Abstract
The synthesis and sensing properties of a new fluorescent probe designed to have a 4-amino-1,8-naphthalimide fluorescent platform functionalized with a 3-hydroxy-4-pyridinone bidentate chelating unit at the 4-position and a terminal aliphatic dimethylamino group at the imide site, are reported. The absorption and fluorescence properties of the ligand were investigated in DMSO and in aqueous solution at variable pH and in the presence of increasing concentration of Fe3+, Cu2+ and Zn2+. Analysis of the UV-Vis spectra at variable pH allowed the determination of three pK(a) values (PKa1 = 3.19, pK(a2) = 8.38, pK(a3) = 9.95) and establishment of the corresponding speciation diagram. Fluorescence spectra obtained in the same conditions show that the fluorescence intensity of the probe decreases with increasing pH and are off above pH 9 as a result of photo-induced electron transfer arising from the aliphatic dimethylamino group. Under physiological pH conditions, the probe shows an absorption band centred at 439 nm and emits in the green at lambda = 536 nm. Analysis of UV-Vis and EPR spectra of the ligand in the presence of Fe3+ and Cu2+ is consistent with the formation of the corresponding metal ion complexes. The fluorescence intensity of the ligand is quenched in the presence of variable concentrations of Fe3+, Cu2+ and Zn2+ and under physiological pH conditions the fluorescence of the probe is ca 92%, 88% and 91% quenched in the presence of Fe3+, Cu2+ and Zn2+ respectively.

Abstract
A previously reported fluorescein-based dye containing a catechol unit showed high sensitivity to Fe(III) at physiological pH, but also undesirable pH sensitivity, mainly due to the lower pK(a) values of the phenolic hydroxyl groups of the fluorescein core. Aiming to synthesize compounds that interact with metal ions at physiological pH, exhibiting no pH sensitivity, we designed two novel fluorescent compounds by assembling, through amide linkage, a rhodamine fluorophore with two selected chelating moieties, catechol and 3-hydroxy-4-pyridinone, both possessing high affinity for Fe(III) but distinct pK(a) values. The fluorescent compounds were prepared using straightforward synthetic protocols and characterized by NMR, mass spectrometry and electronic spectroscopy (UV-Vis and fluorescence) and one of the compounds was also characterized by single crystal X-ray diffraction. The results reveal that, while the fluorescent 3-hydroxy-4-pyridinone derivative exhibits a significant dependence of fluorescence emission with increasing pH, due to the pK(a) values arising from the 3-hydroxy-4-pyridinone residue, the fluorescent catechol ligand responds mainly to interactions with metal ions, preferentially to Fe(III), showing less sensitivity to pH than the related ligands over the pH range 3-8, fact that is relevant concerning the application of this compound as an ion sensor in biological media.

Abstract
Microbial resistance to antibiotics is one of the biggest public health threats of the modem world. Antibiotic resistance is an area of much clinical relevance and therefore research that has the potential to identify agents that may circumvent it or treat resistant infections is paramount. Solution behavior of various fluoroquinolone (FQ) complexes with copper(II) in the presence and absence of 1,10-phenanthroline (phen) was studied in aqueous solution, by potentiometry and/or spectrophotometiy, and are herein described. The results obtained showed that under physiological conditions (micromolar concentration range and pH 7.4) only copper(II):FQ:phen ternary complexes are stable. Hence, these complexes were synthesised and characterised by means of UV-visible and IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. In these complexes, the FQ acts as a bidentate ligand that coordinates the metal cation through the carbonyl and carboxyl oxygen atoms and phen coordinates through two N-atoms forming the equatorial plane of a distorted square-pyramidal geometry. The fifth position of the penta-coordinated Cu(II) centre is generally occupied axially by an oxygen atom from a water molecule or from a nitrate ion. Minimum inhibitory concentration (MIC) determinations of the complexes and comparison with free FQ in various E. coil strains indicate that the Cu-complexes are as efficient antimicrobials as the free antibiotic. Moreover, results strongly suggest that the cell intake route of both species is different supporting, therefore, the complexes' suitability as candidates for further biological testing in FQ-resistant microorganisms.