      – SubjectFull: Time-resolved spectroscopy
        Type: general
      – SubjectFull: Ligands (Chemistry)
        Type: general
      – SubjectFull: Biomarkers
        Type: general
      – SubjectFull: Chemical detectors
        Type: general
    Titles:
      – TitleFull: Rational design and evaluation of the sensing mechanism of a europium(III)-based luminescent turn-ON chemosensor for citrate.
        Type: main
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            NameFull: Shaw, Ashwini Kumari
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            NameFull: Shukla, Nitin
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            NameFull: Patra, Ashis K.
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            – D: 28
              M: 04
              Text: 4/28/2026
              Type: published
              Y: 2026
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              Value: 55
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            – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry
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