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Eryngium amethystinum L. belonging to the Apiaceae family, is a perennial plant distributed in Southeast Europe. Even though this plant is used in traditional medicine, its phytochemical characterization is still incomplete. In this study composition of bioactive constituents of the methanol extract are reported for the first time. By means of the UPLC-LTQ-Orbitrap-MS n method, altogether sixty-three constituents were characterized: eight hydroxybenzoic acid derivatives (7-13, 32), fifteen cinnamic acid derivatives (

Soluções de AlCl 3 foram analisadas em concentrações de 0,03 a 5,0 mmol dm-3 e pH de 3,5 a 6,0 por espectrometria de massas com ionização por electrospray e analizador quadrupolar (ESI-Q-MS). Esses dados espectrais foram comparados com os obtidos por ressonância magnética nuclear (NMR) de 27 Al e potenciometria. Espécies resultantes da hidrólise do cátion alumínio em solução apresentaram-se principalmente como complexos carregados positivamente (+1) com moléculas de água coordenadas (n = 1-3) ao metal. As análises revelaram que complexos poliméricos de carga +2 e +3 (em concentrações mais elevadas de Al e pH > 4) contêm íons cloretos coordenados. O aspecto geral dos espectros de massas é dependente de parâmetros instrumentais tais como taxa de fluxo de solvente, temperatura na fonte de ionização e voltagens do cone e capilar. Assim, o ajuste fino do instrumento com relação a estes parâmetros foi realizado. Uma tensão de cone de amostra não superior a 50 V levou à melhor correspondência entre dados de potenciometria, ressonância magnética nuclear de 27 Al e espectrometria de massas. Solutions of AlCl 3 were analyzed at concentrations from 0.03 to 5.0 mmol dm-3 and pH from 3.5 to 6.0 using an electrospray ionization quadrupole mass spectrometer (ESI-Q-MS). Mass spectral data were compared with those obtained by 27 Al nuclear magnetic resonance (NMR) spectroscopy and potentiometry. Hydrolytic aluminum species were present in solution mainly as +1 positively charged complexes with n coordinated water molecules (n = 1-3). Analysis revealed that polymeric complexes of +2 and +3 charges (at higher Al concentrations and pH > 4) contained coordinated chloride ions. The general appearance of the mass spectra is dependent on instrumental parameters such as solvent flow rate, ionization source temperature and cone and capillary voltages. Thus, fine tuning of the instrument with respect to these parameters was performed. Sample cone voltages not exceeding 50 V led to the best agreement between potentiometric, 27 Al NMR and mass spectral data.

Chlorpyrifos (CPS) is a toxic pesticide present in several pesticide formulations, with low degradability by natural processes. The degradation leads to the toxic metabolite chlorpyrifos-oxon (CPO). The analytical techniques used for the CPS and CPO analysis, like UPLC-PDA and GC-MS, are accurate but also expensive and time consuming, and they need sample pretreatment. In the search of a more rapid and simple analytical procedure, atmospheric solids analysis probe with mass spectrometry (ASAP-MS) was optimized for the determination of CPS and CPO in apples (Malus domestica "Idared"). The identification of the analytes was based on protonated ion and isotopic pattern, while the quantification was based on peak intensities. The obtained results were confirmed by re-validated UPLC-PDA and GC-MS techniques. CPS and CPO concentrations determined by ASAP-MS and UPLC-PDA showed moderate discrepancies (on average by 10-20%), thus demonstrating that ASAP-MS can be a semiquantitative tool for the quantification of these compounds. As additional goal of this work, the efficiency of a gamma irradiation treatment to remove CPS and CPO from apples was tested by analyzing their content before and after the irradiation: 89-99% of CPS and CPO were degraded with doses of 3.5-3.8 kGy and 66-72 h of irradiation per sample. Identical degradation results were obtained by UPLC-PDA and ASAP-MS, indicating that the latter technique is well suitable to rapidly check pesticide degradation in apples.

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