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%).

Synergetic combination of the properties of phthalocyanines and metal nanoparticles is known to result in the improvement of various properties of their hybrid materials. This review provides an overview of the application of hybrid materials based on phthalocyanines and metal nanoparticles for the development of chemiresistive and electrochemical sensors, with a focus on methods and approaches for their preparation.