填充吸附剂微萃取技术及其在微小体积样品萃取应用中的研究进展

Microextraction is a rapidly developing sample preparation technology in the field of analytical chemistry, which is seeing widespread application. Accurate sample preparation can not only save time but also improve the efficiency of analysis, determination, and data quality. At present, sample pretreatment methods must be rapid, allow for miniaturization, automation, and convenient online connection with analytical instruments. To meet the requirements of green analytical methods and improve the extraction efficiency, microextraction techniques have been introduced as suitable replacements to conventional sample preparation and extraction methods. Microextraction using a packed sorbent (MEPS) is a new type of sample preparation technology. The MEPS equipment was prepared using microsyringe with a volume of 50-500 μL, including MEPS syringes and MEPS adsorption beds (barrel insert and needle, BIN), which is essentially similar to a miniaturized solid phase extraction device. The BIN contains the adsorbent and is built into the syringe needle. A typical MEPS extraction procedure involves repeatedly pumping the sample solution in two directions (up and down) through the adsorbent multiple times in the MEPS syringe. The specific operation course of MEPS includes conditioning, loading, washing, elution, and introduction into the analysis instrument. The conditioning process is adopted to infiltrate the dry sorbent and remove bubbles between the filler particles. The adsorption process is accomplished by pulling the liquid plunger of the syringe so that the sample flows through the adsorbent in both directions multiple times. The washing process involves rinsing the sorbent to remove unwanted components after the analyte is retained. The elution process involves the use of an eluent to ensure that the sample flows through the adsorbent in both directions multiple times, so that elution can be realized by the pumping-pushing action. The target analyte is eluted with the eluent, which can be directly used for chromatographic analysis. However, when processing complex biological matrix samples by MEPS, pretreatment steps such as dilution of the sample and removal of proteins are commonly required. At present, the operation modes of the MEPS equipment are classified into three types: manual, semi-automated, and fully automated. This increase in the degree of automation is highly conducive to processing extremely low or extremely high sample volumes. Critical factors affecting the MEPS performance have been investigated in this study. The conditions for MEPS optimization are the operating process parameters, including sample flow rate, sample volume, number of sample extraction cycles, type and volume of the adsorbent, and elution solvents. It is also necessary to consider the effect of the sample matrix on the performance of MEPS. The MEPS sorbent should be cleaned by a solvent to eliminate carryover and reuse. The sorbent is a core aspect of MEPS. Several types of commercial and non-commercial sorbents have been used in MEPS. Commercial sorbents include silica-based sorbents such as unmodified silica (SIL), C2, C8, and C18. Unmodified silicon-based silica is a normal phase adsorption material, which is highly polar and can be used to retain polar analytes. C18, C8, and C2 materials are suitable for reversed-phase adsorption, while SCX, SAX, APS, and M1 (C8+SCX) adsorbents are suitable for the mixed-mode and ion-exchange modes. Noncommercial sorbents include molecularly imprinted materials, restricted-access molecularly imprinted materials, graphitized carbon, conductive polymer materials, modified silicon materials, and covalent-organic framework materials. The performance of MEPS has recently been illustrated by online with LC-MS and GC-MS assays for the analysis of biological matrices, environmental samples, and food samples. Pretreatment in MEPS protocols includes dilution, protein precipitation, and centrifugation in biological fluid matrices. Because of the small sample size, fast operation, etc., MEPS is expected to be more widely used in the analysis of bio-matrix samples. MEPS devices could also play an important role in field pretreatment and analysis.