Elucidation of the Complete Biosynthetic Pathway of Phomoxanthone A and Identification of a Para-Para Selective Phenol Coupling Dimerase.

Fungal cytochrome P450 enzymes have been shown to catalyze regio- and stereoselective oxidative intermolecular phenol coupling. However, an enzyme capable of catalyzing undirected para-para (C4-4') coupling has not been reported. Here, we revealed the biosynthetic gene cluster (BGC) of phomoxanthone A from the marine fungus Diaporthe sp. SYSU-MS4722. We heterologously expressed 14 biosynthetic genes in Aspergillus oryzae NSAR1 and found that PhoCDEFGHK is involved in the early stage of phomoxanthone A biosynthesis to give chrysophanol and that chrysophanol is then processed by PhoBJKLMNP to yield penexanthone B. A feeding experiment suggested that PhoO, a cytochrome P450 enzyme, catalyzed the regioselective oxidative para-para coupling of penexanthone B to give phomoxanthone A. The mechanism of PhoO represents a novel enzymatic 4,4'-linkage dimerization method for tetrahydroxanthone formations, which would facilitate biosynthetic engineering of structurally diverse 4,4'-linked dimeric tetrahydroxanthones.

A new monoterpene glycoside from Pedicularis verticillata and anticomplementary activity of its compounds.

A new monoterpene glycoside named as pedivertoside D (1), together with 13 known compounds (2-14, resp.) were isolated from the whole plant of Pedicularis verticillata L. The new compound was identified as (2E,6E,5R)-5,8-dihydrooxy-2,6-dimethyl-3,7-octadienyl-ß-D-glucopyranoside by spectroscopic methods including 2 D-NMR techniques. The known compounds were determined spectroscopically and compared with previously reported spectral data. Compounds 6 and 9 exhibited anticomplementary effects against the classical pathway (CP) with CH50 values of 0.07 mM and 0.23 mM, respectively, which are plausible candidates for developing potent anti-complementary agents from this plant.

Intermolecular C-H Amidation of (Hetero)arenes to Produce Amides through Rhodium-Catalyzed Carbonylation of Nitrene Intermediates.

Amide bond formation is one of the most important reactions in organic chemistry because of the widespread presence of amides in pharmaceuticals and biologically active compounds. Existing methods for amides synthesis are reaching their inherent limits. Described herein is a novel rhodium-catalyzed three-component reaction to synthesize amides from organic azides, carbon monoxide, and (hetero)arenes via nitrene-intermediates and direct C-H functionalization. Notably, the reaction proceeds in an intermolecular fashion with N2 as the only by-product, and either directing groups nor additives are required. The computational and mechanistic studies show that the amides are formed via a key Rh-nitrene intermediate.

A novel dimeric flavonol glycoside from Cynanchum acutum subsp. sibiricum.

A novel dimeric flavonol glycoside, Cynanflavoside A (1), together with six analogues, kaempferol-3-O-α-L-rhamnopyranosyl-(1→2)-ß-D-glucopyranoside (2), quercetin-3-O-α-L-rhamnopyranosyl-(1→2)-ß-D-glucopyranoside (3), kaempferol-3-O-α-L-rhamnopyranosyl-(1→2)-ß-D-xylopyranoside (4), quercetin-3-O-α-L-rhamnopyranosyl-(1→2)-ß-D-xylopyranoside (5), kaempferol-3-O-ß-D-glucopyranosyl-7-O-α-L-rhamnopyranoside (6), and quercetin-3-O-galactoside (7) were isolated from the n-butyl alcohol extract of Cynanchum acutum subsp. sibiricum. Their structures were determined spectroscopically and compared with previously reported spectral data. All compounds were evaluated for their anti-complementary activity in vitro, and only compound 5 exhibited anti-complement effects with CH50 value of 0.33 mM.

Iridoids from Pedicularis verticillata and Their Anti-Complementary Activity.

Three new iridoids named as pediverticilatasin A - C (1 - 3, resp.), together with five known iridoids (4 - 8, resp.) were isolated from the whole plants of Pedicularis verticillata. The structures of three new compounds were identified as (1S,7R)-1-ethoxy-1,5,6,7-tetrahydro-7-hydroxy-7-methylcyclopenta[c]pyran-4(3H)-one (1), (1S,4aS,7R,7aS)-1-ethoxy-1,4a,5,6,7,7a-hexahydro-7-hydroxy-7-methylcyclopenta[c]pyran-4-carboxylic acid (2), (1S,4aS,7R,7aS)-1-ethoxy-1,4a,5,6,7,7a-hexahydro-7-hydroxy-7-methylcyclopenta[c]pyran-4-carbaldehyde (3). Their structures were elucidated on the basis of spectroscopic methods and compared with the NMR spectra data in the literature. All compounds were evaluated for their anti-complementary activity on the classical pathway of the complement system in vitro. Among which, compounds 1, 3, and 6 exhibited anti-complementary effects with CH50 values ranging from 0.43 to 1.72 mm, which are plausible candidates for developing potent anti-complementary agents.

[Effects of Different Modifier Concentrations on Lead-Zinc Tolerance, Subcellular Distribution and Chemical Forms for Four Kinds of Woody Plants].

Four kinds of lead-zinc tolerant woody plants: Nerium oleander, Koelreuteria paniculata, Paulownia and Boehmeria were used as materials to estimate their enrichment and transferable capacity of lead (Pb) and zinc (Zn) and analyze the subcellular distribution and chemical speciation of Zn and Ph in different parts of plants, under different modifier concentrations (CK group: 100% lead-zinc slag plus a small amount of phosphate fertilizer, improved one: 85% of lead-zinc slag ± 10% peat ± 5% bacterial manure plus a small amount of phosphate fertilizer, improved two: 75% lead-zinc slag ± 20% peat ± 5% bacterial manure ± a small amount of phosphate). Results showed that: (1) The content of Pb, Zn in matrix after planting four kinds of plants was lower than before, no significant difference between improved one and improved two of Nerium oleander and Boehmeria was found, but improved two was better than improved one of Paulownia, while improved one was better than improved two of Koelreuteria paniculata; Four plants had relatively low aboveground enrichment coefficient of Pb and Zn, but had a high transfer coefficient, showed that the appropriate modifier concentration was able to improve the Pb and Zn enrichment and transfer ability of plants. (2) In subcellular distribution, most of Pb and Zn were distributed in plant cell wall components and soluble components while the distribution in cell organelles such as mitochondria, chloroplasts and nucleus component were less. Compared with CK group, two improved group made soluble components of the cell walls of Pb fixation and retention of zinc role in the enhancement. (3) As for the chemical forms of Pb and Zn in plants, the main chemical forms of Pb were hydrochloric acid, sodium chloride and ethanol extractable forms, while other chemical form contents were few, the main chemical forms of Zn were different based on plant type. Compared with CK group, the proportion of the active Pb chemical form in different plant parts decreased in two improved groups, while the proportion of strong activity chemical forms increased; two improved groups led strong activity Zn chemical form of root increased, while strong activity Zn chemical form of aboveground decreased.