Nitric oxide (NO) is a highly reactive toxic gas that forms as an intermediate compound during the oxidation of ammonia and is used for the manufacture of hydroxylamine in the chemical industry. Moreover, NO is a signaling molecule in many physiological and pathological processes in mammals, as well as a biomarker indicating the course of inflammatory processes in the respiratory tract. For this reason, the detection of NO both in the gas phase and in the aqueous media is an important task. This review analyzes the state of research over the past ten years in the field of applications of phthalocyanines, porphyrins and their hybrid materials as active layers of chemical sensors for the detection of NO, with a primary focus on chemiresistive and electrochemical ones. The first part of the review is devoted to the study of phthalocyanines and porphyrins, as well as their hybrids for the NO detection in aqueous solutions and biological media. The second part presents an analysis of works describing the latest achievements in the field of studied materials as active layers of sensors for the determination of gaseous NO. It is expected that this review will further increase the interest of researchers who are engaged in the current level of evaluation and selection of modern materials for use in the chemical sensing of nitric oxide.

In this work, the sensor response of MPcF_x (M = Cu, Co, Zn; x = 0, 4, 16) films toward gaseous NH₃ (10–50 ppm) was studied by a chemiresistive method and compared to that of unsubstituted MPc films to reveal the effects of central metals and F-substituents on the sensing properties. A combination of atomic force microscopy and X-ray diffraction techniques have been used to elucidate the structural features of thin MPcF_x films deposited by organic molecular beam deposition. It has been shown that the sensor response of MPcF₄ films to ammonia is noticeably higher than that of MPc films, which is in good correlation with the values of binding energy between the metal phthalocyanine and NH₃ molecules, as calculated by the density functional theory (DFT) method. At the same time, in contrast to the DFT calculations, MPcF₁₆ demonstrated the lesser sensor response compared with MPcF₄, which appeared to be connected with the different structure and morphology of their films. The ZnPcF₄ films were shown to exhibit a sensitivity to ammonia up to concentrations as low as 0.1 ppm, and can be used for the selective detection of ammonia in the presence of some reducing gases and volatile organic compounds. Moreover, the ZnPcF₄ films can be used for the detection of NH₃ in the gas mixture simulating exhaled air (N₂ 76%, O₂ 16%, H₂O 5%, and CO₂ 3%).

Metal phthalocyanines bearing electron-withdrawing fluorine substituents were synthesized a long time ago, but interest in the study of their films has emerged in recent decades. This is due to the fact that, unlike unsubstituted phthalocyanines, films of some fluorinated phthalocyanines exhibit the properties of n-type semiconductors, which makes them promising candidates for application in ambipolar transistors. Apart from this, it was shown that the introduction of fluorine substituents led to an increase in the sensitivity of phthalocyanine films to reducing gases. This review analyzes the state of research over the last fifteen years in the field of applications of fluoro-substituted metal phthalocyanines as active layers of gas sensors, with a primary focus on chemiresistive ones. The active layers on the basis of phthalocyanines with fluorine and fluorine-containing substituents of optical and quartz crystal microbalance sensors are also considered. Attention is paid to the analysis of the effect of molecular structure (central metal, number and type of fluorine substituent etc.) on sensor properties of fluorinated phthalocyanine films.

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.

In this work, thin films of vanadyl phthalocyanines (VOPc and VOPcF₄) are studied as active layers for the detection of gaseous ammonia and hydrogen. The effect of F-substituents on the structural features of vanadyl phthalocyanine films and their sensor response toward ammonia (10–50 ppm) and hydrogen (100–500 ppm) is investigated by X-ray diffraction (XRD) and chemiresistive methods, respectively. It is shown that the sensor response of VOPcF₄ films to ammonia is 2–3 times higher than that of VOPc films. By contrast, the sensor response to hydrogen is higher in the case of VOPc films. Apart from this, the hybrid structures of vanadyl phthalocyanine films with Pd nanoparticles deposited on their surface by a chemical vapor deposition method are also tested to reveal the effect of Pd nanoparticles on the sensitivity of VOPc films to hydrogen. Deposition of Pd nanoparticles on the surface of VOPc films leads to the noticeable increase of their sensitivity to hydrogen.

In this work, the effect of fluorine and chlorine substituents in tetrasubstituted zinc phthalocyanines, introduced into the non-peripheral (ZnPcR₄-np, R = F, Cl) and peripheral (ZnPcR₄-p, R = F, Cl) positions of macrocycle, on their structure and chemiresistive sensor response to low concentration of ammonia is studied. The structure and morphology of the zinc phthalocyanines films (ZnPcR₄) were investigated by X-ray diffraction and atomic force microscopy methods. To understand different effects of chlorine and fluorine substituents, the strength and nature of the bonding of ammonia and ZnPcHal₄ molecules were studied by quantum chemical simulation. It was shown on the basis of comparative analysis that the sensor response to ammonia was found to increase in the order ZnPcCl₄-np < ZnPcF₄-np < ZnPcF₄-p < ZnPcCl₄-p, which is in good agreement with the values of bonding energy between hydrogen atoms of NH₃ and halogen substituents in the phthalocyanine rings. ZnPcCl₄-p films demonstrate the maximal sensor response to ammonia with the calculated detection limit of 0.01 ppm; however, they are more sensitive to humidity than ZnPcF₄-p films. It was shown that both ZnPcF₄-p and ZnPcCl₄-p and can be used for the selective detection of NH₃ in the presence of carbon dioxide, dichloromethane, acetone, toluene, and ethanol.