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Historically, botanical preparations have been used to improve human health. Their active ingredients are influenced by multiple factors such as intraspecies variations, environmental conditions, collection time and methods, and the part of the plant used. To ensure the efficiency and safety of these herbal drugs, qualitative and quantitative analyses are required. A Tessaria absinthioides decoction (DETa) was reported as having hypocholesterolemic, anti-inflammatory, cytotoxic, antitumor, and antioxidative properties. This work aimed to analyze DETa by correlating its chemical composition with cytotoxic and antioxidative properties, with the aim of promoting research on it as an anticancer agent. DETa collections (2017, 2018, 2019, and 2022) were analyzed by UHPLC-DAD, UHPLC-DAD-FLD, and UPLC-MS/MS; cytotoxicity was assessed on the MCF-7 breast cancer cell line; antioxidative capacity was evaluated by the DPPH and FRAP methods; and correlation analysis was used to determine biological and chemical markers. The results provide evidence that biological activities were consistent across the collections. Among the quantified compounds, apigenin, naringin, gallocatechin gallate, ginnalin A, myricetin, epicatechin, OH-tyrosol, quercetin, and chlorogenic, tessaric, p-coumaric, vanillic, caffeic, caftaric, ellagic, and rosmarinic acids correlated as bioactive and chemical markers. Moreover, tessaric acid could be established as a species marker. Altogether, these findings add relevant information to DETa properties, encouraging further exploration of its potential application as an anticancer botanical. [ABSTRACT FROM AUTHOR]

Taxonomy—the classification of species—is an important branch of biology that allows us to systematically understand and study biodiversity. Conventional taxonomy relies heavily on morphological and anatomical structures for classification, but recent discoveries of potentially cryptic species and morphological plasticity in many species underscore the importance of having an alternative or complementary method for species classification. In this paper, we discuss the emerging method of classification using biochemical signals, i.e., chemotaxonomy. We also present a case study on the feasibility of biomarker-based chemotaxonomy on the marine red alga Laurencia snackeyi using halogenated snyderane-type sesquiterpenes, which were proposed in earlier studies. [ABSTRACT FROM AUTHOR]

Taxonomy—the classification of species—is an important branch of biology that allows us to systematically understand and study biodiversity. Conventional taxonomy relies heavily on morphological and anatomical structures for classification, but recent discoveries of potentially cryptic species and morphological plasticity in many species underscore the importance of having an alternative or complementary method for species classification. In this paper, we discuss the emerging method of classification using biochemical signals, i.e., chemotaxonomy. We also present a case study on the feasibility of biomarker-based chemotaxonomy on the marine red alga Laurencia snackeyi using halogenated snyderane-type sesquiterpenes, which were proposed in earlier studies.

Background: As one of the four most valuable animal medicines, Fel Ursi, named Xiong Dan (XD) in China, has the effect of clearing heat, calming the liver, and brightening the eyes. However, due to the special source of XD and its high price, other animals' bile is often sold as XD or mixed with XD on the market, seriously affecting its clinical efficacy and consumers' rights and interests. In order to realize identification and adulteration analysis of XD, UHPLC-QTOF-MSE and multivariate statistical analysis were used to explore the differences in XD and six other animals' bile. Methods: XD, pig gall (Zhu Dan, ZD), cow gall (Niu Dan, ND), rabbit gallbladder (Tu Dan, TD), duck gall (Yan Dan, YD), sheep gall (Yang Dan, YND), and chicken gall (Ji Dan, JD) were analyzed by UHPLC-QTOF-MSE, and the MS data, combined with multivariate analysis methods, were used to distinguish between them. Meanwhile, the potential chemical composition markers that contribute to their differences were further explored. Results: The results showed that XD and six other animals' bile can be distinguished from each other obviously, with 27 ions with VIP > 1.0. We preliminarily identified 10 different bile acid-like components in XD and the other animals' bile with significant differences (p < 0.01) and VIP > 1.0, such as tauroursodeoxycholic acid, Glycohyodeoxycholic acid, and Glycodeoxycholic acid. Conclusions: The developed method was efficient and rapid in accurately distinguishing between XD and six other animals' bile. Based on the obtained chemical composition markers, it is beneficial to strengthen quality control for bile medicines. [ABSTRACT FROM AUTHOR]

Historically, botanical preparations have been used to improve human health. Their active ingredients are influenced by multiple factors such as intraspecies variations, environmental conditions, collection time and methods, and the part of the plant used. To ensure the efficiency and safety of these herbal drugs, qualitative and quantitative analyses are required. A Tessaria absinthioides decoction (DETa) was reported as having hypocholesterolemic, anti-inflammatory, cytotoxic, antitumor, and antioxidative properties. This work aimed to analyze DETa by correlating its chemical composition with cytotoxic and antioxidative properties, with the aim of promoting research on it as an anticancer agent. DETa collections (2017, 2018, 2019, and 2022) were analyzed by UHPLC-DAD, UHPLC-DAD-FLD, and UPLC-MS/MS; cytotoxicity was assessed on the MCF-7 breast cancer cell line; antioxidative capacity was evaluated by the DPPH and FRAP methods; and correlation analysis was used to determine biological and chemical markers. The results provide evidence that biological activities were consistent across the collections. Among the quantified compounds, apigenin, naringin, gallocatechin gallate, ginnalin A, myricetin, epicatechin, OH-tyrosol, quercetin, and chlorogenic, tessaric, p-coumaric, vanillic, caffeic, caftaric, ellagic, and rosmarinic acids correlated as bioactive and chemical markers. Moreover, tessaric acid could be established as a species marker. Altogether, these findings add relevant information to DETa properties, encouraging further exploration of its potential application as an anticancer botanical.

