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Herein, a synchrotron radiation photoionization time\u2010of\u2010flight mass spectrometry method was established to online distinguish isobars and isomers in HNB cigarette aerosol, where photoionization efficiency (PIE) curves of HNB cigarette aerosol were scanned at different photon energies, and more than 43 components including aldehydes, ketones, alkenes, alkanes, and heterocyclic compounds were identified based on multiple linear regression (MLR) simulation. 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