Abstract
A perennial challenge in harnessing the rich biological activity of medicinal and edible plants is the accurate identification and sensitive detection of their active compounds. In this study, an innovative, ultra-sensitive detection platform for plant chemical profiling is created using surface-enhanced Raman spectroscopy (SERS) technology. The platform uses silver nanoparticles as the enhancing substrate, excess sodium borohydride prevents substrate oxidation, and methanol enables the tested molecules to be better adsorbed onto the silver nanoparticles. Subsequently, nanoparticle aggregation to form stable “hot spots” is induced by Ca2+, and the Raman signal of the target molecule is strongly enhanced. At the same time, deuterated methanol was used as the internal standard for quantitative determination. The method has excellent reproducibility, RSD ≤ 1.79%, and the enhancement factor of this method for the detection of active ingredients in the medicinal plant Coptis chinensis was 1.24 × 109, with detection limits as low as 3 fM. The platform successfully compared the alkaloid distribution in different parts of Coptis chinensis: root > leaf > stem, and the difference in content between different batches of Coptis chinensis decoction was successfully evaluated. The analytical technology adopted by the platform can speed up the determination of Coptis chinensis and reduce the cost of analysis, not only making better use of these valuable resources but also promoting development and innovation in the food and pharmaceutical industries. This study provides a new method for the development, evaluation, and comprehensive utilization of both medicinal and edible plants. It is expected that this method will be extended to the modern rapid detection of other medicinal and edible plants and will provide technical support for the vigorous development of the medicinal and edible plants industry.
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References
Teixidor-Toneu I, Jordan FM, Hawkins JA (2018) Comparative phylogenetic methods and the cultural evolution of medicinal plant use. Nat Plants 4(10):754–761
Ooi GL (1993) What future for traditional Chinese medicine outside China? World Health Forum 14(1):79
Tasneem S, Liu B, Li B, Choudhary MI, Wang W (2019) Molecular pharmacology of inflammation: medicinal plants as anti-inflammatory agents. Pharmacol Res 139:126–140
Manukumar HM, Shiva Kumar J, Chandrasekhar B, Raghava S, Umesha S (2017) Evidences for diabetes and insulin mimetic activity of medicinal plants: present status and future prospects. Crit Rev Food Sci 57(12):2712–2729
Shang A, Gan RY (2021) Effects and mechanisms of edible and medicinal plants on obesity: an updated review. Crit Rev Food Sci 61(12):2061–2077
Schafhauser T, Jahn L, Kirchner N, Kulik A, Flor L, Lang A, Caradec T, Fewer DP, Sivonen K (2019) Antitumor astins originate from the fungal endophyte Cyanodermella asteris living within the medicinal plant Aster tataricus. P Natl Acad Sci Usa 116(52):26909–26917
Tahir Ul Qamar M, Alqahtani SM, Alamri MA, Chen L-L (2020) Structural basis of SARS-CoV-2 3CLpro and anti-COVID-19 drug discovery from medicinal plants. J Pharm Anal 10(4):313–319
Jiang Y, David B, Tu P, Barbin Y (2010) Recent analytical approaches in quality control of traditional Chinese medicines–a review. Anal Chim Acta 657(1):9–18
Yang Y, Li SS, Teixeira Da Silva JA, Yu XN, Wang LS (2020) Characterization of phytochemicals in the roots of wild herbaceous peonies from China and screening for medicinal resources. Phytochemistry 174:112331
Zhan W, Yang X, Lu G, Deng Y, Yang L (2022) A rapid quality grade discrimination method for Gastrodia elata powder using ATR-FTIR and chemometrics. Spectrochim Acta A 264:120189
Liu W, Dai LK (2017) Online analysis of dynamic trend regression and endpoint determination for Chinese traditional medicine extraction process based on ultraviolet spectroscopy. Guang Pu Xue Yu Guang Pu Fen Xi 37(2):497–502
