Iron is essential in the growth and physiological functioning of plants and coumarins have been described in the literature to promote the mobilization of this metal element through its chelation in the oxidation state III. However, the exact mechanism remains unclear. Therefore, this article proposes immobilized iron(III) ion affinity chromatography (IMAC-Fe³⁺) coupled online with mass spectrometry (MS) to investigate the iron(III)-chelating capacity of coumarins. The protocol is based on a differential analysis between IMAC-Fe³+ and a control experiment carried out on the unmodified chromatographic support. An index of retention by complexation (IRC) is calculated for each compound to overcome the problem of possible non-specific interactions. Among the tested eluting competitors compatible with a MS detection, trichloroacetic acid (TCA) appears to be the most suitable to highlight the chelating property of coumarins towards iron(III). The results clearly show that only catecholic coumarins are retained on IMAC-Fe3+ support, demonstrating that the catechol moiety is the key structural feature governing iron(III) complexation in this class of compounds.

The study of the dialogue between microorganisms at the molecular level is becoming essential to understand their relationship (antagonist, neutral, or beneficial interactions) and its impact on the organization of the microbial community. Mass spectrometry imaging (MSI) with matrix-assisted laser desorption/ionization (MALDI) is a technique that reveals the spatial distribution of molecules on a sample surface that may be involved in interactions between organisms. An experimental limitation to perform MALDI MSI is a flat sample surface, which in many cases could not be achieved for bacterial colonies such as filamentous bacteria (e.g., Streptomyces). In addition, sample heterogeneity affects sample dryness and MALDI matrix deposition prior to MSI. To avoid such problems, we introduce an additional step in the sample preparation. A polymeric membrane is interposed between the microorganisms and the agar-based culture medium, allowing the removal of bacterial colonies prior to MSI of the homogeneous culture medium. A proof of concept was evaluated on Streptomyces ambofaciens (a soil bacterium) cultures on solid media. As the mycelium was removed at the same time as the polymeric membrane, the metabolites released into the medium were spatially resolved by MALDI MSI. In addition, extraction of the recovered mycelium from the membrane confirmed the identification of the metabolites by ESI MS/MS analysis. This approach allows both the spatial distribution of metabolites produced by microorganisms in an agar medium to be studied under well-controlled sample preparation and their structure to be elucidated. This capability is illustrated using desferrioxamine E, a siderophore produced by S. ambofaciens.

This review provides an overview of the online hyphenation of Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with separation methods to date. The online coupling between separation techniques (gas and liquid chromatography, capillary electrophoresis) and FT-ICR MS essentially raises questions of compromise and is not look as straightforward as hyphenation with other analyzers (QTOF-MS for instance). FT-ICR MS requires time to reach its highest resolving power and accuracy in mass measurement capabilities whereas chromatographic and electrophoretic peaks are transient. In many applications, the strengths and the weaknesses of each technique are balanced by their hyphenation. Untargeted "Omics" (e.g. proteomics, metabolomics, petroleomics, …) is one of the main areas of application for FT-ICR MS hyphenated to online separation techniques because of the complexity of the sample. FT-ICR MS achieves the required high mass measurement accuracy to determine accurate molecular formulae and resolution for isobar distinction. Meanwhile separation techniques highlight isomers and reduce the ion suppression effects extending the dynamic range. Even if the implementation of FT-ICR MS hyphenated with online separation methods is a little trickier (the art of compromise), this review shows that it provides unparalleled results to the scientific community (the art of the possible), along with raising the issue of its future in the field with the relentless technological progress.