Honey is a popular healthy product, but the honey fraud is serious on the market, so the various characteristics of honey have been explored to identify its authenticity. In this study, a method of solid-phase extraction (SPE) combined with liquid chromatography-tandem mass spectrometry (LC–MS/MS) was developed for the simultaneous determination of trigonelline and caffeine in honey. Under the optimized conditions, both trigonelline and caffeine have good linearity (R2 > 0.999), good accuracy (spiked recoveries ranged from 92.1 to 107.9%) and good precision (relative standard deviations < 8.1%), with the limits of detection of 6 μg/L. The developed method was applied to 330 Chinese honey samples of 23 botanical origins. The results indicated that caffeine was only detected in Citrus honey (5.8 mg/kg) and Coffee honey (90.7 mg/kg), and trigonelline was detected with high levels in Coffee honey (81.9 mg/kg) and in Rape honey (71.1 mg/kg), which were much higher than that in the honey samples from other botanical origins (ranged from 0.5 to 7.0 mg/kg). To our knowledge, the high level of trigonelline in Rape honey is a novel finding. Samples were classified by cluster analysis according to the contents of trigonelline and caffeine, and the result indicated that the samples could be divided into four cluster groups based on their botanical origins. Furthermore, a criterion was built based on the level of trigonelline and caffeine for the identification of Rape honey, Citrus honey and Coffee honey, and it provides some support for the identification of honey botanical origins. [ABSTRACT FROM AUTHOR]

The Urticaceae family (Rosales) comprises six tribes containing 61 genera, with about 2000 species distributed throughout tropical and subtropical regions. Taxonomic controversies concerning Urticaceae remain unresolved. This study aimed to characterize the specialized metabolites in Urticaceae genera and tribes in order to define their chemical profiles, micromolecular markers and the group evolutionary trends. Chemosystematic indexes—occurrence number (ON), oxidation index (OI) and skeleton specialization (SS)—and their evolutionary advancement parameters were calculated based on chemical literature data on Urticaceae flavonoids and triterpenes. Principal component analysis and hierarchical clusters were also performed. Altogether, 356 flavonoids and 607 terpenoids were analyzed. Flavonols and flavones with low protection indexes of flavonoid hydroxyls by O-glycosylation were observed. Moreover, triterpenes were predominant in the Urticaceae. The chemometric analysis confirmed that the Cecropieae tribe belongs to the Urticaceae family indicating similarities and dissimilarities due to metabolic micromolecular variability. Chemometric analysis revealed chemical similarities among several tribes of Urticaceae, including Urticeae, Elatostemateae, Boehmerieae, Parietarieae, Forsskaoleeae, and Cecropieae. C-glycosylated flavones in Cecropieae suggest an evolutionary transition consistent with their phylogenetic position in Urticaceae. These results demonstrate the usefulness of chemosystematics as a reliable tool for describing specialized metabolites in Urticaceae and for supporting molecular phylogenetic studies. [ABSTRACT FROM AUTHOR]

Ginseng is a popular tonic worldwide, and its effects can be enhanced by steaming. Previous studies regarding the steaming of ginseng mainly focus on the contained saponins but are rare on the volatile components. In the present study, we developed headspace sampling gas chromatography-mass spectrometry (HS-GC-MS)-based untargeted metabolomics to holistically characterize the altered volatile components of P. ginseng (PG), P. quinquefolius (PQ), and P. notoginseng (PN) during the process of steaming. Chromatographic separation conditions for GC-MS were optimized, by which the volatile components in both the raw and the steaming-processed products (at 1–10 h) for PG, PQ, and PN were characterized within 38 min on an HP-5MS elastic quartz capillary column. We could characterize 106 volatile components from PG, 106 from PQ, and 105 from PN. Multivariate statistical analysis could depict the transformation trajectory for PG, PQ, and PN induced by steaming at different times. Ultimately, 13, 16, and 14 significantly differential volatile components for the steaming of PG, PQ, and PN were discovered by GC-MS-based untargeted metabolomics analysis. Notably, 3-methyl-1-butanol, 2-pentylfuran, hexanal, caryophyllene, and (−)-aristolene were diagnostic to distinguish the raw and processed products for PG. α-Pinene, 2-pentylfuran, hexanoic acid, 2,3-butanediol, and pyruvic acid could distinguish the raw and processed PQ. Cyperene, furfural, 1-isopropyl-4,7-dimethyl-1,2,3,5,6,8a-hexahydronaphthalene, hydroxyacetone, and 1-pentanol could discriminate the raw and processed products of PN. The established GC-MS approach can be a practical tool to investigate the underlying processing mechanism of traditional Chinese medicine by revealing changes in its volatile components. [ABSTRACT FROM AUTHOR]

