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A cobalt porphyrin(CY-B)was presented,and its interaction with tobacco-specific nitrosamines(TSNAs)was investigated by UV–Vis spectroscopy and high-resolution mass spectrometry.The results revealed that the stoichiometry of the host–guest interaction was 1:2 and that the binding constant between CY-B and TSNAs was within the range of 0.78 108–7.83 108 M2.The coordination strength between CY-B and TSNAs decreased in the sequence of NNN > NAB > NAT > NNK based on the binding constant.The interaction mechanism of CY-B with TSNAs involved a coordination interaction,and the p–p interaction between the porphyrin macrocycle and the aromatic frame of the TSNAs pyridines may also have been a driving force.The measured thermodynamic properties demonstrated that the reaction of CY-B with TSNAs was spontaneous and that the driving force for the interaction was a change in enthalpy.The reaction was exothermic,and an increasing temperature inhibited the interaction.The IR spectrum of the complex revealed that the ANAN@O group of TSNAs and the metal cobalt of CY-B formed the six-coordinate complex.