Glyphosate sensing in aqueous solutions by fluorescent zinc(<scp>ii</scp>) complexes of [9]aneN<sub>3</sub>-based receptors

Garau, Alessandra; Picci, Giacomo; Bencini, Andrea; Caltagirone, Claudia; Conti, Luca; Lippolis, Vito; Paoli, Paola; Romano, Giammarco Maria; Rossi, Patrizia; Scorciapino, Mariano Andrea

doi:10.1039/d2dt00738j

Cited by 11 publications

(8 citation statements)

References 67 publications

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“…This can be highlighted, for example, by LogK values of 6.97 and 3.54, respectively found for the addition of HPMG 2− to [Zn(H −1 L2)] + and [Zn(H −1 L1)] + . Overall, the LogK values relative to the PMG coordination emerge to be comparable or up to 2 log units higher relative to the ones reported in literature for the binding of this substrate by analogous Zn(II)-polyamine receptors [56][57][58].…”

Section: Potentiometric Measurementssupporting

confidence: 72%

A New Family of Macrocyclic Polyamino Biphenolic Ligands: Acid-Base Study, Zn(II) Coordination and Glyphosate/AMPA Binding

et al. 2023

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In this study, the ligands 23,24-dihydroxy-3,6,9,12-tetraazatricyclo[17.3.1.1(14,18)]eicosatetra-1(23),14,16,18(24),19,21-hexaene, L1, and 26,27-dihidroxy-3,6,9,12,15-pentaazatricyclo[20.3.1.1(17,21)]eicosaepta-1(26),17,19,21(27),22,24-hexaene, L2, were synthesized: they represent a new class of molecules containing a biphenol unit inserted into a macrocyclic polyamine fragment. The previously synthesized L2 is obtained herein with a more advantageous procedure. The acid-base and Zn(II)-binding properties of L1 and L2 were investigated through potentiometric, UV-Vis, and fluorescence studies, revealing their possible use as chemosensors of H+ and Zn(II). The new peculiar design of L1 and L2 afforded the formation in an aqueous solution of stable Zn(II) mono (LogK 12.14 and 12.98 for L1 and L2, respectively) and dinuclear (LogK 10.16 for L2) complexes, which can be in turn exploited as metallo-receptors for the binding of external guests, such as the popular herbicide glyphosate (N-(phosphonomethyl)glycine, PMG) and its primary metabolite, the aminomethylphosphonic acid (AMPA). Potentiometric studies revealed that PMG forms more stable complexes than AMPA with both L1- and L2-Zn(II) complexes, moreover PMG showed higher affinity for L2 than for L1. Fluorescence studies showed instead that the L1-Zn(II) complex could signal the presence of AMPA through a partial quenching of the fluorescence emission. These studies unveiled therefore the utility of polyamino-phenolic ligands in the design of promising metallo-receptors for elusive environmental targets.

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Section: Potentiometric Measurementssupporting

confidence: 72%

A New Family of Macrocyclic Polyamino Biphenolic Ligands: Acid-Base Study, Zn(II) Coordination and Glyphosate/AMPA Binding

et al. 2023

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“…How to cite this article: P. Behera, K. Jaiswal, M. De, Luminescence 2023, 38 (7), 1339. https://doi.org/10.1002/bio. 4424…”

Section: Author Contributionsmentioning

confidence: 99%

“…Moreover, water‐soluble (aminomethyl)phosphonic acid, a microbially degraded product of glyphosates, is a potential risk to water sources. [ 6,7 ] Due to their biological and environmental relevance, the detection of phosphates via benign protocols is quite significant. Several photoelectric and spectroscopic strategies have been used to detect various phosphate ions.…”

Section: Introductionmentioning

confidence: 99%

Time‐resolved fluorescence sensor array for the discrimination of phosphate anions using transition metal dichalcogenide quantum dots and Tb(III)

Behera

Jaiswal

2022

Luminescence

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Phosphate detection has garnered widespread attention due to its biological and environmental impact. Among several optical techniques, time‐resolved fluorescence (TRF) provides a sensitive way for the discrimination of analytes in a complex mixture as it exhibits less interference from the background, therefore providing a high signal‐to‐noise ratio. The sensitization of rare earth metal (REM) ions by semiconducting quantum dots (QDs) can help the former overcome the drawback of low absorption coefficient, therefore allowing exploitation of the additional advantage of the REM, namely the long‐excited state lifetime. Here, we have developed a TRF‐based sensor array consisting of three QDs, i.e. MoS2, WS2 and MoSe2 as energy sensitizers for Tb3+ ions. Different QDs possess variable energy transfer abilities for Tb3+ ions. Therefore, they can be used to discriminate phosphates. It was also observed that CrO42− can competitively bind to Tb3+ and further enhance the efficiency of the sensor array so that it could discriminate six different phosphates at 200 μM concentration in aqueous as well as serum medium with a detection limit of 10 μM in aqueous medium. Therefore, the sensitivity of the TRF‐based sensor array is rarely compromised in a complex mixture, which is advantageous over a fluorescence‐based sensor array.

