Laura Guarcini

Phytochemical analysis of Achillea ligustica All. from Lipari Island (Aeolian Islands)

Abstract A complete chemical investigation of Achillea ligustica All. growing at Lipari (Aeolian Island, Sicily) has been carried out. Seventeen metabolites have been isolated and characterised from dichloromethane and methanol extracts of flowers and aerial parts, and GC/MS analyses of petroleum ether extracts was carried out, revealing a composition in sesquiterpenoids similar to those reported for populations from Greece, Sicily and Algeria, showing the presence of (3RS,6RS)-2,6-dimethyl-1,7-octadiene-3,6-diol (1), 2,6-dimethyl-octa-3(E),7-diene-2,6-diol (2), iso-seco-tanapartholide (3) from DCM fraction. In addition from the methanolic extract of the aerial parts, peculiar flavonoid glucuronides have been isolated: i.e. apigenin-7-O-glucuronide (12) and quercetin 3-O-glucuronide (14). These metabolites have been reported in this species for the first time. The isolated flavonoids were previously recognised in several species of this complex genus and for this reason seems to be highly retained secondary metabolites of importance from the chemotaxonomic point of view.

Iridoid glucosides from Pentas lanceolata (Forssk.) Deflers growing on the Island of Sardinia

The ethanolic extract of Pentas lanceolata (Forssk.) Deflers was investigated from a phytochemical point of view and in particular on the monoterpenoid glucosides content. Iridoid glucosides have a taxonomic relevance, e.g., asperuloside and its derivative are characteristic of the Rubioideae subfamily where this species is comprised. In the light of earliest phylogenetic molecular study which proposed to merge P. lanceolata in the Spermacoceae tribe, a phytochemical approach also becomes necessary for a correct classification of this species. A total of 12 compounds were identified in detail, ten of these are iridoid glucosides: asperuloside, asperulosidic acid, tudoside, E-uenfoside and Z-uenfoside previously identified in this genus; whereas, deacetyl-asperulosidic acid, ixoside, griselinoside, 6β,7β-epoxysplendoside were recognized here for the first time from P. lanceolata. Among the non-iridoidic compounds ursolic acid and d-xylose were identified.

Spectroscopic evidence for a gas-phase librating G-quartet–Na+ complex

The IRMPD spectrum of the G-quartet-Na(+) complex, in combination with an ab initio molecular dynamic simulation, revealed the presence of two metastable populations of conformers separated by a free energy barrier easily accessible at room temperature.

Reassessment of Melittis melissophyllum L. subsp. melissophyllum iridoidic fraction

The analysis of the polar fraction of Melittis melissophyllum L. subsp. melissophyllum led to the identification of several iridoid glycosides: monomelittoside (1), melittoside (2), harpagide (3), acetyl-harpagide (4) and ajugoside (5). Compounds 3 and 4 are considered marker compounds for the genus and, as well as compounds 1, 2 and 5, were already evidenced in a previous study on the nominal species. It was noteworthy of the presence of allobetonicoside (6) which was never reported for this genus. The isolation of 6 is very relevant because of its allose residue on the structure. Allose has been often found in the species of the subfamily Lamioideae even if it mostly regarded flavonoids considered of chemotaxonomical relevance for some correlated genera of Lamiaceae. Same as allosyl-glycosidic flavonoids, the presence of allosyl-glycosidic iridoids may also be an additional chemosystematic evidence of botanical relationships among Lamiaceae species and genera.

Phytochemical pattern of Gentiana species of Appennino in Central Italy

The molecular pattern of two Gentiana species, G. dinarica and G. lutea, present in a protected area of Appennino Centrale in Italy, was examined. Results were compared with literature data, examining the differences between the two species.

Spectroscopic Discrimination of Diastereomeric Complexes Involving an Axially Chiral Receptor

The infrared multiphoton dissociation (IRMPD) spectra of electrospray ionization (ESI)-formed proton-bound complexes between the axially chiral multifunctional macrocycle MaR and d- and l-phenylalanine (PD and PL ) or d- and l-3,4-dihydroxyphenylalanine (DD and DL ) are recorded in the ν˜ =2800-3700 cm-1 region. Whereas the diastereomeric [MaR ⋅H⋅PD ]+ and [MaR ⋅H⋅PL ]+ complexes do not show any significant spectral differences, the spectrum of [MaR ⋅H⋅DD ]+ clearly diverges from that of its [MaR ⋅H⋅DL ]+ diastereomer. A comparison of the experimental spectra with the B3LYP/6-31G**-calculated harmonic vibrational frequencies of a number of stable structures indicates the formation, in the ESI source, of very similar spectroscopically active structures, with the protonated amino acid placed outside the flat cavity of the macrocycle and hydrogen-bonded at its O2 center. Different spectral signatures of the [MaR ⋅H⋅DD ]+ and [MaR ⋅H⋅DL ]+ complexes are attributed to the coexistence of several stable rotamers in the ESI source.

