Improved Quality Control Method for Prescriptions of Polygonum capitatum through Simultaneous Determination of Nine Major Constituents by HPLC Coupled with Triple Quadruple Mass Spectrometry
Abstract
:1. Introduction
2. Results and Discussion
2.1. Optimization of LC-MS/MS Conditions
2.2. Method Validation
2.2.1. Linearity and Detection Limit
Compounds | Characterization of 11 markers | MRM parameters | ||||
---|---|---|---|---|---|---|
RT (min) | M-H/M (m/z) | Lost ions | Quantification transition (m/z) | Frag (V) | CE (V) | |
Gallic acid | 0.774 | 169 | 125[M-COOH]-; 79[M-COOH-3OH+3H]- | 169→125 | 80 | 10 |
Protocatechuic acid | 0.793 | 153 | 109[M-COOH-H]-; 91[M-COOH-H20]- | 153→109 | 80 | 10 |
Vanillic acid | 0.837 | 167 | 152[M-CH3]-; 123[M-COOH]- | 167→152 | 80 | 10 |
Syringic acid | 0.846 | 197 | 182[M-CH3]-; 153[M-COOH]- | 197→182 | 80 | 20 |
Catechin | 6.184 | 289 | 245[M-CH3CHO]-; 109[M-2OH-C6H5-CH3CHO-CH3]- | 289→109 | 150 | 20 |
Schizandriside | 7.634 | 491 | 359[M-xylose]-; 344[M-xylose-CH3]- | 491→359 | 200 | 20 |
Quercitrin | 8.129 | 447 | 301[M-rhamnose]-; 255[M-rhamnose-COOH]- | 447→301 | 180 | 20 |
Quercetin | 8.677 | 301 | 179[M-2OH-C6H4-CH2]-; 151[M-2OH-C6H4-CH3CHO] | 301→151 | 150 | 15 |
Kaempferol | 9.046 | 285 | 117[M-2OH-C6H6-CH2O-2H2O]-; 93[C6H5+OH] | 285→ 93 | 150 | 25 |
Internal standard1 | 3.021 | 151 | 107[M-COOH]-; 92[M-COOH-CH3]- | 151→107 | 80 | 5 |
Internal standard2 | 7.749 | 579 | 459[M-glucose+CH3COOH]-; 271[M-glucose-rhamnose]- | 579→271 | 200 | 30 |
Compounds | Calibration curves | Linear ranges (ng·mL−1) | Correlation coefficient | LOD (ng·mL−1) | LOQ (ng·mL−1) |
---|---|---|---|---|---|
Gallic acid | Y = 0.7624X − 1.8747 | 100–10,000 | 0.9937 | 5.0 | 10 |
Protocatechuic acid | Y = 0.9881X − 0.0169 | 5–500 | 0.9974 | 1.0 | 5.0 |
Vanillic acid | Y = 0.6889X − 0.6085 | 100–10,000 | 0.9982 | 1.0 | 5.0 |
Syringic acid | Y = 11.5119X + 68.0960 | 5–1,000 | 0.9992 | 1.0 | 5.0 |
Catechin | Y = 72.2795X + 637.9497 | 5–1,000 | 0.9965 | 1.0 | 5.0 |
Schizandriside | Y = 0.0019X − 0.0032 | 50–10,000 | 0.9971 | 5.0 | 10 |
Quercitrin | Y = 9.6795X − 0.8127 | 5–10,000 | 0.9989 | 1.0 | 5.0 |
Quercetin | Y = 0.7283X − 0.0865 | 50–10,000 | 0.9991 | 1.0 | 5.0 |
Kaempferol | Y = 0.3322X − 0.0300 | 10–5,000 | 0.9987 | 1.0 | 5.0 |
2.2.2. Precision, Repeatability and Stability
2.2.3. Recovery
Compounds | Precision (RSD, n = 6) % | Repeatability (RSD, n = 6) % | Stability (RSD, n = 6) % | |||
---|---|---|---|---|---|---|
Intra-day | Inter-day | G1 C1 T1 | ||||
Gallic acid | 1.68 | 2.11 | 2.75 | 2.27 | 2.35 | 3.16 |
Protocatechuic acid | 1.59 | 2.35 | 2.17 | 2.38 | 2.67 | 2.78 |
Vanillic acid | 2.36 | 2.47 | 3.03 | 2.79 | 2.08 | 2.91 |
