Date palm (Phoenix dactylifera L.) is an important fruit tree, native to the hot arid regions of the world, mainly grown in the Middle East and North Africa. Since the ancient time, this plant has been widely used as a food and also in the folk medicine, due to its health-promoting properties. In spite of many previous works concerning the phenolic composition of dates fruits, studies on the phenolic composition of the other different parts of the tree are still scarce. In this sense, analysis of dates composition has been carried out by HPLC–DAD-ESI/MSⁿ as a powerful screening tool for exploring its phenolic metabolites. Thus, over 50 phenolics have been characterized in the date palm samples analyzed. Of which, about 30 compounds are described herein in the dates' material for the first time. Remarkably, kaempferol glycosides and malonyl derivatives detected in this work haven’t been reported previously in P. dactylifera. The method used provides more information on dates’ chemical composition, which may be advantageous for further research to understand the effects of this plant on the human health. Also, the information obtained should help nutritionists and food technologists to become aware of the benefits of using this traditional plant in contemporary diets as potential sources of antioxidants. Additionally, data in this work may support the ancient and current use of this plant parts in as a source for functional ingredients in the medicinal, pharmaceutical, and dietary uses.

Parkinson’s disease (PD) is a neurodegenerative disorder characterized by fibrillar cytoplasmic aggregates of α-synuclein (i.e., Lewy bodies [LB]) and the associated loss of dopaminergic cells in the substantia nigra. But, mutations in genes such as α-synuclein (SNCA) account for only 10% of PD occurrences.  The exposure to environmental toxicants including pesticides (e.g. paraquat [PQ]) and manganese (Mn), are also recognized as important PD risk factors. Thus, aging, genetic alterations and environmental factors all contribute to the etiology of PD.  In fact, both genetic and environmental factors are thought to interact in the promotion of idiopathic PD, but the mechanisms involved are still unclear.  In this study, we report a toxic synergistic effect between α-synuclein and either paraquat or Mn treatment. We identified an essential role for central carbon (glucose) metabolism in dopaminergic cell death induced by paraquat or Mn treatment that is enhanced by the overexpression of α-synuclein. PQ “hijacks” the pentose phosphate pathway (PPP) to increase NADPH reducing equivalents and stimulate paraquat redox cycling, oxidative stress, and cell death. PQ also stimulated an increase in glucose uptake, the translocation of glucose transporters to the plasma membrane, and AMPK activation. The overexpression of α-synuclein further stimulated an increase in glucose uptake and AMPK activity, but impaired glucose metabolism. In effect, α-synuclein activity directs additional carbon to the PPP to supply paraquat redox cycling. Alternatively, Mn induces an upregulation in glycolysis and the malate-aspartate shuttle to compensate for energy depletion due to Mn toxicity. Mn treatment causes a decrease in carbon flow through the TCA cycle and a disruption in pyruvate metabolism, which are consistent with a dysfunctional mitochondria and inhibition of pyruvate dehydrogenase. The overexpression of α-synuclein was shown to potentiate Mn toxicity by glycolysis impairment by inhibiting aldolase activity. In effect, α-synuclein overexpression negates the metabolic response to alleviate Mn toxicity that results in an increase in cell death.

Almost automatic quantitative analysis of biofluids is now behind only a few clicks from sample to EXCEL table after minimal sample preparation (move 0.3 ml sample into NMR tube and add buffer), without separations, calibration and reference materials, even for unknown compounds!  Each organic compound with protons gives a highly diagnostic and unique NMR spectrum which is practically identical with any spectrometer operating at certain field. A distinctive feature of high-resolution 1D NMR spectra is that even the most complex spectrum of a compound can be described by a few spectral parameters within experimental accuracy, employing a quantum mechanical theory. The NMR spectral parameters offer also a very efficient way to store the spectra in Adaptive Spectral Libraries (ASL), instead of variable quality experimental spectra. Once metabolite spectra have been measured and modelled in one magnetic field strength using Quantum Mechanical Spectral Analysis (QMSA), the spectra can be simulated in every detail in any other field and mixtures – to be used in quantification of the mixtures with ChemAdder software. The protocol has been applied so far to plasma [1], volatile fatty acids from biowaste [2] and slaughterhouse waste [3]. These projects and the software (see http://chemadder.com) are described in our presentation.

 [1]   M. Tiainen, P. Soininen, R. Laatikainen, Quantitative Quantum Mechanical Spectral Analysis (qQMSA) of ¹H NMR Spectra of Complex Mixtures and Biofluids,   J.Magn.Reson., 242, 67 (2014); [2] E. den Boer, A. Łukaszewska, W. Kluczkiewicz, D.  Lewandowska, K. King, T. Reijonen, T. Kuhmonen, A. Suhonen, A. Jääskeläinen, A. Heitto, R. Laatikainen, E. Hakalehto. Volatile fatty acids as an added value from biowaste, Waste Management, Available online, http://dx.doi.org/10.1016/j.wasman.2016.08.006; [3] S. Schwede, E. Thorin, J. Lindmark, P. Klintenberg, A. Jääskeläinen, A. Suhonen, R. Laatikainen, E. Hakalehto. Using slaughterhouse waste in a biochemical based biorefinery -results from pilot scale tests. Environmental Technology, Available online, http://dx.doi.org/10.1080/09593330.2016.1225128

The leaves of horehound (Marrubium vulgare), were investigated for their phytochemical composition by using high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS²), this besides evaluating the antioxidant activity of methanol and acetone extracts. Total contents of phenols, flavonoids, and tannins have also been determined. The antioxidant potential was evaluated by DPPH^•, activity against H₂O₂, antioxidant capacity, and iron-reducing power. The HPLC-MS² analysis of the methanol extract revealed the presence of about 30 compounds of various families, of which 15 compounds have been tentatively identified for the first time. Flavonoids and phenylethanoid derivatives were the major compounds. Methanol extract was shown to contain more flavonoids and tannins. The ability of the methanol extract to scavenge H₂O₂ was found considerable (~60%). The best whole antioxidant capacity was demonstrated in the methanol leaf extract, indicating its use as a promising source of natural antioxidants for pharmaceutical and food applications, as well as in prevention of oxidative-stress-related diseases.

