Chinese Journal of Chromatography ›› 2022, Vol. 40 ›› Issue (8): 746-752.DOI: 10.3724/SP.J.1123.2021.12016
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LI Hongyan, YANG Huan, MA Chenyi, ZHANG Wanyue, XU Qingyu, CHEN Mingxue, MA Youning()
Received:
2021-12-16
Online:
2022-08-08
Published:
2022-07-29
Contact:
MA Youning
Supported by:
CLC Number:
LI Hongyan, YANG Huan, MA Chenyi, ZHANG Wanyue, XU Qingyu, CHEN Mingxue, MA Youning. Determination of three oryzanols in rice by mixed-mode solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(8): 746-752.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2021.12016
Compound | Parent ion (m/z) | Product ion (m/z) | Declustering potential/V | Collision energy/ eV |
---|---|---|---|---|
Campesteryl ferulate | 575.4 | 560.4* | -50.45 | -51.46 |
(Camp-FA) | 193.0 | -50.45 | -49.25 | |
Cycloartenyl ferulate | 601.4 | 586.6* | -56.86 | -55.60 |
(CA-FA) | 175.0 | -56.86 | -55.89 | |
24-Methylenecycloartenyl | 615.5 | 600.5* | -63.45 | -56.64 |
ferulate (24MCA-FA) | 175.3 | -63.45 | -58.28 |
Table 1 MS parameters of the three oryzanols under the multiple reaction monitoring (MRM) mode
Compound | Parent ion (m/z) | Product ion (m/z) | Declustering potential/V | Collision energy/ eV |
---|---|---|---|---|
Campesteryl ferulate | 575.4 | 560.4* | -50.45 | -51.46 |
(Camp-FA) | 193.0 | -50.45 | -49.25 | |
Cycloartenyl ferulate | 601.4 | 586.6* | -56.86 | -55.60 |
(CA-FA) | 175.0 | -56.86 | -55.89 | |
24-Methylenecycloartenyl | 615.5 | 600.5* | -63.45 | -56.64 |
ferulate (24MCA-FA) | 175.3 | -63.45 | -58.28 |
Fig. 1 Influence of different mobile phase B on the resolutions and chromatographic peaks for the three oryzanol a. acetonitrile; b. methanol; c. methanol∶ acetonitrile=1∶1 (v/v).
No. | Solid-liquid ratio/ (g/mL) | φ(Methanol)/ % | Soak time/h | Ultrasonic temperature/ ℃ | Ultrasonic time/min | Camp-FA/ (mg/kg) | 24MCA-FA/ (mg/kg) | CA-FA/ (mg/kg) |
---|---|---|---|---|---|---|---|---|
1 | 1∶15 | 85 | 6 | 35 | 20 | 0.36 | 2.66 | 1.10 |
2 | 1∶15 | 90 | 9 | 40 | 30 | 0.42 | 3.46 | 1.42 |
3 | 1∶15 | 95 | 12 | 45 | 40 | 0.53 | 5.10 | 1.93 |
4 | 1∶15 | 100 | 15 | 50 | 50 | 0.52 | 3.45 | 1.31 |
5 | 1∶20 | 85 | 9 | 45 | 50 | 0.30 | 2.30 | 0.91 |
6 | 1∶20 | 90 | 6 | 50 | 40 | 0.58 | 4.56 | 1.80 |
7 | 1∶20 | 95 | 15 | 35 | 30 | 0.50 | 3.94 | 1.55 |
8 | 1∶20 | 100 | 12 | 40 | 20 | 0.63 | 6.16 | 2.24 |