The leaves of Panax species (e.g., Panax ginseng-PGL, P. quinquefolius-PQL, and P. notoginseng-PNL) can serve as a source for healthcare products. Comprehensive characterization and unveiling of the metabolomic difference among PGL, PQL, and PNL are critical to ensure their correct use. For this purpose, enhanced profiling and chemometrics were integrated to probe into the ginsenoside markers for PGL/PQL/PNL by ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry (UHPLC/IM-QTOF-MS). A hybrid scan approach (HDMSE-HDDDA) was established achieving the dimension-enhanced metabolic profiling, with 342 saponins identified or tentatively characterized from PGL/PQL/PNL. Multivariate statistical analysis (33 batches of leaf samples) could unveil 42 marker saponins, and the characteristic ginsenosides diagnostic for differentiating among PGL/PQL/PNL were primarily established. Compared with the single DDA or DIA, the HDMSE-HDDDA hybrid scan approach could balance between the metabolome coverage and spectral reliability, leading to high-definition MS spectra and the additional collision-cross section (CCS) useful to differentiate isomers. [ABSTRACT FROM AUTHOR]

Precise identification and differentiation among those congeneric Traditional Chinese Medicines (TCMs) or derived from the same plant trend to be more challenging, particularly in the absence of appearance characteristics. Three TCMs, involving Gleditsiae Sinensis Fructus (GSF), Gleditsiae Fructus Abnormalis (GFA), and Gleditsiae Spina (GS), recorded in Chinese Pharmacopoeia (2020 edition) are derived from Gleditsia sinensis, but prescribed for different clinical uses. The documents aimed to compare their chemical differences are rare, to date. An untargeted metabolomics approach, based on ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UHPLC/QTOF-MS), was elaborated to unveil the potential chemical markers to differentiate among GSF, GFA, and GS. Good chromatographic separation of all the GSF/GFA/GS components was achieved within 33 min by utilizing a BEH C18 column, while data-independent MSE in the positive mode was selected for profiling the metabolic features. Notably, the high-mass saponins (1300–2500 Da) gave unique protonated precursors ([M + H]+) in the positive ESI mode, compared with those complicated ion species occurring in the negative mode. Pattern recognition chemometrics analysis of 45 batches of G. sinensis samples could unveil 70 significantly altered ions assigned as 46 potentially differential components. The positive/negative high-accuracy MS2 data analysis, phytochemical isolation/NMR analysis, and searching of an in-house library of G. sinensis, were utilized for structural elucidation. Three compounds (saikachinoside A, locustoside A, and locustoside B) rich in GSF could be the markers to differentiate from GFA/GS, while four components were characteristic for GS. These results obtained can greatly benefit the quality control of TCMs derived from G. sinensis.

Place of origin has an important influence on walnut quality and commercial value, which results in the requirement of rapid geographical traceability method. Thus, a method for geographical origin identification of walnuts on the basis of nutritional quality of walnuts from China was conducted. The concentrations of 43 phytochemical components were analyzed in walnut samples from five different walnut-producing regions of China. Based on 14 chemical markers selected by the Random Forest method from these phytochemical components, a new discriminant model for geographical origin was built, with the corresponding correct classification rate of 99.3%. In addition, the quantitative quality differences of walnuts from five regions were analyzed, with values of 0.17–1.43. Moreover, the top three chemical markers for the geographical origin discriminant analysis were Mo, V, and stearic acid, with contribution rates of 26.8%, 18.9%, and 10.9%, respectively. This study provides a potentially viable method for application in food authentication. [ABSTRACT FROM AUTHOR]

Chrysanthemum indicum is a polymorphic species with many ecological, geographical or eco-geographic populations, but there are few studies on the metabolic characteristics of different populations. This study conducted widely targeted metabolomics studies on Ch. indicum from seven typical producing areas. As a result, a total of 802 metabolites were detected and identified, among which the top three categories of metabolites were flavonoids, organic acids and amino acids and derivatives. Through multivariate statistical analysis, the seven samples from different habitats could be divided into four categories, and the significantly changed metabolites between different categories were mainly concentrated in the flavonoid synthesis pathway. Through a variety of cluster analysis, it was observed that the Ch. nankingense (Nakai) Tzvel (Chinese name Juhuanao) had the largest separation degree from other samples and were clustered into a single category. Furthermore, the corresponding candidate chemical markers were screened in this study to distinguish the Juhuanao. Correlation analysis showed that climatic factors were not the main reason for the differences in the metabolic characteristics of Ch. indicum in different populations, which indicated that Ch. indicum is indeed a species with rich variation. [ABSTRACT FROM AUTHOR]

