Crystallographic Deciphering of Spontaneous Self-Assembly of Achiral Calciphores to Chiral Complexes.

Thiapyricins (TPC-A/B, 1 and 2), which are new metallophore scaffolds exhibiting selective divalent cation binding property, were produced in response to metal-deprived conditions by Saccharothrix sp. TRM_47004 isolated from the Lop Nor Salt Lake. TPCs represent a thiazolyl-pyridine skeleton of a calcium-binding natural product, calciphore, owing to the selectivity to calcium ions among diverse metal ions. The thiapyricins exhibited notable co-crystalline characteristics of the apo- and holo-forms with racemic enantiomers comprising a pair of space isomers in a Δ/Λ-form. Therefore, we postulated a mechanism for the four-hierarchical self-assembly of achiral natural products into chiral complexes. Furthermore, their metal-chelating trait aided the adaptation of the host during metal starvation by increasing the production of TPCs. This study presents a structural paradigm of a new calciphore, provides insight into the mechanism of natural product assembly, and highlights the causality between the production of the metallophore and metallic habitats.

Structurally diverse diterpenoids from the roots of Euphorbia fischeriana Steud.

Four new diterpenoids (1-4), and 18 known ones were isolated from the roots of Euphorbia fischeriana Steud (Euphorbiaceae). These diterpenoids shared six skeleton types, including ent-atisane, kaurane, 3,4-secokaurane, lathyrane, 4,5-secoatisane and ingenane diterpenoids. The structures of the new diterpenoids were characterized by a combination of spectroscopic techniques and X-ray crystallography. Moreover, biological evaluation revealed that compounds (16S*)-atisan-3ß,16,17-triol (7), (16S*)-3ß,16,17,18-tetrahydroxykaurane (12) and (16S*)-3α-hydroxykauran-16,17-acetonide (15) showed inhibitory activity against the interferon regulatory factors (IRFs) involved pathway.

Antifungal Activities of Isoflavonoids from Uromyces striatus Infected Alfalfa.

Fungal pathogens constitute a severe yield-limiting factor for the pasture crop alfalfa (Medicago sativa L.). Eleven phenolic compounds, including a new isoflavane, were isolated from the Uromyces striatus Schroet. infected alfalfa. The effect of infection with U. striatus Schroet. on the phytochemical profile of alfalfa was investigated using ultra-performance liquid chromatography (UPLC), and the antifungal properties of isolated compounds against a range of pathogens were tested. It was found that the contents of most of the isolated compounds in U. striatus infected alfalfa were higher than those in healthy alfalfa. Compounds 1-5 exhibited a moderate inhibitory activity against Curvularia lunata with 40.14±1.63 %, 48.03±1.22 %, 57.54±1.18 %, 50.10±1.56 %, and 61.54±2.14 % inhibition ratio at the concentration of 50 µg/mL. Compounds 3 and 5 showed a weak inhibitory activity against Fusarium graminearum with the EC50 values of 104.2±2.66 and 123.0±1.23 µg/mL, and a moderate inhibitory activity against Bipolaris sorokinianum with the EC50 values of 39.1±2.05 and 95.0±1.01 µg/mL, respectively. In pot experiments with wheat, compounds 1-5 possessed desirable protective efficacy of over 80 % and curative effectiveness of over 50 % against Puccinia striiformis f. sp. tritici at a concentration of 0.5 mg/mL.

Structurally Diverse Highly Oxygenated Triterpenoids from the Roots of Ailanthus altissima and Their Cytotoxicity.

Ten new triterpenoids, ailanaltiolides A-J (1-10), and three known analogues (11-13) were isolated from the roots of Ailanthus altissima. Compounds 1-7 are apotirucallane-type, compounds 8 and 9 are tirucallane-type, and compound 10 is a trinordammarane-type triterpenoid. This is the first study indicating the genus Ailanthus as a potential source for apotirucallane derivatives, which contain an α,ß-unsaturated-ε-lactone A-ring and diversely modified C-17 side chains. Spectroscopic data interpretation, electronic circular dichroism analysis, and X-ray crystallographic data defined the structures and absolute configurations of these triterpenoids. Compounds 2, 7, and 8 showed cytotoxicity against four tumor cell lines (HeLa, 786-O, HepG2, and A549). In particular, compound 2 exhibited the highest activity against 786-O cells with an IC50 value of 8.2 µM in vitro.