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“…NMR titrations are commonly performed to characterize chemical equilibria 1–7 . To save chemicals, the titration is performed by adding small aliquots of the titrating agent into the NMR tube containing the analyte solution.…”

Section: Introductionmentioning

confidence: 99%

“…NMR titrations are commonly performed to characterize chemical equilibria. [1][2][3][4][5][6][7] To save chemicals, the titration is performed by adding small aliquots of the titrating agent into the NMR tube containing the analyte solution. The insertion of the glass electrode in the NMR tube at each addition would progressively alter the total volume making the titration largely inaccurate.…”

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The combination of inorganic phosphate and pyrophosphate ³¹P‐NMR for the electrodeless pH determination in the 5–12 range

Carta,

Scorciapino

2024

Magnetic Reson in Chemistry

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Potentiometry is the primary pH measurement method, but alternatives are sought beyond glass electrodes operative limitations. In nuclear magnetic resonance (NMR) experiments, electrodeless pH sensing is important to track changes along titrations, during chemical reactions or inside compartmentalized environments inaccessible to electrodes, for instance. Although several interesting NMR pH indicators have been already presented, the potential of inorganic phosphate is overlooked, despite its common presence in NMR samples as the buffer main component. Its use for electrodeless pH determination can be expanded by exploiting all its three proton dissociations. This study was aimed at verifying the use of inorganic phosphate 31P chemical shift to sense pH variations, and at exploring the complementary use of pyrophosphate ions to cover a wide pH range. A simple set of equations is presented to utilize both phosphate and pyrophosphate 31P chemical shift in combination for accurate pH determination without a glass electrode over the 5–12 pH range, and without affecting the spectrum of other nuclei. The present study demonstrated an average deviation of 0.09 (maximum <0.2) pH unit from glass electrode measurements. The trimethylphosphate can be used as a suitable chemical shift reference for both 31P and 1H (also 13C), with its hydrolysis being significant only at pH > 12. The method was also demonstrated by determining the pKa of three distinct molecules in a mixture and by comparing the results to those obtained when the glass electrode was used to measure the pH. The approach shown here can be easily tuned to different experimental conditions.

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Glyphosate sensing in aqueous solutions by fluorescent zinc(ii) complexes of [9]aneN₃-based receptors

Abstract: Herein we describe the binding abilities of Zn(II) complexes of [12]aneN4- (L1) and [9]aneN3-based receptors (L2, L3) towards the herbicides N-(phosphonomethyl)glycine (glyphosate, H3PMG) and 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid (glufosinate, H2GLU), and also...

Cited by 11 publications

References 67 publications

A New Family of Macrocyclic Polyamino Biphenolic Ligands: Acid-Base Study, Zn(II) Coordination and Glyphosate/AMPA Binding

A New Family of Macrocyclic Polyamino Biphenolic Ligands: Acid-Base Study, Zn(II) Coordination and Glyphosate/AMPA Binding

Time‐resolved fluorescence sensor array for the discrimination of phosphate anions using transition metal dichalcogenide quantum dots and Tb(III)

The combination of inorganic phosphate and pyrophosphate ³¹P‐NMR for the electrodeless pH determination in the 5–12 range

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Glyphosate sensing in aqueous solutions by fluorescent zinc(ii) complexes of [9]aneN3-based receptors

Abstract: Herein we describe the binding abilities of Zn(II) complexes of [12]aneN4- (L1) and [9]aneN3-based receptors (L2, L3) towards the herbicides N-(phosphonomethyl)glycine (glyphosate, H3PMG) and 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid (glufosinate, H2GLU), and also...

Cited by 11 publications

References 67 publications

A New Family of Macrocyclic Polyamino Biphenolic Ligands: Acid-Base Study, Zn(II) Coordination and Glyphosate/AMPA Binding

A New Family of Macrocyclic Polyamino Biphenolic Ligands: Acid-Base Study, Zn(II) Coordination and Glyphosate/AMPA Binding

Time‐resolved fluorescence sensor array for the discrimination of phosphate anions using transition metal dichalcogenide quantum dots and Tb(III)

The combination of inorganic phosphate and pyrophosphate 31P‐NMR for the electrodeless pH determination in the 5–12 range

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Glyphosate sensing in aqueous solutions by fluorescent zinc(ii) complexes of [9]aneN₃-based receptors

The combination of inorganic phosphate and pyrophosphate ³¹P‐NMR for the electrodeless pH determination in the 5–12 range