Comparative Metabolomics of Reproductive Organs in the Genus Aesculus (Sapindaceae) Reveals That Immature Fruits Are a Key Organ of Procyanidin Accumulation and Bioactivity

Fruit from A. hippocastanum L. are used commercially for chronic venous insufficiency (CVI). The isomeric mixture of pentacyclic triterpenoid saponins (β-aescin) exert anti-inflammatory effects. Hence, research has focused on β-aescin, yet the diversity, accumulation, and bioactivity of organ-specific secondary metabolites represent missed pharmacological opportunities. To this end, we applied an untargeted metabolomics approach by liquid chromatography—tandem mass spectrometry (LC–MS/MS) to the chemical profiles of flowers, immature fruits, and pedicels from 40 specimens across 18 species of Aesculus. Principal component analysis (PCA), orthogonal partial least squares (OPLS-DA), and molecular networking revealed stronger chemical differences between plant organs, than between species. Flowers are rich in glycosylated flavonoids, pedicels in organic acids and flavonoid aglycones, and immature fruits in monomeric flavan-3-ols and procyanidins. Although a high diversity of flavonoids and procyanidins was observed, the relative amounts differed by plant organ. Fruit extracts demonstrated the strongest antifungal (Saccharomyces cerevisiae) and antioxidant activity, likely from the procyanidins. Overall, secondary metabolite profiles are organ-specific, and fruits accumulate antifungal and antioxidant compounds. Due to the chemical similarity between species, similar effects may be achieved between species. This creates incentives for further exploration of the entire genus, in bioprospecting for potential therapeutic leads.

Response of Wheat Storage Proteins and Breadmaking Quality to Dimethylpyrazole-Based Nitrification Inhibitors under Different Nitrogen Fertilization Splitting Strategies

Improving fertilizer nitrogen (N) use efficiency is essential to increase crop productivity and avoid environmental damage. This study was conducted during four crop cycles of winter wheat under humid Mediterranean conditions (Araba, northern Spain). The effects of N-fertilization splitting and the application of the nitrification inhibitors (NIs) 3,4-dimethylpyrazole phosphate (DMPP) and 2-(3,4-dimethyl-1H-pyrazol-1-yl) succinic acid isomeric mixture (DMPSA) as strategies to improve grain quality were examined. The hypothesis of this study was to test if the partial ammonium nutrition and the reduction of fertilizer losses presumably induced by the application of NIs can modify the grain gliadin and glutenin protein contents and the breadmaking quality (dough rheological properties). Among both NIs assayed, only DMPP showed a slight effect of decreasing the omega gliadin fraction, following splitting either two or three times, although this effect was dependent on the year and was not reflected in terms of dough extensibility. The slight decreases observed in grain quality in terms of dough strength and glutenin content induced by DMPP suggest that DMPSA is more promising in terms of maintaining grain quality. Nonetheless, these poor effects exerted by NI application on grain quality parameters did not lead to changes in the quality parameters defining the flour aptitudes for breadmaking.

Mechanistic Study on the Reaction of pinB-BMes2 with Alkynes Based on Experimental Investigation and DFT Calculations: Gradual Change of Mechanism Depending on the Substituent

Transition-metal free direct and base-catalyzed 1,2-diborations of arylacetylenes using pinB-BMes2 provided syn/anti-isomeric mixture of diborylalkenes. The kinetic analysis showed that the reaction rate and isomer ratio were affected by reaction...

