Polymerization of acetylenes carrying precursors of aminyl radicals

In the search for organic ferromagnets polymers with a conjugated backbone and pendant persistent radicals are one route of interest. The synthesis of poly[4-(4-ethynylphenyl)-2′,4′,6′-trinitro-2,6-diphenyldiphenylamine] (p-3) and poly[4-(3-ethynylphenyl)-2′,4′,6′-trinitro-2,6-diphenyldiphenylamine] (m-3) as precursors of polyradicals are described. A dinuclear rhodium cyclooctadiene chloride complex as polymerization catalyst was used to yield polymers with molecular weights (gel-permeation chromatography) of 100 000 for m-3 and 210 000 for p-3 .     

Time-resolved imaging of hydrogel printing via laser-induced forward transfer

In this work, the printing mechanism of an alginate-based hydrogel via laser-induced forward transfer (LIFT) is investigated by spatial and temporal high-resolved stroboscopic imaging. First, the generation of the liquid jet is studied at two different laser fluences in a process without collector slide. Furthermore, the impingement process onto the collector slide at the same fluence levels is observed. With the help of these images the development of the jet is explained. Besides the influences of the collector slide as well as the applied laser fluence on the transfer are demonstrated.     

Physical processes during development of upward leaders from tall structures

The objective of our study was to identify and interpret the various processes during development of upward positive leaders from tall structures. We provide a physical interpretation for the varying luminosity of the leader channel during its initial ascent and the pulsing luminosity during much later stages of the established leader. Our analysis confirms that pulsed luminosity is a result of recoil leaders intercepting the current-carrying channel connected to ground. This interception produces an M-component. Applying the bidirectional leader concept and a simplified electrostatic approximation, we introduce physical models of the dart leader-return stroke sequence and the M-component.     

Reductive decomplexation of pi-allyltricarbonyliron lactone complexes; a new route to stereo-defined 1,7-diols and 2,3-diene-1,7-diols

Treatment of pi-allyltricarbonyliron lactone complexes bearing an adjacent leaving group, with lithium naphthalenide causes decomplexation to acyclic dienols in excellent yield and without any scrambling of the allylic centre.     

Synthesis of taurospongin A: a potent inhibitor of DNA polymerase and HIV reverse transcriptase,using pi-allyltricarbonyliron lactone complexes

The synthesis of taurospongin A has been achieved using, as a key step, a pi-allyltricarbonyliron lactone complex to control a highly stereoselective addition of a methyl group to a carbonyl unit located in the side chain of the complex.     

Encapsulation of palladium in polyurea microcapsules

An interfacial polymerisation approach is adopted to encapsulate palladium(II) acetate and palladium nanoparticles in polyurea microcapsules for use in catalysis.     

Stilbazulenyl nitrone (STAZN): a nitronyl-substituted hydrocarbon with the potency of classical phenolic chain-breaking antioxidants

Stilbazulenyl nitrone (STAZN), 8, a nitronyl-substituted hydrocarbon, is a novel second-generation azulenyl nitrone with significantly enhanced potency as a chain-breaking antioxidant vs conventional alpha-phenyl nitrones previously investigated as antioxidant therapeutics. A convenient (1)H NMR-based assay for assessing the potency of chain-breaking antioxidants has shown that STAZN is ca. 300 times more potent in inhibiting the free radical-mediated aerobic peroxidation of cumene than is PBN and the experimental stroke drug NXY-059. Such levels of antioxidant efficacy are unprecedented among archetypal alpha-phenyl nitrone spin traps. Furthermore, STAZN outperforms such classical phenolic antioxidants as BHT and probucol and rivals the antioxidant potency of Vitamin E in a polar medium comprised of 80% cumene and 20% methanol. The Volodarskii electron-transfer mechanism involving the intermediacy of the STAZN radical cation has been implicated in attempts to ascertain the basis for the increased potency of STAZN over the three alpha-phenyl nitrones PBN, S-PBN, and NXY-059.     

Synthesis of high-mannose type neoglycolipids: active targeting of liposomes to macrophages in gene therapy

The concise synthesis of five biantennary oligomannose neoglycolipids is presented. Employing a strategy based on the principles of reactivity tuning and orthogonal activation, the oligomannose moieties, isolated from the glycoprotein 63 of the parasite Leishmania mexicana amazonensis, were rapidly assembled taking advantage of common structural motifs found in these N-glycans. Deprotection of all structures was achieved in high yield by hydrogenolysis. The deprotected glycoconjugates were subsequently coupled to a cholesteroldiamine derivative using diethylsquarate as a linker. The resulting neoglycolipids will be used as additives to cationic liposome formulations in the active targeting of liposomes to macrophages.