Background: As one of the four most valuable animal medicines, Fel Ursi, named Xiong Dan (XD) in China, has the effect of clearing heat, calming the liver, and brightening the eyes. However, due to the special source of XD and its high price, other animals' bile is often sold as XD or mixed with XD on the market, seriously affecting its clinical efficacy and consumers' rights and interests. In order to realize identification and adulteration analysis of XD, UHPLC-QTOF-MS E and multivariate statistical analysis were used to explore the differences in XD and six other animals' bile., Methods: XD, pig gall (Zhu Dan, ZD), cow gall (Niu Dan, ND), rabbit gallbladder (Tu Dan, TD), duck gall (Yan Dan, YD), sheep gall (Yang Dan, YND), and chicken gall (Ji Dan, JD) were analyzed by UHPLC-QTOF-MS E , and the MS data, combined with multivariate analysis methods, were used to distinguish between them. Meanwhile, the potential chemical composition markers that contribute to their differences were further explored., Results: The results showed that XD and six other animals' bile can be distinguished from each other obviously, with 27 ions with VIP > 1.0. We preliminarily identified 10 different bile acid-like components in XD and the other animals' bile with significant differences ( p < 0.01) and VIP > 1.0, such as tauroursodeoxycholic acid, Glycohyodeoxycholic acid, and Glycodeoxycholic acid., Conclusions: The developed method was efficient and rapid in accurately distinguishing between XD and six other animals' bile. Based on the obtained chemical composition markers, it is beneficial to strengthen quality control for bile medicines.

The leaves of Panax species (e.g., Panax ginseng-PGL, P. quinquefolius-PQL, and P. notoginseng-PNL) can serve as a source for healthcare products. Comprehensive characterization and unveiling of the metabolomic difference among PGL, PQL, and PNL are critical to ensure their correct use. For this purpose, enhanced profiling and chemometrics were integrated to probe into the ginsenoside markers for PGL/PQL/PNL by ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry (UHPLC/IM-QTOF-MS). A hybrid scan approach (HDMSE-HDDDA) was established achieving the dimension-enhanced metabolic profiling, with 342 saponins identified or tentatively characterized from PGL/PQL/PNL. Multivariate statistical analysis (33 batches of leaf samples) could unveil 42 marker saponins, and the characteristic ginsenosides diagnostic for differentiating among PGL/PQL/PNL were primarily established. Compared with the single DDA or DIA, the HDMSE-HDDDA hybrid scan approach could balance between the metabolome coverage and spectral reliability, leading to high-definition MS spectra and the additional collision-cross section (CCS) useful to differentiate isomers.

Chemical methods are the most important and widely used traditional plant identification techniques recommended by national and international pharmacopoeias. We have reviewed the successful use of different chemical methods for the botanical authentication of 2,386 commercial herbal products, sold in 37 countries spread over six continents. The majority of the analyzed products were reported to be authentic (73%) but more than a quarter proved to be adulterated (27%). At a national level, the number of products and the adulteration proportions varied very widely. Yet, the adulteration reported for the four countries, from which more than 100 commercial products were purchased and their botanical ingredients chemically authenticated, was 37% (United Kingdom), 31% (Italy), 27% (United States), and 21% (China). Simple or hyphenated chemical analytical techniques have identified the total absence of labeled botanical ingredients, substitution with closely related or unrelated species, the use of biological filler material, and the hidden presence of regulated, forbidden or allergenic species. Additionally, affecting the safety and efficacy of the commercial herbal products, other low quality aspects were reported: considerable variability of the labeled metabolic profile and/or phytochemical content, significant product-to-product variation of botanical ingredients or even between batches by the same manufacturer, and misleading quality and quantity label claims. Choosing an appropriate chemical technique can be the only possibility for assessing the botanical authenticity of samples which have lost their diagnostic microscopic characteristics or were processed so that DNA cannot be adequately recovered.

The plant Scutellaria barbata (SB) is commonly used as herbal medicines for treating cancer. The present pre‐clinical study aimed to validate the Chinese Pharmacopoeia (CP) recommended dosages of SB water extract (SBW) in treating colon tumors. The content of chemical marker scutellarin in SBW was quantified using UPLC. Mice bearing human HCT116 xenografts or murine colon26 tumors received oral administration of SBW or scutellarin for 4 weeks. Results showed that SBW (615 and 1,230 mg/kg) and scutellarin (7 mg/kg) treatments significantly reduced human xenograft weights by 28.7, 36.9 and 28.8%, respectively. Lung metastasis area could be ameliorated after SBW (615 mg/kg) and scutellarin (7 mg/kg) treatments by 23.4 and 29.5%, respectively. Expressions of colon cancer metastasis‐related proteins E‐cadherin, Tspan 8 and CXCR4, as well as Src kinase in tumors were first shown to be regulated by SBW. Furthermore, in murine colon26 tumor‐bearing mice, SBW (615 mg/kg) and scutellarin (7 mg/kg) treatments reduced the orthotopic tumor burden by 94.7% and lung metastatic tumor burden by 94.1%, respectively. Our findings provided evidences that SBW (at the mouse equivalent dosages to clinical dosages recommended by CP) could exert anti‐tumor and anti‐metastatic effects in colon cancer animal models. [ABSTRACT FROM AUTHOR]

