Microscopic measurement of the linear compressibilities of two-dimensional fatty acid mesophases

The linear compressibility of two-dimensional fatty acid mesophases has determined by grazing incidence x-ray diffraction. Surface pressure vs molecular area isotherms were reconstructed from these measurements, and the linear compressibility (relative distortion along a given direction for isotropic applied stress) was determined both in the sample plane and in a plane normal to the aliphatic chain director (transverse plane). The linear compressibilities range over two orders of magnitude from 0.1 to 10 m/N and are distributed depending on their magnitude in 4 different sets which we are able to associate with different molecular mechanisms. The largest compressibilities (10m/N) are observed in the tilted phases. They are apparently independent of the chain length and could be related to the reorganization of the headgroup hydrogen-bounded network, whose role should be revalued. Intermediate compressibilities are observed in phases with quasi long-range order (directions normal to the molecular tilt in L_2 or L_2' phases, S phase), and could be related to the ordering of these phases. The lowest compressibilities are observed in the solid untilted CS phase and for 1 direction of the S and L_2'' phases. They are similar to the compressibility of crystalline polymers and correspond to the interactions between methyl groups in the crystal. Finally, negative compressibilities are observed in the transverse plane for L_2' and L_2'' phases and can be traced to subtle reorganizations upon untilting.Comment: 24 pages, 17 figure

Relative Rates of Metal-Free Azide-Alkyne Cycloadditions: Tunability over 3 Orders of Magnitude.

The thermal (3 + 2) dipolar azide-alkyne cycloaddition, proceeding without copper or strained alkynes, is an underutilized ligation with potential applications in materials, bioorganic, and synthetic chemistry. Herein, we investigate the effects of alkyne substitution on the rate of this reaction, both experimentally and computationally. Electron-withdrawing groups accelerate the reaction, providing a range of relative rates from 1.0 to 2100 between the slowest and fastest alkynes studied. Unexpectedly, aryl groups conjugated to the alkyne significantly retard the reaction rate. In contrast, a sulfonyl, ester-substituted alkyne is reactive enough that it couples with an azide at room temperature in a few hours. This reactivity scale should provide a guide to those who wish to use this ligation under mild conditions

Binary separation in very thin nematic films: thickness and phase coexistence

The behavior as a function of temperature of very thin films (10 to 200 nm) of pentylcyanobiphenyl (5CB) on silicon substrates is reported. In the vicinity of the nematic/isotropic transition we observe a coexistence of two regions of different thicknesses: thick regions are in the nematic state while thin ones are in the isotropic state. Moreover, the transition temperature is shifted downward following a 1/h^2 law (h is the film thickness). Microscope observations and small angle X-ray scattering allowed us to draw a phase diagram which is explained in terms of a binary first order phase transition where thickness plays the role of an order parameter.Comment: 5 pages, 3 figures, submitted to PRL on the 26th of Apri

Surface Roughness of Water Measured by X-Ray Reflectivity

The roughness of the liquid-vapor interface for pure water was measured by a technique of x-ray reflectivity. With synchrotron radiation $(\lambda \sim1.5 \mathring{A})$, the angular dependence of the x-ray reflectivity was measured from grazing incidence $(\sim 0.0021 rad)$, where the reflectivity was greater than 0.96, to an incident angle of $\sim 0.05 rad$, where the reflectivity was $\sim 7×10^{-8}$. A fit to the data by a theory with only one adjustable parameter obtains $3.2 \mathring{A}$ for the root-mean-square roughness of the water surface.Engineering and Applied Science

Surface Structure of Liquid Metals and the Effect of Capillary Waves: X-ray Studies on Liquid Indium

We report x-ray reflectivity (XR) and small angle off-specular diffuse scattering (DS) measurements from the surface of liquid Indium close to its melting point of $156^\circ$C. From the XR measurements we extract the surface structure factor convolved with fluctuations in the height of the liquid surface. We present a model to describe DS that takes into account the surface structure factor, thermally excited capillary waves and the experimental resolution. The experimentally determined DS follows this model with no adjustable parameters, allowing the surface structure factor to be deconvolved from the thermally excited height fluctuations. The resulting local electron density profile displays exponentially decaying surface induced layering similar to that previously reported for Ga and Hg. We compare the details of the local electron density profiles of liquid In, which is a nearly free electron metal, and liquid Ga, which is considerably more covalent and shows directional bonding in the melt. The oscillatory density profiles have comparable amplitudes in both metals, but surface layering decays over a length scale of $3.5\pm 0.6$ \AA for In and $5.5\pm 0.4$ \AA for Ga. Upon controlled exposure to oxygen, no oxide monolayer is formed on the liquid In surface, unlike the passivating film formed on liquid Gallium.Comment: 9 pages, 5 figures; submitted to Phys. Rev.

Surface layering of liquids: The role of surface tension

Recent measurements show that the free surfaces of liquid metals and alloys are always layered, regardless of composition and surface tension; a result supported by three decades of simulations and theory. Recent theoretical work claims, however, that at low enough temperatures the free surfaces of all liquids should become layered, unless preempted by bulk freezing. Using x-ray reflectivity and diffuse scattering measurements we show that there is no observable surface-induced layering in water at T=298 K, thus highlighting a fundamental difference between dielectric and metallic liquids. The implications of this result for the question in the title are discussed.Comment: 5 pages, 4 figures, to appear in Phys. Rev. B. 69 (2004