Chronic diseases such as cystic fibrosis, inflammatory bowel diseases, rheumatoid arthritis, and cardiovascular illness have been linked to a decrease in selenium levels and an increase in oxidative stress. Selenium is an essential trace element that exhibits antioxidant properties, with selenocysteine enzymes like glutathione peroxidase being particularly effective at reducing peroxides. In this study, a series of synthetic organoselenium compounds were synthesized and evaluated for their potential antioxidant activities. The new selenohydantoin molecules were inspired by selenoneine and synthesized using straightforward methods. Their antioxidant potential was evaluated and proven using classical radical scavenging and metal-reducing methods. The seleno-hydantoin derivatives exhibited glutathione peroxidase-like activity, reducing hydroperoxides. Theoretical calculations using Density Functional Theory (DFT) revealed the selenone isomer to be the only one occurring in solution, with selenolate as a possible tautomeric form in the presence of a basic species. Cytocompatibility assays indicated that the selenohydantoin derivatives were non-toxic to primary human aortic smooth muscle cells, paving the way for further biological evaluations of their antioxidant activity. The results suggest that selenohydantoin derivatives with trifluoro-methyl (-CF3) and chlorine (-Cl) substituents have significant activities and could be potential candidates for further biological trials. These compounds may contribute to the development of effective therapies for chronic diseases such cardiovascular diseases.

As RNA post-transcriptional modifications are of growing interest, several methods were developed for their characterization. One of them established for their identification, at the nucleosidic level, is the hyphenation of separation methods, such as liquid chromatography or capillary electrophoresis, to tandem mass spectrometry. However, to our knowledge, no software is yet available for the untargeted identification of RNA post-transcriptional modifications from MS/MS data-dependent acquisitions. Thus, very long and tedious manual data interpretations are required. To meet the need of easier and faster data interpretation, a new user-friendly search engine, called Nucleos'ID, was developed for CE-MS/MS and LC-MS/MS users. Performances of this new software were evaluated on CE-MS/MS data from nucleoside analyses of already well-described Saccharomyces cerevisiae transfer RNA and Bos taurus total tRNA extract. All samples showed great true positive, true negative, and false discovery rates considering the database size containing all modified and unmodified nucleosides referenced in the literature. The true positive and true negative rates obtained were above 0.94, while the false discovery rates were between 0.09 and 0.17. To increase the level of sample complexity, untargeted identification of several RNA modifications from Pseudomonas aeruginosa 70S ribosome was achieved by the Nucleos'ID search following CE-MS/MS analysis.

As part of RNA characterization, the identification of post-transcriptional modifications can be performed using hyphenation of separation methods with mass spectrometry. To identify RNA modifications with those methods, a first total digestion followed by a dephosphorylation step are usually required to reduce RNA to nucleosides. Even though effective digestion and dephosphorylation are essential to avoid further complications in analysis and data interpretation, to our knowledge, no standard protocol is yet referenced in the literature. Therefore, the aim of this work is to optimize the dephosphorylation step using a total extract of transfer RNA (tRNA)(1) from B. taurus as a model and to determine and fix two protocols, leading to complete dephosphorylation, based on time and bacterial alkaline phosphatase (BAP)(2) consumptions. Capillary electrophoresis-tandem mass spec-trometry (CE-MS/MS) was used to estimate the dephosphorylation efficiency of both protocols on many canonical and modified nucleotides. For a timesaving protocol, we established that full dephosphorylation was obtained after a 4-hour incubation at 37 ? with 7.5 U of BAP for 1 mu g of tRNA. And for a BAP-saving protocol, we established that full dephosphorylation was obtained 3.0 U of BAP after an overnight incubation at 37 ?. Both protocols are suitable for quantitative analyses as no loss of analytes is expected. Moreover, they can be widely used for all other RNA classes, including messenger RNA or ribosomal RNA.

