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result(s) for
"LC-DAD-MS"
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Development of an LC–DAD–MS-Based Method for the Analysis of Hydroxyanthracene Derivatives in Food Supplements and Plant Materials
by
Peron, Gregorio
,
Faggian, Marta
,
Dall’Acqua, Stefano
in
Aloe
,
botanicals
,
Chromatography, Liquid
2022
Products based on plants containing hydroxyanthracene derivatives (HADs)—such as Rheum, Cassia, and Aloe species—are widely used in food supplements or nutraceuticals due to their laxative effects. A more restricted control of HAD contents in food supplements has been implemented by EU Regulation 2021/468, in order to increase the safety of these preparations. Due to their toxicity, aloin A, aloin B, aloe emodin, emodin, and the synthetic derivative danthron have been listed as prohibited substances in food supplements, being tolerated in amounts < 1 mg kg−1 in marketed products. In this work, we report the development of a sensitive and fast LC–DAD–MS-based procedure for the determination of these five compounds in food supplements and plant materials or extracts. The entire procedure includes a simple sample preparation step, where target analytes are concentrated by means of solvent extraction and evaporative concentration (solid samples), or by lyophilisation (liquid samples). The average LOQ of 0.10 mg/L, LOD of 0.03 mg/L, accuracy, and precision with CVs below 12.72 were obtained for the studied analytes. This method is suitable for assessing the compliance of commercial products and raw materials with EU Regulation 2021/468. Furthermore, the proposed method can represent a starting point for the development of a unique and standardised analytical approach for the determination of other HADs under the attention of EU authorities.
Journal Article
Solvent Fractionation and Acetone Precipitation for Crude Saponins from Eurycoma longifolia Extract
by
Lau, Cher Haan
,
Chew, Chee Yung
,
Chua, Lee Suan
in
acetone precipitation
,
Chromatography
,
Cold
2019
Eurycoma longifolia is a popular folk medicine in South East Asia. This study was focused on saccharide-containing compounds including saponins, mainly because of their medical potentials. Different organic solvents such as ethyl acetate, butanol, and chloroform were used to fractionate the phytochemical groups, which were consequently precipitated in cold acetone. Solvent fractionation was found to increase the total saponin content based on colorimetric assay using vanillin and sulfuric acid. Ethyl acetate fraction and its precipitate were showed to have the highest crude saponins after acetone precipitation. The samples were shown to have anti-proliferative activity comparable with tamoxifen (IC50 = 110.6 µg/mL) against human breast cancer cells. The anti-proliferative activities of the samples were significantly improved from crude extract (IC50 = 616.3 µg/mL) to ethyl acetate fraction (IC50 = 185.4 µg/mL) and its precipitate (IC50 = 153.4 µg/mL). LC-DAD-MS/MS analysis revealed that the saccharide-containing compounds such as m/z 497, 610, 723, 836, and 949 were abundant in the samples, and they could be ionized in negative ion mode. The compounds consisted of 226 amu monomers with UV-absorbing property at 254 nm, and were tentatively identified as formylated hexoses. To conclude, solvent fractionation and acetone precipitation could produce saccharide-containing compounds including saponins with higher anti-proliferative activity than crude extract against MCF-7 cells. This is the first study to use non-toxic solvents for fractionation of bioactive compounds from highly complex plant extract of E. longifolia.
Journal Article
NMR, LC-MS Characterization of Rydingia michauxii Extracts, Identification of Natural Products Acting as Modulators of LDLR and PCSK9
by
Dall’Acqua, Stefano
,
Maggi, Filippo
,
Panighel, Giovanni
in
Biological Products - pharmacology
,
Carbon
,
Cholesterol
2022
Rydingia michauxii (Briq.) Scheen and V.A.Albert (Lamiaceae) is used in Iranian traditional medicine to treat malaria, diabetes, hyperlipidemia, rheumatism and cardiovascular diseases. NMR and LC-DAD-MSn analyses were used to establish extract composition and phenylethanoid, flavonoid glycosides, lignans, labdane diterpenes and iridoids were identified and quantified. The main constituents were isolated, and structures were elucidated based on NMR, polarimetric and MS measurements. A new natural compound, ent-labda-8(17),13-dien-18-glucopyranosyl ester-15,16-olide is described here. The effects of ent-labda-8(17),13-dien-18-oic acid-15,16-olide (1), ent-labda-8(17),13-dien-18-glucopyranosyl es-ter-15,16-olide (2), antirrhinoside (3), echinacoside (4), verbascoside (5), and apigenin 6,8-di-C-glucoside (6), on the low-density lipoprotein receptor (LDLR) and proprotein convertase subtilisin/kexin type 9 (PCSK9), were studied in the human hepatocarcinoma cell line Huh7. Among the six constituents, (3) showed the strongest induction of the LDLR (3.7 ± 2.2 fold vs. control) and PCSK9 (3.2 ± 1.5 fold vs. control) at a concentration of 50 µM. The in vitro observations indicated a potential lipid lowering activity of (3) with a statin-like mechanism of action.
