Development, validation, and application of a liquid chromatography-tandem mass spectrometry method for the determination of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol in human hair.

The tobacco-specific nitrosamine metabolite 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) is a valuable biomarker for human exposure to the carcinogenic nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) in tobacco and tobacco smoke. In this work, an efficient and sensitive method for the analysis of NNAL in human hair was developed and validated. The hair sample was extracted by NaOH solution digestion, purified by C(18) solid-phase extraction (SPE) and molecularly imprinted solid-phase extraction, further enriched by reverse-phase ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) into 1.0 % aqueous formic acid, and finally analyzed by liquid chromatography-electrospray ionization tandem mass spectrometry. Good linearity was obtained in the range of 0.24-10.0 pg/mg hair with a correlation coefficient of 0.9982, when 150 mg hair was analyzed. The limit of detection and lower limit of quantification were 0.08 and 0.24 pg/mg hair, respectively. Accuracies determined from hair samples spiked with three different levels of NNAL ranged between 87.3 and 107.7 %. Intra- and inter-day relative standard deviations varied from 4.1 to 8.5 % and from 6.9 to 11.3 %, respectively. Under the optimized conditions, an enrichment factor of 20 was obtained. Finally, the developed method was applied for the analysis of NNAL in smokers' hair. The proposed sample preparation procedure combining selectivity of two-step SPE and enrichment of DLLME significantly improves the purification and enrichment of the analyte and should be useful to analyze NNAL in hair samples for cancer risk evaluation and cancer prevention in relation to exposure to the tobacco-specific carcinogen NNK.

New shape-selectivity discovered on graphene-based materials in catching tobacco specific nitrosamines.

New shape-selectivity of graphene-based materials was discovered on this article. To explore the new selectivity, the structure and surface state of graphene and carbon nanotube were examined firstly, and their specific selectivity was verified and was compared with that of ZSM-5 zeolite in aqueous solutions of tobacco specific nitrosamines (TSNA) along with dyes. These two adsorbents trapped about 55% and 70% of 4-methylnitrosamino-1-3-pyridyl-1-butanone (NNK) but only 3% of N'-nitrosonornicotine (NNN) in solution, having an obvious selectivity for the former, due to its stronger interaction with graphene. NNK on graphene sheet obtained more electrons (0.015 e) and owned larger adsorption energy (15.63 kcal mol-1) than that of NNN (0.003 e, 9.19 kcal mol-1), according to theoretical calculation and FTIR results. More 95 or 136 mg g -1 acid red 88 than methyl orange was captured by graphene or carbon nanotube, demonstrating this special and abnormal selectivity again. With new selectivity, graphene showed a higher capacity (6.9%) and shorter adorption equilibrium time (5 min) for TSNA than the typical selecive sorbent ZSM-5 zeolite (1.7% and 20 min) in tobacco solution but kept the similar selctivity to NNK, paving a new way to control the carcinogens like TSNA in environment.

Creating an Optimal Microenvironment within Mesoporous Silica MCM-41 for Capture of Tobacco-Specific Nitrosamines in Solution.

To meet the requirement of capturing tobacco-specific nitrosamines (TSNA) for environment protection, a unique microenvironment was carefully created inside the channels of mesoporous silica MCM-41. In situ carbonization of template micelles at 923 K, combined with the excess aluminum used in one-pot synthesis of MCM-41, is adopted to tailor the tortuosity of mecsoporous channels, while loaded metal oxides (5 wt %) and the Al component in the framework are employed to exert the necessary electrostatic interaction toward the target carcinogens TSNA in solution. The elaborated microenvironment created in mesoporous sorbents was characterized with XRD, N2 adsorption-desorption, TEM, XPS, and TG-DSC methods. Various solutions of Burley- and Virginia-type tobaccos were used to assess the adsorption performance of new mesoporous sorbents, and the influence of the solid-to-liquid ratio, adsorption time, and loading amount of CuO on the adsorption was carefully examined. The representative sample 5%Cu/AM-10c could capture 27.2% of TSNA in Burley tobacco solution, and its capacity reached 0.3 mg g-1 in Snus tobacco extract solution, offering a promising candidate for the protection of the environment and public health.