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Phytopharmaceuticals, phytomedicines and botanical dietary supplements are products of wide interest considering the increase of their use. The development of fast and effective analytical methods able to give a fingerprinting of the product, on the basis of the plant extracts declared to be contained in it, is surely of high interest. In a previous investigation electrospray mass spectrometry was proved to be effective for the characterization of plant extracts. The direct infusion of the samples and the analyses in both positive and negative ion mode lead to a clear differentiation of the different samples. To verify if the same approach can be effective also for mixtures of plant extracts, five different commercial dietary supplements [Sedivitax gocce (1), Finocarbo Plus opercoli (2), Sollievo Bio tavolette (3), MiniMas opercoli (4) and Ruscoven gocce (5), all products from Aboca S.p.A., Sansepolcro, Italy] were analyzed by ESI. In order to evaluate possible changes in the metabolic profile with respect to different years of production, ten different batches of the commercial dietary supplements were considered. The mass spectral data were evaluated by multivariate analysis and the obtained results suggest that the method allows a satisfactory and rapid characterization of complex mixtures of commercial dietary supplements

The mass spectrometric behavior of palladium(II) halide complexes of three types of quinolinylaminophosphonates, diethyl and dibutyl esters of [α-anilino-(quinolin-2-yl)methyl] phosphonic (L1, L2), [α-anilino-(quinolin-3-yl) + is observed in the mass spectra of all the complexes, and its abundance as well as the fragmentation pathway depend on the type of the complex. In the cis complexes (1-4) the initial decomposition goes under two fragmentation routes: those in which the sodium molecular adduct sequentially loses halides HX/NaX and those in which this loss is in the competition with the loss of dialkyl phosphite. The predominant pathways for decomposition of trans dihalide (5-8) and tetrahalide (9-12) complexes include three competitive reactions; the loss of halides, dialkyl phosphites and the intact phosphonate ligand molecule and its fragments formed by ester dissociation or complete loss of the phosphonate ester moiety. A series of acetonitrile adducts and cluster ions derived from dimolecular clusters [2M + Na] + were also detected. The most important fragmentation patterns are rationalized and supported by the MS n studies.

Crystal and molecular structures of three aminophosphonate diesters, diethyl and dibutyl [a-(quinolin-3-ylamino)-N-benzyl]phosphonates (1 and 2) and dibutyl [a-anilino-(quinolin-3-yl)methyl]phosphonate (3) were reported and comparatively discussed. Characteristic structural features for these compounds are strong N-HÁÁÁO=P hydrogen bonds that connect two organophosphorus molecules in cyclic centrosymmetric dimer. Phosphoryl oxygen forms additional interaction with a C-H donor from the nearby aromatic group. Dimer formation in solution was also confirmed using electrospray ionization mass spectrometry. Mass spectra of six structurally similar aminophosphonate derivatives, 1-3 along with diethyl [a-anilino-(quinolin-3-yl)methyl]phosphonate (4), diethyl and dibutyl [a-anilino-(quinolin-2-yl)methyl]phosphonates (5 and 6) were studied and dimolecular ions [2M ? Na] ? and [2M ? H] ? were observed.Keywords Aminophosphonate Á Hydrogen-bonded dimers Á X-ray structure analysis Á ESI mass spectrometry Electronic supplementary material The online version of this article (