During a previous study that identified plants used in traditional medicine in Togo to treat infectious diseases, Daniellia oliveri was specifically reported to treat intertrigo and candidiasis. Consequently, to explore the anti-infective potential of this plant, we investigated the antibacterial and the antifungal activity of the plant’s parts, as well as the cytotoxic activities of raw extracts and subsequent fractions, and the chemical composition of the most active fractions. In order to evaluate the antimicrobial activity, MICs were determined using the broth dilution method. Then, the most active fractions were evaluated for cytotoxicity by using normal human cells (MRC-5 cells) via the MTT assay. Finally, the most active and not toxic fractions were phytochemically investigated by GC-MS. Interestingly, all the raw extracts and fractions were active against the bacteria tested, with MICs ranging from 16 µg/mL to 256 µg/mL, while no antifungal activity was observed at 256 µg/mL, the highest tested concentration. Moreover, no toxicity was observed with most of the active fractions. The subsequent chemical investigation of the most interesting fractions led to identifying terpenes, phytosterols, phenolic compounds, and fatty acids as the main compounds. In conclusion, this study demonstrated that D. oliveri possesses valuable antibacterial activities in accordance with traditional use.

Homemade capillaries are a very common practice for the users of capillary electrophoresis (CE), notably in CE-UV. With the advent of the capillary electrophoresis-mass spectrometry coupling since the end of the 1980s, several interfaces have been developed. Among those interfaces, the porous tip sprayer allows great sensitivity at nano flow rates and has been used in numerous applications over the past few years. However, the homemade implementation of a suitable capillary for the porous tip sprayer is more challenging. The porous tip is created by etching the bare-fused silica capillary with hydrofluoric acid. Here we describe the complete process of etching bare-fused silica capillaries, from length cutting to quality control of the newly etched capillary.

The looper caterpillar, O. obstipata is one of the defoliator species of cultivated mint in Morocco. Its identification and its biology constitute the preliminary step for the development of a program aiming at its integrated management. The larvae were collected from a plot of mint grown in a region of northern central Morocco, and reared in the laboratory. The identification of the species was based on comparing the male aedeagus and the female spermatheca to the reference slides. In this study, the elements of biology and morphological characteristics of the different ecophases of O. obstipata are clarified and discussed. The life cycle of the species, from egg to egg, is completed in 31.3 ± 2.16 days. The emergence occurs linearly in time after the 27th and 28th days of oviposition according the sex. The sex ratio (Male/Female) is 0.88:1. The fecundity of the females is positively correlated with their lifespan. Females have an average fecundity of 210 eggs and a fertility rate of 97%. Adults live on average 22.0 ± 6.27 days. The highest mortality rates occur in the last larval instar and pupa. Keywords: Orthonama obstipata, Biology, Reproduction, Mentha spicata

This review aims to summarize the fundamental classes of antioxidants, the utilization of the supplement with antioxidants as ergogenic benefits in exercise and sport, the efficiency, and the consequence of their chronic uses. Antioxidants have been used for a long time in different sports disciplines and at all degrees of rivalry. The supplement with antioxidants anticipates muscle damage by reducing immune dysfunction, inflammation, and fatigue syndrome for athletes. Subsequently, antioxidant supplementation will improve the physical performances and health of athletes. Polyphenol compounds as incredible antioxidants that are abundant in numerous plants. The consumption of antioxidants could be hazardous whenever taken in high dosages. Researchers found that overdoses may cause undesirable symptoms and might grow the risk of death.

The bacteria of the genus Streptomyces and Basidiomycete fungi harbor many biosynthetic gene clusters (BGCs) that are at the origin of many bioactive molecules with medical or industrial interests. Nevertheless, most BGCs do not express in standard lab growth conditions, preventing the full metabolic potential of these organisms from being exploited. Because it generates biotic cues encountered during natural growth conditions, co-culture is a means to elicit such cryptic compounds. In this study, we explored 72 different Streptomyces-fungus interaction zones (SFIZs) generated during the co-culture of eight Streptomyces and nine fungi. Two SFIZs were selected because they showed an elicitation of anti-bacterial activity compared to mono-cultures. The study of these SFIZs showed that co-culture had a strong impact on the metabolic expression of each partner and enabled the expression of specific compounds. These results show that mimicking the biotic interactions present in this ecological niche is a promising avenue of research to explore the metabolic capacities of Streptomyces and fungi.

