Mentha pulegium L. (Pennyroyal, Lamiaceae) Extracts Impose Abortion or Fetal-Mediated Toxicity in Pregnant Rats; Evidenced by the Modulation of Pregnancy Hormones, MiR-520, MiR-146a, TIMP-1 and MMP-9 Protein Expressions, Inflammatory State, Certain Related Signaling Pathways, and Metabolite Profiling via UPLC-ESI-TOF-MS.

Pregnant women usually turn to natural products to relieve pregnancy-related ailments which might pose health risks. Mentha pulegium L. (MP, Lamiaceae) is a common insect repellent, and the present work validates its abortifacient capacity, targeting morphological anomalies, biological, and behavioral consequences, compared to misoprostol. The study also includes untargeted metabolite profiling of MP extract and fractions thereof viz. methylene chloride (MecH), ethyl acetate (EtOAc), butanol (But), and the remaining liquor (Rem. Aq.) by UPLC-ESI-MS-TOF, to unravel the constituents provoking abortion. Administration of MP extract/fractions, for three days starting from day 15th of gestation, affected fetal development by disrupting the uterine and placental tissues, or even caused pregnancy termination. These effects also entailed biochemical changes where they decreased progesterone and increased estradiol serum levels, modulated placental gene expressions of both MiR-(146a and 520), decreased uterine MMP-9, and up-regulated TIMP-1 protein expression, and empathized inflammatory responses (TNF-α, IL-1ß). In addition, these alterations affected the brain's GFAP, BDNF, and 5-HT content and some of the behavioral parameters escorted by the open field test. All these incidences were also perceived in the misoprostol-treated group. A total of 128 metabolites were identified in the alcoholic extract of MP, including hydroxycinnamates, flavonoid conjugates, quinones, iridoids, and terpenes. MP extract was successful in terminating the pregnancy with minimal behavioral abnormalities and low toxicity margins.

Antioxidant, Antimicrobial Activities and Characterization of Polyphenol-Enriched Extract of Egyptian Celery (Apium graveolens L., Apiaceae) Aerial Parts via UPLC/ESI/TOF-MS.

Medicinal plant extracts are increasingly considered a major source of innovative medications and healthcare products. This study focused on preparing a polyphenol enriched water extract of Egyptian celery "Apium graveolens L., Apiaceae" aerial parts (TAE) in an endeavor to accentuate its antioxidant capacity as well as its antimicrobial activity. (TAE) of celery was partitioned against different organic solvents to yield dichloromethane (DCM), ethyl acetate (EAC), and butanol (BUOH) fractions. (TAE) and the organic fractions thereof besides the remaining mother liquor (ML) were all screened for their antioxidant capacity using various protocols viz. monitoring the reducing amplitudes for ferric ions (FRAP), and radical scavenging potentials of oxygen (ORAC), 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and metal chelation assays. The examination procedure revealed both (TAE) extract and (DCM) fraction, to pertain the highest antioxidant potentials, where the IC50 of the (TAE) using ABTS and metal chelation assays were ca. 34.52 ± 3.25 and 246.6 ± 5.78 µg/mL, respectively. The (DCM) fraction recorded effective results using the FRAP, ORAC, and DPPH assays ca. 233.47 ± 15.14 and 1076 ± 25.73 µM Trolox equivalents/mg sample and an IC50 474.4 ± 19.8 µg/mL, respectively. Additionally, both (TAE) and (DCM) fraction exerted antimicrobial activities recording inhibition zones (mm) (13.4 ± 1.5) and (12.0 ± 1.0) against Staphylococcus aureus and (11.0 ± 1.2) and (10.0 ± 1.3) against Escherichia coli, respectively, with no anti-fungal activity. Minimum inhibitory concentration (MIC) of (TAE) and (DCM) fraction were 1250 and 2500 µg/mL, respectively. UPLC/ESI/TOF-MS unveiled the chemical profile of both (TAE) and (DCM) fraction to encompass a myriad of active polyphenolic constituents including phenylpropanoids, coumarins, apigenin, luteolin, and chrysoeriol conjugates.

UPLC-PDA-ESI/MS metabolic profiling of dill shoots bioactive fraction; evidence of its antioxidant and hepatoprotective effects in vitro and in vivo.