Phytochemical investigation through cytotoxicity bioassay-guided isolation of Geniotrigona thoracica propolis led to the identification of five cycloartane-type triterpenes, including mangiferonic acid 1 , ambonic acid 2 , mangiferolic acid 3 , ambolic acid 4 and cycloartenol 5 . Their structures were established based on detailed spectroscopic analysis and comparison with literature data. Compounds 1 - 5 were isolated for the first time in this species. From cytotoxicity MTT assay, compound 3 inhibited the growth of breast (MCF-7) and hepatocellular carcinoma (HepG2) cancer cell lines with IC 50 of 5.08 and 4.82 µg/mL, respectively. Cytotoxicity of compounds 1 - 5 were reported for the first time against HepG2 cancer cell lines. Compounds 1 - 4 were suggested to serve as main and/or analytical markers for G. thoracica propolis based on HPLC analysis. To our knowledge, this is the first report on the isolation of bioactive constituents and identification of chemical markers for G. thoracica propolis.

Identification of chemical markers is important to ensure the authenticity of monofloral honey; however, the formation of chemical markers in honey has received little attention. Herein, using comparative metabolomics, we first identified chemical markers in chaste honey and then explored their formation and accumulation from nectar to mature honey. We identified agnuside and p -hydroxybenzoic acid glucosides as chemical markers for chaste honey. Besides, we developed an UHPLC-MS/MS method for quantifying these markers and found that their levels varied significantly across sample sources. We compared the presence of these compounds in chaste nectar and mature honey. The outcomes underscore that these characteristic compounds are not simply delivered from nectar to mature honey, and activities of honeybees (collecting and processing) play a pivotal role in their formation and accumulation. These observations shed light on how mature honey can form its unique qualities with a rich assortment of natural bioactive compounds, potentially supporting health benefits.

Authenticity of food is of great importance to ensure food safety and quality, and to protect consumer rights. A rapid and accurate method for authentication of edible bird’s nest (EBN) was proposed by using nutritional profile and chemical composition, and pattern recognition analysis. The authentication of EBN includes identification and classification of EBN by production origin (houses or caves), species origin (Aerodramus fuciphagus or Aerodramus maximus) and geographical origin (Peninsular Malaysia or East Malaysia) based on their active compositional content. Three pattern recognition methods, principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA), were employed to develop classification models for authentication of EBN origins. Compared to PCA and HCA, LDA is more accurate and efficient in distinguishing EBN by different production, species, and geographical origins, having classification ability of 100% and prediction ability of 92% as validated by cross-validation method. The key chemical markers for production origin differentiation are total phenolic content, zinc, valine, and calcium, while for species origin discrimination are sialic acid, serine, phenylalanine and valine, and for geographical origin differentiation are arsenic and mercury. The findings suggest that nutritional and chemical profiles combined with pattern recognition analysis are promising strategy for rapid authentication of EBN and its products.

An approach exploiting ultrahigh-performance liquid chromatography (UHPLC) fingerprints and multivariate chemometrics to explore the rationality of processing for Aconiti Lateralis Radix is here proposed. UHPLC fingerprints were established to analyze crude Aconiti Lateralis Radix and two processed products (black slices and white slices). The implemented chemometrics methods, including Ward's method and principal component analysis (PCA), could lead to better visualized classification of crude and processed products. Inspection of a Ward's method dendrogram and PCA score plot indicated that all samples belonged to two clusters (crude group and processed group). Subsequently, partial least squares discriminant analysis (PLS-DA) was conducted to obtain the significant chemical markers for discrimination of the crude and processed productions. Additionally, a counter-propagation artificial neural network (CP-ANN) was performed to confirm the chemical markers obtained from PLS-DA. Finally, the chemical markers were identified using ultrahigh-performance liquid chromatography/quadrupole-time-of-flight mass spectrometer (UHPLC-Q-TOF/MS). This strategy has the potential to assess the rationality of processing for Aconiti Lateralis Radix and other Chinese herbal medicines. [ABSTRACT FROM AUTHOR]

