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The determination of tobacco derived nicotine alkaloids in biofluid samples is of great importance to testing for tobacco use, tobacco cessation treatment, and studies on exposure to secondhand smoke. Paper spray mass spectrometry (MS) has been adapted for direct, quantitative analysis of tobacco alkaloids from biofluid samples, such as blood, urine, and saliva in liquid and dried form. Limits of quantitation as low as several nanograms per milliliter were obtained for nicotine, cotinine, trans-3'-hydroxycotinine, and anabasine. Direct analysis of fresh blood samples has also been achieved with improved sensitivity using print paper substrates of high density. Quantitation of the cotinine in the blood of a rat was performed with both direct analysis using paper spray and a traditional analysis protocol using liquid chromatography MS. Comparable results were obtained and the precision of the two methods was similar. The paper spray MS method is rapid and shows potential for significantly improved analytical efficiency in clinical laboratories as well as for point-of-care tobacco use assessment.

[Display omitted] • PVC-diphenylamine modified cellulose was proposed as sorptive phase. • The synthesis, using the dip-coating technique, is simple and cost-effective. • Opioids interact with the membrane by a mixed-mode interaction. • Direct infusion mass spectrometry allows to reduce the time of analysis. • The approach was successfully applied to real saliva samples containing codeine and tramadol. This article evaluates the potential of cellulose paper as a substrate for preparing a polyvinylchloride (PVC)-diphenylamine sorptive phase that can be used under the thin film microextraction (TFME) format. This phase was easily synthesized using the dip-coating technique to coat the filter paper with PVC, followed by the covalent bonding of diphenylamine. As a result, aromatics rings are available on paper surface to isolate the target analytes by a mixed-mode interaction at physiological pH. The resulting material was characterized by infrared spectroscopy, UV–Vis diffuse reflection spectroscopy, and scanning electron microscopy. As analytical problem, three opioids (methadone, codeine, and tramadol) were determined in saliva samples by direct infusion mass spectrometry. Different variables involved in the extraction procedure have been optimized (e.g. sample pH, extraction time, and sample dilution). The proposed method provides good linearity (R2 > 0.9817) and sensitivity (detection limits in the range from 1.5 µg L−1 to 15 µg L−1). The intra-day and inter-day precision, expressed as relative standard deviation, were better than 16.4 % and 18.5 % respectively. The accuracy, expressed as relative recovery, provides values in the interval from 82 % to 105 %. Finally, the proposed approach has been successfully applied to real saliva samples of patients under codeine and tramadol medical prescription. [ABSTRACT FROM AUTHOR]