Antimalarials and Phytotoxins from Botryosphaeria dothidea Identified from a Seed of Diseased Torreya taxifolia

The metabolic pathways in the apicoplast organelle of Plasmodium parasites are similar to those in plastids in plant cells and are suitable targets for malaria drug discovery. Some phytotoxins released by plant pathogenic fungi have been known to target metabolic pathways of the plastid; thus, they may also serve as potential antimalarial drug leads. An EtOAc extract of the broth of the endophyte Botryosphaeria dothidea isolated from a seed collected from a Torreya taxifolia plant with disease symptoms, showed in vitro antimalarial and phytotoxic activities. Bioactivity-guided fractionation of the extract afforded a mixture of two known isomeric phytotoxins, FRT-A and flavipucine (or their enantiomers, sapinopyridione and (-)-flavipucine), and two new unstable γ-lactam alkaloids dothilactaenes A and B. The isomeric mixture of phytotoxins displayed strong phytotoxicity against both a dicot and a monocot and moderate cytotoxicity against a panel of cell lines. Dothilactaene A showed no activity. Dothilactaene B was isolated from the active fraction, which showed moderate in vitro antiplasmodial activity with high selectivity index. In spite of this activity, its instability and various other biological activities shown by related compounds would preclude it from being a viable antimalarial lead.

ANTIRADICAL ACTIVITY OF 1,4-AND 1,2-BENZENE DICARBOXYL ESTERS FROM DEINBOLLIA PINNATA LEAVES

The family Sapindaceae are tropical and sub-tropical continental plants. In this study, 1,4-Benzene dicarboxyl ester (1) and 1,2-Benzene dicarboxyl ester (2) from methanolic extracts of Deinbollia pinnata leaves. The successful separation of the isomeric mixture is by freezing the sub-fraction with methanol for seventy-two hours; followed by filtration, isolation and purification. The compounds were characterized spectroscopically (1H &13C NMR, FTIR and GC-MS). The methanolic extracts showed good DPPH scavenging activity with percentage inhibition greater than 70% at 125 ppm, an excellent antioxidant activity towards ABTS assay with the IC50 value of 13.68 µg/mL and also exhibits most potent ferric ion reducer at 3.45 ± 1.30 mM FRAP equivalent compared to other extracts. The 1,4-Benzene dicarboxyl ester (1) displayed high antioxidant radical scavenging activity towards DPPH assay with IC50 value of (IC50 32.99; 73.491%) and 1,2-Benzene dicarboxyl ester (2) at (IC50 33.99; 71.11%);ABTS activity with SC50 value at 48.81µg/mL; 87.98% (1) and 49.55µg/mL; 83.85% (2) and a good potential as ferric ion reducer ranging from 0.05±0.00 to 1.37±0.02 (1) and 0.16±0.04 to 1.29±0.03 (2) mM FRAP equivalent respectively.

Formation of an Isomeric Mixture of Dienynes Instead of a Diallene

Attempts to convert 1,1,2,2,7,7,8,8-octaethoxyocta-3,5-diyne to a symmetric allene by reduction with lithium aluminum hydride failed. Instead reduction accompanied by isomerization occurred and afforded 1,1,2,7,8,8-hexaethoxyocta-2,6-dien-4-yne as a mixture of three isomers in 63% total isolated yield.

Antimicrobial activity of isolated compounds and semisynthetic derivatives from Miconia ferruginata

This study evaluated the antimicrobial activity of isolated compounds and semisynthetic derivatives from Miconia ferruginata (Melastomataceae) against five microorganisms: Staphylococcus aureus (ATCC 25923), Escherichia coli (ATCC 25922), Bacillus subtilis (ATCC 6623), Pseudomonas aeruginosa (ATCC 15442), and Candida albicans (ATCC 10231). The isomeric mixture of ursolic and oleanolic acids was active against S. aureus (MIC = 250 μg mL-1) and against E. coli, B. subtilis, and P. aeruginosa (MIC = 500 μg mL-1). The flavone 5,6,7-trihydroxy-4’-methoxyflavone and the methyl esters, semisynthetic derivatives of a mixture of ursolic and oleanolic acids, showed no activity against the tested microorganisms. These results suggest that the carboxyl group present in the triterpenes may contribute to antimicrobial activity.

Imine–carbene-based ruthenium complexes for dye-sensitized solar cells: the effect of isomeric mixture on the photovoltaic performance

New isomeric sensitizers containing an imine–carbene (IC)-based ancillary ligand, isomers IC101 and IC102, were designed for application in dye-sensitized solar cells (DSSCs).