Nutrients and Main Secondary Metabolites Characterizing Extracts and Essential Oil from Fruits of Ammodaucus leucotrichus Coss. & Dur. (Western Sahara).

The ethnobotany of the Sahrawi people considers various species of plants and crude drugs as food, cooking spices and traditional health remedies. From among these, the fruits of Ammodaucus leucotrichus Coss. & Dur. (Apiaceae), known as Saharan cumin, were chosen for our research. The present paper reports a proximate composition and mineral element analysis of various samples of A. leucotrichus fruits, collected during the balsamic period (full fruiting) from plants grown in Bir Lehlu (Western Sahara) and purchased in a local market (Tindouf). These analyses pointed out interesting nutritional values of the crude drug. Decoction and alcoholic extract, analyzed by HPLC-DAD, evidenced ammolactone-A and R-perillaldehyde as the two main isolated constituents, particularly in the ethanolic extracts (ammolactone-A, market sample: 51.71 ± 0.39 mg/g dry extract; wild sample: 111.60 ± 1.80 mg/g dry extract; R-perillaldehyde, market sample: 145.95 ± 0.35 mg/g dry extract; wild sample: 221.40 ± 0.30 mg/g dry extract). The essential oils, obtained through hydrodistillation, were characterized by GC-MS and evidenced R-perillaldehyde (market sample: 53.21 ± 1.52%; wild sample: 74.01 ± 1.75%) and limonene (market sample: 35.15 ± 1.68%; wild sample: 19.90 ± 1.86%) as the most abundant compounds. The R configuration of perillaldehyde was ascertained and a complete description of the 1H and 13C NMR spectra of ammolactone-A was performed.

Mass spectrometry in the characterization of reactive metal alkoxides.

Metal alkoxides are metal-organic compounds characterized by the presence of MOC bonds (M = metal). Their chemistry seems to be, in principle, relatively simple but the number of possible reactant species arising as a consequence of their behavior is very remarkable. The physico-chemical properties of metal alkoxides are determined by many different parameters, the most important ones being the electronegativity of the metal, the ramification of the ligand, and the acidity of the corresponding alcohol. Their reactivity makes them suitable and versatile candidates for many applications, including homogeneous catalysis, synthesis of new ceramic materials through the sol-gel process and, recently, also for Cultural Heritage. Metal alkoxides are characterized by a strong tendency to give clusters and/or oligomers through oxo-bridges. Mass spectrometry has been successfully employed for the characterization of metal alkoxides in the gas-phase. Electron ionization (EI) allowed the assessment of the molecular weight and of the most relevant decomposition pathways giving information on the relative bond strength of differently substituted molecules. On the other hand, information on the reactivity in solution of these molecules have been obtained by electrospray ionization (ESI)-matrix assisted laser desorption ionization (MALDI) experiments performed on their reaction products. These data were relevant to investigate the sol-gel process. In this review, these aspects are described and the results obtained are critically evaluated. © 2016 Wiley Periodicals, Inc. Mass Spec Rev.

Effects of Aqueous Extracts from Amazon Plants on Plutella xylostella (Lepidoptera: Plutellidae) and Brevicoryne brassicae (Homoptera: Aphididae) in Laboratory, Semifield, and field trials.

We evaluated the insecticide activities of aqueous extracts of five species of plants from the Ecuadorian Amazon (Deguelia utilis (ACSm.) AMGAZEVEDO (Leguminosae: Papilionoideae), Xanthosoma purpuratum K. Krause (Alismatales: Araceae), Clibadium sp. (Asteracea: Asterales), Witheringia solanacea L'Hér (Solanales: Solanaceae), and Dieffenbachia costata H. Karst. ex Schott (Alismatales: Araceae)) plus Cymbopogon citratus Stapf. (Poales: Poaceae) under laboratory, open-field conditions in Plutella xylostella L. (diamondback moth), and semifield conditions in Brevicoryne brassicae L. Tap water was used as a negative control, and synthetic insecticides were used as positive controls. In a laboratory bioassay, aqueous extracts of D. utilis resulted in P. xylostella larval mortality. In contrast to chlorpyrifos, all botanicals were oviposition deterrents. All extracts except Clibadium sp. decreased leaf consumption by P. xylostella larvae. In semifield experiments, D. utilis, Clibadium sp., D. costata, and X. purpuratum initially controlled the population of B. brassicae, but 7 d after application, all botanicals except the D. utilis lost their ability to control the pest. In field experiments on broccoli crops in both dry and rainy seasons, the extracts did not control the abundance of P. xylostella, where as a mixture of two insecticides (chlorpyrifos + lambda cyhalothrin) did. These results show some incongruences from laboratory to semifield and field conditions, indicating that more studies, including the identification of the chemicals responsible for the biological activity, its stability, and the effects of chemotypes on insecticidal activity, are needed to understand the potential of these plant species as botanical insecticides.

Study of challenging calcium alkoxides in solution by electrospray ionization mass spectrometry (Part 1).

Electrosprayionization was applied on calcium altkoxides studying the mostsuitableoperativeconditions for their detection/identification. To reach this aim, calcium methoxide and ethylate were obtained by two different synthetic pathways, in order to understand their possible different aggregation states. The reaction mixture shows the presence of a supernatant and of a precipitate poorly soluble in most organic solvents. The purpose of this preliminary study is to understand the qualitative differences between the precipitated species and the ones in solution by analyzing both of them with the same analytical method. The electrospray ionization (ESI) operating conditions (voltages, temperatures, solvents) allow not only the detection of single species but also the study of clusters present in solution. Particular attention was paid to establishing the role of ESI conditions in the formation of the detected species. Experiments performed at different sprayer voltages (1 kV, 2kV, 3 kV and 4 kV) proved that ESI does not perturbate the equilibria present in the original solution, demonstrating that the technique can be a useful tool to achieve information on this class of compounds.

