Ice premelting layer of ice-rubber friction studied using resonance shear measurement.

We performed a resonance shear measurement (RSM) based on a low-temperature surface force apparatus to evaluate the frictional properties of the interface between butadiene rubber and ice at various temperatures below 0 °C. Friction between the rubber and ice was high and constant at temperatures below -5 °C, but sharply decreased when the temperature rose above -5 °C. We performed the same measurement by replacing the rubber with polystyrene and silica films which were rigid and exhibited practically minimal elastic deformation in comparison to the rubber. The friction decreased gradually with the increase in temperature from -20 °C to 0 °C at both the polystyrene-ice and the silica-ice interfaces. These results indicated that the elasticity of rubber was responsible for the differences in the rubber-ice interface and the other two samples. To understand the detailed mechanism of friction between the rubber and the ice, we analyzed the obtained RSM data using a physical model. The result indicated that the friction between ice and rubber was determined by the elastic deformation of the rubber film at temperatures below -5 °C, and by the viscosity of the ice premelting layer above -5 °C.

Low-Temperature Surface Forces Apparatus to Determine the Interactions between Ice and Silica Surfaces.

We have developed a low-temperature surface forces apparatus (SFA) using a thermoelectric Peltier module inserted below the bottom surface of the lower sample holder, giving easy access to the samples and allowing quick temperature changes. In air, the temperature can be decreased to ca. -20 °C. To demonstrate the performance of the apparatus, we measured the interactions between ice and a silica surface at -11.5 ± 0.5 °C. An exponentially decaying repulsion of the decay length, 11.2 ± 1.0 nm, was observed, and attributed to the electric double layer (EDL) repulsion. The surface potential of the ice was calculated to be -35 mV by fitting the data to the EDL model.

1,4-Dialkynylbutatrienes: synthesis, stability, and perspectives in the chemistry of carbo-benzenes.

The π-electron-rich C(8)-conjugated sequence of 1,4-dialkynylbutatrienes is identified as a fragile and fascinating motif occurring in carbo-benzene derivatives, and in Diederich's 1,4-bis(arylethynyl)- or 1,4-bis(triisopropylsilylethynyl)butatriene "capped" representatives, in particular, in tetraalkynylbutatriene. The family of symmetrical 1,4-dialkynylbutatrienes (E-C≡C)RC=C=C=CR(C≡C-E) is extended to functional caps (E=H, CH(3), C≡CPh, CPh=CHBr, or CPh=CBr(2)) with non-alkynyl substituents at the sp(2) vertices (R=Ph or CF(3)). The targets were selected for their potential in appealing retrosynthetic routes to carbo-benzenes, in which the aromatic C(18) macrocycle would be directly generated by sequential metathesis or reductive coupling processes. The functional 1,4-dialkynylbutrienes were synthesized by either classical methods used for the preparation of generic butatrienes (R'Li/CuX-mediated reductive coupling of gem-dihaloenynes or SnCl(2)/HCl-mediated reduction of 3,6-dioxy-octa-1,4,7-triyne precursors). Their spectroscopic and electrochemical properties are compared and analyzed on the basis of the relative extent of total conjugation.

Changing the volume of a giant macrocycle: the swelling of the macrocycle with organic solvents.

The novel tetrahedral macrocycles 1a-1c have been synthesized. Macrocycles 1a and 1c were revealed to have the property to increase in volume in solution by complexation between the macrocycle and the solvent molecules.