Globularia alypum L. (Globulariaceae) is a plant growing in the Mediterranean basin and is known and used in the folk medicine for its several pharmacological properties against typhoid, fever, gout, diabetes, and rheumatism. The methanol extract of Globularia alypum has been characterized for its phytochemical composition using the liquid chromatography hyphenated with an ESI-QTOF-MS. Thus, in this work the used technique leads to the tentative characterization of a total of 60 phytochemical compounds. The major compounds identified belong to the iridoids and phenolic acids derivatives. More than 20 iridoids and secoiridoids were identified, including several compounds not previously documented in Globularia alypum, such as gentiopicroside, acetylbarlerin isomers, serratoside A, specioside, shanziside, and decumbeside D isomers. Besides, the presence of 10 flavonoids, together with other nine polar compounds, has been confirmed. The methanol extract of Globularia alypum could thus be considered as a promising source of bioactive ingredients promoting the further use of this plant in the folk medicine.

Modifications in growing techniques can affect the yield and nutritional quality of various cultivated plant species. Owing to its high nutritional value, sweet pepper (Capsicum annuum L.) was used in this study as a model plant to investigate the effect of abiotic stress (Electrical conductivity [EC]) and elicitor (Salicylic acid [SA]) on yield and fruit quality parameters under conditions of greenhouse. Nonetheless, the application of elicitors, are stable molecules that induce the activation of transduction cascades and hormonal pathways, which trigger induced resistance to environmental stress. The combination in metabolomics of advanced analytical methods and bioinformatics tools provides wide chemical compositional data that contributes to corroborate (or not) the substantial equivalence. The aim was evaluated the endogenous H₂O₂ production caused by the effect of different concentrations of (SA) in Capsicum annuum L. in production after elicitation in seedling, and the production of secondary metabolites using GC-MS (flavonoids, tannins and phenolic content as well as the antioxidant properties) in plant and fruit of Capsicum annuum L. to relate their response in metabolic pathways. Results displayed that the use SA, induced an endogenous H₂O₂ and enzymatic activities related with plant defense as phenylalanine ammonia lyase and catalase. This production showed results that could be an indicator for determining application opportunity uses in agriculture for maintaining plant alert systems against a stress. These results were correlated with those obtained from cultivation of capsicum annum until obtaining the fruit at ripe stage had a high content of bioactive compounds that exhibited significant antioxidant properties. The correlation of the contents of flavonoids, tannins and total phenolics and the ability to remove free radicals of the sweet pepper was significant (r = 0.99, P <0.000) in treatment 3 (0.1 mM SA/36 dS/m EC) showed a correlation between the DPPH and ABTS compared with the control. The analysis revealed that significant increased activity of CAT and PAL and H2O2 endogenous were significantly (p < 0.05) perturbed in the stress-induced treatments: in some metabolic pathways as aminoacyl t-RNA biosynthesis.

Introduction

Spodoptera frugiperda (Lepidoptera: Noctuidae) is one of the main plagues of maize cultivation and it is resistant to the most used insecticides. Plants are important source of biopesticides due to their own mechanisms of interaction and diversified composition. Thus, fractions (hexane, acetate and hydro-ethanol ) of extracts from different parts of Caesalpinia pluviosa var. peltophoroides (Fabaceae) have insecticidal activity investigated. Chemical composition of the fractions were evaluated by UHPLC-HRFTMS, thereafter processed on MZmine 2.2 software  and exported to do multivariate statistical analysis (MSA) - O2PLS-DA (SIMCA-P 13.0). The dereplication of compounds were performed using DNP^© , Scifinder^® and our in house Caesalpinia database.

Results and Discussion

Six fractions were inactive and five displayed pupal or larval mortality. The O2PLS-DA analysis found a clear separation of inactive and insecticidal group (R²= 0,72) and indicated the metabolites highly correlated with the insecticidal property (VIP>1.95): eugenyl vicianoside; gluconic acid lactone and gallic acid.

Conclusions

Thus, through metabolomic strategies was possible to dereplicate the compounds most correlated with insecticidal property and this knowledge can be very useful to  development of new techniques to the crop pest control.

Acknowledgements

FAPEMIG and CNPQ for the financial funding and the AsterBioChem for the UHPLC-HRMS analysis.

Synechococcus elongatus PCC7942 represents a classical microbial model that has been widely studied. Its genome-scale metabolic network was recently published (iSyf715), allowing the integration of high-throughput data with the network connectivity. The high-dimensionality of this analysis paves the way not only for the designing of metabolic engineering strategies but also for the principles elucidation of certain cellular processes functioning. Here we present a reporter metabolites analysis of transcriptional profile of S. elongatus PCC7942 under inorganic carbon acclimation by the integration with the connectivity structure of iSyf715. The analysis is based on the published transcriptional changes after 6 and 24 hours of cells growth, when the CO₂ concentration was shifted from high to low levels. The Reporter Features algorithm was applied to unveil the 52 scattered reporter metabolites (p<0.05) across the whole cyanobacterium metabolism, which could represent key regulatory nodes during the CO₂ regime transitions. In addition, clusters of metabolic genes that significantly and coordinately change their expression during this perturbation were identified by using the Reporter Subnetwork algorithm. These results could support the subsequent inference of feasible transcriptional regulatory maps as well as the assessment of the metabolic network capabilities of iSyf715.