9 | 1∶25 | 85 | 12 | 50 | 30 | 0.28 | 3.24 | 1.34 |
10 | 1∶25 | 90 | 15 | 45 | 20 | 0.38 | 3.82 | 1.56 |
11 | 1∶25 | 95 | 6 | 40 | 50 | 0.50 | 3.50 | 1.37 |
12 | 1∶25 | 100 | 9 | 35 | 40 | 0.50 | 3.22 | 1.25 |
13 | 1∶30 | 85 | 15 | 40 | 40 | 0.29 | 2.31 | 0.95 |
14 | 1∶30 | 90 | 12 | 35 | 50 | 0.47 | 3.68 | 1.47 |
15 | 1∶30 | 95 | 9 | 50 | 20 | 0.49 | 3.19 | 1.25 |
16 | 1∶30 | 100 | 6 | 45 | 30 | 0.56 | 4.30 | 1.63 |
K1 | 5.56 | 4.01 | 5.73 | 5.17 | 5.96 | |||
K2 | 6.37 | 5.90 | 4.67 | 5.85 | 5.66 | |||
K3 | 5.24 | 5.96 | 6.77 | 5.83 | 5.75 | |||
K4 | 5.15 | 6.44 | 5.14 | 5.5 | 4.94 | |||
R | 1.22 | 2.43 | 2.09 | 0.65 | 1.02 |
Table 2 Orthogonal test results
No. | Solid-liquid ratio/ (g/mL) | φ(Methanol)/ % | Soak time/h | Ultrasonic temperature/ ℃ | Ultrasonic time/min | Camp-FA/ (mg/kg) | 24MCA-FA/ (mg/kg) | CA-FA/ (mg/kg) |
---|---|---|---|---|---|---|---|---|
1 | 1∶15 | 85 | 6 | 35 | 20 | 0.36 | 2.66 | 1.10 |
2 | 1∶15 | 90 | 9 | 40 | 30 | 0.42 | 3.46 | 1.42 |
3 | 1∶15 | 95 | 12 | 45 | 40 | 0.53 | 5.10 | 1.93 |
4 | 1∶15 | 100 | 15 | 50 | 50 | 0.52 | 3.45 | 1.31 |
5 | 1∶20 | 85 | 9 | 45 | 50 | 0.30 | 2.30 | 0.91 |
6 | 1∶20 | 90 | 6 | 50 | 40 | 0.58 | 4.56 | 1.80 |
7 | 1∶20 | 95 | 15 | 35 | 30 | 0.50 | 3.94 | 1.55 |
8 | 1∶20 | 100 | 12 | 40 | 20 | 0.63 | 6.16 | 2.24 |
9 | 1∶25 | 85 | 12 | 50 | 30 | 0.28 | 3.24 | 1.34 |
10 | 1∶25 | 90 | 15 | 45 | 20 | 0.38 | 3.82 | 1.56 |
11 | 1∶25 | 95 | 6 | 40 | 50 | 0.50 | 3.50 | 1.37 |
12 | 1∶25 | 100 | 9 | 35 | 40 | 0.50 | 3.22 | 1.25 |
13 | 1∶30 | 85 | 15 | 40 | 40 | 0.29 | 2.31 | 0.95 |
14 | 1∶30 | 90 | 12 | 35 | 50 | 0.47 | 3.68 | 1.47 |
15 | 1∶30 | 95 | 9 | 50 | 20 | 0.49 | 3.19 | 1.25 |
16 | 1∶30 | 100 | 6 | 45 | 30 | 0.56 | 4.30 | 1.63 |
K1 | 5.56 | 4.01 | 5.73 | 5.17 | 5.96 | |||
K2 | 6.37 | 5.90 | 4.67 | 5.85 | 5.66 | |||
K3 | 5.24 | 5.96 | 6.77 | 5.83 | 5.75 | |||
K4 | 5.15 | 6.44 | 5.14 | 5.5 | 4.94 | |||
R | 1.22 | 2.43 | 2.09 | 0.65 | 1.02 |
Compound | Linear equation | Linear range/(μg/L) | r2 | LOD/(μg/L) | LOQ/(μg/L) |
---|---|---|---|---|---|
Camp-FA | y=2.45×105x+1.21×104 | 1.0-500.0 | 0.9991 | 0.5 | 2.0 |
CA-FA | y=2.31×105x+6.33×103 | 1.0-500.0 | 0.9992 | 0.5 | 2.0 |
24MCA-FA | y=4.24×104x-9.44×103 | 5.0-1000.0 | 0.9983 | 1.0 | 3.5 |
Table 3 Linear equations, linear ranges, correlation coefficients (r2), LODs and LOQs of the three oryzanols
