In this work, we describe the synthesis of a novel 9-aminoacridine derivative that presents surprisingly different colors when exposed to neutral, acidic or basic mediums with potential application as pH indicator in organic solvents. Furthermore, pKa and molar absorptivity values were determined and theoretical studies supported by density functional theory (DFT) calculations were performed to elucidate the different structures of this compound.Keywords: 9-aminoacridine derivative, pH indicator, organic medium Introduction 9-Aminoacridine (9-AA) is a polycyclic heteroaromatic compound with three fused rings that can be used as specific fluorescent.1,2 Its derivatives, which also have fluorescence properties and are typically colored, have a wide range of applications such as biological activity 3 against neurodegenerative diseases and protozoal parasites. 4 The anticancer effect of nitro-9-aminoacridine derivatives is reported in the literature. 5,6 The 9-AA is also described to be a suitable matrix for the matrix assisted laser desorption/ionization (MALDI) and can even be used as indicator of transmembrane pH difference.7-9 A pH indicator highlights changes in the hydrogenionic potential and can be used to determine chemical processes involving acids and bases. More complex methods of quantifying acidity require expensive instrumentation, what makes the usage of pH indicators still important.
10A relevant application of pH indicators concerns the monitoring of biochemical processes through color changes at visible wavelengths representing protonation and deprotonation of species.11 Several dyes have been used as pH indicators by the reversible action of acid and base forms.
12The pKa value is an important physicochemical parameter to predict the ionization state of a substance for the measurements of pH-dependent molecular properties (solubility and lipophilicity, for example) and in applications such as liquid chromatography and capillary electrophoresis for the separation of ionizable compounds. 13,14 There are several methods to determine pKa values, such as potentiometric titration, 15 ultravioletvisible (UV-Vis) absorption spectroscopy, 16 calorimetry, 17 nuclear magnetic resonance (NMR) spectroscopy, 18 and capillary electrophoresis.19 These are useful techniques for the determination of equilibrium constants due to its accuracy and reproducibility.In this work, it was synthesized the compound 2,4,5,7-tetranitro-9-aminoacridine (TNA), introducing four nitro groups in the aromatic rings of 9-AA (Figure 1), and the new derivative presented different colorations when exposed to neutral, acidic or basic mediums. Moreover, we performed a potentiometric titration to determine its pKa values in different mediums and we also confirmed the structures present in each medium through density functional theory (DFT) calculations.
ExperimentalMaterials 9-Aminoacridine hydrochloride monohydrate 98% (Aldrich, São Paulo, Brazil), sulfuric acid 98% (Vetec, Rio de Janeiro, Brazil), nitric acid 65% (Cromoline, São Paulo, B...