Caralluma hexagona Lavranos (Family Asclepiadaceae) is an endemic herb in Yemen and Saudi Arabia, traditionally used to treat diabetes, abdominal pain, and stomach ulcers. Different extracts, fractions, and main constituents of C. hexagona were evaluated for their inhibitory activity against key enzymes in diabetes and hyperlipidemia, i.e., α-glucosidase and pancreatic lipase. In addition, the antioxidative effect and inhibition of advanced glycation end products (AGEs) were also assayed. Using a bioguided approach, the crude aqueous, methanolic extracts, methylene chloride (CH2Cl2), Diaion HP20 50% MeOH (DCF-1), and 100% MeOH (DCF-2) fractions of C. hexagona were evaluated for their possible α-glucosidase and pancreatic lipase inhibition and antioxidant activity. In addition, inhibition of AGE generation using bovine serum albumin (BSA)-fructose, BSA-methylglyoxal, and arginine-methylglyoxal models was carried out. Moreover, the main constituents of the most active fraction were isolated and identified using different chromatographic and sprectroscopic methods. From the most active CH2Cl2 fraction, four new pregnane glycosides were isolated and identified as 12β-O-benzoyl 3β,8β,12β,14β,20-pentahydroxy-(20S)-pregn-5-ene-3-O-β-d-glucopyranosyl-(1 → 4)-O-β-d-digitaloside (1), 3β,8β,14β,20-tetrahydroxy-(20S)-pregn-5-ene-3-O-β-d-glucopyranosyl-(1 → 4)-O-β-d-digitaloside-20-O-3-isoval-β-d-glucopyranoside (2), 3β,8β,14β,20-tetrahydroxy-(20R)-pregn-5-ene-3-O-β-d-glucopyranosyl-(1 → 4)-O-β-d-digitaloside-20-O-3-isoval-4-benzoyl-β-d-glucopyranoside (3A), and 3β,8β,14β,20-tetrahydroxy-(20R)-pregn-5-ene-3-O-β-d-glucopyranosyl-(1 → 4)-O-β-d-digitaloside-20-O-3,4 di-benzoyl-β-d-glucopyranoside (3B). Among the tested samples, the highest trolox equivalent (TE) antioxidant capacity (TEAC) was observed for DCF-1 with values of 128.53 ± 5.07, 378.58 ± 5.19, and 106.71 ± 5.66 μM TE/mg using 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), and ferric reducing antioxidant potential (FRAP) assays, respectively. The isolated apigenin-8-C-neohesperoside showed the highest antioxidant capacity (168.80 ± 1.80 and 278.21 ± 13.26 μM TE/mM) in DPPH and FRAP, respectively, while luteolin 4′-O-β-d-neohesperidoside had the highest TEAC (599.19 ± 9.57 μM TE/mM) in ABTS assay. Compounds 1, 2, and the mixture 3A and 3B inhibited α-glucosidase with IC50 values of 0.92 ± 0.02, 0.67 ± 0.01, and 0.74 ± 0.02 mM, respectively. In the AGE assays, DCF-1 showed the highest inhibitory effect in BSA-fructose and arginine-methylglyoxal models with IC50 values of 0.39 ± 0.02 and 0.77 ± 0.10 mg/mL, respectively. Among the isolated compounds, flavonoid compounds showed the highest antiglycation effect, while pregnanes revealed higher α-glucosidase inhibition. In conclusion, the current study revealed that C. hexagona is a promising Yemeni natural remedy, of which the major content of pregnane glycosides and flavonoids could be considered as a new therapeutic candidate targeting the metabolic syndrome.

