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Hedyotis diffusa Willd., a herbal remedy for cancer, has a complex chemical profile that is difficult to analyze in detail. Here, we introduce an optimized sample preparation method coupled with two-dimensional gas chromatography-time-of-flight mass spectrometry (GC ​× ​GC-TOF/MS) to enhance the chemical profiling of H. diffusa. By employing dichloromethane extraction for nonpolar compounds, aqueous extraction, and solid-phase extraction fractionation into moderately polar and polar fractions, we extracted and analyzed a comprehensive range of chemicals from H. diffusa. GC ​× ​GC-TOF/MS analysis revealed a rich chemical landscape, identifying 185, 325, and 483 peaks in the dichloromethane extract, solid-phase extraction elution, and unretained fractions, respectively. Library matching against known compounds confirmed 155, 178, and 184 hits with a similarity of 80% or greater. Notably, this method also involves group-type elution of steroids and anthraquinones, facilitating the identification and screening of similar compounds. This comprehensive approach to herbal chemical analysis offers a high-dimensional perspective and greatly advances our understanding of the chemical constituents of H. diffusa.

This study presents a comprehensive investigation into the potential anticancer properties and chemical constituents of an unexplored plant (Grewia velutina) extracts. Three distinct extracts of hexane (GVH), chloroform (GVC) and methanol(GVM) of the plant were used to check their anticancer activity against four prominent cancer cell lines (HepG2, DU145, Hela, A549), and the results were compared with the standard chemotherapeutic agent doxorubicin. Anticancer assays revealed that the GVC extract exhibited highest activity than others, with IC50 values of 61.06 µg/mL, 47.87 µg/mL, 88.76 µg/mL, and 87.99 µg/mL against HepG2, DU145, Hela, and A549 cell lines, respectively and reflected a comparable activity to doxorubicin, highlighting its potential as an effective anticancer agent. With the help of chemical profiling data, molecular docking studies were performed and this study suggested that ionol, present in GVC extract is the most active compound against all the cancerous cells.

The interest in characterization of drugs abused started in 1948 with the aim of determining the origin of opium. After 75 years there is still a great interest in this approach, called geo-profiling, chemical or forensic profiling in the following decades. Recently chemical attribution signatures (CAS) were proposed by the authors who studied “synthesis precursors and byproducts, impurities, degradation products, and metabolites in various biological matrices” of fentanyl. Forensic profiling evolved during these decades: new analytical approaches were tested and it was applied to more and more products, which threaten the health and security of citizens worldwide.In substances of natural origins (e.g. opium, cannabis and cocaine), it is possible to exploit the great variability of both elements and organic chemical compounds and to study chemical compounds such as reagents and solvents, by-products, and cutting agents used in the production chain. Profiles can be used to classify products from different seizures into groups of similar samples (tactical intelligence) or to determine the origin of samples (strategic intelligence).Chromatographic approaches coupled to mass spectrometry are very common to determine organic profiles, while elemental profiles are obtained by nuclear activation analysis, inductively coupled plasma mass spectrometry or ion beam analysis. A very important role in the field is played by isotope ratio analysis. Approaches to obtain forensic profiles are available also for chemical warfare agents, explosives, illegal medicines, doping agents, supplements, food. Chemometrics can be particularly useful to establish the authenticity of products and for the interpretation of large amount of forensic data. The future of forensic profiling is a challenge for forensic sciences. Organized crime is involved in the manufacturing of a large number of illegal products and forensic profiling is a very powerful tool to support the health of citizens and the administration of justice worldwide.

Ginseng, the roots of Panax species, is an important medicinal herb used as a tonic. As ginsenosides are key bioactive components of ginseng, holistic chemical profiling of them has provided many insights into understanding ginseng. Mass spectrometry has been a major methodology for profiling, which has been applied to realize numerous goals in ginseng research, such as the discrimination of different species, geographical origins, and ages, and the monitoring of processing and biotransformation. This review summarizes the various applications of ginsenoside profiling in ginseng research over the last three decades that have contributed to expanding our understanding of ginseng. However, we also note that most of the studies overlooked a crucial factor that influences the levels of ginsenosides: genetic variation. To highlight the effects of genetic variation on the chemical contents, we present our results of untargeted and targeted ginsenoside profiling of different genotypes cultivated under identical conditions, in addition to data regarding genome-level genetic diversity. Additionally, we analyze the other limitations of previous studies, such as imperfect variable control, deficient metadata, and lack of additional effort to validate causation. We conclude that the values of ginsenoside profiling studies can be enhanced by overcoming such limitations, as well as by integrating with other -omics techniques.