Syringic acid | 2.07 | 2.58 | 2.69 | 2.67 | 3.24 | 3.56 |
Catechin | 1.73 | 2.72 | 2.78 | 3.29 | 2.49 | 2.44 |
Schizandriside | 2.32 | 2.78 | 3.47 | 2.88 | 2.37 | 3.72 |
Quercitrin | 1.25 | 1.47 | 2.05 | 1.84 | 2.16 | 2.38 |
Quercetin | 1.54 | 1.87 | 2.19 | 2.17 | 3.24 | 2.27 |
Kaempferol | 1.68 | 2.31 | 2.57 | 2.74 | 2.35 | 3.04 |
Compounds | Granules | Capsule | Tablet | |||
---|---|---|---|---|---|---|
Recovery (%) | RSD (%) | Recovery (%) | RSD (%) | Recovery (%) | RSD (%) | |
Gallic acid | 98.61% | 2.18 | 99.50% | 3.03 | 101.38% | 2.13 |
100.65% | 2.33 | 96.91% | 2.45 | 99.76% | 2.65 | |
95.68% | 2.46 | 101.05% | 2.19 | 101.33% | 2.29 | |
Protocatechuic acid | 97.34% | 2.98 | 96.57% | 3.17 | 96.57% | 3.15 |
98.29% | 3.10 | 101.47% | 2.27 | 102.25% | 3.27 | |
102.51% | 2.78 | 95.00% | 3.66 | 97.70% | 3.26 | |
Vanillic acid | 98.91% | 2.59 | 104.50% | 2.49 | 101.38% | 3.55 |
101.70% | 2.84 | 97.70% | 2.85 | 98.05% | 2.64 | |
103.12% | 3.14 | 108.54% | 3.14 | 103.82% | 2.74 | |
Syringic acid | 102.07% | 3.19 | 102.72% | 2.19 | 101.84% | 2.15 |
102.43% | 3.28 | 98.13% | 3.28 | 97.40% | 3.28 | |
95.58% | 2.97 | 95.29% | 2.87 | 95.14% | 2.97 | |
Catechin | 98.68% | 2.46 | 103.88% | 3.26 | 101.85% | 2.46 |
107.80% | 2.79 | 95.79% | 2.89 | 102.40% | 2.79 | |
98.23% | 3.13 | 95.93% | 3.13 | 97.63% | 3.03 | |
Schizandriside | 101.36% | 3.28 | 101.98% | 3.08 | 101.20% | 3.48 |
101.53% | 3.24 | 95.01% | 3.24 | 100.57% | 2.14 | |
98.30% | 2.85 | 97.94% | 2.85 | 97.59% | 2.15 | |
Quercitrin | 100.97% | 3.77 | 101.22% | 3.27 | 101.83% | 3.67 |
102.73% | 3.54 | 101.53% | 3.54 | 104.04% | 3.34 | |
99.53% | 3.42 | 98.27% | 3.62 | 98.27% | 2.62 | |
Quercetin | 97.13% | 2.79 | 95.26% | 2.79 | 101.89% | 2.79 |
104.62% | 2.57 | 95.81% | 2.57 | 97.74% | 2.57 | |
97.62% | 2.84 | 104.03% | 2.84 | 96.30% | 2.53 | |
Kaempferol | 93.60% | 2.13 | 95.25% | 2.23 | 97.15% | 2.13 |
105.60% | 2.15 | 104.64% | 2.15 | 102.32% | 2.42 | |
95.07% | 3.08 | 96.03% | 2.38 | 97.43% | 3.18 |
2.3. Sample Determination
Samples | Contents of each compound in different relinqing samples | ||||||||
---|---|---|---|---|---|---|---|---|---|
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | |
G1 | 21,751.04 | 568.31 | 463.72 | 68.92 | 56.31 | 852.04 | 699.64 | 84.32 | 46.95 |
G2 | 19,667.32 | 587.64 | 457.58 | 70.25 | 58.67 | 657.38 | 687.81 | 80.77 | 45.57 |
G3 | 20,996.64 | 495.94 | 471.46 | 69.67 | 53.71 | 789.68 | 696.79 | 93.94 | 44.82 |
G4 | 19,589.24 | 488.73 | 482.88 | 75.39 | 59.86 | 856.41 | 663.84 | 95.63 | 46,78 |
20,501.06 | 535.15 | 468.91 | 71.05 | 57.14 | 788.87 | 687.02 | 88.66 | 45.78 | |
RSD | 5.14% | 9.37% | 2.32% | 4.13% | 4.76% | 11.76% | 2.36% | 8.17% | 2.36% |
