Analysis of melatonin in human plasma by gas chromatography negative chemical ionization mass spectrometry.

Three techniques have been used to measure human plasma melatonin: bioassay, radioimmunoassay, and gas chromatography--mass spectrometry (GC-MS). GC-MS is theoretically capable of the greatest specificity, but in general suffers from insufficient sensitivity. Negative chemical ionization, a new technique, provides a 150-fold increase in GC-MS sensitivity for electron-capturing compounds. Negative chemical ionization GC-MS permits routine measurement in human plasma of melatonin at a concentration as low as 1 picogram per milliliter.