Eight Ribes magellanicum collections from three different places in southern Patagonia were compared for content of different groups of phenolics, antioxidant capacity and inhibition of enzymes related to metabolic syndrome (α-amylase, α-glucosidase and pancreatic lipase). The sample with the highest antioxidant capacity was assessed for glutathione (GSH) synthesis stimulation in human gastric adenocarcinoma (AGS) cells. The chemical profile was determined by high performance liquid chromatography with tandem mass spectrometry detection (HPLC-MS/MS) and the main phenolics were quantified. The samples from Navarino Island and Reserva Nacional Magallanes showed higher content of anthocyanins and caffeoylquinic acid, with better activity towards α-glucosidase and antioxidant capacity. A sample from Omora (Navarino Island), significantly increased intracellular GSH content in AGS cells. Some 70 compounds were identified in the fruit extracts by HPLC-MS/MS. The glucoside and rutinoside from delphinidin and cyanidin and 3-caffeoylquinic acid were the main compounds. Different chemical profiles were found according to the collection places.

This article presents two types of phytochemical data obtained from Brucea javanica (L.) Merr. roots, a medicinal plant belonging to the Simaroubaceae family. The high-resolution LC–MS dataset comprised the chemical profile of dichloromethane extract, which was utilised to annotate 35 chemical constituents. For annotations, the measured spectral data were compared with the in-silico spectral data generated from 920 molecular structures previously reported in Simaroubaceae. Indole alkaloids, quassinoids, aliphatics and lignan were the chemical groups identified in the root extract. The second dataset provides NMR spectra (1H, 13C, COSY, HMQC and HMBC) for the six indole alkaloids previously detected in LC–MS analysis and isolated through centrifugal partition chromatography. The chemical structures of all compounds were confirmed based on NMR data as bruceolline J (compound 7), canthin-6-one-N-oxide (compound 10), bruceolline E (compound 15), 5-methoxycanthin-6-one (compound 16), canthin-6-one (compound 20), and 1‑hydroxy-11-methoxycanthin-6-one (compound 22). This phytochemical data was generated to support an ongoing anti-cancer and anti-dengue study.

Honey is a natural food often used as an auxiliary material in Traditional Chinese Medicine (TCM). Cortex Mori (CM) is a commonly used Chinese medicinal material that requires honey preparation before use. Our research discovered that various factors including honey temperature, color intensity, moisture content, viscosity, TPC, 5-HMF content, and FRAP all increased over time during the honey refining process. To systematically study the excipients that play a unique role in TCM processing, this study focuses on honey as the representative and CM as the model drug. The overall components of honey-processed CM, stir-fried CM, and raw CM were determined using the fingerprint method, resulting in 36 chromatographic peaks with significant differences. The principal component analysis (PCA) results showed significant differences among honey-fried, stir-fried, and raw CM. Orthogonal partial least squares-discriminant analysis (OPLS-DA) and artificial neural network (ANN) were used to screen the important differential components. Network pharmacology and molecular docking technology were used to correlate the efficacy of the marker components. Oxyresveratrol, kuwanon G, and morusin were identified as potential markers. This study proved that the addition of honey as an excipient can affect the chemical composition of the drug itself, thereby impacting its efficacy.

The aim of this research was to investigate the chemical profiles of Cannabis sativa from 11 Tanzanian regions using preliminary tests as well as instrumental analyses with GC-MS and LC-MS. Generally, all the seized samples tested positive for the presence of (Δ9-THC. The preliminary test with Duquenois method followed by chloroform addition revealed the presence of Δ9-tetrahydrocannabinol (Δ9-THC) in all the samples. GC-MS analyses of the samples revealed the presence of nine cannabinoids including Δ9-THC, Δ8-THC, cannabidivarol, cannabidiol, Δ9-tetrahydrocannabivarin (Δ9-THCV), cannabichromene, cannabinol, caryophyllene, and cannabicouramaronone, whereas LC-MS chemical profiling revealed the presence 24 chemical substances, including 4 cannabinoids, 15 different types of drugs and 5 amino acids. The Pwani region had the highest percentage composition of Δ9-THC (13.45%), the main psychoactive ingredient of Cannabis sativa, followed by Arusha (10.92%) and Singida (10.08%). The sample from Kilimanjaro had the lowest percentage of Δ9-THC (6.72%). Apart from cannabinoids, the majority of other chemical substances were found in the Dar es Salaam region sample, which could be attributed to the fact that the city is the epicenter of business rather than the cultivation area, implying that the samples were obtained from different sources and blended as a single package.

Justicia vahlii Roth. (acanthaceae) is an important medicinal food plant used in pain relief and topical inflammation. The present study aimed to evaluate phytochemical composition, toxicity, anti-inflammatory, antioxidant and enzyme inhibition potential of n-butanol extract of J. vahlii (BEJv). The extract prepared through maceration was found rich in total phenolic contents (TPC) 196.08 ± 6.01 mg of Gallic acid equivalent (mg GAE/g DE) and total flavonoid contents (TFC) 59.08 ± 1.32 mg of Rutin equivalent (mg RE/g DE). The UPLC-Q-TOF-MS analysis of BEJv showed tentative identification of 87 compounds and 19 compounds were detected in GC–MS analysis. The HPLC-PDA quantification showed the presence of 14 polyphenols amongst which kaempferol (3.45 ± 0.21 µg/ mL DE) and ferulic acid (2.31 ± 1.30 µg/ mL DE) were found in highest quantity. The acute oral toxicity study revealed the safety and biocompatibility of the extract up to 3000 mg/kg in mice. There was no effect of BEJv on human normal liver cells (HL 7702) and very low cytotoxic effect on liver cancer cells (HepG2) and breast cancer cells (MCF-7). In anti-inflammatory evaluation, the BEJv treated groups showed significant inhibition (p

