Development of a novel solid phase microextraction calibration method for semi-solid tissue sampling.

Accurate quantitative analysis using in vivo solid phase microextraction (SPME) for semi-solid tissue can be challenging due to the complexity of the sample matrix. In this paper, a comprehensive study was carried out on the extraction kinetics of SPME in the semi-solid sample, and subsequently proposed a new theoretical model to interpret the kinetic extraction process. Theoretically derived mathematical expressions well described the experimental desorption time profiles of the SPME process. Modelling experiments were also carried out to study the effect of sample tortuosity and binding matrix on the parameters affecting the extraction kinetics. Seven polyaromatic hydrocarbons (PAHs) and eight polychlorinated biphenyls (PCBs) in agarose gel and in real fish tissue were used for these experiments. The experimental data showed excellent agreement with theoretical prediction while providing excellent interpretation of the effect of tortuosity and binding matrix. Based on the theoretical model, an on-fiber standard calibration method with fewer internal standards was developed. The newly developed calibration method was used to quantify PAHs and PCBs in agarose gel and fish tissue. By using the proposed calibration method, a large number of organic compounds can be quantified with fewer internal standards. Current study provides the theoretical foundation for in vivo SPME quantitative semi-solid tissue analysis in the future.