Synthesis of BODIPY-labeled alkylphosphocholines with leishmanicidal activity, as fluorescent analogues of miltefosine

Two general synthetic methods are described, by which the highly fluorescent and photostable BODIPY group can be inserted in and aligned with the alkyl backbone of linear lipids. These methods have been used to prepare strongly emitting analogues of the leishmanicidal drug miltefosine, in which the antiparasite activity in vitro of the original drug is preserved.     

New palaeoecological evidence for the potential role of fire in the Gran Sabana, Venezuelan Guayana, and implications for early human occupation

The neotropical Gran Sabana region of Venezuela is dominated by apparently anomalous vegetation types, treeless savannas and savanna-forest mosaics, considering the present-day warm and wet bioclimatic conditions. Past climatic changes and fire have been proposed as the more probable causes. Recent palynological studies show that savanna vegetation has been present since the beginning of the Holocene, but the earliest fires recorded so far only go back to 3,800 cal years b.p. This paper uses pollen and charcoal analyses to show the existence of early Holocene regional fires in the Gran Sabana, and to show the intimate connection between the proxies for fire (charcoal) and savanna vegetation (pollen) throughout the Holocene. Although the cause of such fires is not yet known, the possibility of early Holocene human occupation of the Gran Sabana is suggested.     

Preparation of D-galactofuranosyl nitromethanes: a revision and a new approach

Sodium methoxide-promoted methanolysis of 7-deoxy-7-nitro-L-glycero-L-galacto-heptitol peracetate rapidly and nearly quantitatively accumulates 7-deoxy-6-O-methyl-7-nitro-L-glycero-L-galacto-heptitol. The prolonged treatment then provides 76% of D-galactofuranosyl nitromethanes and finally results in the equilibrium of 77% of β-D-galactopyranosyl nitromethane and 7-9% of three other tautomeric D-galactosyl nitromethanes. Thermal treatment of 7-deoxy-7-nitro-L-glycero-L-galacto-heptitol in boiling water peaks at a 58% content of D-galactofuranosyl nitromethanes and ends in a similar equilibrium mixture of four D-galactosyl tautomers. The relevant kinetic parameters of the latter transformation are determined by a curve fitting using the nonlinear least-squares Marquardt-Levenberg algorithm.     

Identification of phenolic compounds in isolated vacuoles of the medicinal plant Catharanthus roseus and their interaction with vacuolar class III peroxidase: an H₂O₂ affair?

Class III peroxidases (Prxs) are plant enzymes capable of using H(2)O(2) to oxidize a range of plant secondary metabolites, notably phenolic compounds. These enzymes are localized in the cell wall or in the vacuole, which is a target for secondary metabolite accumulation, but very little is known about the function of vacuolar Prxs. Here, the physiological role of the main leaf vacuolar Prx of the medicinal plant Catharanthus roseus, CrPrx1, was further investigated namely by studying its capacity to oxidize co-localized phenolic substrates at the expense of H(2)O(2). LC-PAD-MS analysis of the phenols from isolated leaf vacuoles detected the presence of three caffeoylquinic acids and four flavonoids in this organelle. These phenols or similar compounds were shown to be good CrPrx1 substrates, and the CrPrx1-mediated oxidation of 5-O-caffeoylquinic acid was shown to form a co-operative regenerating cycle with ascorbic acid. Interestingly, more than 90% of total leaf Prx activity was localized in the vacuoles, associated to discrete spots of the tonoplast. Prx activity inside the vacuoles was estimated to be 1809 nkat ml(-1), which, together with the determined concentrations for the putative vacuolar phenolic substrates, indicate a very high H(2)O(2) scavenging capacity, up to 9 mM s(-1). Accordingly, high light conditions, known to increase H(2)O(2) production, induced both phenols and Prx levels. Therefore, it is proposed that the vacuolar couple Prx/secondary metabolites represent an important sink/buffer of H(2)O(2) in green plant cells.     

First records and potential palaeoecological significance of Dianella (Xanthorrhoeaceae), an extinct representative of the native flora of Rapa Nui (Easter Island)

Easter Island, a remote island in the Pacific Ocean, is currently primarily covered by grasslands, but palaeoecological studies have shown the former presence of different vegetation. Much of its original biota has been removed during the last two millennia, most likely by human activities, and little is known about the native flora. Macrofossil and pollen analyses of a sediment core from the Raraku crater lake have revealed the occurrence of a plant that is currently extinct from the island: Dianella cf. intermedia/adenanthera (Xanthorrhoeaceae), which grew and disappeared at the Raraku site long before human arrival. The occurrence of Dianella within the Raraku sedimentary sequence (between 9.4 and 5.4 cal. kyr b.p.) could have been linked to the existence of favorable palaeoenvironmental conditions (peatland rather than the present-day lacustrine environment) during the early to mid Holocene. This finding contributes new knowledge about indigenous plant diversity on Easter Island and reinforces the usefulness of further macrofossil and pollen analyses to identify native species on Easter Island and elsewhere.