The discovery of novel allylboration reagents enabled to the stereoselective synthesis of parthenolides. Biological screening for microtubule detyrosination and nerve growth promotion revealed protein target selectivity.
A series of four donor aryl alkynyl substituted thiazole derivatives 3a-d and three similar aryl donor-acceptor systems 6a-c have been synthesized. All compounds bear different electron-donating groups in the 5-position of the thiazole core. The influence of both electron donor strength and the additional phenylethynyl unit on photophysical properties, i.e. UV/Vis absorption, fluorescence emission and fluorescence lifetime, has been evaluated. Additionally, theoretical calculations have been performed at the CAM-B3LYP/6-31+G(d,p) level and good agreement with the experimental data has been achieved. The new derivatives synthesized via palladium catalyzed cross coupling are characterised by moderately strong emission between 474 and 538 nm (ΦF = 0.35-0.39) and Stokes' shifts ranging from 0.54 to 0.79 eV (4392-6351 cm(-1)). The smaller chromophores of type 6 exhibit modest to high fluorescence emission (ΦF = 0.45-0.76) between 470 and 529 nm and their Stokes' shifts range from 0.59 to 0.65 eV (4765-5251 cm(-1)).
Solution self-assembly of poly(ethylene oxide)-block-poly(furfuryl glycidyl ether)-block-poly(allyl glycidyl ether) based triblock terpolymers: a field-flow fractionation study † A well-defined ABC triblock terpolymer, poly(ethylene oxide)-block-poly(furfuryl glycidyl ether)-blockpoly(allyl glycidyl ether) (PEO-b-PFGE-b-PAGE), was synthesized via sequential living anionic ringopening polymerization, and subsequently functionalized by thiol-ene click chemistry. In that way, either a fluorocarbon chain or carboxy groups were introduced into the C segment (PAGE). The self-assembly of the resulting materials in water as selective solvent was studied in detail by asymmetric flow field-flow fractionation (AF4) coupled to multi-angle laser light scattering and dynamic light scattering (DLS). The obtained results were compared with batch DLS and cryogenic transmission electron microscopy (cryo-TEM) results. The influence of the separation conditions on the retention behavior of the triblock terpolymers was evaluated to reveal possible limitations associated with AF4 measurements. The influence of pH value and ionic strength on the solution behavior of the materials, in particular for PEO-b-PFGE-b-PAGE COOH , was investigated as well. Crosslinking of the PAGE COOH by chelating metal ions (Fe 3+ ) was studied under different conditions. In case of PEO-b-PFGE-b-PAGE, spherical micelles of approximately 20 nm (R h ) were observed, whereas the introduction of a fluorocarbon chain led to an increase in size (30 nm, R h ) and the formation of worm-like structures. Carboxy functionalization rendered small (5 nm) disk-like structures. In the latter case, subsequent addition of FeCl 3 resulted in the formation of spherical nanostructures ranging from 10 to 60 nm in size, depending on the pH value and the polymer/metal ion ratio. † Electronic supplementary information (ESI) available. See
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