The effects of water-deficit stress on irrigated and unirrigated field plants of Coffea arabica L. genotype IAPAR 59 were investigated. Plant extracts were obtained following an ethanol-dichloromethane-hexane statistical mixture design. Proton nuclear magnetic resonance (1H NMR) fingerprints of the extracts were discriminated using factor analysis (FA) and hierarchical clustering techniques. Extracts from the 1:1:1 ternary mixture presented the largest discriminations compared with those from the pure solvents or their 1:1 binary mixtures. Metabolites resulting from fermentation processes and nutritional deficiencies as well as senescence and abscission precursors such as lactate, arginine and methionine were prevalent in unirrigated plants that can provoke expressive decreases in bean productivity as well as premature plant aging. Amino acids that control regulatory, physiological processes and soil salinization have higher concentrations in the irrigated plants. The NMR assignments of eighteen substances observed here were confirmed by electrospray ionization mass spectrometry.

Rollinia mucosa fruit has generated great interest due to the presence of bioactive compounds, which exhibit promising biological activities. Fingerprinting analytical techniques, chromatographic-diode array detection (DAD), infrared, mass spectrometric, 1H and 13C nuclear magnetic resonance (NMR) spectra, associated with chemometric analysis and mixture design, were used to determine chemical discriminations of sun-exposed and self-shaded leaves of Rollinia mucosa in each of the four seasons. Sunlit leaves in winter presented higher metabolite signals related to the acetogenins, whereas shaded leaves have higher abundances of carbohydrates and terpenes. Sunlit leaves harvested in the summer had the smallest metabolite abundances. Fingerprints confirmed the presence of two acetogenins, annonacin A and annonastatin. Ternary and quaternary mixtures of the statistical mixture design were most effective for revealing important discriminations.

Species of the Annonaceae family are used in traditional medicine, and several antitumor acetogenins have been isolated from the leaves of Annona muricata and Rollinia mucosa. Leaves samples (self-shaded and sun-exposed) of these species were collected during winter and summer seasons. Extraction media were prepared from mixtures of five solvents according to a simplex centroid design. Plant extracts were analysed by injection into a high-performance liquid chromatography with diode array detection (HPLC-DAD) and evaluated after applying by multivariate curve resolution-alternating least-squares (MCR-ALS) and discriminant-unfolded partial least-squares (D-UPLS). The objective was to check whether the chemometric resolution of chromatographic profiles could help in the discrimination of samples according to taxonomic classification, sun exposition and/or harvest season. The results indicate that extraction media containing ethanol as main solvent achieved discrimination of self-shaded versus sun-exposed plants and harvest season of Annona muricata. Also, D-UPLS analysis allowed taxonomic discrimination between Annona muricata and Rollinia mucosa extract samples.

Vernonia condensata Baker leaves have different uses in Brazilian folk medicine, including as analgesic and anti-inflammatory agents. The purpose of this study was to evaluate the seasonal effects on their high performance liquid chromatography with a diode array detector (HPLC-DAD-UV) and ultra-performance liquid chromatography coupled to a mass spectrometer with an electrospray interface (UPLC-ESI-MS) fingerprints, as well as their analgesic activities in mice. There were significant seasonal effects on the relative abundances of the metabolites of the V. condensate leaves as well as on their activities. Analgesic activities in the writhing test were observed with the polar fraction of the leaf extracts collected in autumn, winter and summer (400 mg kg-1); and with the intermediate fraction of leaves collected in autumn (25 and 400 mg kg-1) and in the summer (100 mg kg-1). In conclusion, the results confirm peripherally-mediated anti-inflammatory and analgesic activities for V. condensata leaves and suggest that these are influenced by the harvesting season. N-oxides alkaloids as well as vernonioside play important roles in determining this activity.