Journal Article
Evaluation of In Vitro Antioxidant and Anticancer Properties of the Aqueous Extract from the Stem Bark of Stryphnodendron adstringens
by
Baldivia, Débora da Silva
,
Santos, Uilson Pereira dos
,
Castro, David Tsuyoshi Hiramatsu de
in
Animals
,
Antineoplastic Agents, Phytogenic - chemistry
,
Antineoplastic Agents, Phytogenic - pharmacology
2018
Stryphnodendron adstringens (Mart.) Coville (Fabaceae) is a tree species native to the Brazilian Cerrado commonly known as barbatimão. In traditional medicine, decoctions or infusions of the stem bark of this plant are used in the treatment of several diseases. The objective of this study was to analyze the chemical composition of Stryphnodendron adstringens aqueous extracts (SAAE) prepared from the stem bark to assess their antioxidant activity and anticancer effects as well as characterize cell death mechanisms against murine B16F10Nex-2 melanoma cells. From the SAAE, gallic acid, gallocatechin, epigallocatechin, dimeric and trimeric proanthocyanidins mainly composed of prodelphinidin units and the isomeric chromones C-hexosyl- and O-pentosyl-5,7-dihydroxychromone were identified. The SAAE showed antioxidant activity through direct free-radical scavenging as well as through oxidative hemolysis and lipid peroxidation inhibition in human erythrocytes. Furthermore, SAAE promoted apoptosis-induced cell death in melanoma cells by increasing intracellular reactive oxygen species (ROS) levels, inducing mitochondrial membrane potential dysfunction and activating caspase-3. Together, these data show the antioxidant and anticancer effects of Stryphnodendron adstringens. These results open new perspectives for studies against other tumor cell lines and in vivo models as well as for the identification and isolation of the chemical constituents responsible for these effects.
Journal Article
Phytochemical analysis and antioxidant activity of Lycium barbarum (Goji) cultivated in Greece
by
Benchennouf, Amina
,
Loupassaki, Sofia
,
Grigorakis, Spyros
in
Acetic acid
,
Antioxidants
,
Butanol
2017
Context: The fruit of Lycium barbarum L. (Solanaceae), known as goji berry, has been exploited for a long time in traditional Chinese medicine. In recent decades, it has received much attention as one of the trendiest functional foods with a wide array of pharmacological activities in Western diets.Objective: In this study the phenolic profile and potential antioxidant capacity of Lycium barbarum cultivated in Crete (Greece) were investigated.Materials and methods: The berries were defatted with hexane and then extracted with dichloromethane and methanol using a Soxhlet apparatus. Furthermore, the methanol extract was fractionated with ethyl acetate and butanol. All fractions/extracts were tested for their antioxidant activity (DPPH, FRAP, chemiluminescence). Folin–Ciocalteu and LC-DAD-MS analyses were utilized for the identification of the phenolic compounds.Results: The total phenolic content ranged from 14.13 ± 0.40 (water fraction) to 109.72 ± 4.09 (ethyl acetate fraction) mg gallic acid equivalent/g dry extract. Ethyl acetate extract exhibited the highest scavenging activities determined as EC50 (4.73 ± 0.20 mg/mL) and IC50 (0.47 ± 0.001 mg/mL) using DPPH and chemiluminescence assays. Seventeen phenolic compounds, including cinnamoylquinic acids and derivatives, hydrocinnamic acids and flavonoid derivatives, were tentatively identified. To the best of our knowledge, quercetin 3-O-hexose coumaric ester and quercetin 3-O-hexose-O-hexose-O-rhamnose are reported for the first time in goji berry fruits.Discussion and conclusion: The results of this study suggest that consumption of goji berry fruits could serve as a potential source of natural antioxidant compounds and that goji berry phenolic extracts could be exploited for nutritional pharmaceutical purposes.
