Electrochemical Sensor Based on Iron(II) Phthalocyanine and Gold Nanoparticles for Nitrite Detection in Meat Products.

Nitrites are widely used in the food industry, particularly for the preservation of meat products. Controlling the nitrate content in food is an important task to ensure people's health is not at risk; therefore, the search for, and research of, new materials that will modify the electrodes in the electrochemical sensors that detect and control the nitrate content in food products is an urgent task. In this paper, we describe the electrochemical behavior of a glass carbon electrode (GCE), modified with a Fe(II) tetra-tert-butyl phthalocyanine film (FePc(tBu)4/GCE), and decorated with gold nanoparticles (Au/FePc(tBu)4/GCE); this electrode was deposited using gas-phase methods. The composition and morphology of such electrodes were examined using spectroscopy and electron microscopy methods, whereas the main electrochemical characteristics were determined using cyclic voltammetry (CV) and amperometry (CA) methods in the linear ranges of CV 0.25-2.5 mM, CA 2-120 µM in 0.1 M phosphate buffer (pH = 6.8). The results showed that the modification of bare GCEs, with a Au/FePc(tBu)4 heterostructure, provided a high surface-to-volume ratio, thus ensuring its high sensitivity to nitrite ions of 0.46 µAµM-1. The sensor based on the Au/FePc(tBu)4/GCE has a low limit of nitrite detection at 0.35 µM, good repeatability, and stability. The interference study showed that the proposed Au/FePc(tBu)4/GCE exhibited a selective response in the presence of interfering anions, and the analytical capability of the sensor was demonstrated by determining nitrite ions in real samples of meat products.

Heterostructures Based on Cobalt Phthalocyanine Films Decorated with Gold Nanoparticles for the Detection of Low Concentrations of Ammonia and Nitric Oxide.

This work is aimed at the development of new heterostructures based on cobalt phthalocyanines (CoPc) and gold nanoparticles (AuNPs), and the evaluation of the prospects of their use to determine low concentrations of ammonia and nitric oxide. For this purpose, CoPc films were decorated with AuNPs by gas-phase methods (MOCVD and PVD) and drop-casting (DC), and their chemiresistive sensor response to low concentrations of NO (10-50 ppb) and NH3 (1-10 ppm) was investigated. A comparative analysis of the characteristics of heterostructures depending on the preparation methods was carried out. The composition, structure, and morphology of the resulting hybrid films were studied by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission (ICP-AES) spectroscopy, as well as electron microscopy methods to discuss the effect of these parameters on the sensor response of hybrid films to ammonia and nitric oxide. It was shown that regardless of the fabrication method, the response of Au/CoPc heterostructures to NH3 and NO gases increased with an increase in the concentration of gold. The sensor response of Au/CoPc heterostructures to NH3 increased 2-3.3 times compared to CoPc film, whereas in the case of NO it increased up to 16 times. The detection limits of the Au/CoPc heterostructure with a gold content of ca. 2.1 µg/cm2 for NH3 and NO were 0.1 ppm and 4 ppb, respectively. It was shown that Au/CoPc heterostructures can be used for the detection of NH3 in a gas mixture simulating exhaled air (N2-74%, O2-16%, H2O-6%, CO2-4%).

The Theoretical and Experimental Investigation of the Fluorinated Palladium ß-Diketonate Derivatives: Structure and Physicochemical Properties.

To search for new suitable Pd precursors for MOCVD/ALD processes, the extended series of fluorinated palladium complexes [Pd(CH3CXCHCO(R))2] with ß-diketone [tfa-1,1,1-trifluoro-2,4-pentanedionato (1); pfpa-5,5,6,6,6-pentafluoro-2,4-hexanedionato (3); hfba-5,5,6,6,7,7,7-heptafluoro-2,4-heptanedionato (5)] and ß-iminoketone [i-tfa-1,1,1-trifluoro-2-imino-4-pentanonato (2); i-pfpa-5,5,6,6,6-pentafluoro-2-imino-4-hexanonato (4); i-hfba-5,5,6,6,7,7,7-heptafluoro-2-imino-4-heptanonato (6)] ligands were synthesized with 70-80% yields and characterized by a set of experimental (SXRD, XRD, IR, NMR spectroscopy, TG) and theoretical (DFT, Hirshfeld surface analysis) methods. Solutions of Pd ß-diketonates contained both cis and trans isomers, while only trans isomers were detected in the solutions of Pd ß-iminoketonates. The molecules 2-6 and new polymorphs of complexes 3 and 5 were arranged preferentially in stacks, and the distance between molecules in the stack generally increased with elongation of the fluorine chain in ligands. The H…F contacts were the main ones involved in the formation of packages of molecules 1-2, and C…F, F…F, NH…F contacts appeared in the structures of complexes 4-6. The stability of complexes and their polymorphs in the crystal phases were estimated from DFT calculations. The TG data showed that the volatility differences between Pd ß-iminoketonates and Pd ß-diketonates were minimized with the elongation of the fluorine chain in the ligands.