The “depict” strategy for discovering new compounds in complex matrices: Lycibarbarspermidines as a case

Chen Han; Zhixin Zhang; Zhiyang Feng; Chuanjia Zhai; Xuejiao Li; Yulian Shi; Xiang Li; Miao Li; Ying Wang; Gan Luo; Xiaoyan Gao

doi:10.1016/j.jpha.2023.10.007

Volume 14 Issue 3

Mar. 2024

Turn off MathJax

Article Contents

Article Navigation > Journal of Pharmaceutical Analysis > 2024 > 14(3): 416-426

Chen Han, Zhixin Zhang, Zhiyang Feng, Chuanjia Zhai, Xuejiao Li, Yulian Shi, Xiang Li, Miao Li, Ying Wang, Gan Luo, Xiaoyan Gao. The “depict” strategy for discovering new compounds in complex matrices: Lycibarbarspermidines as a case[J]. Journal of Pharmaceutical Analysis, 2024, 14(3): 416-426. doi: 10.1016/j.jpha.2023.10.007

Citation:

Chen Han, Zhixin Zhang, Zhiyang Feng, Chuanjia Zhai, Xuejiao Li, Yulian Shi, Xiang Li, Miao Li, Ying Wang, Gan Luo, Xiaoyan Gao. The “depict” strategy for discovering new compounds in complex matrices: Lycibarbarspermidines as a case[J]. Journal of Pharmaceutical Analysis, 2024, 14(3): 416-426. doi: 10.1016/j.jpha.2023.10.007

Citation:

Chen Han, Zhixin Zhang, Zhiyang Feng, Chuanjia Zhai, Xuejiao Li, Yulian Shi, Xiang Li, Miao Li, Ying Wang, Gan Luo, Xiaoyan Gao. The “depict” strategy for discovering new compounds in complex matrices: Lycibarbarspermidines as a case[J]. Journal of Pharmaceutical Analysis, 2024, 14(3): 416-426. doi: 10.1016/j.jpha.2023.10.007

PDF( 3155 KB)

The “depict” strategy for discovering new compounds in complex matrices: Lycibarbarspermidines as a case

doi: 10.1016/j.jpha.2023.10.007

Department of Chinese Medicine Analysis, School of Chinese Materia Medica, Beijing University of Chinese Medicine, Beijing, 102488, China

Funds:

This work was supported by the Fundamental Research Funds for the Central Universities in China (Grant No.: 2020-JYB-ZDGG-033).

Received Date: Apr. 16, 2023
Accepted Date: Oct. 19, 2023
Rev Recd Date: Oct. 08, 2023
Publish Date: Oct. 28, 2023

Abstract

Abstract

The comprehensive detection and identification of active ingredients in complex matrices is a crucial challenge. Liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) is the most prominent analytical platform for the exploration of novel active compounds from complex matrices. However, the LC-HRMS-based analysis workflow suffers from several bottleneck issues, such as trace content of target compounds, limited acquisition for fragment information, and uncertainty in interpreting relevant MS² spectra. Lycibarbarspermidines are vital antioxidant active ingredients in Lycii Fructus, while the reported structures are merely focused on dicaffeoylspermidines due to their low content. To comprehensively detect the new structures of lycibarbarspermidine derivatives, a “depict” strategy was developed in this study. First, potential new lycibarbarspermidine derivatives were designed according to the biosynthetic pathway, and a comprehensive database was established, which enlarged the coverage of lycibarbarspermidine derivatives. Second, the polarity-oriented sample preparation of potential new compounds increased the concentration of the target compounds. Third, the construction of the molecular network based on the fragmentation pathway of lycibarbarspermidine derivatives broadened the comprehensiveness of identification. Finally, the weak response signals were captured by data-dependent scanning (DDA) followed by parallel reaction monitoring (PRM), and the efficiency of acquiring MS² fragment ions of target compounds was significantly improved. Based on the integrated strategy above, 210 lycibarbarspermidine derivatives were detected and identified from Lycii Fructus, and in particular, 170 potential new compounds were structurally characterized. The integrated strategy improved the sensitivity of detection and the coverage of low-response components, and it is expected to be a promising pipeline for discovering new compounds.
- Mass spectrometric detection,
- Weak response signals,
- Complex matrices,
- Novel lycibarbarspermidines

