Electrochemical Sensors Containing Schiff Bases and their Transition Metal Complexes to Detect Analytes of Forensic, Pharmaceutical and Environmental Interest. A Review.

Schiff bases and their transition metal complexes are inexpensive and easy to synthesize. These compounds display several structural and electronic features that allow their application in numerous research fields. Over the last three decades, electroanalytical scientists of various areas have developed electrochemical sensors from many compounds. The present review discusses the applicability of Schiff bases, their transition metal complexes and new materials containing these compounds as electrode modifiers in sensors to detect analytes of forensic, pharmaceutical and environmental interest. In forensic sciences, Schiff bases are mainly used to analyze illicit drugs: chemical reactions involving Schiff bases can help to elucidate illicit drug production and to determine analytes in seized samples. In the environmental area, given that most methodologies provide Limit of Detection (LOD) values below the values recommended by regulatory agencies, Schiff bases constitute a promising strategy. As for pharmaceutical applications, Schiff bases represent an approach for analysis of complex biological samples containing low levels of the target analytes in the presence of a large quantity of interfering compounds. This review will show that new highly specific materials can be synthesized based on Schiff bases and applied in the pharmaceutical industry, toxicological studies, electrocatalysis and biosensors. Most literature papers have reported on Schiff bases combined with carbon paste to give a chemically modified electrode that is easy and inexpensive to produce and which displays specific and selective sensing capacity for different applications.

Synthesis, Characterization and Biological Activities of Biopolymeric Schiff Bases Prepared with Chitosan and Salicylaldehydes and Their Pd(II) and Pt(II) Complexes.

In an attempt to enhance chitosan biological activities, biopolymeric Schiff bases of chitosan and different salicylaldehydes and their palladium(II) and platinum(II) complexes were synthesized and tested. The chemical structures of these derivatives were characterized using ¹H-NMR, FTIR spectroscopy and XPRD. Thermal analysis was done through TGA/DTG-DTA. Electronic absorption spectra and surface morphologies were analyzed by SEM-EDAX. Chitosan and its derivatives were evaluated for their in vitro antimicrobial activity against two common bacterial and fungal plant pathogens Pseudomonas syringae pv. tomato and Fusarium graminearum, respectively, and for their antitumor activity against a human breast cancer cell line (MCF-7). It was found that, compared to the nonmodified chitosan, chitosan modified with Schiff bases and their complexes was highly toxic against the MCF-7 cell line and had antibacterial effects against P. syringea. However, the modified chitosan derivatives had less pronounced antifungal effects against F. graminearum compared to the nonmodified chitosan, suggesting different modes of action.

Synthesis, characterization and biological activity of Cu(II), Ni(II) and Zn(II) complexes of biopolymeric Schiff bases of salicylaldehydes and chitosan.

Schiff bases have been prepared from biopolymer chitosan and salicylaldehyde, 5-methoxysalicylaldehyde, and 5-nitrosalicylaldehyde. Ligands were synthesized in a 1:1.5mol ratio, and their Cu(II), Ni(II) and Zn(II) complexes in a 1:1mol ratio (ligand:metal). Ligands were characterized by 1H NMR and FTIR, resulting in degrees of substitution from 43.7 to 78.7%. Complexes were characterized using FTIR, electronic spectra, XPRD. The compounds were confirmed by the presence of an imine bond stretching in the 1630-1640cm-1 and νMetal-N and νMetal-O at <600cm-1. Electronic spectra revealed that both Cu(II) and Ni(II) complexes present a square plane geometry. The crystallinity values were investigated by X-ray powder diffraction. Thermal behavior of all compounds was evaluated by TGA/DTG and DTA curves with mass losses related to dehydration and decomposition, with characteristic events for ligand and complexes. Schiff base complexes presented lower thermal stability and crystallinity than the starting chitosan. Residues were the metallic oxides as confirmed by XPRD, whose amounts were used in the calculation of the percentage of complexed metal ions. Surface morphologies were analyzed with SEM-EDAX. Preliminary cytotoxicity tests were performed using MTT assay with HeLa cells. Despite the differences in solubility, the free bases presented relatively low toxicity.

Voltammetric determination of cocaine in confiscated samples using a carbon paste electrode modified with different [UO2(X-MeOsalen)(H2O)] · H2O complexes.

A fast and non-destructive voltammetric method to detect cocaine in confiscated samples based on carbon paste electrode modified with methoxy-substituted N,N'-ethylene-bis(salcylideneiminato)uranyl(VI)complexes, [UO2(X-MeOSalen)(H2O)] · H2O, where X corresponds to the positions 3, 4 or 5 of the methoxy group on the aromatic ring, is described. The electrochemical behavior of the modified electrode and the electrochemical detection of cocaine were investigated using cyclic voltammetry. Using 0.1 mol · L(-1) KCl as supporting-electrolyte, a concentration-dependent, well-defined peak current for cocaine at 0.62 V, with an amperometric sensitivity of 6.25 × 104 µA · mol · L(-1) for cocaine concentrations ranging between 1.0 × 10(-7) and 1.3 × 10(-6) mol · L-1 was obtained. Chemical interference studies using lidocaine and procaine were performed. The position of the methoxy group affects the results, with the 3-methoxy derivative being the most sensitive.