Analytical Sciences

Abstract − Analytical Sciences, 37(6), 879 (2021).

Effects of Residual Silanol on Solid Phase Extraction of Organic Compounds to Octadecylsilyl Silica
Satoshi OHMURO, Ryo ISHIZAKI, Masashi TSUKAMOTO, Shizuka NASU, Takashi YASUI, Kazutake TAKADA, and Akio YUCHI
Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555, Japan
Batchwise equilibrium study was carried out on the retention of nonpolar and polar organic compounds to octadecylsilyl (ODS) silicas of different properties at atmospheric pressure. While nonpolar compounds were retained only by distribution on the ODS phase, polar compounds were retained by both distribution and Langmuir-type adsorption on residual silanol. Retention on ODS silica with more silanol proceeded at a higher rate than retention on ODS silica with less silanol and was reversible on this solid phase extraction time-scale. An increase in surface density of ODS decreased the distribution constant, due to a decrease in fraction of ODS functioning as an extracting medium and also decreased the saturated adsorption amount, due to reductions of the residual silanol and the functioning ODS. The ODS silica with the lowest ODS density showed a distribution constant 31 times higher and a saturated adsorption amount 27 times higher than the ODS silica with the highest ODS density. On the other hand, because the interaction between the organic part and the ODS group introduced at higher density is strengthened, the adsorption constant is increased by about 5 times compared to the low density ODS silica. The electronic effects of substituents to nitrogen- and oxygen-containing compounds on retention were discussed. In conclusion, ODS silica with an appreciable amount of residual silanol is superior for solid phase extraction.