Journal Article
The Manufacture of Lake Pigments from Artificial Colours: Investigating Chemistry and Recipes in the First Book on Synthetic Dyes-Based Lakes
2025
In 1900, Francis Herbert Jennison’s book The Manufacture of Lake Pigments from Artificial Colours was published in London. In the early 20th century, the technical literature focussing on synthetic dyes mainly dealt with their use for dyeing. Conversely, the literature on lake pigment manufacture is less comprehensive, and Jennison’s publication was the first monograph on this topic. His book comprises descriptions of the dyes, substrates, and various methods for lake making. Practical examples complete the work: sixteen colour plates with original samples of lake pigments showcase the practical effect on colour of the different dyes and preparation methods. Herein, we present an overview of the context of Jennison’s research and delve into a selection of formulations. Green lake pigment plates were sampled and analysed by liquid chromatography coupled with spectroscopic and spectrometric detectors and by X-ray fluorescence spectroscopy to correlate the chemical composition with the recipes reported in the book. Seldom or no longer used and unexplored historical dyes were detected, along with polyphenolic compounds possibly used as precipitating agents in lake pigment formulations. Moreover, the examination of two different editions of the Jennison manuscript (i.e., the English and German books) revealed different chemical profiles corresponding to the same lake pigment formulation. This emphasizes the significance of Jennison’s book, confirming how understanding of early formulations is needed to elucidate the later ones.
Journal Article
Milking the Orchil: How the Presence of Goat Milk in the Orchil Dyebath May Affect the Color of Dyed Wool
by
Chen, Victor J.
,
Smith, Gregory D.
,
Whitworth, Isabella
in
Biodegradation
,
Coloring matter
,
cultural heritage
2025
Among the craft recipes for artisans collected in the 4th-century Egyptian documents the Leyden and Stockholm papyri, there is one calling for adding animal milk to orchil for wool dyeing. To understand the rationale for this practice, wool yarns were dyed with and without goat milk added to orchil dyebaths, each made using lichens from three different sources. The results showed orchil containing milk dyed yarns a noticeably deeper red hue. The colorants extracted from the dyed yarns were analyzed by liquid chromatography-diode-array-detector-mass spectrometry to assess the relative amounts of nine identifiable orceins. The data showed that the yarns dyed with milk gave extracts exhibiting several fold more α-aminoorcein and α-hydroxyorcein, with only small differences in the other seven. Scanning electron microscopic analysis of a representative pair of dyed yarns showed that milk promoted surface changes in the fiber that may indicate increased cutaneous damage. Hypotheses for the milk’s effects on orchil dyeing were proposed that included the formation of milk–protein complexes with the two enriched orceins that possibly enhanced wool binding and/or better wool uptake of free and/or complexed orceins due to biodegradation of the wool’s surface cuticle caused by microbial growth promoted by the addition of milk.
Journal Article
Dye Analysis of a 17th-Century Mattens Workshop Tapestry Based on Raphael’s Drawing, The Miraculous Draught of Fishes
2024
This paper describes the identification of dyes on fifty yarn samples from a tapestry created by the well-known 17th-century Flemish workshop of the Mattens family. The design of the tapestry is based on the first of ten drawings known as the Acts of the Apostles by the famed 16th-century Italian painter Raphael. The drawings were commissioned by Pope Leo X and translated into tapestries by Pieter van Aelst; these original tapestries are still in the collection of the Vatican Museums. The present work was reproduced over a century later from the original drawing and is one in a possible set of nearly fifty known copies of the original tapestry cycle. Most of the Mattens yarn samples were found to be dyed by weld, indigo, and madder, as well as a few using brazilwood and lichen, but no insect dyes were detected. A significant finding in the present study was the detection of the dye component pseudoindirubin 1, alongside indigotin and indirubin, as well as yarns that only yielded the latter two dyes. The implication of using this new marker as objective evidence of the use of both woad and most likely Asian indigo is explored. The historical and conservation significance of the dyestuffs identified is also discussed.