Photodegradation of plastic consumer products is known to accelerate weathering and facilitate the release of chemicals and plastic particles into the aquatic environment. However, these processes are complex. In our presented pilot study, eight plastic consumer products were leached in distilled water under strong ultraviolet (UV) light simulating eight months of Central European climate and compared to their respective dark controls (DCs). The leachates and formed plastic particles were exploratorily characterized using a range of chemical analytical tools to describe degradation and leaching processes. These techniques covered (a) microplastic analysis, showing substantial liberation of plastic particles further increased under UV exposure, (b) non-targeted mass spectrometric characterization of the leachates, revealing several hundreds of chemical features with typically only minor agreement between the UV exposure and the corresponding DCs, (c) target analysis of 71 organic analytes, of which 15 could be detected in at least one sample, and (d) metal(loid) analysis, which revealed substantial release of toxic metal(loid)s further enhanced under UV exposure. A data comparison with the US-EPA's ToxVal and ToxCast databases showed that the detected metals and organic additives might pose substantial health and environmental concerns, requiring further study and comprehensive impact assessments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The co-elution, pervasive isomers, and frequently occurring in-source fragmentation definitely hinder the comprehensive characterization of the multiple components from traditional Chinese medicine (TCM) by liquid chromatography/mass spectrometry. Herein, a dimension-enhanced strategy, by utilizing an ion mobility quadrupole time-of-flight mass spectrometer coupled to ultra-high performance liquid chromatography (UHPLC/IM-QTOF-MS) with the ability of offering four-dimensional information (retention time, Rt; drift time or collision cross section, CCS; accurate mass of precursors; and accurate MS2 product ions), is presented. Shuanghe Decoction (SHD) is a classic tonifying formula composed of nine herbs, however, little is known to its chemical complexity, hitherto. Good chromatographic separation was achieved on an HSS T3 column, and by the Vion™ IMS-QTOF high-resolution mass spectrometer, data-independent MSE and High-Definition MSE (HDMSE) in both the negative and positive electrospray ionization modes were employed for acquiring the collision-induced dissociation-MS2 data. A self-built database, including 642 known compounds, was established, which assisted to perform the automated peak annotation by UNIFI™. By reference to 55 compounds, totally 236 components were identified or tentatively characterized from SHD with 4D data recorded. The combination of negative and positive modes could yield more information complementary to structural elucidation. Compared with the conventional MSE, HDMSE exhibit of merits in the provision of CCS, better separation and detection those easily co-eluting components, and reduction of the false positives in the identification results. Conclusively, the combination of HDMSE acquisition, in-house library, and UNIFI-facilitated automated peak annotation, renders a potent approach dedicated to deconvoluting the chemical composition of complex systems like TCM formulae.

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.

