Total synthesis of the potent androgen receptor antagonist (-)-arabilin: a strategic, biomimetic [1,7]-hydrogen shift

The first total synthesis of (-)-arabilin, a Streptomyces metabolite that inhibits hormone activation of the androgen receptor, has been completed. The key step, a [1,7]-hydrogen shift, establishes the enol ether-containing skipped-tetraene substructure. This nonenzymatic pericyclic reaction is considered to be biomimetic.     

Tetrahedral atom ordering in a zeolite framework: a key factor affecting its physicochemical properties

Three gallosilicate natrolites with closely similar chemical composition but differing in the distribution of Si and Ga over crystallographically different tetrahedral sites (T-sites) show striking differences in their cation exchange performance. The ability to exchange Na(+) by the larger alkali metal cations decreases upon increasing the size of the cation, as expected, but also with the degree of T-atom ordering. To seek an insight into this phenomenon, the crystal structures of 11 different zeolites, which show variations in degree of T-atom ordering, nature of countercation, and hydration state, have been refined using synchrotron diffraction data. While the three as-made sodium materials were characterized to have a low, medium, and high degree of ordering, respectively, their pore sizes are close to the size of the bare Na(+) cation and much smaller than that of the larger alkali cations, which are nonetheless exchanged into the materials, each one at a different level. Interestingly, large differences are also manifested when the Na(+) back-exchange is performed on the dehydrated K(+) forms, with crystallographic pore sizes too small even to allow the passage of Na(+). Although the thermodynamic data point to small differences in the enthalpy of the Na(+)/K(+) exchange in the three materials, comparison of the "static" crystallographic pore sizes and the diameter of the exchanged cations lead us to conclude that during the exchange process these zeolites undergo significant deformations that dynamically open the pores, allowing cation traffic even for Cs(+) in the case of the most disordered material. In addition to the very large topological flexibility typical of the natrolite framework, we propose as a hypothesis that there is an additional flexibility mechanism that decreases the rigidity of the natrolite chain itself and is dependent on preferential siting of Si or Ga on crystallographically different T-sites.     

TIRF microscopy as a screening method for non-specific binding on surfaces

We report a method for studying nanoparticle-biosensor surface interactions based on total internal reflection fluorescence (TIRF) microscopy. We demonstrate that this simple technique allows for high throughput screening of non-specific adsorption (NSA) of nanoparticles on surfaces of different chemical composition. Binding events between fluorescent nanoparticles and functionalized Zeonor? surfaces are observed in real-time, giving a measure of the attractive or repulsive properties of the surface and the kinetics of the interaction. Three types of coatings have been studied: one containing a polymerized aminosilane network with terminal -NH(2) groups, a second film with a high density of -COOH surface groups and the third with sterically restraining branched poly(ethylene)glycol (PEG) functionality. TIRF microscopy revealed that the NSA of nanoparticles with negative surface charge on such modified coatings decreased in the following order -NH(2)>-branched PEG>-COOH. The surface specificity of the technique also allows discrimination of the degree of NSA of the same surface at different pH.     

Isolation and structural characterization of the elusive 1:1 adduct of hydrazine and carbon dioxide

A solid hydrazine was isolated as a crystalline powder by reacting aqueous hydrazine with supercritical CO(2). Its structure determined by single crystal X-ray diffraction shows a zwitterionic form of NH(3)(+)NHCO(2)(-). The solid hydrazine is remarkably stable but is as reactive as liquid hydrazine even in the absence of solvents.     

Control of ZnO morphologies on carbon nanotube electrodes and electrocatalytic characteristics toward hydrazine

We controlled the morphologies of zinc oxide (ZnO) nanostructures on single-walled carbon nanotube electrodes by an electrochemical deposition method and investigated the dependence of the electrocatalytic characteristics toward hydrazine on the different morphologies. ZnO nanorods provided high electrocatalytic activity with unique electrochemical behaviours, associated with the H(+) ion generated by the electro-oxidation of hydrazine.     

Oxidative properties of a nonheme Ni(II)(O2) complex: Reactivity patterns for C-H activation, aromatic hydroxylation and heteroatom oxidation

Density functional theory calculations on the reactivity of a Ni(II)-superoxo complex in C-H bond activation, aromatic hydroxylation and heteroatom oxidation reactions have been explored; the Ni(II)-superoxo complex is able to react with substrates with weak C-H bonds and PPh(3).     

Photoreversible cellular imaging using photochrome-conjugated fullerene silica nanoparticles

Photochromic compound-conjugated fluorescent fullerene-silica nanoparticles prepared by the reverse-microemulsion method was utilized for photoswitchable cellular imaging by repeatable irradiation of ultraviolet and visible light.     

Antioxidant and antityrosinase activities of various extracts from the fruiting bodies of Lentinus lepideus

Lentinus lepideus is an edible mushroom currently available in Korea. The acetone, methanol and hot water extracts were prepared and assayed for their antioxidant and antityrosinase inhibitory activities. The hot water extract showed the strongest β-carotene-linoleic acid inhibition compared to the other extracts. At 8 mg/mL, the methanolic extract showed a high reducing power of 1.21. The acetone and methanol extracts were more effective in scavenging DPPH radicals than the hot water extract. The strongest chelating effect was obtained from the methanolic extract. Xanthine oxidase and tyrosinase inhibitory activities of the acetonic, methanol and hot water extracts increased with increasing concentration. Gallic acid, chlorogenic acid, vanillin, naringin, naringenin, formononetin, and biochanin-A were detected in the acetonitrile and hydrochloric acid (5:1) solvent extract. This study suggests that fruiting bodies of L. lepideus can potentially be used as a readily accessible source of natural antioxidants.     

Strain stiffening of non-colloidal hard sphere suspensions dispersed in Newtonian fluid near liquid-and-crystal coexistence region

Concentrated hard sphere suspensions often show an interesting nonlinear behavior, called strain stiffening, in which the viscosity or modulus starts to increase at critical strain amplitude. Sudden increase of rheological properties is similar to shear thickening; however, the particle dynamics in the strain stiffening under oscillatory shear flow does not necessarily coincide with the mechanism of shear thickening under step shear flow. In this study, we have systematically investigated the nonlinear rheology of non-colloidal (>1???m) hard sphere suspensions dispersed in Newtonian fluid near liquid-and-crystal coexistence region in order to better understand the strain stiffening behavior. The suspensions near liquid-and-crystal coexistence region are known to locally form the closed packing structure. The critical strain amplitude which is the onset of strain stiffening was different for the storage and loss modulus. But they converged to each other as the suspension forms a more crystalline structure. The critical strain amplitude was independent of medium viscosity, imposed angular frequency, and particle size, but was strongly dependent upon particle volume fraction. The onset of strain stiffening was explained in terms of shear-induced collision due to particle motion in the closed packing structure. Nonlinear stress wave-forms, which reflect the micro-structural change, were observed with the onset of strain stiffening. During the strain stiffening, enhanced elastic stress before and after flow reversal was observed which originates from changes in the suspension microstructure. Nonlinearity of the shear stress in terms of Fourier intensity was extremely increased up to 0.55. Beyond the strain stiffening, the suspension responded liquid-like and the nonlinearity decreased but the elastic shear stress was still indicating the microstructure rearrangement within a cycle.