Four monoterpene hydroperoxides were isolated from aerial parts of Chenopodium ambrosioides along with ascaridole (1), the anthelmintic principle of this plant, as anti-trypanosomal compounds. The structures of these monoterpenes were determined to be (-)-(2S,4S)- and (-)-(2R,4S)-p-mentha-1(7),8-dien-2-hydroperoxide (2a and 3a) and (-)-(1R,4S)- and (-)-(1S,4S)-p-mentha-2,8-dien-1-hydroperoxide (4a and 5a) on the basis of spectroscopic methods and chemical correlations. In vitro trypanocidal activities of ascaridole (1) and these hydroperoxides (2a-5a) against epimastigotes of Trypanosoma cruzi were 23, 1.2, 1.6, 3.1, and 0.8 microM, respectively. Fresh leaves of C. ambrosioides also contained isomeric hydroperoxides 6a and 7a, and the content ratio of 2a-7a suggested that these hydroperoxides were formed through the singlet-oxygen oxidation of limonene.

Adenosine 3‘-O(PO2 -)OCH2R phosphate esters have been synthesized with R = 8-hydroxyquinol-2-yl (1a) and 8-(hydroxyquinolyl)-2-methylene (1b). The adenosine 3‘-O(PO2 -)OCH2R structure has the essential features of an RNA dinucleotide. Equilibrium binding studies with metal ions Mg2+, Zn2+, Cu2+, and La3+ have been carried out with 1a, 1b, HOCH2R (7a and 7b), and 8-hydroxyquinoline (8), and equilibrium constants (K as) have been determined for the formation of 1:1 (L)M n + complexes. The hydrolysis of 1a and 1b as well as (1a)M n + and (1b)M n + species are first order in HO-. The rate enhancement for hydrolysis of 1a by complexation with metal ions is as follows:  ∼105 with Zn2+, ∼103 with Mg2+, ∼105 with Cu2+, and ∼109 with La3+. Molecular modeling indicates that metal ions ligated to the 8-hydroxyquinoline moiety in the complexes (1a)M n + and (1b)M n + catalyze 1a and 1b hydrolysis by interacting as Lewis acid catalysts with the negatively charged oxygen atom of the phosphate group. In the instance of La3+ complexes, the ligated metal ion is within an interactive distance with both the negative phosphate oxygen and the leaving oxygen. This bimodal assistance by La3+ to the displacement reaction at phosphorus by the 2‘-hydroxyl anion results in remarkable rate accelerations for the hydrolysis of (1a)La3+ and (1b)La3+ complexes. The complexes (1a)M n + and (1b)M n + are themselves hydrolyzed by metal ion catalysis in a reaction that is first order in HO-, an observation consistent with a transition state composition of [(1a,b)M n +][M n +][HO-]. We assume the kinetic equivalent [(1a,b)M n +][M n +OH] to represent the reacting species. In this catalysis the M n +OH is proposed to play the role of general base to deprotonate the 2‘-OH while the metal in the complexes (1a,b)M n + is coordinated to a negative oxygen of the −(PO2 -)− moiety. This double metal ion catalysis mimics a mechanism proposed for the ribozyme self-cleavage of RNA.

The remodelling of organelle function is increasingly appreciated as a central driver of eukaryotic biodiversity and evolution. Kinetoplastids including Trypanosoma and Leishmania have evolved specialized peroxisomes, called glycosomes. Glycosomes uniquely contain a glycolytic pathway as well as other enzymes, which underpin the physiological flexibility of these major human pathogens. The sister group of kinetoplastids are the diplonemids, which are among the most abundant eukaryotes in marine plankton. Here we demonstrate the compartmentalization of gluconeogenesis, or glycolysis in reverse, in the peroxisomes of the free-living marine diplonemid, Diplonema papillatum. Our results suggest that peroxisome modification was already under way in the common ancestor of kinetoplastids and diplonemids, and raise the possibility that the central importance of gluconeogenesis to carbon metabolism in the heterotrophic free-living ancestor may have been an important selective driver. Our data indicate that peroxisome modification is not confined to the kinetoplastid lineage, but has also been a factor in the success of their free-living euglenozoan relatives.

BackgroundThe status of Toxoplasma gondii infection among primary schoolchildren (PSC) of the Democratic Republic of São Tomé and Príncipe (DRSTP), West Africa, remains unknown to date.MethodsA serologic survey and risk factors associated T. gondii infection among PSC in the DRSTP was assessed by the latex agglutination (LA) test and a questionnaire interview including parents’ occupation, various uncomfortable symptoms, histories of eating raw or undercooked food, drinking unboiled water, and raising pets, was conducted in October 2010. Schoolchildren from 4 primary schools located in the capital areas were selected, in total 255 serum samples were obtained by venipuncture, of which 123 serum samples were obtained from boys (9.8 ± 1.4 yrs) and 132 serum samples were obtained from girls (9.7 ± 1.3 yrs).ResultsThe overall seroprevalence of T. gondii infection was 63.1% (161/255). No significant gender difference in seroprevalence was found between boys (62.6%, 77/123) and girls (63.6%, 84/132) (p = 0.9). The older age group of 10 years had insignificantly higher seroprevalence (69.9%, 58/83) than that of the younger age group of 8 year olds (67.7%, 21/31) (p = 0.8). It was noteworthy that the majority of seropositive PSC (75.8%, 122/161) had high LA titers of ≥1: 1024, indirectly indicating acute or repeated Toxoplasma infection. Parents whose jobs were non-skilled workers (73.1%) showed significantly higher seroprevalence than that of semiskilled- (53.9%) or skilled workers (48.8%) (p < 0.05). Children who had a history of raising cats also showed significantly higher seroprevalence than those who did not (p < 0.001).Children who claimed to have had recent ocular manifestation or headache, i.e. within 1 month, seemed to have insignificantly higher seroprevalence than those who did not (p > 0.05).ConclusionsParents’ educational level and cats kept indoors seemed to be the high risk factors for PSC in acquisition of T. gondii infection. While, ocular manifestation and/or headache of PSC should be checked for the possibility of being T. gondii elicited. Measures such as improving environmental hygiene and intensive educational intervention to both PSC and their parents should be performed immediately so as to reduce T. gondii infection of DRSTP inhabitants including PSC and adults.