Toward the total synthesis of tetrodotoxin: stereoselective construction of the 7-oxanorbornane intermediate

The stereoselective synthesis of 7-oxanorbornane regarding as a key synthetic intermediate of tetrodotoxin (TTX) is reported. The bicyclo ring bearing various functional groups was successfully elaborated by a furan Diels–Alder (DA) reaction. The stereoselective installation of a quaternary amino carbon center to the DA product was achieved with the Tsuji–Trost allylation. The stereochemistry was unambiguously confirmed with X-ray.     

Electrorheology of dielectric liquids

Dielectric liquids that show striking electrorheological (ER) effects are formulated by controlling the conductivity. Although the viscosity is increased on the application of a d.c. field, the flow of electrified fluids is Newtonian in the plain electrodes with smooth surfaces. When the liquids are sandwiched between the electrodes with flocked fabrics, the viscosity behavior is converted from Newtonian to shear-thinning flow. In electric fields, the convective flow is induced over the system due to the electrohydrodynamic(EHD) effect. The interactions between EHD convection and external shear give rise to the additional energy dissipation and in turn the increase in viscosity. The ER effects of simple liquids are very attractive in application to new fluid devices.     

Electrochemical monitoring of intracellular enzyme activity of single living mammalian cells by using a double-mediator system

We evaluated the intracellular NAD(P)H:quinone oxidoreductase (NQO) activity of single HeLa cells by using the menadione–ferrocyanide double-mediator system combined with scanning electrochemical microscopy (SECM). The double-mediator system was used to amplify the current response from the intracellular NQO activity and to reduce menadione-induced cell damage. The electron shuttle between the electrode and menadione was mediated by the ferrocyanide/ferricyanide redox couple. Generation of ferrocyanide was observed immediately after the addition of a lower concentration (10 μM) of menadione. The ferrocyanide generation rate was constant for 120 min. At a higher menadione concentration (100 μM), the ferrocyanide generation rate decreased within 30 min because of the cytotoxic effect of menadione. We also investigated the relationship between intracellular reactive oxygen species or glutathione levels and exposure to different menadione concentrations to determine the optimal condition for SECM with minimal invasiveness. The present study clearly demonstrates that SECM is useful for the analysis of intracellular enzymatic activities in single cells with a double-mediator system.     

Isolation and quantification of messenger RNA from tissue models by using a double-barrel carbon probe

In this study, we introduce the double-barrel carbon probe (DBCP)—a simple, affordable microring electrode—which enables the collection and analysis of single cells independent of cellular positioning. The target cells were punctured by utilizing an electric pulse between the two electrodes in DBCP, and the cellular lysates were collected by manual aspiration using the DBCP. The mRNA in the collected lysate was evaluated quantitatively using real-time PCR. The histograms of single-cell relative gene expression normalized to GAPDH were fit to a theoretical lognormal distribution. In the tissue culture model, we focused on angiogenesis to prove that multiple gene expression analysis was available. Finally, we applied DBCP for the embryonic stem (ES) cell-derived cardiomyocytes to substantiate the capability of the probe to collect cells, even from high-volume samples such as spheroids. This method achieves high sensitivity for mRNA at the single-cell level and is applicable in the analysis of various biological samples independent of cellular positioning.

Gravitational radiation by a particle with nonzero orbital angular momentum falling into a Kerr black hole

We have computed the energy of the gravitational waves induced by a particle with nonzero orbital angular momentum μL_z plunging into a Kerr black hole in an equatorial plane. It is found that for the same |L_z| a corotating particle emits more energy than a counter-rotating one, which is due to the change of the frequency of the quasi-normal mode with the increase of the angular momentum of the black hole.     

Effect of electric fields on the surface profiles of electrorheological suspensions

The surface deformation induced in electric fields is studied on the comb pattern electrodes for silica suspensions. On the application of electric fields, a fine pattern with a waveform is developed from the smooth surface. The surface profiles can be approximated by single sinusoidal waves or their superposition depending on the sample thickness. In electric fields, the silica suspensions shows the viscosity decrease in steady shear and yield stress in the limit of zero shear rates. The viscosity decrease can be attributed to electrophoretic migration of particles to one electrode and the development of yield stress to eletrorheological effects due to chain formation of particles between electrodes. In thick liquid films, the dielectric polarization forces are predominant and the sinusoidal profiles with a wavelength of pitch of electrodes are formed. In thin films, the electrophoretic forces are predominant and the wavelength coincides with twice the pitch of electrodes. At intermediate thicknesses, the surface profiles can be expressed by a superposition of two sinusoidal waves.     

High-pressure (up to 140 MPa) density and derivative properties of some (pentyl-, hexyl-, and heptyl-) amines between (293.15 and 353.15) K

This work reports the density data (315 points) of a series of amines consisting of pentylamine, hexylamine, and heptylamine at seven temperatures between (293.15 and 353.15) K, and pressures up to 140 MPa (every 10 MPa) which allows to study the influence of the chain length. A new Anton-Paar vibrating tube densimeter, calibrated with water and vacuum with an uncertainty of ±5 · 10^?4 g · cm^?3 was used to perform these measurements. The experimental density data were fitted with the Tait-like equation with low standard deviations. In addition, the isobaric thermal expansivity and the isothermal compressibility have been derived from this equation.