Hydroxyl radical (• OH) scavenging capacity of aqueous dill (Anethum graveolens L.) shoot (ADSh) extract was assessed using electron paramagnetic resonance (EPR) spectroscopy. ADSh extract (at concentrations of 0.5 and 10 mg/ml) exerted high (OH) radical scavenging power. ADSh extract was further fractionated on Diaion HP-20 column to yield five fractions. EPR spin-trapping assay revealed fraction 4 (eluted with 75% aq. MeOH) to possess (• OH) radical scavenging capacity over a concentration range (0.01-10 mg/ml), whereas fraction 2 (eluted with 25% aq. MeOH) appeared to be pro-oxidant at concentration 0.01 mg/ml. UPLC-PDA-ESI-MS metabolite profiling of ADSh extract revealed 87 metabolites, of which 64 compounds were identified in fraction 4, the most active fraction. Furthermore, ADSh extract demonstrated a hepatoprotective effect against acetaminophen (APAP)-induced hepatotoxicity in rats. Pretreatment of rats with ADSh extract (200 mg/kg b.wt) markedly attenuated the increased in the serum hepatic enzyme levels. It also increased free glutathione level and total antioxidant capacity in the serum of treated rats. [Correction added on May 3, 2021, after first online publication: "rates" has been changed to "rats" in the previous sentence.] Additionally, levels of (TNF-α and IL-1ß) were back to almost normal levels compared to the control group. The above findings suggest that ADSh extract has a protective effect against APAP-induced liver damage.

Novel trends and applications of multidimensional chromatography in the analysis of food, cosmetics and medicine bearing essential oils.

The analysis of aroma composition in scented plants and natural products to probe their quality and safety is an important topic, particularly when such ingredients are intended for long term use as in food or cosmetic products. The development of fast, comprehensive, and effective analytical tools for essential oil analysis in such complex mixtures is of interest and moreover when present in blend of several oils, as typical in case of nutraceuticals or cosmetics. Comprehensive studies of volatiles could be achieved via coupling the separation power of multidimensional chromatography with selective detectors as mass spectrometers. This strategy enables high-throughput and global analysis of hundreds of metabolites in a single step. Different multidimensional setups such as GC × GC and LC-GC in addition to various chemometric approaches applied for essential oils analysis form a fundamental part of this review. Asides, applications of multidimensional chromatography for essential oils chemotyping, enantio-separation, quality control and adulteration detection in the different matrices are also presented.

Metabolome-Based Analysis of Herbal Cough Preparations Via Headspace Solid-Phase Microextraction GC/MS and Multivariate Data Analyses: A Prospect for Its Essential Oil Equivalency.

Liquid cough preparations containing essential oils pose a challenge for isolating and quantifying their volatile components from such a complex matrix enriched with nonvolatile constituents and excipients. This study aims to develop a strategy integrating QC analysis of seven natural cough preparations in the Egyptian market and to assess volatile variation among the preparations using multivariate data analyses. Cough preparations were subjected to headspace solid-phase microextraction (HS-SPME) for determination of their essential oil composition mediating for their actions and to assess volatile differences among them. HS-SPME is a suitable technique for sample preparation that allows for extraction and enrichment of volatiles from complex nonvolatile matrices and their direct desorption into the gas chromatography analytical system. A total of 88 volatile components were identified belonging to seven classes, viz. aromatics, aliphatic hydrocarbons, mono/sesquiterpene hydrocarbons, and oxygenated mono/sesquiterpenes. Oxygenated monoterpenes, viz., menthol, cineole, thymol, and (E)-anethole, were the major volatiles identified in five cough preparations (79.5-98.6%), whereas aromatics, chiefly cinnamate derivatives, constituted the second class amounting for 50.5 and 27.4% in the other two cough preparations. Meaningful results regarding the products' efficacy and safety were extrapolated from this analytical procedure, where artificial preservatives (parabens) were detected in five cough preparations. This study established an efficient strategy for exploring volatile profiling and defining different markers among the different cough preparations. Additionally, authenticity of listed herbal ingredients in the cough preparations was also confirmed in certain preparations, while other formulations failed to show representative volatile components. Volatile variation among preparations was assessed using multivariate data analyses in an attempt to prioritize cough preparations for usage, suggesting the preference of Bronchicum and Babetone among examined cough products.

Comparative analysis of Hibiscus sabdariffa (roselle) hot and cold extracts in respect to their potential for α-glucosidase inhibition.

Roselle (Hibiscus sabdariffa) is a functional food with potential health benefits, consumed either as hot or cold beverage. To ensure quality control of its various products, accurate measurement of active metabolites is warranted. Herein, we propose a combination of ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS) and nuclear magnetic resonance (NMR) analytical platforms for the untargeted characterization of metabolites in two roselle cultivars, Aswan and Sudan-1. The analyses revealed 33 metabolites, including sugars, flavonoids, anthocyanins, phenolic and aliphatic organic acids. Their relative contents in cultivars were assessed via principle component analysis (PCA) and orthogonal projection to latent structures analysis (OPLS). Impact of the different extraction methods (decoction, infusion and maceration) was compared by quantitative 1H NMR spectroscopy, revealing cold maceration to be optimal for preserving anthocyanins, whereas infusion was more suited for recovering organic acids. The metabolite pattern revealed by the different extraction methods was found in good correlation for their ability to inhibit α-glucosidase enzyme.

