Targeted metabolite profiling provides a functional link among eucalypt taxonomy, physiology and evolution

Adaptation to aridity is considered a major factor in the evolution of the genus Eucalyptus. For the first time, targeted metabolite profiling has uncovered a quantitative yet discrete phytochemical link with eucalypt taxonomy. The distribution of cyclitols among Eucalyptus species, and a range of other Australian tree genera, support their proposed functions in plant tissues and provide putative links with the acclimation of trees to arid environments.     

A window on cyclitols: Characterization and analytics of inositols

Cyclitols are cycloalkanes with one hydroxyl group on each of three or more ring atoms, also called cycloalkane polyols or sugar alcohol which attract attention since they have numerous pharmaceutical properties and are widespread in the plants. Inositols are important cyclitols, which constitute a group of naturally occurring polyhydric alcohols and some isomers of this group can be commonly found in most plants, provided adequate methods of detection are employed. This review presents plant containing cyclitols, with emphasis put on their pharmaceutical properties. The text focuses on sample preparation, extraction and purification and on analysis of cyclitols in plants. In addition, it addresses the application of different methodologies utilized in the analysis of cyclitol compounds in plant.     

First derivatives of myo-inositol 1,4,6-trisphosphate modified at positions 2 and 3: structural analogues of D-myo-inositol 1,4,5-trisphosphate

Novel, structurally modified potential mimics of the second messenger D-myo-inositol 1,4,5-trisphosphate, based on the biologically active regioisomer D-myo-inositol 1,4,6-trisphosphate, were synthesised. DL-5-O-Benzyl-1,4,6-tri-O-p-methoxybenzyl-myo-inositol was the key intermediate for the preparation of the following compounds: DL-3-deoxy-, DL-3-deoxy-2-O-methyl-, DL-3-O-(2-hydroxyethyl)-, DL-3-O-(3-hydroxypropyl)- and DL-3-O-(4-hydroxybutyl)-myo-inositol 1,4,6-trisphosphate. DL-1,4,6-Tri-O -allyl-5-O-benzyl-myo-inositol was used to prepare DL-2-O-methyl-myo-inositol 1,4,6-trisphosphate. Deoxy-compounds were prepared by reduction of the corresponding tosylated intermediate using Super Hydride. The hydroxyalkyl groups were introduced at the C-3 of myo-inositol using the corresponding benzyl protected hydroxy alkyl bromide via the cis-2,3-O-dibutylstannylene acetal. Methylation and benzylation at C-2 was accomplished using methyl iodide and benzyl bromide, respectively, in the presence of sodium hydride. Deblocking of p-methoxybenzyl groups was accomplished with TFA in dichloromethane and the allyl groups were removed by isomerisation to the cis-prop-1-enyl derivative, which was hydrolysed under acidic conditions to give the corresponding 1,4,6-triol. The 1,4,6-triols were phosphitylated with the P(III) reagent bis(benzyloxy)(diisopropylamino)phosphine in the presence of 1H-tetrazole then oxidised with 3-chloroperoxybenzoic acid followed by deblocking by hydrogenolysis to give DL-2-O-methyl-, DL-3-O-deoxy-, DL-3-O-deoxy-2-O-methyl-, DL-3-O-(2-hydroxyethyl)-, DL-3-O-(3-hydroxypropyl)- and DL-3-O-(4-hydroxybutyl)-myo-inositol 1,4,6-trisphosphate, respectively.     

Determination of the structures of four new isomeric cyclitols

A series of impurities, which were all of the same molecular formula, C17H33NO7, were obtained in the process of voglibose synthesis. After isolation and purification, four isomeric cyclitols were completely assigned by 2D NMR experiments. One of the compounds was established by single-crystal X-ray diffraction analysis as 5,6-dideoxy-5-{[2-hydroxy-1-(hydroxymethyl)ethyl]amino}-1-C-(methoxycyclohexylmethyl)-D-epi-inositol.     

