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Selective binding and optical sensing of Zn(II) and Cd(II) by L1, HL2, L3, H2L4 and H2L5 receptors were analysed in aqueous solutions by coupling potentiometric, UV-vis absorption and fluorescence emission measurements, with the aim to determine the effect of complex stability on selective signalling of metals with similar electronic configurations. All receptors share the same cyclic tetra-amine binding unit attached to a single quinoline (Q) or 8-hydroxyquinoline (8-OHQ) unit (L1 and HL2, respectively), two Q or 8-OHQ moieties (L3 and H2L4, respectively), and, finally, two Q and two acetate groups (H2L5). The crystal structures of the Cd(II) and Zn(II) complexes show that L3 and H2L4 feature a cavity in which the larger Cd(II) complex is better fitted than the Zn(II) complex, leading to the formation of more stable Cd(II) complexes. In turn, Zn(II) forms more stable complexes with L1 and HL2, owing to its high tendency to give 5-coordinated complexes. Considering optical selectivity, Zn(II) gives the most emissive complex with L3, while the corresponding Cd(II) complex is basically quenched. The gathered structure of the Zn(II) complex, in which the two Q units are associated with one another—a structural motif not observed in the [CdL3]2+ complex—leads to poor solvation of the Q units, favouring complex emission. Among 8-OHQ-containing receptors, the most emissive complex is formed by Cd(II) with HL2, containing a single 8-OHQ moiety. H2L4 forms non-emissive complexes: the presence of two coordinating 8-OHQ moieties weakens metal interactions with the tetra-amine unit, favouring PET to the excited fluorophore that quench the emission. [ABSTRACT FROM AUTHOR]

The globally widespread perfluorooctanoic acid (PFOA) is a concerning environmental contaminant, with a possible toxic long-term effects on the environment and human health The development of sensible, rapid, and low-cost detection systems is a current change in modern environmental chemistry. In this context, two triamine-based chemosensors, L1 and L2, containing a fluorescent pyrene unit, and their Zn(II) complexes are proposed as fluorescent probes for the detection of PFOA in aqueous media. Binding studies carried out by means of fluorescence and NMR titrations highlight that protonated forms of the receptors can interact with the carboxylate group of PFOA, thanks to salt bridge formation with the ammonium groups of the aliphatic chain. This interaction induces a decrease in the fluorescence emission of pyrene at neutral and slightly acidic pH values. Similarly, emission quenching has also been observed upon coordination of PFOA by the Zn(II) complexes of the receptors. These results evidence that simple polyamine-based molecular receptors can be employed for the optical recognition of harmful pollutant molecules, such as PFOA, in aqueous media.

The synthesis of a new RuII complex, in which the metal is coordinated by two 1,10-phenanthroline ligands and a 2,2′-bipyridyl unit linked, via methylene bridges in its 4 and 4′ positions, to two 1,4,7,10-tetraazacyclododecane (cyclen) macrocycles ([Ru(phen)2L]2+) is reported. Protonation and ZnII binding by [Ru(phen)2L]2+ have been analyzed by potentiometric titration, evidencing the formation of mixed hetero-binuclear and hetero-trinuclear ZnII/RuII complexes. These complexes were tested as bis-phenol A (BPA) binders. Only the dizinc complex with [Ru(phen)2L]2+ is able to bind BPA in aqueous solution, affording a remarkably stable {Zn2[Ru(phen)2L]BPA(H−2)}4+ adduct at neutral pH, in which BPA is bound in its doubly deprotonated form to the two ZnII ions. BPA binding was found to quench the luminescence emission of the RuII(phen)2bipy core. Although the quenching effect is modest, this study demonstrates that appropriately designed dizinc complexes can be used for binding and optical sensing of BPA in water.

Correction for 'Selective binding and fluorescence sensing of Zn(II)/Cd(II) using macrocyclic tetra-amines with different fluorophores: insights into the design of selective chemosensors for transition metals' by Giammarco Maria Romano et al., Dalton Trans., 2025, https://doi.org/10.1039/d4dt02415j. [ABSTRACT FROM AUTHOR]

Triamine receptors containing anthracene units are able to bind and sense ketoprofen via fluorescence enhancement in a H2O/EtOH 50 : 50 (Vol : Vol) mixture exploiting their protonation features, which are tuned by the interaction with the analyte. [ABSTRACT FROM AUTHOR]

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 aminomethylphosphonic acid (H2AMPA), the main metabolite of H3PMG, and phosphate. All ligands form stable Zn(II) complexes, whose coordination geometries allow a possible interaction of the metal center with exogenous anionic substrates. Potentiometric studies evidenced the marked coordination ability of the L2/Zn(II) system for the analytes considered, with a preferential binding affinity for H3PMG over the other substrates, in a wide range of pH values. 1H and 31P NMR experiments supported the effective coordination of such substrates by the Zn(II) complex of L2, while fluorescence titrations and a test strip experiment were performed to evaluate whether the H3PMG recognition processes could be detected by fluorescence signaling. [ABSTRACT FROM AUTHOR]

The synthesis of a new RuII complex, in which the metal is coordinated by two 1,10-phenanthroline ligands and a 2,2′-bipyridyl unit linked, via methylene bridges in its 4 and 4′ positions, to two 1,4,7,10-tetraazacyclododecane (cyclen) macrocycles ([Ru(phen)2L]2+) is reported. Protonation and ZnII binding by [Ru(phen)2L]2+ have been analyzed by potentiometric titration, evidencing the formation of mixed hetero-binuclear and hetero-trinuclear ZnII/RuII complexes. These complexes were tested as bis-phenol A (BPA) binders. Only the dizinc complex with [Ru(phen)2L]2+ is able to bind BPA in aqueous solution, affording a remarkably stable {Zn2[Ru(phen)2L]BPA(H−2)}4+ adduct at neutral pH, in which BPA is bound in its doubly deprotonated form to the two ZnII ions. BPA binding was found to quench the luminescence emission of the RuII(phen)2bipy core. Although the quenching effect is modest, this study demonstrates that appropriately designed dizinc complexes can be used for binding and optical sensing of BPA in water. [ABSTRACT FROM AUTHOR]

Herein, we report on a polyamine receptor L1 bearing pyrene fluorogenic groups for the optical assessment of the non-opioid analgesic drug ketoprofen (KP). L1, composed of a diethylenetriamine moiety linked at its extremities to the 1 position of two pyrene units via methylene linkers, produced an emission at 460 nm in 1 : 1 (v/v) water/ethanol mixture at pH 7, which can be attributed to the excimer formation between the two aromatic groups. In the presence of KP, a salt-bridging interaction between the carboxylate group of the analyte and the central ammonium group of L1 induced a redistribution of acidic protons in the polyamine chain, causing a marked increase in the emission. This optical signal was used to detect KP in aqueous media. Based on this observation, the properties of all-solid-state optodes with plasticized PVC membranes doped with L1 and deposited on an appropriate solid support material were further investigated. The best membrane contained 1 wt% of fully protonated L1, plasticized with DOS and doped with 3 equiv. of the TDMACl anion-exchanger, which detected KP in the 2 μM-0.1 mM range with a low influence of interfering ions. Furthermore, this membrane was applied for the assessment of the amount of KP in OkiTask, achieving an RSD of 2.1% and recovery of 102%. Moreover, the possibility to decrease the LOD of KP to 0.84 μM (0.21 mg L -1 ) through the application of L1-based fluorescent sensor arrays and chemometrics was studied.