The technological advances of analytical instrumentation and techniques has laid the ground for the rapid expansion of metabolomics or in a wider sense, untargeted analysis applied to life sciences themes. However, the objective of identifying all existing metabolites within organisms remains a daunting challenge. All analytical techniques exhibit varying degrees of sensitivity and versatility for the detection of metabolites and none of the existing analytical platforms can be expected to be ideal for exhaustive chemical profiling. Planar liquid chromatography, and in particular, high performance thin layer chromatography (HPTLC), has been used for chemical profiling of natural products in conjunction with metabolomics. HPTLC has specific advantages which include its ability to generate reliable chemical fingerprinting data and facilitate preparative work for metabolite isolation during later stages of metabolomics analysis. In this study, we investigated the chemical profiles of four commercially available basil cultivars, namely Dolly, Emily, Keira, and Rosie. We used HPTLC as the primary analytical tool for the separation of basil cultivars based on detected metabolites, and then compared the results with those obtained with other analytical platforms. We identified the characteristic marker compounds of each basil cultivar from the HPTLC plates and validated their potential using LC-MS and GC-MS analyses as a metabolomics tool. Firstly, we compared the HPTLC data of the four cultivars, obtained with two systems that used silica gel 60 and two mobile phases composed of toluene-EtOAc (8:2, v/v) and EtOAc-formic acid-acetic acid-water (100:11:11:27, v/v), with 1 H NMR data to evaluate their separation power. Despite providing lower resolution and detecting fewer compounds, the HPTLC separation power was comparable, and in some cases even better than that of 1 H NMR. Additionally, we investigated the potential of HPTLC as a tool for chemical fingerprinting and demonstrated its suitability for preparative purposes that are essential for identifying metabolites in mixture analysis. Metabolites were easily isolated from sample mixtures, and identified with the assistance of GC-MS, LC-MS, and TLC-densitometry.. Several marker compounds were thus identified, including 2,4 di-tertbutylphenol, palmitic acid, hexadecanamide, 9-octadecenamide, squalene, hentriacontane, methyl 3-(3,5-ditert‑butyl‑4-hydroxyphenyl)propanoic acid, sagerinic acid, and cyanidin-3-O-sophoroside., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Objective: To clear the amounts of the principal active/toxic components in herbs containing aristolochic acids (HCAAs), which are still used as medicine and/or seasoning in many ethnic minority areas of China., Methods: In this study, six major active and toxic components in HCAAs were extracted with ultrasonic extraction. With 6- O -methyl guanosine as internal standard, the target compounds were analyzed qualitatively and quantitatively by using ultrahigh performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/MS) with multiple reaction monitoring-information dependent acquisition-enhanced production ion scanning mode (MRM-IDA-EPI) combined with dynamic background subtraction (DBS) function., Results: The method showed good linearity in the linear range of the six analytes. The limit range of detection was from 0.01 ng/mL to 0.27 ng/mL. All of the detection repeatability, extraction repeatability and accuracy of the method were good. After extraction, the samples remained stable at 15 °C within 24 h. Six analytes were all found in samples except aristolactam (AL) in sample 2, and the contents varied greatly. The contents of these compounds decreased in fruits, leaves and stems of Aristolochia delavayi successively., Conclusion: This method has the advantages of less sample dosage, simple operation, short analysis cycle, high sensitivity, specificity and accuracy. It laid a good foundation for guiding the safety of HCAAs, the in-depth study of pharmacological and toxicological effects and the scientific and standardized processing and compatibility of HCAAs., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 Tianjin Press of Chinese Herbal Medicines. Published by ELSEVIER B.V.)

Bupleuri Radix has been widely used in traditional Chinese medicine. In the current herbal market, the species Bupleurum marginatum Wall. ex DC. is the main source of Bupleuri Radix. Although Bupleuri Radix from the roots of B. marginatum grown wild in the North West of Hubei province has higher quality compared with those from other regions according to the previous investigations, the exhaustive exploitation driven by increasing demand has drastically reduced the wild resource. As a result, germplasm evaluation and quality resource exploration are important for the sustainable utilization and cultivation of B. marginatum. A preliminary study indicated differences in the tissue structure of B. marginatum grown in different areas of North Western Hubei province. In the current study, various tissues of the roots of B. marginatum grown in different areas of North Western Hubei were subjected to laser microdissection and analyzed by microscopy and ultra-high performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC–Q-TOF-MS). The results show that wild plants from Maqiao Town, Baokang County contain the most saikosaponins distributed mainly in cork, cortex and phloem. This study provides key chemical information for evaluating the quality of B. marginatum roots.