Introduction: Curcuma caesia (black turmeric), an essential oil‐bearing rhizomatous herb has been a part of ethnomedicinal practices in India and southeast Asian countries since ancient time. Oleochemical profile of black turmeric has been investigated previously by gas chromatography coupled to mass spectrometry (GC–MS) technique from different geographical regions showing a large variation in the identity as well as abundance of the constituents. Objectives: To develop an analytical method for the reliable analysis of essential oil from black turmeric rhizome through identified chemical markers and to show the credibility of the developed method on real samples. Methods: The essential oil of black turmeric was analysed through proton nuclear magnetic resonance (1H‐NMR) based method using an internal standard. Results: Four thermolabile sesquiterpene markers were unambiguously identified from the essential oil of black turmeric rhizome. GC–MS based analysis produced an erroneous identification of the constituents. A standardised 1H‐NMR spectroscopy based method was developed for the qualitative and quantitative analysis of the identified chemical markers. The developed method was further utilised for analysing the variation in oleochemical profile across multiple batches of harvest and the rhizomes subjected to different post‐harvest storage or drying conditions. Conclusion: The identified marker molecules and developed 1H ‐NMR spectroscopic method might prove to be a useful tool for the analysis of essential oil and quality control of this endangered crop material. Also, the present study provided information on the preferred drying and storage condition of black turmeric rhizome prior to the extraction of essential oil. Curcuma caesia (black turmeric), an essential oil bearing rhizomatous herb has been a part of ethnomedicinal practices in Asian countries since ancient time. A 1H‐NMR (Nuclear Magnetic Resonance) spectroscopy based method was developed for the qualitative and quantitative analysis of the essential oil from black turmeric rhizome using four sesquiterpenoid chemical markers. The developed method was utilized for analyzing the essential oil from multiple batches of harvest and the rhizome subjected to different post‐harvest storage or drying conditions. [ABSTRACT FROM AUTHOR]

Cimicifugae Rhizoma (Sheng ma) is a Ranunculaceae herb belonging to a composite family and well known in China. has been widely used in traditional Chinese medicine. The Pharmacopoeia of the People׳s Republic of China contains three varieties (Cimicifuga dahurica (Turcz.), Cimicifuga foetida L. and Cimicifuga heracleifolia Kom.) which have been used clinically as “Sheng-ma”. However, the chemical constituents of three components of “Sheng-ma” have never been documented. In this study, a rapid method for the analysis of the main components of “Sheng-ma” was developed using ultra-high performance liquid chromatography with quadrupole-time-of-flight mass spectrometry (UPLC/Q-TOF-MS). The present study reveals the major common and distinct chemical constituents of C. dahurica, C. foetida and C. heracleifolia and also reports principal component and statistical analyses of these results. The components were identified by comparing the retention time, accurate mass, mass spectrometric fragmentation characteristic ions and matching empirical molecular formula with that of the published compounds. A total of 32 common components and 8 markers for different “Sheng-ma” components were identified. These findings provide an important basis for the further study and clinical utilities of the three “Sheng-ma” varieties.

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Abstract We successfully designed a nanohybrid sensor based on carboxyl-functionalized multi-walled carbon nanotubes (MWCNTs-COOH) co-functionalized with both carboxymethyl cellulose (CMC) and chitosan nanosphere (CSN) for a simple, low-cost, highly-sensitive voltammetric recognition and determination of Methylglyoxal (MG) as chemical marker of New Zealand Manuka honey. Morphology and structure revealed that CSN-CMC was adhered onto MWCNTs-COOH surface. Interactions between modifying layers and both reduction potential and response mechanism of MG were confirmed by theoretical calculations. The nanohybrid sensor displayed large electrochemical effective area, excellent electrocatalytic activity, a wide linear range of 5 × 10−8–8 × 10−4 mol/L, a low detection limit of 9.6 × 10−9 mol/L, and good stability as well as selectivity under the optimal conditions. The applicability of the fabricated sensor was assessed using three Chinese honeys and one New Zealand Manuka honey. This work will put forward a new strategy for electrochemical recognition and detection of MG as chemical markers of many agricultural production, processing, products and food and a new alternative tool for assessing economically motivated fraud and counterfeit issues in Chinese honey markets using electrochemical nanohybrid sensor. Graphical abstract The preparation process of simple, low-cost, and sensitive nanohybrid electrochemical sensor based on CSN-CMC-MWCNTs-COOH/GCE and electrochemical recognition and determination of MG as a chemical marker of Manuka honey from Chinese honey. Unlabelled Image Highlights • MWCNTs-COOH-CMC-CSN nanohybrid voltammetric sensor was designed and characterized. • Interaction between modifying layers, reaction mechanism and reduction potential were verified by DFT. • This method is an alternative tool for recognition and detection of MG as chemical markers in honey products. [ABSTRACT FROM AUTHOR]

