Total synthesis of broussonetine F: the orthoamide Overman rearrangement of an allylic diol

A first total synthesis of broussonetine F from diethyl L-tartrate was achieved. The cornerstone of our synthesis was an orthoamide Overman rearrangement, which provided an allylic amino alcohol with complete diastereoselectivity.     

Diastereoselective construction of 7-methylenebicyclo[3.2.1]oct-3-en-2-one derivatives by palladium-catalyzed cyclization of propargylic acetates with 2-oxocyclohex-3-enecarboxylates

The reaction of propargylic acetates with 2-oxocyclohex-3-enecarboxylates in the presence of a palladium catalyst is described. Substituted 7-methylenebicyclo[3.2.1]oct-3-en-2-ones were synthesized in a highly diastereoselective manner.     

Structure and rheology of reverse micelles in dipentaerythrityl tri-(12-hydroxystearate)/oil systems

We report the formation of reverse rod-like micelles and their rheological properties in novel nonionic surfactant, dipentaerythrityl tri-(12-hydroxystearate) (designated as WO-6)/oil systems without external water addition. Small-angle X-ray scattering (SAXS) was used to investigate the structure of the micelles and their flow properties were studied by rheological measurements. We found that WO-6 spontaneously self-assembles into reverse micelles in a variety of organic solvents at ambient conditions, their structure depending on solvent molecular architecture, surfactant concentration, and temperature. Rod-like micelles with a maximum length of ca. 12 nm and a cross section diameter of ca. 2 nm were observed in cyclohexane. When cyclohexane was replaced with a linear chain octane, the length and the cross section diameter were simultaneously increased. With a further increase of hydrocarbon chain length of solvent oils from octane to hexadecane, the rod-like micelles grew axially, keeping the cross section diameter (ca. 3 nm) virtually constant. Increasing surfactant concentration also favored one-dimensional micellar growth. On the other hand, micelles shrunk with the rise of temperature, which is similar to a rod-to-sphere transition, and is essentially the opposite temperature dependence to that often observed in aqueous micellar systems. A structural picture drawn by SAXS is well supported by rheology; the relative (zero-shear) viscosity of the WO-6/oil systems was found to be markedly greater than that expected for a dispersion of spherical particles due to the elongated micellar structure, despite quantitative inconsistency with semi-empirically predicted values for rigid rod-like particles.     

Experimental and computational study of intermolecular migration of N,N-dimethylcarbamoyl group from N(7) to N(1) on a 7-azaindoline derivative

N,N-Dimethylcarbamoylation of the anilinic nitrogen atom N(1) on the spiro 7-azaindoline consists of two steps. The first step is N,N-dimethylcarbamoylation of the pyridyl nitrogen atom N(7), leading to the formation of an isolable intermediate. The second step is intermolecular migration of the N,N-dimethylcarbamoyl group from the pyridyl nitrogen atom N(7) to the anilinic nitrogen atom N(1). We accomplished optimization of the reaction conditions based on the revealed reaction mechanism and a large scale synthesis of compound 3 in quantitative yield.     

Removal of fluoride ions using calcined paper sludge

Paper sludge (PS) is generated as an industrial waste during the manufacture of recycled paper products, and amounts discharged globally are increasing annually. In this study, PS is converted into an effective sequestration agent for fluoride through calcination. PS contains mainly cellulose fibers and inorganic fillers together with coating materials such as calcite, kaolinite, and talc. The sludge was fired at temperatures between 200 and 1,000 °C for 6 h. Crystalline phases originally present were altered at increasing temperatures (up to 800 °C) in the order of kaolinite < calcite < talc. An amorphous phase was formed at 800 °C, and gehlenite was formed at 1,000 °C. The uptake of fluoride by these fired samples was investigated at room temperature. PS fired at 800 °C shows a higher uptake of fluoride than that calcined at other temperatures. It also shows a high selective removal for fluoride in solutions containing chloride, nitrate, and sulfate. The main process responsible for fluoride sequestration is the formation of fluorite by reaction between labile calcium and fluoride in solution. The fluoride removal behavior fits a Freundlich isotherm model than Langmuir, and indicates the spontaneous nature of this reaction.     

InTaO<Subscript>4</Subscript>-based nanostructures synthesized by reactive pulsed laser ablation

Nanostructured Ni-doped indium–tantalum–oxides (InTaO₄) were synthesized by a reactive pulsed laser ablation process, aiming at the final goal of direct splitting of water under visible sunbeam irradiation. The third harmonics beam of a Nd:YAG laser was focused onto a sintered In_0.9Ni_0.1TaO_4−δ target in pure oxygen background gases (0.05–1.00 Torr). Increasing the oxygen gas pressure, via thin films having nanometer-sized strong morphologies, single-crystalline nanoparticles were synthesized in the reactive vapor phases. The nanostructured deposited materials have the monoclinic layered wolframite-type structure of bulk InTaO₄, without oxygen deficiency.     

Visualizing of skin chromophore concentrations by use of RGB images

A method is proposed for visualizing simply the concentrations of melanin, oxygenated blood, and deoxygenated blood in skin tissue using digital RGB images. The total blood concentration and oxygen saturation can also be reconstructed. Monte Carlo simulation of light transport specifies a relation between the chromophore concentrations and Commission Internationale de l'Eclairage XYZ, which are compatible with the common RGB working space. Experiments with a tissuelike agar gel phantom demonstrated the possibility of the method. In vivo imaging of a human hand during forearm occlusion demonstrated the ability of the method to evaluate hemodynamics of skin tissue.     

Fabrication of a complex InAs ring-and-dot structure by droplet epitaxy

An InAs ring structure accompanying the formation of quantum dots (QDs) was fabricated on (1 0 0)GaAs using droplet epitaxy. The QDs were located in the vicinity of the ring, due to the diffusion of In atoms from the In droplets. In addition, the dots were found to have distributed elliptically and preferentially along the [0 1 1] direction, implying that In itself prefers to diffuse along the [0 1 1] direction, which is the opposite of the favorable diffusion orientation of group III atoms on (1 0 0)GaAs under a commonly used As-stabilized growth condition. This is the first observation of a ring structure accompanying the formation of quantum dots in droplet epitaxy.     

MD simulation study of the sputtering process by high-energy gas cluster impact

We performed molecular dynamics (MD) simulations to study the characteristic sputtering process with large cluster ion impact. The statistical properties of incident Ar and sputtered Si atoms were examined using 100 different MD simulations with Ar₁₀₀₀ cluster impacting on a Si(0 0 1) target at a total acceleration energy of 50 keV. The results show that the kinetic energy distribution of Ar atoms after impact obeys the high-temperature Boltzmann distribution due to thermalization through high-density multiple collisions on the target. On the other hand, the kinetic energy distribution of sputtered target atoms demonstrates a hybrid model of thermalization and collision-cascade desorption processes.