Environmental chemicals are commonly studied one at a time, and there is a need to advance our understanding of the effect of exposure to their combinations. Here we apply high-content microscopy imaging of cells stained with multiplexed dyes (Cell Painting) to profile the effects of Cetyltrimethylammonium bromide (CTAB), Bisphenol A (BPA), and Dibutyltin dilaurate (DBTDL) exposure on four human cell lines; both individually and in all combinations. We show that morphological features can be used with multivariate data analysis to discern between exposures from individual compounds, concentrations, and combinations. CTAB and DBTDL induced concentration-dependent morphological changes across the four cell lines, and BPA exacerbated morphological effects when combined with CTAB and DBTDL. Combined exposure to CTAB and BPA induced changes in the ER, Golgi apparatus, nucleoli and cytoplasmic RNA in one of the cell lines. Different responses between cell lines indicate that multiple cell types are needed when assessing combination effects. The rapid and relatively low-cost experiments combined with high information content make Cell Painting an attractive methodology for future studies of combination effects. All data in the study is made publicly available on Figshare., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The quality control of Chinese herbal medicines (CHM) is a key concern on the modernization and globalization. However, it is still a difficult task due to its multi-component, multi-target, multi-pathways. This study aims to provide a novel and comprehensive strategy for quality control in complex Chinese medicines (CHM) formulas by UHPLC-Q-Orbitrap HRMS and UHPLC-MS/MS combined with network pharmacology analysis. Tangshen formula (TSF) was used as an example for complex CHM formulas. The UHPLC-Q-Orbitrap HRMS was firstly applied to identify or tentatively assign 85 compounds in TSF. Subsequently, key active compounds for TSF treating diabetic nephropathy (DN) were chose by chemical-target-pathways network in network pharmacology. The results showed that 13 key bioactive compounds against DN including naringin, daidzein, genistein, formononetin, chlorogenic acid, aloe-emodin, nobiletin, tangeritin, ginsenoside Rg1, hesperetin, hesperidin, rhein, and limonin with three high topological features in chemical-target-pathways network were selected as Q-markers for quality control of TSF. Finally, the UHPLC-MS/MS was performed to simultaneously determine the concentrations of 13 Q-markers. And their concentrations were ranged from 11.57 to 3 788 µg·g -1 . It suggested that many key bioactive compounds not only have high contents but also have wide range contents for the quality of complex CHM formulas. This study should be helpful to guide the selection of the Q-markers and provide new strategy for quality control of complex CHM formulas., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Diarylheptanoids, known to be rich in the Zingiberaceae family, have been reported to have various pharmacological activities including neuraminidase (NA) inhibitory activity. In this study, to analyze the correlation between NA and diarylheptanoid, A. officinarum, belonging to the Zingiberaceae family, was selected as a natural resource. Four new compounds along with 26 known diarylheptanoids from the rhizomes of A. officinarum were isolated using various chromatographic techniques. The Structure-based virtual screening (SBVS) was performed to discover putative binding ligand and corresponding binding conformation of the isolated compounds. Among the isolated compounds, 10 compounds showed stable binding energy levels in NA. Five of these 10 potential hits showed the potent inhibitory activity through in vitro NA enzyme assay. Moreover, it can be deduced that hydrogen-bonding formation between carbonyl group of active diarylheptanoids and arginine 555 and arginine 615 of NA allowed for the most stable binding between the enzyme and docked compounds., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Extra Virgin Olive Oil (EVOO), the emblematic food of the Mediterranean diet, is recognized for its nutritional value and beneficial health effects. The main authenticity issues associated with EVOO's quality involve the organoleptic properties (EVOO or defective), mislabeling of production type (organic or conventional), variety and geographical origin, and adulteration. Currently, there is an emerging need to characterize EVOOs and evaluate their genuineness. This can be achieved through the development of analytical methodologies applying advanced "omics" technologies and the investigation of EVOOs chemical fingerprints. The objective of this review is to demonstrate the analytical performance of High Resolution Mass Spectrometry (HRMS) in the field of food authenticity assessment, allowing the determination of a wide range of food constituents with exceptional identification capabilities. HRMS-based workflows used for the investigation of critical olive oil authenticity issues are presented and discussed, combined with advanced data processing, comprehensive data mining and chemometric tools. The use of unsupervised classification tools, such as Principal Component Analysis (PCA) and Hierarchical Clustering Analysis (HCA), as well as supervised classification techniques, including Linear Discriminant Analysis (LDA), Support Vector Machine (SVM), Partial Least Square Discriminant Analysis (PLS-DA), Orthogonal Projection to Latent Structure-Discriminant Analysis (OPLS-DA), Counter Propagation Artificial Neural Networks (CP-ANNs), Self-Organizing Maps (SOMs) and Random Forest (RF) is summarized. The combination of HRMS methodologies with chemometrics improves the quality and reliability of the conclusions from experimental data (profile or fingerprints), provides valuable information suggesting potential authenticity markers and is widely applied in food authenticity studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS)-based dereplicative method was developed for identifying oplopane- and bisabolane-type sesquiterpenoids from buds of Tussilago farfara L. The analysis of these chemical analogues, sesquiterpene esters, is challenging by MS-based nontargeted metabolomic approaches because of their in-source fragmentation and structural diversity. To profile these sesquiterpenoids, four diagnostic ions (m/z 215.143, 217.158, 229.123, and 231.138) were suggested in the positive ion mode and the developed method utilized two sequential MS/MS scan modes to identify common skeletons and investigate the fragmentation patterns of their parent molecules. Precursor ion scan by triple quadrupole MS/MS provided the parent molecular ions from their diagnostic ions, and product ion scan by quadrupole time-of-flight MS/MS confirmed their fragmentation behaviors. Under the optimized UHPLC-MS/MS method, 74 sesquiterpenoids were characterized from the Farfarae Flos and 11 compounds were isolated for the method validation. Among those compounds, three sesquiterpenoids were newly separated from the Farfarae Flos. Furthermore, the diagnostic ions and the MS/MS fragment behaviors were applied to the accurate quantification of the 8 isolated sesquiterpenoids. Therefore, the developed LC-MS/MS-based method highlighted the chemical composition of the Farfarae Flos and could be extended to the screening and quantification of other sesquiterpene esters., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Source attribution profiling of five species of Amanita mushrooms from four European countries was performed using Liquid Chromatography-High Resolution Mass Spectrometry (LC-HRMS) combined with multivariate statistical analysis. Initially, species determination was carried out morphologically and was verified by DNA-analysis. This data was then combined with chemical profiling, generated from LC-HRMS full scan analysis. The untargeted data was processed and the 720 most abundant peaks in the LC-HRMS chromatogram were used to build a multivariate PLS-DA model. The two independent methods for species determination showed 100% correlation, indicating the potential use of chemical profiling as a supporting technique to genetic methods. When specimens of one species were studied, significant variation related to the region of growth was found. The potential of the geo-positioning was shown for A. phalloides from Sweden, Denmark and UK and A. virosa from Sweden and Denmark. Additionally, A. virosa specimens could be attributed to three geographically different regions of Sweden., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Ying-zhi-huang Injection (YZH-I) is a classic intravenous formulation of polyherbal Chinese medicine which has been prescribed to treat severe jaundice and acute hepatitis for nearly 50 years. Despite some published data on its major components in the constituent herbs, the overall chemical profile of the potentially bioactive ingredients in YZH-I formula remains largely unknown. Here we developed a multispectral integration approach towards nontargeted phytochemical profiling of YZH-I by liquid chromatography-ultraviolet diode array detector coupled to ion trap/time-of-flight multistage mass spectrometry (LC-DAD-IT(MS n )/TOF) with fast polarity-switching mode. A simple generic dilute-and-shoot procedure was introduced as a non-destructive pretreatment method for facile wide-scope component profiling of herbal injection samples. A total of 61 constituents were isolated and characterized by the multiplex data acquisition, among which 45 components were identified from YZH-I, including 21 organic acid derivatives, 8 iridoid glycosides, 15 flavones and adenosine. Of the 45 identified compounds, 8 were unequivocally confirmed by comparing authentic standards, and 37 were tentatively assigned by elucidating accurate MS n spectra and retrieving published data. It is the first report of systematic chemical profiling of YZH preparations with online integration of dilute-and-shoot LC-DAD and accurate multistage mass spectra. This study is expected to present an effective integrated strategy to comprehensive quality control of complex herbal injection formulas., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Natural deep eutectic solvents (NADES) made mainly with abundant primary metabolites are being increasingly applied in green chemistry. The advantages of NADES as green solvents have led to their use in novel green products for the food, cosmetics and pharma markets. However, one of the main difficulties encountered in the development of novel products and their quality control arises from their low vapour pressure and high viscosity. These features create the need for the development of new analytical methods suited to this type of sample. In this study, such a method was developed and applied to analyse the efficiency of a diverse set of NADES for the extraction of compounds of interest from two model plants, Ginkgo biloba and Panax ginseng. The method uses high-performance thin-layer chromatography (HPTLC) coupled with multivariate data analysis (MVDA). It was successfully applied to the comparative quali- and quantitative analysis of very chemically diverse metabolites (e.g., phenolics, terpenoids, phenolic acids and saponins) that are present in the extracts obtained from the plants using six different NADES. The composition of each NADES was a combination of two or three compounds mixed in defined molar ratios; malic acid-choline chloride (1:1), malic acid-glucose (1:1), choline chloride-glucose (5:2), malic acid-proline (1:1), glucose-fructose-sucrose (1:1:1) and glycerol-proline-sucrose (9:4:1). Of these mixtures, malic acid-choline chloride (1:1) and glycerol-proline-sucrose (1:1:1) for G. biloba leaves, and malic acid-choline chloride (1:1) and malic acid-glucose (1:1) for P. ginseng leaves and stems showed the highest yields of the target compounds. Interestingly, none of the NADES extracted ginkgolic acids as much as the conventional organic solvents. As these compounds are considered to be toxic, the fact that these NADES produce virtually ginkgolic acid-free extracts is extremely useful. The effect of adding different volumes of water to the most efficient NADES was also evaluated and the results revealed that there is a great influence exerted by the water content, with maximum yields of ginkgolides, phenolics and ginsenosides being obtained with approximately 20% water (w/w)., (Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.)

