Synthesis of digitoxigenin by remote functionalization

Treatment of a 21-hydroxy-20-keto steroid with the mixed anhydride of trifluoroacetic acid—diethylphosphonoacetic acid leads directly to cardenolides by an intramolecular Horner-Emmons reaction. Photolysis of 3β-acetoxy-5β,14α-card-20(22)-enolide and iodobenzenedichloride in benzene solution then yields 3β-acetoxy-5β-carda-14,20(22)-dienolide (β-anhydrodigitoxigenin acetate).     

A method for the palladium-catalyzed allylic oxidation of olefins

Olefins are converted into allylic acetates by treatment in acetic acid with a catalytic amount of palladium bis(trifluoroacetate) and one equivalent of benzoquinone as oxidant. The reaction is selective for oxidation of a terminal methyl group of geranylacetone.     

Cyclocarbonylation of unsaturated tosylates as a method of cyclanone synthesis

A study has been made to determine the scope of the cyclocarbonylation reaction of olefinic tosylates with Na₂Fe(CO)₄.     

Measuring particle size-dependent physicochemical structure in airborne single walled carbon nanotube agglomerates

As-produced single-walled carbon nanotube (SWCNT) material is a complex matrix of carbon nanotubes, bundles of nanotubes (nanoropes), non-tubular carbon and metal catalyst nanoparticles. The pulmonary toxicity of material released during manufacture and handling will depend on the partitioning and arrangement of these components within airborne particles. To probe the physicochemical structure of airborne SWCNT aggregates, a new technique was developed and applied to aerosolized as-produced material. Differential Mobility Analysis-classified aggregates were analyzed using an Aerosol Particle Mass Monitor, and a structural parameter Γ (proportional to the square of particle mobility diameter, divided by APM voltage) derived. Using information on the constituent components of the SWCNT, modal values of Γ were estimated for specific particle compositions and structures, and compared against measured values. Measured modal values of Γ for 150 nm mobility diameter aggregates suggested they were primarily composed of non-tubular carbon from one batch of material, and thin nanoropes from a second batch of material – these findings were confirmed using Transmission Electron Microscopy. Measured modal values of Γ for 31 nm mobility diameter aggregates indicated that they were comprised predominantly of thin carbon nanoropes with associated nanometer-diameter metal catalyst particles; there was no indication that either catalyst particles or non-tubular carbon particles were being preferentially released into the air. These results indicate that the physicochemistry of aerosol particles released while handling as-produced SWCNT may vary significantly by particle size and production batch, and that evaluations of potential health hazards need to account for this. Disclaimer: The mention of any company or product does not constitute an endorsement by the Centers for Disease Control and Prevention. The findings and conclusions in this paper are those of the authors and do not necessarily represent the views of the National Institute for Occupational Safety and Health.     

Thermal plasma deposition of nanostructured films

A thermal plasma process for the synthesis of nanoparticles and their immediate assembly into nanostructured films is discussed. In this process, known as hypersonic plasma particle deposition, a thermal plasma with injected precursors is expanded through a nozzle to nucleate nanoparticles, which are then inertially deposited onto a cooled substrate in vacuum. A lightly consolidated nanostructured film results. Particle and film diagnostics along with images of the plasma flow are used to explain the formation of nanostructured silicon carbide films by this process     

Nanoparticle-Coated Silicon Nanowires

The synthesis of silicon nanowires that are densely coated with silicon nanoparticles is reported. These structures were produced in a two-step process, using a method known as hypersonic plasma particle deposition. In the first step, a Ti–Si nanoparticle film was deposited. In the second step the Ti-source was switched off, and nanoparticle-coated nanowires grew under the simultaneous action of Si vapor deposition and bombardment by Si nanoparticles. Total process time, including both steps, equaled 5 min, and resulted in formation of a dense network of randomly oriented nanowires covering1.5 cm² of substrate area. The nanowires are composed of single-crystal Si. The diameters of the nanowires vary over the range 100–800 nm. Each nanowire has a crystalline TiSi₂ catalyst particle, believed to have been solid during nanowire growth, at its tip.     

Direct interaction between an allosteric agonist pepducin and the chemokine receptor CXCR4

Cell surface heptahelical G protein-coupled receptors (GPCRs) mediate critical cellular signaling pathways and are important pharmaceutical drug targets. (1) In addition to traditional small-molecule approaches, lipopeptide-based GPCR-derived pepducins have emerged as a new class of pharmaceutical agents. (2, 3) To better understand how pepducins interact with targeted receptors, we developed a cell-based photo-cross-linking approach to study the interaction between the pepducin agonist ATI-2341 and its target receptor, chemokine C-X-C-type receptor 4 (CXCR4). A pepducin analogue, ATI-2766, formed a specific UV-light-dependent cross-link to CXCR4 and to mutants with truncations of the N-terminus, the known chemokine docking site. These results demonstrate that CXCR4 is the direct binding target of ATI-2341 and suggest a new mechanism for allosteric modulation of GPCR activity. Adaptation and application of our findings should prove useful in further understanding pepducin modulation of GPCRs as well as enable new experimental approaches to better understand GPCR signal transduction.     

Synthesis of bicyclogermacrene and lepidozene

Bicyclogermacrene (1) and lepidozene (2) have been synthesized by short routes starting from geranylacetone. Titanium-induced cyclizations of cis- and trans-2,2- dimethyl-3-(3-methyl-7-oxo-3E-octenyl)cyclopropane-carbaldehyde were used as the key steps.