Garlic polysaccharide (GPS) was modified in selenylation respectively by nitric acid-sodium selenite (NA-SS), glacial acetic acid-selenous acid (GA-SA), glacial acetic acid-sodium selenite (GA-SS) and selenium oxychloride (SOC) methods each under nine modification conditions of L9(3(4)) orthogonal design and each to obtain nine selenizing GPSs (sGPSs). Their structures were identified, yields and selenium contents were determined, selenium yields were calculated, and the immune-enhancing activities of four sGPSs with higher selenium yields were compared taking unmodified GPS as control. The results showed that among four methods the selenylation efficiency of NA-SS method were the highest, the activity of sGPS5 was the strongest and significantly stronger than that of unmodified GPS. This indicates that selenylation modification can significantly enhance the immune-enhancing activity of GPS, NA-SS method is the best method and the optimal conditions are 0.8:1 weight ratio of sodium selenite to GPS, reaction temperature of 70 °C and reaction time of 10h.
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