Production of iron-chelating peptides from protein hydrolysates requires robust and adequate screening methods to optimize their purification and subsequently valorize their potential antioxidant properties. An original methodology was developed for direct and sensitive screening of iron(II)-chelating peptides based on ion-pair reverse phase liquid chromatography (IP-RPLC) coupled to high-resolution mass spectrometry (HRMS). Peptide mixture was first added to iron(II) solution to form iron(II)-peptide complexes. Then IP-RPLC-HRMS analysis was conducted on this iron-peptide mixture and on the iron-free peptide solution for comparative mass spectra analysis. This protocol, initially applied to a range of low molecular weight standard peptides, allowed detection of [(Peptide-H)+56FeII]+ complex ion for iron(II)-chelating peptides (GGH, EAH, DAH, βAH, DMH, DTH, DSH). GGH was added in complex peptide mixtures and targeted analysis of [(GGH-H)+56FeII]+ complex showed a limit of detection (LOD) below 0.77 mg L−1 of GGH. This protocol was finally tested in combination with metabolomics software and additional digital processing for non-targeted search for iron(II)-chelating peptides. Applicability of this new screening methodology has been validated by detection of GGH as iron(II)-chelating peptide when added at 0.77 mg L−1 in casein hydrolysate.

Mentha spicata constitue l’une des 4 espèces du genre Mentha cultivées pour, entre autres, la production d’huiles essentielles. Les parcelles de la menthe connaissent l’apparition d’une souche pubescente (Sp.) suite à la germination des graines produite par la souche glabre (Sg.), initialement cultivée dans la région de Meknès. Pour comparer ces deux souches de M. spicata, des analyses chimiques des composés volatils et génétiques ont été entreprises. Les huiles essentielles ont été extraites par hydrodistillation des feuilles sèches et leur composition chimique a été analysée par CPG/SM. Le polymorphisme de l’ADN des deux souches a été caractérisé par l’AFLP (Amplified fragment polymorphism technique). Les rendements en huiles essentielles de Sp. et Sg. sont, respectivement, de l’ordre de 1,61 et 2,32% (v/w). Les nombres de composés chimiques identifiés chez la Sp. et la Sg. sont respectivement de 47 et 37. La souche Sp. se démarque par sa richesse en limonène (7,7%) et gemacrène-D (3,12%) et sa faible teneur en carvone (62,2), comparativement à la souche cultivée (75,6). La souche Sp. est caractérisée par 44 bandes uniques et la Sg. n’en possède que 18. Mots clés : Mentha spicata, Huiles essentielles, CPG/SM, ADN, AFLP, Polymorphisme

Algeria, by its geographical position, is home to an exceptional biodiversity occupied by important medicinal plants. Thymelaea hirsuta, endemic species is a medicinal plant used in Algerian folk medicine for the treatment of various diseases. This work focused on the phytochemical study by liquid chromatography coupled with mass spectrometry (LC-MS) with Electrospray source (ESI) of aqueous extracts from flowers, leaves and twigs. The phytochemical results show that the different organs, more particularly the flowers constitute a privileged source of biologically active molecules belong to the family of polyphenols in which the subfamilies of hydroxycinamic acids (ferulic acid, caffeic acid, chlorogenic acid, feruloylquinic acid…), coumarins (esculetin, scopoletin, sphondine, rutarensin…) and flavonoids (Isochamaejasmine, kaempferol, apigenin…). This study confirms, scientifically, the traditional use of this plant and reveals its interest in the context of industrial pharmaceutical exploitation.

A healthy ageing process is important when it is considered that one-third of the population of Europe is already over 50 years old, although there are regional variations. This proportion is likely to increase in the future, and maintenance of vitality at an older age is not only an important measure of the quality of life but also key to participation and productivity. So, the binomial "nutrition and ageing" has different aspects and poses considerable challenges, providing a fertile ground for research and networks. The NutRedOx network will focus on the impact of redox-active compounds in food on healthy ageing, chemoprevention, and redox control in the context of major age-related diseases. The main aim of the NutRedOx network is to gather experts from Europe, and neighbouring countries, and from different disciplines that are involved in the study of biological redox active food components and are relevant to the ageing organism, its health, function, and vulnerability to disease. Together, these experts will form a major and sustainable EU-wide cluster in form of the NutRedOx Centre of Excellence able to address the topic from different perspectives, with the long-term aim to provide a scientific basis for improved nutritional and lifestyle habits, to train the next generation of multidisciplinary researchers in this field, to raise awareness of such habits among the wider population, and also to engage with industry to develop age-adequate foods and medicines.