Introduction: Coumarin and alkaloids are the major bioactive constituents of Toddalia asiatica, playing an important role in various biological activities such as anti‐inflammatory, analgesic, anti‐bacterial and anti‐tumour. Objective: To establish a method that will simultaneously determine the coumarins and alkaloids compounds in T. asiatica and identify their characteristic fragmentation patterns, while combining fingerprints and chemical identification with chemometrics for discrimination and quality assessment of T. asiatica samples. Methodology: Qualitative characterisation of coumarins and alkaloids compounds in the methanol extracts of T. asiatica was determined by ultra‐high‐performance liquid chromatography‐quadrupole time‐of‐flight tandem mass spectrometry (UPLC‐QTOF‐MS/MS). Quantitative analysis relies on high‐performance liquid chromatography with a diode array detector (HPLC‐DAD). Results: A total of 59 components were characterised by UPLC‐QTOF‐MS/MS, including 29 coumarin, 25 alkaloids, one phenolic acid and four flavonoids. While the 19 characteristic components out of 23 common peaks in the chromatographic fingerprints of T. asiatica were confirmed. Quantitative analysis of seven major compounds from 18 samples were simultaneously detected by HPLC‐DAD at wavelengths of 280 nm. The samples were classified into three groups by hierarchical clustering analysis (HCA) combined with principal component analysis (PCA), and orthogonal partial least squares discriminant analysis (OPLS‐DA) which screened out the main chemical markers responsible for the samples differences. Conclusion: Fingerprints combined with chemometrics and chemical identification are a simple, rapid and effective method for the quality control of T. asiatica. HighlightsA total of 59 compounds in T. asiatica were firstly identified.Seven major compounds in T. asiatica samples were simultaneously detected for the first time, which is meaningful for sample discrimination.By comparing with the reference substances and UPLC‐QTOF‐MS/MS data, 19 characteristic components out of 23 common peaks in the chromatographic fingerprints of T. asiatica were confirmed. [ABSTRACT FROM AUTHOR]

[Display omitted] • The aroma of A. tsao-ko honey (ATH) was characterized as mildly flowery and fruity. • ATH's marker was chemically identified as isorhamnetin 3-O-neohesperidoside. • The content of the marker ranged from 3.62 to 9.38 mg/kg by UHPLC-MS/MS. The precious medicinal plant, Amomum tsao-ko Crevost et Lemarié, is the nectariferous plant from which the rare Amomum tsao-ko Crevost et Lemarié honey (ATH) is produced. Presently, chemical markers for authentication of this honey are not available due to the lack of data on its chemical composition. Here, we analyzed the volatile components and their odor activity values (OAVs), which revealed that the unique aroma was mildly flowery and fruity, accompanied by subtle sweet and fresh undertones. Since non-volatile chemicals are more reliable markers for routine authentication, we used a metabolomic approach combined with NMR-based identification to find and confirm a suitable compound to unambiguously distinguish ATH from other honeys. Isorhamnetin 3-O-neohesperidoside ranged from 3.62 to 9.38 mg/kg in ATH and was absent in the other tested honeys. In sum, the study uncovered unique chemical characteristics of ATH that will be helpful to control its quality. [ABSTRACT FROM AUTHOR]

To differentiate traditional Chinese medicines (TCM) derived from congeneric species in TCM compound preparations is usually challenging. The roots of Panax ginseng (PG), Panax quinquefolium (PQ) and Panax notoginseng (PN) are used as popular TCM. They contain similar triterpenoid saponins (ginsenosides) as the major bioactive constituents. Thus far, only a few chemical markers have been discovered to differentiate these three species. Herein we present a multiple marker detection approach to effectively differentiate the three Panax species, and to identify them in compound preparations. Firstly, 85 batches of crude drug samples (including 32 PG, 30 PQ, and 23 PN) were analyzed by monitoring 40 major ginsenosides in the extracted ion chromatograms (EICs) using a validated LC–MS fingerprinting method. Secondly, the samples were clustered into different groups by pattern recognition chemometric approaches using PLS-DA and OPLS-DA models, and 17 diagnostic chemical markers were discovered. Aside from the previously known Rf and p-F11, ginsenoside Rs1 could be a new marker to differentiate PG from PQ. Finally, the above multiple chemical markers were used to identify the Panax species in 60 batches of TCM compound preparations.

The major active constituents from Amaryllidaceae family were reported to be Amaryllidaceae alkaloids (AAs), which exhibited a wide spectrum of biological activities, such as anti-tumor, anti-viral, and acetyl-cholinesterase-inhibitory activities. In order to better understand their potential as a source of bioactive AAs and the phytochemical variations among three different species of Lycoris herbs, the HPLC fingerprint profiles of Lycoris aurea (L. aurea), L. radiata, and L. guangxiensis were firstly determined and compared using LC-UV and LC-MS/MS. As a result, 39 peaks were resolved and identified as AAs, of which nine peaks were found in common for all these three species, while the other 30 peaks could be revealed as characteristic AAs for L. aurea, L. radiata and L. guangxiensis, respectively. Thus, these AAs can be used as chemical markers for the identification and quality control of these plant species. To further reveal correlations between chemical components and their pharmaceutical activities of these species at the molecular level, the bioactivities of the total AAs from the three plant species were also tested against HepG2 cells with the inhibitory rate at 78.02%, 84.91% and 66.81% for L. aurea, L. radiata and L. guangxiensis, respectively. This study firstly revealed that the three species under investigation were different not only in the types of AAs, but also in their contents, and both contributed to their pharmacological distinctions. To the best of our knowledge, the current research provides the most detailed phytochemical profiles of AAs in these species, and offers valuable information for future valuation and exploitation of these medicinal plants.

