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A novel nano-silicon oxides (SiOx)/chitosan complex film was prepared using ultrasonic assistant in the process of dissolving chitosan and silicon oxides (SiOx), and characterized by transmission electron microscopy. Its effect on quality preservation of tomatoes (Solanum lycopersicum L. cv. Zheza 205) was investigated under ambient temperature. The results revealed that the nano-SiOx/chitosan complex (NSCC) film retarded weight loss and softness, delayed the titratable acids and total soluble solids loss, and thus markedly extended shelf life of green tomatoes. The antimicrobial activity of tomatoes coated with NSCC film was also recorded higher compared to chitosan (Ch) films and control. In addition, the NSCC film-coated tomatoes prevent the increase of malondialdehyde content and total polyphenol content. Moreover, the peroxidase activity, phenylalanine ammonia-lyase activity, and polyphenoloxidase activity of tomatoes coated with NSCC film were found lower than that in other treatments. These data indicated that the beneficial effects of nano-SiOx/chitosan complex coating on postharvest quality were possibly associated with the lower rate of O₂/CO₂ transmission coefficient, limiting food-borne pathogenic bacterial growth, higher antioxidant activities, and also higher reactive oxygen species (ROS) scavenging and anti-browning activities of related enzymes in the tomatoes. Further, the results of the study could be used to successfully develop a novel nano-SiOx/chitosan complex film for improving the postharvested quality of tomatoes and thus effectively utilized by the food packaging industry. Full article