Measurement of endogenous estrogens: analytical challenges and recent advances

Recent developments in the analysis of endogenous estrogens (including both free and conjugated estrogens) are reviewed. Largely due to urging by some cancer researchers, new demands are now being placed on such measurements in terms of sensitivity, throughput, multi-analyte detection and accuracy. Especially high sensitivity is required for detecting estrogens in serum from postmenopausal women, children and men, where concentrations at the low pg/ml level are encountered, and one would prefer to test much less than 1 ml of serum. Aside from throughput, meeting all of these demands may be beyond the reach of immunoassay, the method that has created and continues to dominate this field. Both HPLC and GC versions of mass spectrometry are emerging that have some potential to improve the testing of physiological samples for endogenous estrogens. The following topics are covered in this review: related analyses (e.g. detection of estrogens in environmental samples such as water, where 1-l samples can be collected to provide ng amounts of estrogens); structure and metabolism of estrogens; biological actions (with an emphasis on their role in cancer); immunoassays; HPLC with electrochemical detection; GC-ECD; and various forms of mass spectrometry.