Extractive Atmospheric Pressure Photoionization (EAPPI) Mass Spectrometry: Rapid Analysis of Chemicals in Complex Matrices
Chengyuan Liu1, Jiuzhong Yang1,Jian Wang2, Yonghua Hu2,Wan Zhao1, Zhongyue Zhou3,Fei Qi3, and Yang Pan1,*
1National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China
2 Research and Development Centre, China Tobacco Anhui Industrial Co., Ltd., Hefei, 230088, China
3Power Machinery and Engineering of Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240, China
*Address reprint requests to:
Dr. Yang Pan
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China
E-mail:
Fax: +86-551-65141078
Tel: +86-551-63601986
Fig. S1. The preparation of soil samples, where PAHs were spiked into the soil in advance.
Fig.S2. Variations of [M+H]+ of 0.8 μg/mLmethyltestosterone using toluene as dopant at different volume of sample solution.
Table S1.Ions observed in EAPPI-MS analysis of compound amino acid capsules and their tentative assignments.
Observed m/z / Putative assignment (ions in parenthesis) / Calculated m/z / Mass error/ppm102.0555 / L-Threonine [M+H-H2O]+ / 102.0550 / -4.9
118.0864 / Valine [M+H]+ / 118.0863 / -0.8
123.0546 / Vitamin B3 (nicotinamide) [M+H]+ / 123.0552 / 4.8
132.1020 / Leucine, Isoleucine [M+H]+ / 132.1019 / -0.7
147.1135 / Lysine [M+H]+ / 147.1128 / -4.7
150.0585 / DL-Methionine [M+H]+ / 150.0583 / -1.3
152.0706 / Vitamin B6 [M+H-H2O]+ / 152.0706 / 0
166.0869 / L-Phenylalanine [M+H]+ / 166.0863 / -3.6
170.0819 / Vitamin B6 [M+H]+ / 170.0812 / -4.1
177.0399 / Vitamin C [M+H]+ / 177.0394 / -2.8
205.0981 / Tryptophan [M+H]+ / 205.0972 / -4.3
220.1187 / Vitamin B5 [M+H]+ / 220.1179 / -3.6
265.1112 / Vitamin B1 nitrate [M-NO3]+ / 265.1118 / 2.3
Table S2. Ions observed in EAPPI-MS analyisis of tangerine (Citrus reticulata) and grapefruit(Citrus paradisi) peel and their tentative assignments based on the results of conventional measurements.√means the ion was observed.
Ions observed by EAPPI-MS / Components in citrus peel or citrus grandis peel reported in literatureObserved m/z / Observed in a* / Observed in b* / Putative assignment (ions in parenthesis) / Calculated m/z / Mass error/ ppm
127.0396 / √ / √
136.1249 / √ / √ / Limonene/sabinene/α-pinene/β-pinene/γ-terpinene/(E)-β-ocimene[1](M+) / 136.1247 / -1.5
145.0503 / √ / √
163.0611 / √ / √
219.1753 / √ / β-sinensal[1] ([M+H]+) / 219.1743 / -4.5
265.1543 / √ / √
273.0776 / √ / Naringenin[2] ([M+H]+) / 273.0757 / -3.3
289.0941 / √ / √
303.0876 / √ / √ / Hesperetin[2] ([M+H]+) / 303.0863 / -4.3
325.1144 / √ / √
343.1193 / √ / √ / Tetramethyl-O-isoscutellarein[3] ([M+H]+) / 343.1176 / -4.9
360.1511 / √ / √
373.1295 / √ / √ / Tangeretin[2-4] ([M+H]+)
Isosinensetin/sinensetin[3] ([M+H]+) / 373.1282 / -3.5
389.1244 / √ / √ / 5-hydroxy-6,7,8,3′,4′-pentamethoxyflavone/
5-hydroxy-6,7,3′,4′,5′-pentamethoxyflavone[4] ([M+H]+) / 389.1231 / -3.3
403.1403 / √ / √ / Nobiletin[2-4] ([M+H]+) / 403.1387 / -3.9
430.1929 / √ / √
433.1508 / √ / √ / 3,5,6,7,8,3′,4′-heptamethoxyflavone[3, 5] [M+H]+) / 433.1493 / -3.5
458.1876 / √
465.1408 / √ / Hesperetin 7-O-glucoside[3] ([M+H]+) / 465.1391 / -3.6
581.1874 / √ / Narirutin/naringin[6] ([M+H]+) / 581.1865 / -1.5
595.2029 / √ / √ / Didymin[2, 7] ([M+H]+)
Poncirin[3] ([M+H]+) / 595.2021 / -2.3
598.2148 / √
611.1982 / √ / √ / Hesperidin/neohesperidin[6, 7] ([M+H]+) / 611.1970 / -1.9
628.2245 / √
698.2667 / √
*a and b represent the EAPPI mass spectra of tangerine (Citrus reticulata) and grapefruit(Citrus paradisi) peel, respectively.
Table S3. Bias for analysis of 6 PAHs in soil using toluene/anisole(v:v=1:1) as dopant.
Standard (ngmg-1) / %biasaacenaphthylene / acenaphthene / fluorene / phenanthrene / pyrene / chrysene
0.6 / 0.6% / -17% / 1% / n.a.b / n.a.b / 15%
3 / 10% / -7% / 13% / 20% / 18% / 12%
6 / 10% / 0.7% / 1.6% / -9.6% / 17% / -2.2%
15 / 10% / 1% / 5.3% / 14.7% / 11% / 9%
30 / 1.7% / -2% / -17% / -7.6% / -14% / -16%
75 / 4% / 2% / -2.1% / -3.8% / 0.5% / -2.5%
150 / -8% / -0.5% / 5.1% / 2.4% / 0.3% / 4%
300 / 1.6% / n.a.b / -0.9% / -0.3% / n.a.b / -0.6%
a%bias = (calculated concentration−actual concentration)/actual concentration ×100. bn.a. represents the standard exceeds the detection limit of quantitation.
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