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.

A comprehensive profiling method was established for the determination of various chemicals in Pinellia (P.) ternata and pedatisecta species. The profiling method comprises a fast ultrasonic extraction with various solvents, followed by GC-MS and LC-APCI-MS analysis. A total of 73 polar components as trimethylsilyl (TMS) derivatives were detected in methanol extract by GC-MS. The main components of the P. species were profiled as several kinds of fatty acids, amino acids, nucleic acids, carbohydrates, and phenolic compounds. The hexane extract was analyzed by LC-APCI-MS for the lipid profiling. A total of 35 lipid constituents [fatty acids and their esters, mono-, di-, and tri-acylglycerols] and four phytosterols were observed and tentatively characterized by LC-APCI-MS/MS. Among the phytochemicals detected in the hexane extract, triacylglycerols (TAGs) as the major component were identified by LC-APCI-MS and MS/MS. Based on the identified components, a significant difference in the chemical compositions of P. species tuber and processed P. ternata was found that the complete disappearance of TAGs and a considerable decrement of sucrose were observed in processed P. ternata. Furthermore, the degradation mechanism for TAGs in the presence of alum solution is suggested to occur during the processing P. ternata. Malic acid was found to be a characteristic compound for the classification of P. ternata and pedatisecta with different geographic origins. Based on the validated GC/MS method, twenty-four P. ternata, processed P. ternata and P. pedatisecta samples were profiled to measure the overall abundance of specific groups of compound and to identify diagnostic compounds. In addition, principal component analysis (PCA) on the GC/MS profiling data revealed a clear classification of P. species samples. In this study, the full chemical complement was for the first time reported for quality evaluation of P. species. The method can be usefully applied for phytochemical analysis of related herbal medicines., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This paper reviews a body of work published by the authors over a number of years aimed at providing a complementary "signature" to conventional chemical profiling of methylamphetamine. The work, beginning in 2009, was undertaken because of the changing nature of clandestine methylamphetamine manufacture which has seen a dramatic rise in production and a major shift to a higher quality product. As manufacturing methods changed and methylamphetamine purity increased some conventional drug profiling techniques became less useful as an intelligence tool. For instance, the value of the organic impurity profile, a mainstay of conventional profiling, decreases as there are fewer impurities present in seized samples. However, whilst many seizures may contain less conventional chemical intelligence another property of the methylamphetamine molecule is always available, i.e. the light element stable isotope ratios. The stable isotope ratios of carbon, hydrogen and nitrogen are an integral part of the methylamphetamine molecule itself. This review describes previous work by the authors and by researchers in other national laboratories to investigate and implement the use of stable isotope ratios as an everyday methylamphetamine profiling tool. It also looks at how powerful this technique can be when used to compare samples from different seizures., (Crown Copyright © 2014. Published by Elsevier Ireland Ltd. All rights reserved.)