Luo L, Dong L, Huang Q, Ma S, Fantke P, Li J, Jiang J, Fitzgerald M, Yang J, Jia Z, Zhang J (2021) Detection and risk assessments of multi-pesticides in 1771 cultivated herbal medicines by LC/MS-MS and GC/MS-MS. Chemosphere 262:127477
Ren Y, Wang Z, Wu C, Dong H, Gan C, Fan L, Wang W, Yang C (2019) Ultrahigh-performance liquid chromatography with tandem mass spectrometry for the determination of 10 alkaloids in beagle plasma after the oral administration of the three Coptidis rhizoma extracts. J Ethnopharmacol 239:111896
Huang H, Lv Y, Sun X, Fu S, Lou X, Liu Z (2018) Rapid determination of tannin in Danshen and Guanxinning injections using UV spectrophotometry for quality control. J Innov Opt Heal Sci 11(06):1850034
Xiang L, Wang J, Zhang G, Rong L, Wu H, Sun S, Guo Y, Yang Y, Lu L, Qu L (2016) Analysis and identification of two similar traditional Chinese medicines by using a three-stage infrared spectroscopy: Ligusticum chuanxiong, Angelica sinensis and their different extracts. J Mol Struct 1124:164–172
Yang Y, Peng J, Li F, Liu X, Deng M, Wu H (2017) Determination of alkaloid contents in various tissues of Coptis chinensis Franch. by reversed phase-high performance liquid chromatography and ultraviolet spectrophotometry. J Chromatogr Sci 55(5):556–63
Chen J, Wang F, Liu J, Lee FS-C, Wang X, Yang H (2008) Analysis of alkaloids in Coptis chinensis Franch by accelerated solvent extraction combined with ultra performance liquid chromatographic analysis with photodiode array and tandem mass spectrometry detections. Anal Chim Acta 613(2):184–195
Yilmaz H, Yilmaz D, Taskin IC, Culha M (2022) Pharmaceutical applications of a nanospectroscopic technique: surface-enhanced Raman spectroscopy. Adv Drug Deliv Rev 184:114184
Zanchi C, Lucotti A, Tommasini M, Trusso S, De Grazia U, Ciusani E, Ossi PM (2015) Au nanoparticle-based sensor for apomorphine detection in plasma. Beilstein J Nanotechnol 6:2224–2232
Deng B, Luo X, Zhang M, Ye L, Chen Y (2019) Quantitative detection of acyclovir by surface enhanced Raman spectroscopy using a portable Raman spectrometer coupled with multivariate data analysis. Colloids Surf B Biointerfaces 173:286–294
Sharma B, Frontiera RR, Henry AI, Ringe E, Duyne RPV (2012) SERS: materials, applications, and the future. Mater Today 15(1–2):16–25
Li D, Yao D, Li C, Luo Y, Jiang Z (2020) Nanosol SERS quantitative analytical method: a review. Trac-Trend Anal Chem 127:115885
Tommasini M, Zanchi C, Lucotti A, Bombelli A, Villa NS, Casazza M, Ciusani E, De Grazia U, Santoro M, Fazio E, Neri F, Trusso S, Ossi PM (2019) Laser-synthesized SERS substrates as sensors toward therapeutic drug monitoring. Nanomaterials 9(5):677
Ouyang L, Zhang Q, Ma G, Zhu L, Wang Y, Chen Z, Wang Y, Zhao L (2019) New dual-spectroscopic strategy for the direct detection of aristolochic acids in blood and tissue. Anal Chem 91(13):8154–8161
Song-Bai SU, Zhang YP, Zhang LL, Zhu-Ying HE, Zhang JL (2011) Review on Raman spectroscopy application in quality control of traditional Chinese Medicine. Chinese J ETMF 17(08):284–286
Huang C-C (2016) Applications of Raman spectroscopy in herbal medicine. Appl Spectrosc Rev 51(1):1–11
Lin J, Chen W, Yu Y, Lin D, Feng S, Chen R (2016) Surface-enhanced Raman scattering spectroscopic analysis of Saposhnikovia divaricata decoction. Spectrosc Lett 49(3):204–207
Chen W, Lin J, Chen R, Feng S, Yu Y, Lin D, Huang M, Shi H, Huang H (2015) Detection and identification of Huo–Xue–Hua–Yu decoction (HXHYD) using surface-enhanced Raman scattering (SERS) spectroscopy and multivariate analysis. Laser Phys Lett 12(4):045602
Huang H, Shi H, Feng S, Lin J, Chen W, Yu Y, Lin D, Xu Q, Chen R (2012) Quick detection of traditional Chinese medicine ‘Atractylodis Macrocephalae Rhizoma’ pieces by surface-enhanced Raman spectroscopy. Laser Phys 23(1):015601