Journal Article
Foliar Application of Silicon in Vitis vinifera: Targeted Metabolomics Analysis as a Tool to Investigate the Chemical Variations in Berries of Four Grapevine Cultivars
by
Dall’Acqua, Stefano
,
Sut, Stefania
,
Malagoli, Mario
in
Abiotic stress
,
Amino acids
,
Anthocyanins
2022
Silicon (Si) is a beneficial element for the growth of various crops, but its effect on plant metabolism is still not completely elucidated. Even if Si is not classified as an essential element for plants, the literature has reported its beneficial effects in a variety of species. In this work, the influence of Si foliar application on berry composition was evaluated on four grapevine cultivars. The berries of Teroldego and Oseleta (red grapes) and Garganega and Chardonnay (white grapes) were analyzed after foliar application of silicon by comparing the treated and control groups. A targeted metabolomic approach was used that focused on secondary metabolites, amino acids, sugars, and tartaric acid. Measurements were performed using liquid chromatography coupled with a diode array detector and mass spectrometry (LC-DAD-MSn), a LC-evaporative light scattering detector (ELDS), and LC-MS/MS methods specific for the analysis of each class of constituents. After the data collection, multivariate models, PCA, PLS-DA, OPLS-DA, were elaborated to evaluate the effect of Si application in the treated vs. control samples. Results were different for each grape cultivar. A significant increase in anthocyanins was observed in the Oseleta cultivar, with 0.48 mg g−1 FW in the untreated samples vs. 1.25 mg g−1 FW in the Si-treated samples. In Garganega, Si treatment was correlated with increased proline levels. In Chardonnay, the Si application was related to decreased tartaric acid. The results of this work show for the first time that Si induces cultivar specific changes in the berry composition in plants cultivated without an evident abiotic or biotic stress.
Journal Article
Antioxidant, Antigenotoxic and Cytotoxic Activity of Essential Oils and Methanol Extracts of Hyssopus officinalis L. Subsp. aristatus (Godr.) Nyman (Lamiaceae)
by
Samardžić, Stevan
,
Živković, Lada
,
Jakovljević, Vladimir
in
2,2-diphenyl-1-picrylhydrazyl
,
Acids
,
antigenotoxic activity
2021
Hyssopus officinalis L. is a well-known aromatic plant used in traditional medicine and the food and cosmetics industry. The aim of this study is to assess the antioxidant, genotoxic, antigenotoxic and cytotoxic properties of characterized hyssop essential oils and methanol extracts. Chemical composition was analyzed by gas chromatography - mass spectrometry (GC-MS) and liquid chromatography with diode array detection and mass spectrometry (LC-DAD-MS), respectively. Antioxidant activity was examined by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing/antioxidant power (FRAP) tests; genotoxic and antigenotoxic activity were examined by the comet assay, while cytotoxicity was evaluated by the 3-(4,5-dimethylthiazol-2-yl)-2,5 diphenyltetrazolium bromide dye (MTT) test against tumor cell lines (SW480, MDA-MB 231, HeLa) and non-transformed human lung fibroblast cell lines (MRC-5). The essential oils were rich in monoterpene hydrocarbons (e.g., limonene; 7.99–23.81%), oxygenated monoterpenes (1,8-cineole; 38.19–67.1%) and phenylpropanoids (methyl eugenol; 0.00–28.33%). In methanol extracts, the most abundant phenolics were chlorogenic and rosmarinic acid (23.35–33.46 and 3.53–17.98 mg/g, respectively). Methanol extracts expressed moderate to weak antioxidant activity (DPPH IC50 = 56.04–199.89 µg/mL, FRAP = 0.667–0.959 mmol Fe2+/g). Hyssop preparations significantly reduced DNA damage in human whole blood cells, induced by pretreatment with hydrogen peroxide. Methanol extracts exhibited selective and potent dose- and time-dependent activity against the HeLa cell line. Results of the current study demonstrated notable H. officinalis medicinal potential, which calls for further investigation.
Journal Article