Aconite poisoning continues to be a major type of poisoning caused by herbal drugs in many countries. Nevertheless, despite its toxic characteristics, aconite is used because of its valuable therapeutic benefits. The aim of the present study was to determine the distribution of toxic alkaloids in tissues of aconite roots through chemical profiling. Three species were studied, all being used in traditional Chinese Medicine (TCM) and traditional Indian medicine (Ayurveda), namely: Aconitum carmichaelii, Aconitum kusnezoffii and Aconitum heterophyllum. Laser micro-dissection was used for isolation of target microscopic tissues, such as the metaderm, cortex, xylem, pith, and phloem, with ultra-high performance liquid chromatography equipped with quadrupole time-of-flight mass spectrometry (UHPLC-QTOF MS) employed for detection of metabolites. Using a multi-targeted approach through auto and targeted LC-MS/MS, 48 known compounds were identified and the presence of aconitine, mesaconitine and hypaconitine that are the biomarkers of this plant was confirmed in the tissues. These results suggest that the three selected toxic alkaloids were exclusively found in A. carmichaelii and A. kusnezoffii. The most toxic components were found in large A. carmichaelii roots with more lateral root projections, and specifically in the metaderm, cork and vascular bundle tissues. The results from metabolite profiling were correlated with morphological features to predict the tissue specific distribution of toxic components and toxicity differences among the selected species. By careful exclusion of tissues having toxic diester diterpenoid alkaloids, the beneficial effects of aconite can still be retained and the frequency of toxicity occurrences can be greatly reduced. Knowledge of tissue-specific metabolite distribution can guide users and herbal drug manufacturers in prudent selection of relatively safer and therapeutically more effective parts of the root. The information provided from this study can contribute towards improved and effective management of therapeutically important, nonetheless, toxic drug such as Aconite., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Roman and German chamomile are widely used throughout the world. Chamomiles contain a wide variety of active constituents including sesquiterpene lactones. Various extraction techniques were performed on these two types of chamomile. A packed-column supercritical fluid chromatography-mass spectrometry method was designed for the identification of sesquiterpenes and other constituents from chamomile extracts with no derivatization step prior to analysis. Mass spectrometry detection was achieved by using electrospray ionization. All of the compounds of interest were separated within 15 min. The chamomile extracts were analyzed and compared for similarities and distinct differences. Multivariate statistical analysis including principal component analysis and orthogonal partial least squares-discriminant analysis (OPLS-DA) were used to differentiate between the chamomile samples. German chamomile samples confirmed the presence of cis- and trans-tonghaosu, chrysosplenols, apigenin diglucoside whereas Roman chamomile samples confirmed the presence of apigenin, nobilin, 1,10-epioxynobilin, and hydroxyisonobilin., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Balsamic vinegar (BV) is a typical and valuable Italian product, worldwide appreciated thanks to its characteristic flavors and potential health benefits. Several studies have been conducted to assess physicochemical and microbial compositions of BV, as well as its beneficial properties. Due to highly-disseminated claims of antioxidant, antihypertensive and antiglycemic properties, BV is a known target for frauds and adulterations. For that matter, product authentication, certifying its origin (region or country) and thus the processing conditions, is becoming a growing concern. Striving for fraud reduction as well as quality and safety assurance, reliable analytical strategies to rapidly evaluate BV quality are very interesting, also from an economical point of view. This work employs silica plate laser desorption/ionization mass spectrometry (SP-LDI-MS) for fast chemical profiling of commercial BV samples with protected geographical indication (PGI) and identification of its adulterated samples with low-priced vinegars, namely apple, alcohol and red/white wines., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Over the past six years the Brazilian Federal Police has undertaken major efforts in order to implement and to develop its own drug chemical profiling program. This paper aims to provide a broad perspective regarding the managerial strategies and some examples of subsequent technical issues involved in the implementation of such a project. Close collaboration with local drug enforcement and investigation teams, establishment of proper worldwide partnerships with well recognized institutions in the field of drug analysis and the attainment of suitable funding and human resources are shown to be key success factors. Some preliminary results concerning the chemical profile of cocaine seizures in Brazil during this process are presented., (Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.)

