New urea-modified paper substrate for enhanced analytical performance of negative ion mode paper spray mass...

Electrospray ionization mass spectrometry (ESI-MS) analysis in the negative ion mode is adversely affected by ionization suppression caused by electrical discharge and the presence of salts. Paper spray mass spectrometry (PS-MS) also suffers from the above phenomenon, being built on principles similar to those of ESI. Herein, we report the use of a paper substrate modified by 1-[3-(trimethoxysilyl)propyl]urea to improve the sensitivity of quantitative PS-MS analysis in the negative ion mode. The obtained results demonstrated that the urea modified paper substrate can effectively bind anions and highly polar compounds in the sample solution, decreasing competitive ionization in the negative ion mode of PS-MS and significantly reducing the signal intensity of Cl^- adducts. In addition, the analyte responses were also significantly improved owing to the decreased electrical discharge observed for the less polar surface to decrease electrical discharge. Compared to non-modified PS-MS, urea-modified PS-MS exhibits a much higher sensitivity, showing 2-109 times improved signal-to-noise ratio (S/N). In real sample analysis, the limits of detection (LODs) of salicylic acid in urine and terpene lactones in Ginkgo biloba extract (EGb) were improved 10-fold and 2-40-fold, respectively, compared to that of non-modified PS-MS.