FullText(HTML)

References(29)

References

[1]	M. Dong, Z. Tian, Y. Ma, et al., Rapid screening and characterization of glucosinolates in 25 Brassicaceae tissues by UHPLC-Q-exactive orbitrap-MS, Food Chem. 365 (2021), 130493.
[2]	J. Feng, P. Yu, Q. Zhou, et al., An integrated data filtering and identification strategy for rapid profiling of chemical constituents, with Arnebiae Radix as an example, J. Chromatogr. A 1629 (2020), 461496.
[3]	S. Fu, R. Cheng, Z. Deng, et al., Qualitative analysis of chemical components in Lianhua Qingwen capsule by HPLC-Q Exactive-Orbitrap-MS coupled with GC-MS, J. Pharm. Anal. 11 (2021) 709-716.
[4]	X. Chi, J. Liu, M. Yu, et al., Analysis of bromophenols in various aqueous samples using solid phase extraction followed by HPLC-MS/MS, Talanta 164 (2017) 57-63.
[5]	F. Klont, M.R. Joosten, N.H.T. Ten Hacken, et al., Quantification of the soluble Receptor of Advanced Glycation End-Products (sRAGE) by LC-MS after enrichment by strong cation exchange (SCX) solid-phase extraction (SPE) at the protein level, Anal. Chim. Acta 1043 (2018) 45-51.
[6]	X. Li, S. Li, G. Kellermann, Simultaneous determination of three estrogens in human saliva without derivatization or liquid-liquid extraction for routine testing via miniaturized solid phase extraction with LC-MS/MS detection, Talanta 178 (2018) 464-472.
[7]	J. Guo, T. Huan, Comparison of full-scan, data-dependent, and data-independent acquisition modes in liquid chromatography-mass spectrometry based untargeted metabolomics, Anal. Chem. 92 (2020) 8072-8080.
[8]	C. Li, J. Yang, X. Tong, et al., Precursor ion scan enhanced rapid identification of the chemical constituents of Danhong injection by liquid chromatography-tandem mass spectrometry:An integrated strategy, J. Chromatogr. A 1602 (2019) 378-385.
[9]	J. Bai, W. Chen, J. Huang, et al., Transformation of stilbene glucosides from Reynoutria multiflora during processing, Front. Pharmacol. 13 (2022), 757490.
[10]	A.C. Peterson, J.D. Russell, D.J. Bailey, et al., Parallel reaction monitoring for high resolution and high mass accuracy quantitative, targeted proteomics, Mol. Cell. Proteomics 11 (2012) 1475-1488.
[11]	B. Schilling, B. MacLean, J.M. Held, et al., Multiplexed, scheduled, high-resolution parallel reaction monitoring on a full scan QqTOF instrument with integrated data-dependent and targeted mass spectrometric workflows, Anal. Chem. 87 (2015) 10222-10229.
[12]	J. Zhou, H. Liu, Y. Liu, et al., Development and evaluation of a parallel reaction monitoring strategy for large-scale targeted metabolomics quantification, Anal. Chem. 88 (2016) 4478-4486.
[13]	H. Pan, H. Zhou, S. Miao, et al., An integrated approach for global profiling of multi-type constituents:Comprehensive chemical characterization of Lonicerae Japonicae Flos as a case study, J. Chromatogr. A 1613 (2020), 460674.
[14]	J. Zhang, Z. Wang, Y. Li, et al., A strategy for comprehensive identification of sequential constituents using ultra-high-performance liquid chromatography coupled with linear ion trap-Orbitrap mass spectrometer, application study on chlorogenic acids in Flos lonicerae Japonicae, Talanta 147 (2016) 16-27.