Gao Y, Hu Z, Wu J, Ning Z, Jian J, Zhao T, Liang X, Yang X, Yang Z, Zhao Q, Wang J, Wang Z, Dina NE, Gherman AMR, Jiang Z, Zhou H (2019) Size-tunable Au@Ag nanoparticles for colorimetric and SERS dual-mode sensing of palmatine in traditional Chinese medicine. J Pharm Biomed Anal 174:123–133
Liu E, Han L, Fan X, Yang Z, Jia Z, Shi S, Huang Y, Cai L, Yuan X (2022) New rapid detection method of total chlorogenic acids in plants using SERS based on reusable Cu(2)O-Ag substrate. Talanta 247:123552
Rauf A, Patel S, Uddin G, Siddiqui BS, Ahmad B, Muhammad N, Mabkhot YN, Hadda TB (2017) Phytochemical ethnomedicinal uses and pharmacological profile of genus Pistacia. Biomed Pharmacother 86:393–404
Wu J, Luo Y, Jiang Q, Li S, Huang W, Xiang L, Liu D, Hu Y, Wang P, Lu X, Zhang G, Wang F, Meng X (2019) Coptisine from Coptis chinensis blocks NLRP3 inflammasome activation by inhibiting caspase-1. Pharmacol Res 147:104348
Moeini R, Memariani Z, Asadi F, Bozorgi M, Gorji N (2019) Pistacia genus as a potential source of neuroprotective natural products. Planta Med 85(17):1326–1350
Friedemann T, Schumacher U, Tao Y, Leung AK, Schröder S (2015) Neuroprotective activity of coptisine from Coptis chinensis (Franch). Evid Based Complement Alternat Med 2015:827308
Kim SY, Park C, Kim MY, Ji SY, Hwangbo H, Lee H, Hong SH, Han MH, Jeong J-W, Kim G-Y, Son C-G, Cheong J, Choi YH (2021) ROS-mediated anti-tumor effect of Coptidis rhizoma against human hepatocellular carcinoma Hep3B cells and xenografts. Int J Mol Sci 22(9):4797
Lang L, Hu Q, Wang J, Liu Z, Huang J, Lu W, Huang Y (2018) Coptisine, a natural alkaloid from Coptidis rhizoma, inhibits plasmodium falciparum dihydroorotate dehydrogenase. Chem Biol Drug Des 92(1):1324–1332
Wang J, Ran Q, Zeng H-R, Wang L, Hu C-J, Huang Q-W (2018) Cellular stress response mechanisms of rhizoma Coptidis: a systematic review. Chin Med 13(1):27
Cheng M, Yao C, Li Y, Li Z, Li H, Yao S, Qu H, Li J, Wei W, Zhang J, Guo DA (2021) A strategy for practical authentication of medicinal plants in traditional Chinese medicine prescription, paeony root in ShaoYao-GanCao decoction as a case study. J Sep Sci 44(12):2427–2437
Zhang L, Yan J, Liu X, Ye Z, Yang X, Meyboom R, Chan K, Shaw D, Duez P (2012) Pharmacovigilance practice and risk control of traditional Chinese medicine drugs in China: current status and future perspective. J Ethnopharmacol 140(3):519–525
Zhong XK, Li DC, Jiang JG (2009) Identification and quality control of Chinese medicine based on the fingerprint techniques. Curr Med Chem 16(23):3064–3075
Yao X, Lin J, Zhou Q, Song Y, Sun T, Qiu X, Cao B, Li Y (2023) A new platform for rapid and indiscriminate detection of environmental pollutants based on surface-enhanced Raman spectroscopy. Environ Sci-Nano 10(9):2374–2386
Oćwieja M, Barbasz A, Walas S, Roman M, Paluszkiewicz C (2017) Physicochemical properties and cytotoxicity of cysteine-functionalized silver nanoparticles. Colloid Surface B 160:429–437
Ranishenka BV, Panarin AY, Chelnokova IA, Terekhov SN, Mojzes P, Shmanai VV (2021) Modification of a SERS-active Ag surface to promote adsorption of charged analytes: effect of Cu2+ ions. Beilstein J Nanotech 12:902–912
Guingab JD, Lauly B, Smith BW, Omenetto N, Winefordner JD (2007) Stability of silver colloids as substrate for surface enhanced Raman spectroscopy detection of dipicolinic acid. Talanta 74(2):271–274
Šloufová I, Šišková K, Vlčková B, Štěpánek J (2008) SERS-activating effect of chlorides on borate-stabilized silver nanoparticles: formation of new reduced adsorption sites and induced nanoparticle fusion. Phys Chem Chem Phys 10(16):2233–2242
Kazanci M, Schulte JP, Douglas C, Fratzl P, Pink D, Smith-Palmer T (2009) Tuning the surface-enhanced Raman scattering effect to different molecular groups by switching the silver colloid solution pH. Appl Spectrosc 63(2):214–223