Metabolite profiling in Trigonella seeds via UPLC-MS and GC-MS analyzed using multivariate data analyses.

Trigonella foenum-graecum is a plant of considerable value for its nutritive composition as well as medicinal effects. This study aims to examine Trigonella seeds using a metabolome-based ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) in parallel to gas chromatography-mass spectrometry (GC-MS) coupled with multivariate data analyses. The metabolomic differences of seeds derived from three Trigonella species, i.e., T. caerulea, T. corniculata, and T. foenum-graecum, were assessed. Under specified conditions, we were able to identify 93 metabolites including 5 peptides, 2 phenolic acids, 22 C/O-flavonoid conjugates, 26 saponins, and 9 fatty acids using UPLC-MS. Several novel dipeptides, saponins, and flavonoids were found in Trigonella herein for the first time. Samples were classified via unsupervised principal component analysis (PCA) followed by supervised orthogonal projection to latent structures-discriminant analysis (OPLS-DA). A distinct separation among the investigated Trigonella species was revealed, with T. foenum-graecum samples found most enriched in apigenin-C-glycosides, viz. vicenins 1/3 and 2, compared to the other two species. In contrast to UPLC-MS, GC-MS was less efficient to classify specimens, with differences among specimens mostly attributed to fatty acyl esters. GC-MS analysis of Trigonella seed extracts led to the identification of 91 metabolites belonging mostly to fatty acyl esters, free fatty acids followed by organic acids, sugars, and amino acids. This study presents the first report on primary and secondary metabolite compositional differences among Trigonella seeds via a metabolomics approach and reveals that, among the species examined, the official T. foenum-graecum presents a better source of Trigonella secondary bioactive metabolites.

Volatiles and primary metabolites profiling in two Hibiscus sabdariffa (roselle) cultivars via headspace SPME-GC-MS and chemometrics.

Hibiscus sabdariffa (roselle) is a plant of considerable commercial importance worldwide as functional food due to its organic acids, mucilage, anthocyanins, macro and micro-nutrients content. Although Hibiscus flowers are emerging as very competitive targets for phytochemical studies, very little is known about their volatile composition and or aroma, such knowledge can be suspected to be relevant for understanding its olfactory and taste properties. To provide insight into Hibiscus flower aroma composition and for its future use in food and or pharmaceutical industry, volatile constituents from 2 cultivars grown in Egypt, viz. Aswan and Sudan-1 were profiled using solid-phase microextraction (SPME) coupled to GCMS. A total of 104 volatiles were identified with sugar and fatty acid derived volatiles amounting for the major volatile classes. To reveal for cultivar effect on volatile composition in an untargeted manner, multivariate data analysis was applied. Orthogonal projection to latent structures-discriminant analysis (OPLS-DA) revealed for 1-octen-3-ol versus furfural/acetic acid enrichment in Aswan and Sudan-1 cvs., respectively. Primary metabolites contributing to roselle taste and nutritional value viz. sugars and organic acids were profiled using GC-MS after silylation. The impact of probiotic bacteria on roselle infusion aroma profile was further assessed and revealed for the increase in furfural production with Lactobacillus plantarum inoculation and without affecting its anthocyanin content. This study provides the most complete map for volatiles, sugars and organic acids distribution in two Hibiscus flower cultivars and its fermented product.

Metabolite profiling driven analysis of Salsola species and their anti-acetylcholinesterase potential.

Over 100 species of the genus Salsola are distributed in dry, arid parts of Asia, Europe and Africa, of which many species are recognised as antifungal, anticancer, antihypertensive and anthelmintic agents. Egyptian Salsola received scant characterisation of either its phytochemical composition or its biological effects. In this study, the metabolite profiles of two Salsola species viz. S. vermiculata and S. tetrandra were characterised in the aerial portions and root via ultra-performance liquid chromatography high-resolution qTOF-MS and NMR. Identified metabolites belonged to various classes including hydroxycinnamic acid conjugates, flavonoids, oxygenated fatty acids and alkaloids. Principal component analysis of derived biochemical profiles was also used for species and/or organs classification. Roots were enriched in hydroxycinnamic acid conjugates, whereas flavonoids were more abundant in aerial parts with kaempferol derivatives as major flavonoids in S. tetrandra versus quercetin in S. vermiculata. The root of S. vermiculata exhibited strong anti-acetylcholinesterase activity relative to eserine standard.