New chemical marker-model food systems with D-ribose and NaOH precursors as color indicators and gellan gels as chemical marker carrier were explored for the assessment of the heating pattern of in packaged foods processed in microwave-assisted pasteurization system (MAPS). In determining appropriate precursor concentrations, a solution of 2% (w/w) D-ribose and 60 mM NaOH was heated at 60-90 °C for 0-20 min. The solution absorbance at 420 nm increased linearly, while the color parameters L* decreased linearly with heating time at all processing temperatures. In storage, the produced brown color was stable at 4 and 22 °C within 7 days. The new chemical marker-model foods were prepared by mixing 2% (w/w) D-ribose and 60 mM NaOH with 1% (w/v) low-acyl gellan gum and 20 mM CaCl2·2H2O solution. The dielectric constant of the model food samples decreased with the addition of sucrose, and the loss factors increased with the addition of salt. After processing in the pilot MAPS, the heating pattern and cold and hot spots in the new chemical marker-model food system could be clearly recognized and precisely located through a computer vision method. This is the first time that the caramelization reaction was used as a time-temperature indicator in gellan gel model food. This study shows the possibility of using the new chemical marker-model food system for heating pattern determination of the MAPS. [ABSTRACT FROM AUTHOR]

Abstract: Bupleuri Radix is a commonly used herb in clinic, and raw and vinegar‐baked Bupleuri Radix are both documented in the Pharmacopoeia of People's Republic of China. According to the theories of traditional Chinese medicine, Bupleuri Radix possesses different therapeutic effects before and after processing. However, the chemical mechanism of this processing is still unknown. In this study, ultra‐high‐performance liquid chromatography with quadruple time‐of‐flight mass spectrometry coupled with multivariate statistical analysis including principal component analysis and orthogonal partial least square‐discriminant analysis was developed to holistically compare the difference between raw and vinegar‐baked Bupleuri Radix for the first time. As a result, 50 peaks in raw and processed Bupleuri Radix were detected, respectively, and a total of 49 peak chemical compounds were identified. Saikosaponin a, saikosaponin d, saikosaponin b3, saikosaponin e, saikosaponin c, saikosaponin b2, saikosaponin b1, 4′′‐O‐acetyl‐saikosaponin d, hyperoside and 3′,4′‐dimethoxy quercetin were explored as potential markers of raw and vinegar‐baked Bupleuri Radix. This study has been successfully applied for global analysis of raw and vinegar‐processed samples. Furthermore, the underlying hepatoprotective mechanism of Bupleuri Radix was predicted, which was related to the changes of chemical profiling. [ABSTRACT FROM AUTHOR]

Authenticity of food is of great importance to ensure food safety and quality, and to protect consumer rights. A rapid and accurate method for authentication of edible bird's nest (EBN) was proposed by using nutritional profile and chemical composition, and pattern recognition analysis. The authentication of EBN includes identification and classification of EBN by production origin (houses or caves), species origin (Aerodramus fuciphagus or Aerodramus maximus) and geographical origin (Peninsular Malaysia or East Malaysia) based on their active compositional content. Three pattern recognition methods, principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA), were employed to develop classification models for authentication of EBN origins. Compared to PCA and HCA, LDA is more accurate and efficient in distinguishing EBN by different production, species, and geographical origins, having classification ability of 100% and prediction ability of 92% as validated by cross-validation method. The key chemical markers for production origin differentiation are total phenolic content, zinc, valine, and calcium, while for species origin discrimination are sialic acid, serine, phenylalanine and valine, and for geographical origin differentiation are arsenic and mercury. The findings suggest that nutritional and chemical profiles combined with pattern recognition analysis are promising strategy for rapid authentication of EBN and its products. [ABSTRACT FROM AUTHOR]

Polygonatum cirrhifolium (Meda) plant is being used in number of rejuvenating Ayurvedic formulations. Ever rising demands, lack of natural sources, and insufficient quantity, to meet the requirements of market, the raw material has led toward the use of official substitutes recommended by the Department of AYUSH that has further encouraged manufacturers for adulteration of formulations by other substandard/spurious raw drugs. Literature reveals that more than 60% Ayurvedic parameters as well as pharmacological actions of Ashtawarga plants do not match with their substitutes leading to reduced efficacy of the drugs along with loss of faith for use of herbal drugs. Consumers are forced to pay for the material which has never been used for high-cost claimed formulation. The situation is being exploited by manufacturers because regulatory authorities lack the tools (marker compound) needed for identification of authentic plant. Methanolic extract of rhizomes of plant was subjected to column chromatography. Isolated compound has been characterized as (Z)-4-amino-4-oxobut-2-enoic acid (maleamic acid/maleamate/maleic monoamide/maleic acid monoamide) by chemical test, melting point, IR/NMR/mass/UV spectral analysis. It is the first report in Polygonatum genus and can be used as a marker for identification of the plant in market formulations. [ABSTRACT FROM AUTHOR]