C1 | 17,855.36 | 359.67 | 134.37 | 58.98 | 138.68 | 679.78 | 609.64 | 185.37 | 47.81 |
C2 | 17,015.81 | 468,95 | 147.63 | 72.74 | 156.42 | 516.89 | 626.79 | 168,98 | 46.03 |
C3 | 19,389.43 | 443.64 | 159.83 | 65.81 | 140.17 | 591.57 | 614.46 | 174.46 | 44.42 |
C4 | 18,544.16 | 369,97 | 138.52 | 73.57 | 163.59 | 714,62 | 621.69 | 151.63 | 47.83 |
C | 18,201.19 | 401.65 | 145.08 | 67.77 | 149.71 | 596.08 | 618.14 | 170.48 | 46.52 |
RSD | 5.54% | 14.78% | 7.76% | 10.05% | 8.18% | 13.67% | 1.23% | 10.09% | 3.51% |
T1 | 9,439.76 | 277.79 | 426.14 | 59.42 | 51.37 | 839.17 | 403.48 | 220.17 | 48.96 |
T2 | 12,920.56 | 321.46 | 437.27 | 66.89 | 59.47 | 765.04 | 409.79 | 160.79 | 42.37 |
T3 | 15,145.27 | 258.42 | 419.49 | 72.47 | 62.89 | 323.66 | 302.42 | 345.53 | 54.89 |
T4 | 11,075.44 | 306.54 | 403.72 | 58.81 | 60.34 | 691.74 | 423.54 | 193.41 | 46.54 |
T | 12,145.26 | 291.05 | 421.65 | 64.39 | 58.51 | 654.9 | 564.50 | 229.97 | 48.19 |
RSD | 20.21% | 9.72% | 3.32% | 10.11% | 8.51% | 34.94% | 14.43% | 35.12% | 10.85% |
total | 16,919.17 | 409.28 | 345.21 | 67.73 | 88.45 | 679.95 | 395.07 | 163.03 | 46.83 |
2.4. Discussion
3. Experimental
3.1. Materials and Reagents
3.2. Preparation of Sample Solutions
3.3. Preparation of Standard Solutions
3.4. Chromatographic and Mass Spectrometric Conditions
4. Conclusions
Acknowledgments
Conflicts of Interest
References
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- Sample Availability: Samples of the compounds—(1) gallic acid; (2) protocatechuic acid; (3) vanillic acid; (4) syringic acid; (5) catechin; (6) schizandriside; (7) quercitrin; (8) quercetin; (9) kaempferol—are available from the authors.
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Zhang, K.-X.; Wang, Y.-S.; Jing, W.-G.; Zhang, J.; Liu, A. Improved Quality Control Method for Prescriptions of Polygonum capitatum through Simultaneous Determination of Nine Major Constituents by HPLC Coupled with Triple Quadruple Mass Spectrometry. Molecules 2013, 18, 11824-11835. https://doi.org/10.3390/molecules181011824
Zhang K-X, Wang Y-S, Jing W-G, Zhang J, Liu A. Improved Quality Control Method for Prescriptions of Polygonum capitatum through Simultaneous Determination of Nine Major Constituents by HPLC Coupled with Triple Quadruple Mass Spectrometry. Molecules. 2013; 18(10):11824-11835. https://doi.org/10.3390/molecules181011824
Chicago/Turabian StyleZhang, Kai-Xia, Yue-Sheng Wang, Wen-Guang Jing, Jun Zhang, and An Liu. 2013. "Improved Quality Control Method for Prescriptions of Polygonum capitatum through Simultaneous Determination of Nine Major Constituents by HPLC Coupled with Triple Quadruple Mass Spectrometry" Molecules 18, no. 10: 11824-11835. https://doi.org/10.3390/molecules181011824