Contact Ion Pairs on a Protonated Azamacrocycle: the Role of the Anion Basicity.

AbstractA potassium-containing hexaazamacrocyclic dication, [M•H•K]2+, is able to add in the gas phase mono- and dicarboxylate anions as well as inorganic anions by forming the corresponding monocharged adducts, the structure of which markedly depends on the basicity of the anion. With anions, such as acetate or fluoride, the neutral hexaazamacrocycle M acts as an acceptor of monosolvated K+ ion. With less basic anions, such as trifluoroacetate or chloride, the protonated hexaazamacrocycle [M•H]+ performs the unusual functions of an acceptor of contact K+/anion pairs. Graphical Abstractᅟ

Pivaloylcodeine, a new codeine derivative, for the inhibition of morphine glucuronidation. An in vitro study in the rat.

We have previously found that phenanthrenic opioids, including codeine, modulate morphine glucuronidation in the rat. Here codeine and five of its derivatives were compared in their effects on the synthesis of morphine-3-glucuronide (M3G) and morphine-6-glucuronide (M6G) from morphine by rat liver microsomal preparations, and by primary cultures of rat hepatocytes previously incubated for 72 h with either codeine or its derivatives. Acetylcodeine and pivaloylcodeine shared the capability of the parent compound of inhibiting the synthesis of M3G by liver microsomes through a noncompetitive mechanism of action. Their IC50 were 3.25, 2.27, and 4.32 μM, respectively. Dihydrocodeine, acetyldihydrocodeine, and lauroylcodeine were ineffective. In all the experimental circumstances M6G was undetectable in the incubation medium. In primary hepatocyte cultures codeine only inhibited M3G formation, but with a lower efficacy than that observed with microsomes (IC50 20.91 vs 4.32 μM). Preliminary results show that at micromolar concentrations codeine derivatives exhibit a low rate of affinity for μ opiate receptors. In conclusion, acetyl and pivaloyl derivatives of codeine noncompetitively inhibit liver glucuronidation of morphine interacting with microsomes. This study further strengths the notion that phenanthrenic opioids can modulate morphine glucuronidation independently from their effects on μ opiate receptors.

Anti-HIV Agents From Nature: Natural Compounds From Hypericum hircinum and Carbocyclic Nucleosides From Iridoids

Abstract The presence of antiviral compounds in the Guttiferae family as medicinal plants and the long traditional use of species of the genus Hypericum for the treatment of many viral infections have developed a strong interest. Among the natural products of plant origin, the ones from Hypericum genus were cited as promising anti-HIV agents. This chapter will report an updated review of carbocyclic nucleoside analogues as anti-HIV agents from iridoids. Moreover, the partial synthesis of antiviral agents from iridoid glucosides to carbocyclic nucleosides as new anti-HIV agents is reviewed.

Scenedesmus dimorphus (Turpin) Kützing growth with digestate from biogas plant in outdoor bag photobioreactors

Digestate coming from an Anaerobic Digestion unit in a Biogas Plant, feeded on cow manure and vegetable waste from markets, has been used. About 8–35 L polyethylene transparent bags have been employed as cultivation container, outdoor. Different aliquots of digestate, alone or mixed with commercial liquid fertiliser, were employed to cultivate in batch Scenedesus dimorphus, a freshwater green microalga, in the ENEA facilities of Casaccia Research Center, near Rome, Italy. The cultivation period was June–July 2013. The average daily yields of dry microalgae biomass varied from 20 mg/L/d to 60 mg/L/d, mean 38.2 mg/L/d. Final dry biomass concentration varied from 0.18 to 1.29 g/L, mean 0.55 g/L. S. dimorphus proved to be very efficient in removing N and P from the culture medium. Another fact emerged from these trials is that S. dimorphus inner composition resulted to be variable in response to the tested different culture conditions.