Compound | Linear equation | Linear range/(μg/L) | r2 | LOD/(μg/L) | LOQ/(μg/L) |
---|---|---|---|---|---|
Camp-FA | y=2.45×105x+1.21×104 | 1.0-500.0 | 0.9991 | 0.5 | 2.0 |
CA-FA | y=2.31×105x+6.33×103 | 1.0-500.0 | 0.9992 | 0.5 | 2.0 |
24MCA-FA | y=4.24×104x-9.44×103 | 5.0-1000.0 | 0.9983 | 1.0 | 3.5 |
Compound | Background/ (mg/kg) | Added/ (mg/kg) | Found/ (mg/kg) | Recovery/ % | RSD/ % |
---|---|---|---|---|---|
Camp-FA | 0.3 | 0.6 | 0.96 | 110.1 | 2.6 |
1.5 | 1.76 | 97.6 | 2.1 | ||
3.0 | 3.17 | 95.5 | 1.0 | ||
CA-FA | 0.5 | 1.0 | 1.58 | 108.5 | 0.9 |
2.5 | 2.65 | 86.1 | 1.3 | ||
5.0 | 5.27 | 95.5 | 2.1 | ||
24MCA-FA | 2.5 | 5.0 | 8.03 | 110.6 | 1.6 |
12.5 | 14.52 | 96.2 | 3.2 | ||
25.0 | 28.40 | 103.6 | 3.1 |
Table 4 Spiked recoveries and RSDs of the three oryzanols in rice (n=3)
Compound | Background/ (mg/kg) | Added/ (mg/kg) | Found/ (mg/kg) | Recovery/ % | RSD/ % |
---|---|---|---|---|---|
Camp-FA | 0.3 | 0.6 | 0.96 | 110.1 | 2.6 |
1.5 | 1.76 | 97.6 | 2.1 | ||
3.0 | 3.17 | 95.5 | 1.0 | ||
CA-FA | 0.5 | 1.0 | 1.58 | 108.5 | 0.9 |
2.5 | 2.65 | 86.1 | 1.3 | ||
5.0 | 5.27 | 95.5 | 2.1 | ||
24MCA-FA | 2.5 | 5.0 | 8.03 | 110.6 | 1.6 |
12.5 | 14.52 | 96.2 | 3.2 | ||
25.0 | 28.40 | 103.6 | 3.1 |
No. | Species | Sample name | Camp-FA/(mg/kg) | 24MCA-FA/(mg/kg) | CA-FA/(mg/kg) |
---|---|---|---|---|---|
1 | conventional Indica rice | Zhongzao 39 | 1.68 | 17.19 | 3.08 |
2 | Huanghuazhan | 2.92 | 25.57 | 5.50 | |
3 | conventional Japonica rice | Jia 67 | 2.06 | 17.19 | 9.28 |
4 | Indica Hybrid rice | Zhongzheyou 8 | 5.57 | 42.51 | 8.95 |
5 | Huazheyou 1 | 3.07 | 25.48 | 5.39 | |
6 | Japonica Hybrid rice | Jiayou 5 | 2.49 | 24.70 | 6.89 |
7 | Indica Japonica Hybrid | Yongyou 1540 | 3.90 | 32.49 | 6.44 |
Table 5 Determination results of the three oryzanols in the actual samples
No. | Species | Sample name | Camp-FA/(mg/kg) | 24MCA-FA/(mg/kg) | CA-FA/(mg/kg) |
---|---|---|---|---|---|
1 | conventional Indica rice | Zhongzao 39 | 1.68 | 17.19 | 3.08 |
2 | Huanghuazhan | 2.92 | 25.57 | 5.50 | |
3 | conventional Japonica rice | Jia 67 | 2.06 | 17.19 | 9.28 |
4 | Indica Hybrid rice | Zhongzheyou 8 | 5.57 | 42.51 | 8.95 |
5 | Huazheyou 1 | 3.07 | 25.48 | 5.39 | |
6 | Japonica Hybrid rice | Jiayou 5 | 2.49 | 24.70 | 6.89 |
7 | Indica Japonica Hybrid | Yongyou 1540 | 3.90 | 32.49 | 6.44 |
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