Enhanced Peroxidase-Mimic Catalytic Activity via Cerium Doping of Strontium-Based Metal-Organic Frameworks with Design of a Smartphone-Based Sensor for On-Site Salivary Total Antioxidant Capacity Detection in Lung Cancer Patients.

The development of artificial nanozymes with superior catalytic performance and excellent stability has been a long-standing objective for chemists. The total antioxidant capacity (TAC) is one of the most important bioanalytical measures of oxidative stress in the body. The present work aims to develop a smartphone-assisted visual detection sensor using cerium-doped strontium-based metal-organic frameworks (Ce-SrMOFs) as peroxidase-like nanozymes for the rapid, low-cost, on-site detection of TAC. The pristine SrMOF functioned as a peroxidase nanozyme, and its enzymatic activity was enhanced after doping it with Ce(IV) ions because of the multivalent nature and synergistic impact of the heteroatoms. The Ce-SrMOFs were sensitive to the single electron transfer and hydrogen atom transfer processes, which implies that the Ce-SrMOFs can serve as an ideal nanozyme candidate for TAC analysis. The investigated mechanism revealed that •OH is the most active oxygen species for the peroxidase-like activity. The Ce-SrMOFs exhibited a strong affinity for 3,3',5,5'-tetramethylbenzidine (TMB) and HO, with values of 0.082 and 0.427 mM, which are 5.29- and 8.67-fold lower than those of horseradish peroxidase (HRP), respectively. The Ce-SrMOFs were used for the detection of ascorbic acid, cysteine, and glutathione, with limits of detection of 44, 53, and 512 nM, respectively. The proposed method proved effective in measuring the TAC in saliva samples from lung cancer patients, thereby yielding results with satisfactory precision and accuracy.