This work reports on two thiourea-based receptors with pyridine and amine units including 1-naphthyl (MT1N) and 4-nytrophenyl (MT4N) as signaling units. For both compounds, their affinity and signaling ability toward various anions of different geometry and basicity in DMSO were studied using UV-vis, fluorescence, and 1H NMR techniques. Anion recognition studies revealed that both MT1N and MT4N have, in general, high affinities toward basic anions. In this regard, a higher acidity of the MT4N receptor was demonstrated. Furthermore, MT4N has a higher affinity for fluoride (log K1 = 5.98) than for the other anions and can effectively detect it through colorimetric changes that can be monitored by the UV-vis technique. The interaction between receptors and anions mainly involves the hydrogens of the amino and thiourea groups of the former. Complementary single-crystal X-ray diffraction studies and molecular modeling at the DFT level were also performed.
Two bis-urea type receptors were synthesized containing a polyether bridge and two 4-nitrophenyl groups as chromogenic units, R1 and R2. Molecular recognition studies of receptors towards different tetraalkylammonium and alkali metal salts were carried out in DMSO by UV-Vis and 1H-NMR spectroscopy. The receptors were found to have high affinity for diverse anions and ion-pairs, showing the highest affinities towards the tetramethylammonium and sodium salts. The cation binding ability of the receptors was evidenced by means 1H NMR, mass spectrometric ESI+ studies and the crystal structures of some precursors. Additionally, the molecular modelling at the DFT level of the tetramethylammonium acetate complexes illustrates the potential ion-pair binding ability of the receptors: the anion is recognized through strong hydrogen bonds from the NH─ groups from the two urea sites, while the cation is bound by a combination of cation─π, C-H···O and C-H···π interactions.
In this work, nanoclusters (NCs) of Cu and Ag capped with hyperbranched polyethyleneimine (PEI) were prepared using chemical reduction by a one-step hydrothermal method. The PEI coated-NCs were characterized by high-resolution transmission electron microscopy, ζ potential, thermogravimetric analysis, dynamic light scattering, Fourier-transform infrared, UV-visible, and fluorescence spectroscopy. The PEI-NCs exhibited strong absorption and fluorescence, high stability, and excellent water dispersibility. The resulting PEI-NCs showed a reversible and linear response of fluorescence intensity with pH over a wide range (3–11); however, PEI-AgNCs showed a better reversibility and sensitivity than PEI-CuNCs. Unlike several types of pH sensors based on modified NCs, which are based on a nanoparticle aggregation/disaggregation mechanism, the response of our sensor is based on a photoinduced electron transfer process, which gives it a high reversibility. This method was successfully applied in pH measurements in tap water and green tea samples, with excellent results, indicating its practical utility for these applications. A visual device was obtained by immobilizing PEI-AgNCs into agarose hydrogels at different pH values. The results show that the proposed sensor can be used as a pH visual detector. Besides, the light emission of the nanosensor was corroborated by fluorescence microscopy, confirming that the nanosensor based on PEI-AgNCs has great potential to be used in cellular imaging.