Propolis or bee glue has very diverse composition and is potentially a source of biologically active compounds. Comprehensive chemical profiling was performed on 22 African propolis samples collected from the sub-Saharan region of Africa by using various hyphenated analytical techniques including Liquid Chromatography (LC)-UltraViolet Detection (UV)-Evaporative Light Scattering Detection (ELSD), LC-High Resolution Mass Spectrometry (HRMS), Gas Chromatography (GC)-MS and LC-Diode Array Detector (DAD)-HRMS/MS. The diversity of the composition of these African propolis samples could be observed by heat mapping the LC-UV and ELSD data. The characteristic chemical components were uncovered by applying Principal Component Analysis (PCA) to the LC-HRMS data and a preliminary dereplication was carried out by searching their accurate masses in the Dictionary of Natural Products (DNP). A further identification was achieved by comparing their GC-MS or LC-DAD-HRMS/MS spectra with previously published data. Generally no clear geographic delineation was observed in the classification of these African propolis samples. Triterpenoids were found as the major chemical components in more than half of the propolis samples analysed in this study and some others were classified as temperate and Eastern Mediterranean type of propolis. Based on the comparative chemical profiling and dereplication studies one uncommon propolis from southern Nigeria stood out from others by presenting prenylated isoflavonoids, which indicated that it was more like Brazilian red propolis, and more significantly a high abundance of stilbenoid compounds which could be novel in propolis., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Wu-tou decoction (WTD), a traditional Chinese medicine (TCM) formula, is composed of Aconiti Radix Cocta, Ephedrae Herba, Paeoniae Radix Alba, Astragali Radix and Glycyrrhiza Radix Preparata, and it has been used for more than a thousand years to treat rheumatic arthritis, rheumatoid arthritis and pain of joints, while the active constitutions of WTD are unclear. In this research, an ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) method in both positive and negative ion mode was established to investigate the major constitutions in WTD. A Waters ACQUITY UPLC BEH C18 column was used to separate the aqueous extract of WTD. Acetonitrile and 0.1% aqueous formic acid (v/v) were used as the mobile phase. 74 components including alkaloids, monoterpene glycosides, triterpene saponins, flavones and flavone glycosides were identified or tentatively characterized in WTD based on the accurate mass within 15 ppm error and tandem MS behavior. All the constitutions were also detected in the corresponding individual herbs. These results will provide a basis for further study in vivo of WTD and the information of potential new drug structure for treating rheumatic arthritis and rheumatoid arthritis., (© 2013 Elsevier B.V. All rights reserved.)

Qiong-Yu-Gao (QYG), consisting of Rehmanniae Radix (RR), Poriae (PO) and Ginseng Radix (GR), is a commonly used tonic traditional complex herbal medicine (CHM). So far, three different methods have been documented for preparation of QYG, i.e. method 1 (M1): mixing powders of GR and PO with decoction of RR; method 2 (M2): combining the decoction of RR and PO with the decoction of GR; method 3 (M3): decocting the mixture of RR, GR and PO. In present study, an ultra-high performance liquid chromatography coupled with photo-diode array and quadrupole/time-of-flight mass spectrometry (UHPLC-PDA-QTOF-MS/MS) based chemical profiling approach was developed to investigate the influence of the three preparation methods on the holistic quality of QYG. All detected peaks were unambiguously identified by comparing UV spectra, accurate mass data/characteristic mass fragments and retention times with those of reference compounds, and/or tentatively assigned by matching empirical molecular formula with that of known compounds, and/or elucidating quasi-molecular ions and fragment ions referring to information available in literature. A total of 103 components, mainly belonging to ginsenosides, phenethylalcohol glycosides, iridoid glycosides and triterpenoid acids, were identified, of which 5 degraded ginsenosides were putatively determined to be newly generated during preparation procedures of QYG samples. Triterpenoid acids and malonyl-ginsenosides were detected only in M1 samples, while degraded ginsenosides were merely detectable in M2/M3 samples. The possible reasons for the difference among chemical profiles of QYG samples prepared with three methods were also discussed. It could be concluded that preparation method do significantly affect the holistic quality of QYG. The influence of the altered chemical profiles on the bioactivity of QYG needs further investigation. The present study demonstrated that UHPLC-PDA-QTOF-MS/MS based chemical profiling approach is efficient and reliable for evaluating the holistic quality of traditional CHM., (Copyright © 2013 Elsevier B.V. All rights reserved.)