Bioassay-directed fractionation of a Hymeniacidon sp. yielded as nematocidal agents the equilibrating E/Z bromoindole ethyl esters 1 and 2 and corresponding methyl esters 3 and 4. Also isolated for the first time as a natural product was an equilibrating mixture of seco-xanthine formamides, attributed the trivial name hymeniacidin (5). The structure for 5 was assigned on the basis of detailed spectroscopic analysis and total synthesis.
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http://dx.doi.org/10.1021/np010337u | DOI Listing |
J Synchrotron Radiat
July 2024
Nano and Molecular Systems Research Unit, University of Oulu, Oulu, Finland.
The methanol-to-hydrocarbons (MTH) process involves the conversion of methanol, a C1 feedstock that can be produced from green sources, into hydrocarbons using shape-selective microporous acidic catalysts - zeolite and zeotypes. This reaction yields a complex mixture of species, some of which are highly reactive and/or present in several isomeric forms, posing significant challenges for effluent analysis. Conventional gas-phase chromatography (GC) is typically employed for the analysis of reaction products in laboratory flow reactors.
View Article and Find Full Text PDFPhys Chem Chem Phys
September 2024
Department of Chemistry and the Center for Photochemical Sciences, Bowling Green State University, Bowling Green, OH 43403, USA.
Excited-state relaxation in two prototypical shortwave infrared (SWIR) polymethine dyes developed for bioimaging, heptamethine chromenylium Chrom7 and flavylium Flav7, is studied by means of femtosecond transient absorption with broadband ultraviolet-to-SWIR probing complemented by steady-state and time-resolved fluorescence and phosphorescence measurements. The relaxation processes of the dyes in dichloromethane are resolved with sub-100 fs temporal resolution using SWIR, near-IR, and visible photoexcitation. Different population members of the ground-state inhomogeneous ensemble are found to equilibrate skeletal deformation changes with time constants of 90 fs and either 230 fs (Chrom7) and 350 fs (Flav7) followed by slower evolution matching the 1-ps timescale of diffusive solvation dynamics.
View Article and Find Full Text PDFJ Comput Chem
September 2024
Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan, China.
We show herein that 1,10-dicyano substitution restricts the paragon fluxionality of bullvalene to just 14 isomers which isomerize along a single cycle. The restricted fluxionality of 1,10-dicyanobullvalene (DCB) is investigated by means of: (i) Bonding analyses of the isomer structures using the adaptive natural density partitioning (AdNDP). (ii) Quantum dynamical simulations of the isomerizations along the cyclic intrinsic reaction coordinate of the potential energy surface (PES).
View Article and Find Full Text PDFACS Omega
May 2024
Organic Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, India.
Unprecedented MsOH-promoted diastereoselective cascade dimerization and intramolecular lactonization of readily accessible α,β-unsaturated γ-ketoesters are presented. The results obtained in this work, control experiments, and density functional theory (DFT) calculations suggested that the initial enolization and to isomerization/equilibration of olefin (C=C) of substrate α,β-unsaturated γ-ketoesters give a -isomer preferentially over an -isomer. Subsequently, the -isomer undergoes intermolecular annulation with α,β-unsaturated γ-ketoesters via domino Michael addition/ketalization/lactonization steps to furnish fused tetracyclic pyrano-ketal-lactone.
View Article and Find Full Text PDFChemistry
June 2024
Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, 6020, Innsbruck, Austria.
Breakdown of chlorophyll (Chl), as studied in angiosperms, follows the pheophorbide a oxygenase/phyllobilin (PaO/PB) pathway, furnishing linear tetrapyrroles, named phyllobilins (PBs). In an investigation with fern leaves we have discovered iso-phyllobilanones (iPBs) with an intriguingly rearranged and oxidized carbon skeleton. We report here a key second group of iPBs from the fern and on their structure analysis.
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