Study of challenging calcium alkoxides in solution by electrospray ionisation mass spectrometry (Part 2).

Calcium alkoxides in solution give rise to oligomers with different reactivity and solubility and, as observed in a previous investigation, small differences in the ligand structure lead to strong differences in the cluster composition. Electrospray ionisation mass spectrometry (ESI-MS) gives evidence of this behaviour, allowing the identification of these oligomers. In this paper, ESI was applied in the study of calcium alkoxides with different steric hindrances and with additional donor atoms on the ligands. A systematic analysis was conducted by varying the ESI instrumental parameters (voltages, temperatures) to identify the best conditions for the analysis of this class of compounds. Furthermore, particular attention was paid to the study of the best solvent to be employed, considering the possible occurrence of alcoholysis and decomplexation phenomena.

Re-investigation of lead(II) formate.

The crystal structure of the title compound, poly[di-µ(4)-formato-lead(II)], [Pb(HCOO)(2)](n), has been re-investigated. It consists of a three-dimensional polymeric network of Pb(2+) nodes connected by bridging formate anions. Despite having been described previously, the structural information available so far [Harrison & Steel (1982). J. Organomet. Chem. 239, 105-113] is incomplete and the reported Pnma space group is incorrect. In this work, the space-group assignment to P2(1)2(1)2(1) is discussed and a complete description of the structural features of lead(II) formate is provided.

Larvicidal activity of Ocimum campechianum, Ocotea quixos and Piper aduncum essential oils against Aedes aegypti.

Aedes aegypti, the main arbovirus vector of the Yellow fever, Dengue, Chikungunya and Zika viruses, is widely distributed in tropical and subtropical areas throughout the world. Preventive control efforts have been implemented worldwide aimed at reducing its impact on human health. The recent reduction of chemicals available for vector control due to their negative impact on the environment and human health and the increase in mosquito resistance to insecticides have driven the research community to identify and evaluate sustainable alternatives to synthetic insecticides. In this study, the potential larvicidal effect of essential oils extracted from Ocimum campechianum, Ocotea quixos and Piper aduncum were tested in vitro. GC and GC-MS analyses showed that the main compounds were eugenol (18%), 1,8-cineole (39%) and dillapiole (48%), respectively. Susceptibility to essential oils was measured according to the WHO protocol. After 24 h, the mean percentage mortality ranged from 2.7 to 100% for P. aduncum, from 2.2 to 100% for O. campechianum, and from 2.9 to 100% for O. quixos. The highest potential was displayed by P. aduncum, followed by O. campechianum and O. quixos, with LC50 values of 25.7, 69.3 and 75.5 ppm, respectively. The rapid and effective larvicidal activity of these three oils led us to consider these results to be promising, also considering the possibility of local cultivation of these plants in tropical and subtropical areas and the simple technology for their large-scale preparation and production. Further studies are needed to evaluate the individual components and their activity as larvicides.

Flavonoids in Ecuadorian Oreocallis grandiflora (Lam.) R. Br.: Perspectives of Use of This Species as a Food Supplement.

Oreocallis grandiflora (Lam.) R. Br. is an Ecuadorian species belonging to the Proteaceae family, commonly known as cucharillo (Loja and Zamora provinces), cucharilla (Sierra region), gañal (Bolívar province), and algil (Chimborazo province). Its leaves and flowers, collected during blooming, are traditionally used for oral administration to treat liver diseases, vaginal bleeding, and ovary/uterus inflammation and as digestive, diuretic, and hypoglycemic remedy. Related literature does not report any scientific evidences regarding the chemical composition of the used parts of this species (leaves and flowers), while few indications are reported about the healthy properties of their preparations. Based on these premises, the present research was performed with the objectives to fill the gaps of the chemical and biological knowledge about this species, enriching the knowledge related to the plant biodiversity of Amazonian Ecuador and to the ethnobotanical tradition of Andean communities. Chemical and biological investigation (in vitro antioxidant and anti-inflammatory activity) of flower and leaf hydroalcoholic extracts shed a light on the functional metabolites putatively involved in healthy properties of the O. grandiflora traditional preparations. The chemical fingerprinting achieved by HPTLC and 1HNMR analyses showed the presence of flavonoids, subsequently quantitatively estimated by AlCl3 complexation assay and HPLC-DAD. Silica gel chromatography allowed the isolation of the main compounds of the flower extract: quercetin 3-O-ß-glucuronide and myricetin 3-O-ß-glucuronide. RP-HPLC-DAD-MS analyses showed the presence of quercetin 3-O-rutinoside and isorhamnetin 3-O-rutinoside, in addition to the above-mentioned molecules, in the leaf extract. Regarding the antioxidant (DPPH test, a radical scavenging assay) and anti-inflammatory (WST-1 assay, an oxidative burst test) activities, leaf extract showed the most promising results when compared to the positive controls. The same extract, however, exhibited a higher cytotoxicity compared to the flower extract, indicating the latter preparation as the most interesting anti-inflammatory crude drug.