Directing liquid crystalline self-organization of rod-like particles through tunable attractive single tips

Dispersions of rodlike colloidal particles exhibit a plethora of liquid crystalline states, including nematic, smectic A, smectic B, and columnar phases. This phase behavior can be explained by presuming the predominance of hard-core volume exclusion between the particles. We show here how the self-organization of rodlike colloids can be controlled by introducing a weak and highly localized directional attractive interaction between one of the ends of the particles. This has been performed by functionalizing the tips of filamentous viruses by means of regioselectively grafting fluorescent dyes onto them, resulting in a hydrophobic patch whose attraction can be tuned by varying the number of bound dye molecules. We show, in agreement with our computer simulations, that increasing the single tip attraction stabilizes the smectic phase at the expense of the nematic phase, leaving all other liquid crystalline phases invariant. For a sufficiently strong tip attraction, the nematic state may be suppressed completely to get a direct isotropic liquid-to-smectic phase transition. Our findings provide insights into the rational design of building blocks for functional structures formed at low densities.Comment: 13 pages, 4 figure

Earthquakes as Precursors of Ductile Shear Zones in the Dry and Strong Lower Crust

The rheology and the conditions for viscous flow of the dry granulite facies lower crust are still poorly understood. Viscous shearing in the dry and strong lower crust commonly localizes in pseudotachylyte veins, but the deformation mechanisms responsible for the weakening and viscous shear localization in pseudotachylytes are yet to be explored. We investigated examples of pristine and mylonitized pseudotachylytes in anorthosites from Nusfjord (Lofoten, Norway). Mutual overprinting relationships indicate that pristine and mylonitized pseudotachylytes are coeval and resulted from the cyclical interplay between brittle and viscous deformation. The stable mineral assemblage in the mylonitized pseudotachylytes consists of plagioclase, amphibole, clinopyroxene, quartz, biotite,6garnet6K-feldspar. Amphibole-plagioclase geothermobarometry and thermodynamic modeling indicate that pristine and mylonitized pseudotachylytes formed at 650\u20137508C and 0.7\u20130.8 GPa. Thermodynamic modeling indicates that a limited amount of H2O infiltration (0.20\u20130.40 wt. %) was necessary to stabilize the mineral assemblage in the mylonite. Diffusion creep is identified as the main deformation mechanisms in the mylonitized pseudotachylytes based on the lack of crystallographic preferred orientation in plagioclase, the high degree of phase mixing, and the synkinematic nucleation of amphiboles in dilatant sites. Extrapolation of flow laws to natural conditions indicates that mylonitized pseudotachylytes are up to 3 orders of magnitude weaker than anorthosites deforming by dislocation creep, thus highlighting the fundamental role of lower crustal earthquakes as agents of weakening in strong granulites

Gas-phase solvolysis type reactions of SiCl3+ cations

Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier

Creep cavitation bands control porosity and fluid flow in lower crustal shear zones

Shear zones channelize fluid flow in Earth’s crust. However, little is known about deep crustal fluid migration and how fluids are channelized and distributed in a deforming lower crustal shear zone. This study investigates the deformation mechanisms, fluid-rock interaction, and development of porosity in a monzonite ultramylonite from Lofoten, northern Norway. The rock was deformed and transformed into an ultramylonite under lower crustal conditions (temperature = 700–730 °C, pressure = 0.65–0.8 GPa). The ultramylonite consists of feldspathic layers and domains of amphibole + quartz + calcite, which result from hydration reactions of magmatic clinopyroxene. The average grain size in both domains is \u3c25 µm. Microstructural observations and electron backscatter diffraction analysis are consistent with diffusion creep as the dominant deformation mechanism in both domains. Festoons of isolated quartz grains define C\u27-type bands in feldspathic layers. These quartz grains do not show a crystallographic preferred orientation. The alignment of quartz grains is parallel to the preferred elongation of pores in the ultramylonites, as evidenced from synchrotron X-ray microtomography. Such C\u27-type bands are interpreted as creep cavitation bands resulting from diffusion creep deformation associated with grain boundary sliding. Mass-balance calculation indicates a 2% volume increase during the protolith-ultramylonite transformation, which is consistent with synkinematic formation of creep cavities producing dilatancy. Thus, this study presents evidence that creep cavitation bands may control deep crustal porosity and fluid flow. Nucleation of new phases in creep cavitation bands inhibits grain growth and enhances the activity of grain size–sensitive creep, thereby stabilizing strain localization in the polymineralic ultramylonites