The popular use of Pterocarpus erinaceus as antimicrobial prompted us to study the antifungal properties of its bark, leaves and roots against Candida albicans, Aspergillus fumigatus, and Aspergillus niger. Thus, the broth microdilution method was used to perform the test and only the root extract showed significant antifungal activity against A. fumigatus with value at MIC 16 mu g/mL. This root extract was further partitioned by immiscible liquid-liquid extraction into five fractions. Successive chromatographic columns were used for the purification of the organic fractions which led to the isolation and the identification of five compounds including two new (3 and 5) and three known (1, 2, and 4). Their structures were established as muningin 1, the mixture of formononetin and pseudobaptigenin 2, boutotone 3, isoliquiritigenin 4, and boutomycone 5, by the mean of spectroscopic data compared to those reported in the literature. Compounds 1-5 were also tested on A. fumigatus against which 1, 2, and 5 showed antifungal effects with MIC values at 853.3, 28.7, and 452.3 mu M, respectively. The obtained results indicated that the traditional use of this plant as antimicrobial could be related to its roots.

Two novel compounds were isolated for the first time from Calycotome spinosa (L.) Link, an alkaloid 5-Hydroxy-1H-indole (4) and a cyclitol D-pinitol (5), together with the three well-known flavonoids; Chrysin 7-O-(beta-D-glucopyranoside) (1), Chrysin-7-O-beta-D-(6 '' acetyl)glycopyranoside (2) and Apigenin-7-O-beta-D-glycopyranoside (3). The chemical structures of the isolated compounds were elucidated by spectroscopic data and mass spectrometric analyses; including a fresh approach 1D-NMR, 2D-NMR with LC-ESI-MS/MS. In this study, the new compound (4) that has been obtained from the leaves MeOH extract presented the best radical scavenging activity (DPPH) (IC50 < 10 mu g/mL) compared to the standard butylated hydroxytoluene (BHT, IC50 = 34.73 +/- 0.23 mu g/mL) and showed the highest total antioxidant capacity (TAC = 985.54 +/- 0.13 mg AAE/g extract) in contrast to ascorbic acid (TAC = 905.95 +/- 0.07 mg AAE/g extract). Furthermore, the strongest reducing power (EC50 = 344.82 +/- 0.02 mu g/mL), as well as the remarkable scavenging potential by ABTS assay (IC50 = 7.8 +/- 0.43 mu g/mL), were exhibited by the same composite (4). Followed by the methanol crude extract and the compound (3) that also showed a potent antioxidant (DPPH; IC50 = 41.04 +/- 0.15 and 47.36 +/- 0.21 mu g/mL, TAC; 671.02 +/- 0.21 and 608.67 +/- 0.34 mg AAE/g extract, FRAP; EC50 = 763.73 +/- 0.32 and 814.61 +/- 0.31 mu g/mL, ABTS; IC50 = 19.18 +/- 0.06 and 63.72 +/- 0.64 mu g/mL, respectively), but less than the previous samples. On the opposite side, compound (5) had the lowest activity, in which its values were less interesting to determine. Moreover, compound (4) has equally exerted an attractive antibacterial activity against Staphylococcus aureus (ATTC-25923), Pseudomonas aeruginosa (ATTC-27853) and Salmonella abony (NCTC 6017), as measured by the disc diffusion assay, with inhibition zones of 16 +/- 0.5, 9.83 +/- 0.29 and 8 +/- 0.28 mm, in that order. To the best of our knowledge, 5-Hydroxy-1H-indole was isolated from plants for the second time in our current work. Thus, the obtained results from this investigation propose that the leaves of C. spinosa are a rich natural source for value molecules as potential antioxidants and antimicrobial agents for best human health.