Identification and quantification of polyphenol phytoestrogens in foods and human biological fluids

We review the methods used to measure phytoestrogens (genistein, daidzein, lignans and their derivatives) in foods and biological fluids, and discuss advantages and disadvantages of each. The range of detection limits reported varies widely between individual laboratories, but generally the best reported sensitivity is as follows: immunoassay>HPLC-mass spectrometry=HPLC-multichannel electrochemical detection (coularray)>GC-single ion monitoring-mass spectrometry>HPLC-UV diode array>HPLC-single channel electrochemical detection. The best sensitivity reported so far is 0.002 pmol per assay for daidzein by radioimmunoassay. HPLC with UV diode array detection is the most commonly employed, but is the least sensitive and specific. GC and HPLC coupled with mass spectrometry or electrochemical detection are the most accurate and reproducible methods for a wide variety of analytes. Generally most methods, with the exception of immunoassay, have not been correlated with other methods. Recoveries from extraction methods, limits of detection, nature of compounds analysed and the internal standards used are summarised for more than 90 reports in the literature. From this data, it is clear that an inter-laboratory validation and correlation between a wide range of methods for phytoestrogen analysis is required. One underdeveloped area that requires particular attention is the analysis of plant lignans.