[15]	D. Chen, S. Guo, J. Zhou, et al., Chemical constituents from Lycium barbarum (Solanaceae) and their chemophenetic significance, Biochem. Syst. Ecol. 97 (2021), 104292.
[16]	A. Lopatriello, R. Previtera, S. Pace, et al., NMR-based identification of the major bioactive molecules from an Italian cultivar of Lycium barbarum, Phytochemistry, 144 (2017) 52-57.
[17]	D. Qian, J. Chen, C. Lai, et al., Dicaffeoyl polyamine derivatives from bitter goji:Contribution to the bitter taste of fruit, Fitoterapia 143 (2020), 104543.
[18]	Z.-Q. Zhou, H.-X. Fan, R.-R. He, et al., Lycibarbarspermidines A-O, new dicaffeoylspermidine derivatives from wolfberry, with activities against alzheimer's disease and oxidation, J. Agric. Food Chem. 64 (2016) 2223-2237.
[19]	H. Ahad, H. Jin, Y. Liu, et al., Chemical profiling of spermidines in goji berry by strong cation exchange solid-phase extraction (SCX-SPE) combined with ultrahigh-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS/MS), J. Chromatogr. B Analyt. Technol. Biomed. Life Sci. 1137 (2020), 121923.
[20]	G.S. dos Santos, A. de Almeida Veiga, J. Carlotto, et al., Identification and fingerprint analysis of novel multi-isomeric Lycibarbarspermidines and Lycibarbarspermines from Lycium barbarum L. by liquid chromatography with high-resolution mass spectrometry (UHPLC-Orbitrap), J. Food Compos. Anal. 105 (2022), 104194.
[21]	W. Boerjan, J. Ralph, M. Baucher, Lignin biosynthesis, Annu. Rev. Plant Biol. 54 (2003) 519-546.
[22]	W. Leonard, P. Zhang, D. Ying, et al., Lignanamides:Sources, biosynthesis and potential health benefits-a minireview, Crit Rev Food Sci. Nutr. 61 (2021) 1404-1414.
[23]	S. Liu, J. Jiang, Z. Ma, et al., The role of hydroxycinnamic acid amide pathway in plant immunity, Front. Plant Sci. 13 (2022), 922119.
[24]	D.R. Zeiss, L.A. Piater, I.A. Dubery, Hydroxycinnamate amides:Intriguing conjugates of plant protective metabolites, Trends Plant Sci. 26 (2021) 184-195.
[25]	N. Fontanals, R.M. Marce, F. Borrull, et al., Mixed-mode ion-exchange polymeric sorbents:Dual-phase materials that improve selectivity and capacity, Trends Analyt. Chem. 29 (2010) 765-779.
[26]	N. Gilart, P.A.G. Cormack, R.M. Marce, et al., Selective determination of pharmaceuticals and illicit drugs in wastewaters using a novel strong cation-exchange solid-phase extraction combined with liquid chromatography-tandem mass spectrometry, J. Chromatogr. A 1325 (2014) 137-146.
[27]	D. Salas, F. Borrull, R.M. Marce, et al., Study of the retention of benzotriazoles, benzothiazoles and benzenesulfonamides in mixed-mode solid-phase extraction in environmental samples, J. Chromatogr. A 1444 (2016) 21-31.
[28]	P.A. Shah, P.S. Shrivastav, A. George, Mixed-mode solid phase extraction combined with LC-MS/MS for determination of empagliflozin and linagliptin in human plasma, Microchem. J. 145 (2019) 523-531.
[29]	T. Wu, H. Lv, F. Wang, et al., Characterization of polyphenols from Lycium ruthenicum fruit by UPLC-Q-TOF/MSE and their antioxidant activity in Caco-2 cells, J. Agric. Food Chem. 64 (2016) 2280-2288.