Solutes and succulence in southern African mistletoes

The inorganic ion and organic solute composition of Tapinanthus oleifolius (Loranthaceae) and Viscum rotundifolium (Viscaceae) growing on various host trees in Namibia were investigated. Organic osmolytes accounted for 22.8–45.1% of the total solutes determined in leaves of the mistletoes parasitizing Acacia nebrownii, Catophractes alexandri, Grewia flava and Ziziphus mucronata. On other hosts (Acacia karroo, Euphorbia virosa, Salvadora persica and Tamarix usneoides) T. oleifolius showed distinct succulence with increasing leaf age, with leaves more than 3 mm thick on E. virosa. In the more succulent leaves (> 1.1 kg H₂O m^–2 leaf area) organic solutes were only of minor importance. Water content per leaf area was significantly correlated with chloride content per leaf area, suggesting that succulence served as a means to keep ion concentration at a physiological tolerable level. At whole plant levels 93.7% of the total sodium of the mistletoe bush was located in leaves thicker than 1 mm for T. oleifolius parasitizing Tamarix usneoides. This pronounced sequestration of sodium in older leaves as well as the high variability of the K/Na ratio in various parts of the parasite-host system point to highly selective ion distribution processes in this association.     

Cyclitols protect glutamine synthetase and malate dehydrogenase against heat induced deactivation and thermal denaturation

The accumulation of cyclitols in plants is a widespread response that provides protection against various environmental stresses. The capacity of myo-Inositol, pinitol, quercitol, and other compatible solutes (i.e., sorbitol, proline, and glycinebetaine) to protect proteins against thermally induced denaturation and deactivation was examined. Enzymatic activity measurements of l-glutamine synthetase from Escherichia coli and Hordeum vulgare showed that the presence of cyclitols during heat treatment resulted in a significantly higher percentage of residual activity. CD spectroscopy experiments were used to study thermal stabilities of protein secondary structures upon the addition of myo-Inositol, pinitol, and glucose. 0.4 M myo-Inositol was observed to raise the melting temperature (T_m) of GS from E. coli by 3.9 °C and MDH from pig heart by 3.4 °C, respectively. Pinitol showed an increase in T_m of MDH by 3.8 °C, whereas glucose was not effective. Our results show a great potential of stabilizing proteins by the addition of cyclitols.     

Stereospecific synthesis of a new class of compounds: bis-homoconduritol-A, -D, and -F

Bis-homoconduritol derivatives with conduritol-A, -D, and -F structures have been synthesized starting from cyclooctatetraene. The photooxygenation of trans-7,8-dibromo- and cis-7,8-dichlorobicyclo[4.2.0]octa-2,4-dienes afforded the bicyclic endoperoxides. Reduction of the endoperoxides with thiourea followed by acetylation gave the corresponding diacetates. The KMnO(4) oxidation and epoxidation of the diacetates followed by acetylation gave the tetraacetates. Removal of the halides either with zinc-dust or Na-anthracene followed by the ammonolysis of tetraacetates afforded the bis-homoconduritol derivatives in high yield.     

Influence of sequential prolonged periods of dark and light on pinitol concentration in clover and soybean tissue

The influence of prolonged dark periods on the concentration of pinitol in white clover ( Trifolium repens L. ev. Regal Ladino) and soybean [ Glycine max (L.) Merr.] tissue was investigated. Clover and soybean plants were harvested periodically throughout continuous dark periods of 40 and 44 h, respectively, followed by 24 h of continuous light. The foliage and root tissue of clover and foliage tissue of soybeans were analyzed for the concentration of glucose, fructose, sucrose and pinitol. Pinitol concentration (mg/g dry weight tissue) was unchanged by the prolonged dark period followed by 24 h of continuous light compared to tissue of plants harvested at 0-h and plants receiving normal photoperiods. Concentrations of the carbohydrates, in the tissue were depleted by the prolonged dark period. However after 6 h of light, the concentration of these sugars increased to concentrations equal to 0-h harvested plant tissue and tissue of plants receiving normal photoperiods. These results indicate that pinitol probably does not function as a source of reserve energy comparable to sucrose, glucose, and fructose.