Abstract

In-tube solid phase microextraction is a cutting-edge sample treatment technique offering significant advantages in terms of miniaturization, green character, automation, and preconcentration prior to analysis. During the past years, there has been a considerable increase in the reported publications, as well as in the research groups focusing their activities on this technique. In the present review article, HPLC bioanalytical applications of in-tube SPME are discussed, covering a wide time frame of twenty years of research reports. Instrumental aspects towards the coupling of in-tube SPME and HPLC are also discussed, and detailed information on materials/coatings and applications in biological samples are provided.

Highlights

  • Bioanalysis is the chemical analysis of exogenous or endogenous compounds in biological samples [1]

  • Supel Q porous layer open tubular (PLOT) columns have been successfully employed for the in-tube solid phase microextraction (SPME) of various organic heterocyclic amines from hair [36], endocrine disruptors from liquid medicines and intravenous compounds, including heterocyclic amines from hair [36], endocrine disruptors from liquid injection solutions [51], melatonin from saliva [52], cortisol from human saliva [53], urinary heterocyclic medicines and intravenous injection solutions [51], melatonin from saliva [52], cortisol from human saliva [53], urinary heterocyclic amines [54], testosterone, cortisol, and dehydroepiandrosterone from saliva [55], and anabolic steroids from urine [56]

  • An interesting automated in-tube SPME method has been developed for the determination of interferon alpha 2a in plasma samples using a protein-coated silica Restricted Access Materials (RAMs) sorbent consisting of C18 hydrophobic particles [86]

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Summary

Introduction

Bioanalysis is the chemical analysis of exogenous (mainly drugs, metabolites, biomarkers) or endogenous (i.e., amino acids) compounds in biological samples [1]. Remarkable progress has been achieved in the development of highly efficient analytical systems for the determination of drugs in biological samples Despite these efforts, a sample pretreatment step is still required for the extraction and isolation of the analyte of interest from these matrices prior to the end-point analysis. On-line in-tube microextraction was first assembled by Eisert and Pawliszyn as an automated alternative to fiber SPME [15] This technique was introduced to overcome some difficulties related to the conventional fiber SPME, including fiber fragility, low sorption capacity, bleeding of thick-film coatings, and reduced efficiency for weakly volatile or thermally labile analytes (for GC analysis). SPME in combination with liquid chromatography covering a timeframe of the last two decades, focusing on bioanalytical applications

Instrumental Configurations
Conventional Capillary Columns Coating
Monolithic Capillary Columns
Immunosorbents
Carbon-Based Materials
Metal–Organic Frameworks
Ionic Liquids and Deep Eutectic Solvents
Other Materials
Applications
Plasma and Serum
Saliva
Miscellaneous
Findings
Conclusions

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