Cheng Y, Ding Y, Chen J, Xu W, Wang W, Xu S (2022) Au nanoparticles decorated covalent organic framework composite for SERS analyses of malachite green and thiram residues in foods. Spectrochim Acta A Mol Biomol Spectrosc 281:121644
Pérez-Jiménez AI, Lyu D, Lu Z, Liu G, Ren B (2020) Surface-enhanced Raman spectroscopy: benefits, trade-offs and future developments. Chem Sci 11(18):4563–4577
Wang X, Liu X, Wang X, Wang Y, Xiao Y, Zhuo Z, Li Y (2022) A versatile technique based on surface-enhanced Raman spectroscopy for label-free detection of amino acids and peptide formation in body fluids. Microchim Acta 189(2):82
Zhang F, Wang X, Zhang T, Zhang Z, Gao X, Li Y (2023) Rapid detection of SARS-CoV-2 spike RBD protein in body fluid: based on special calcium ion-mediated gold nanoparticles modified by bromide ions. J Phys Chem Lett 14(1):88–94
Zhang Y, Zeng J, Huang C, Zhu B, Zhang Q, Chen D (2022) Label-free detection of ssDNA base insertion and deletion mutations by surface-enhanced Raman spectroscopy. Anal Bioanal Chem 414(4):1461–1468
Yang N, Wang Y, Wang X, Zhang F, Xiao Y, Yan B, Zhang T, Liu X, Li Y (2022) Label-free detection of DNA supramolecular structure formation by surface-enhanced Raman spectroscopy. J Phys Chem Lett 13(26):6208–6214
Li D, Zhang Z, Wang X, Wang Y, Gao X, Li Y (2022) A direct method for detecting proteins in body fluids by surface-enhanced Raman spectroscopy under native conditions. Biosens Bioelectron 200:113907
Zhang Z, Li D, Wang X, Wang Y, Lin J, Jiang S, Wu Z, He Y, Gao X, Zhu Z, Xiao Y, Qu Z, Li Y (2022) Rapid detection of viruses: based on silver nanoparticles modified with bromine ions and acetonitrile. Chem Eng J 438:135589
Li X, Wang X, Liu J, Dai M, Zhang Q, Li Y (2022) Surface-enhanced Raman spectroscopy detection of organic molecules and in situ monitoring of organic reactions by ion-induced silver nanoparticle clusters. Phys Chem Chem Phys 24(5):2826–2831
Zeng J, Dong M, Zhu B, Gao X, Chen D, Li Y (2021) Label-free detection of c-T mutations by surface-enhanced Raman spectroscopy using thiosulfate-modified nanoparticles. Anal Chem 93(4):1951–1956
Liu L, Zhang T, Wu Z, Zhang F, Wang Y, Wang X, Zhang Z, Li C, Lv X, Chen D, Jiao S, Wu J, Li Y (2023) Universal method for label-free detection of pathogens and biomolecules by surface-enhanced Raman spectroscopy based on gold nanoparticles. Anal Chem 95(8):4050–4058
Li R, Mao Z, Chen L, Lv H, Cheng J, Zhao B (2015) Vibrational spectroscopy and density functional theory study of 3-[4,5-dimethyl-2-thiazolyl]-2,5-diphenyl-2H-tetrazolium bromide. Spectrochim Acta A 135:1–6
Zhao Z, Guo P, Brand E (2012) The formation of daodi medicinal materials. J Ethnopharmacol 140(3):476–481
Chen LL, Verpoorte R, Yen HR, Peng WH, Cheng YC, Chao J, Pao LH (2018) Effects of processing adjuvants on traditional Chinese herbs. J Food Drug Anal 26(2s):S96-s114
Zhang FL, Yin XJ, Yan YL, Wu QF (2022) Pharmacokinetics and pharmacodynamics of Huanglian-Houpo decoction based on berberine hydrochloride and magnolol against H1N1 influenza virus. Eur J Drug Metab Ph 47(1):57–67
Wang Z, Yang Y, Liu M, Wei Y, Liu J, Pei H, Li H (2020) Rhizoma Coptidis for Alzheimer’s disease and vascular dementia: a literature review. Curr Vasc Pharmacol 18(4):358–368
Funding
This work was supported by the Introduce High-Level Talent Incentive Project (no. 0103–31021200052), HMU Marshal Initiative Funding (no. HMUMIF-21012), and National Natural Science Foundation for Youth (no. 82202648).
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Yang, C., Zhao, Y., Jiang, S. et al. A breakthrough in phytochemical profiling: ultra-sensitive surface-enhanced Raman spectroscopy platform for detecting bioactive components in medicinal and edible plants. Microchim Acta 191, 286 (2024). https://doi.org/10.1007/s00604-024-06360-x
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DOI: https://doi.org/10.1007/s00604-024-06360-x