Bowl Shaped Cavitands Dimerize and Complex Certain Organic Guests in Organic Solvents which Themselves are Poor Guests

The syntheses and binding properties of rigidly bowl-shaped polycyclic cavitands (1—4) are reported. Attached to the four aryl rim positions of the bowls are four benzenes substituted in their para positions with four CC^Me, Br, OH or NO2 groups, which deepen the bowls. Attached to the base of the bowls are four pentyl feet, which increase the solubilities of these hosts in organic solvents. Of the four hosts, only the one containing the CO2Me groups dimerized both in the crystalline state and in solution in ten deute- rated solvents which themselves are poor guests. In three other deuterated solvents, no dimerization was observed. A crystal structure of the dimer showed that one p-MeC^CCs^ group of each monomer occupied the cavity of its complexing partner in a reciprocating double host-guest arrangement. Such a structure is compatible with the ^H-NMR spectra of the dimer in solution. The dimer was also detected in its FAB-MS. The tetrabromocavitand at low concentrations in CD2CI2 complexed MeCC^C^Me, MeCC^Me, PhCC^Me and MeCOC^CC^Me. Tetranitrocavitand 4 also complexed MeC02CH2Me in CD2CI2 as solvent

Polar Smectic Films

We report on a new experimental procedure for forming and studying polar smectic liquid crystal films. A free standing smectic film is put in contact with a liquid drop, so that the film has one liquid crystal/liquid interface and one liquid crystal/air interface. This polar environment results in changes in the textures observed in the film, including a boojum texture and a previously unobserved spiral texture in which the winding direction of the spiral reverses at a finite radius from its center. Some aspects of these textures are explained by the presence of a Ksb term in the bulk elastic free energy density that favors a combination of splay and bend deformations.Comment: 4 pages, REVTeX, 3 figures, submitted to PR

Static Scaling Behavior of High-Molecular-Weight Polymers in Dilute Solution: A Reexamination

Previous theories of dilute polymer solutions have failed to distinguish clearly between two very different ways of taking the long-chain limit: (I) $N \to\infty$ at fixed temperature $T$, and (II) $N \to\infty$, $T \to T_\theta$ with $x \equiv N^\phi (T-T_\theta)$ fixed. I argue that the modern two-parameter theory (continuum Edwards model) applies to case II --- not case I --- and in fact gives exactly the crossover scaling functions for $x \ge 0$ modulo two nonuniversal scale factors. A Wilson-type renormalization group clarifies the connection between crossover scaling functions and continuum field theories. [Also contains a general discussion of the connection between the Wilson and field-theoretic renormalization groups. Comments solicited.]Comment: 10 pages including 1 figure, 181159 bytes Postscript (NYU-TH-93/05/01

Boojums and the Shapes of Domains in Monolayer Films

Domains in Langmuir monolayers support a texture that is the two-dimensional version of the feature known as a boojum. Such a texture has a quantifiable effect on the shape of the domain with which it is associated. The most noticeable consequence is a cusp-like feature on the domain boundary. We report the results of an experimental and theoretical investigation of the shape of a domain in a Langmuir monolayer. A further aspect of the investigation is the study of the shape of a ``bubble'' of gas-like phase in such a monolayer. This structure supports a texture having the form of an inverse boojum. The distortion of a bubble resulting from this texture is also studied. The correspondence between theory and experiment, while not perfect, indicates that a qualitative understanding of the relationship between textures and domain shapes has been achieved.Comment: replaced with published version, 10 pages, 13 figures include

Theory of monolayers with boundaries: Exact results and Perturbative analysis

Domains and bubbles in tilted phases of Langmuir monolayers contain a class of textures knows as boojums. The boundaries of such domains and bubbles may display either cusp-like features or indentations. We derive analytic expressions for the textures within domains and surrounding bubbles, and for the shapes of the boundaries of these regions. The derivation is perturbative in the deviation of the bounding curve from a circle. This method is not expected to be accurate when the boundary suffers large distortions, but it does provide important clues with regard to the influence of various energetic terms on the order-parameter texture and the shape of the domain or bubble bounding curve. We also look into the effects of thermal fluctuations, which include a sample-size-dependent effective line tension.Comment: replaced with published version, 21 pages, 16 figures include

Towards a Tetravalent Chemistry of Colloids

We propose coating spherical particles or droplets with anisotropic nano-sized objects to allow micron-scale colloids to link or functionalize with a four-fold valence, similar to the sp3 hybridized chemical bonds associated with, e.g., carbon, silicon and germanium. Candidates for such coatings include triblock copolymers, gemini lipids, metallic or semiconducting nanorods and conventional liquid crystal compounds. We estimate the size of the relevant nematic Frank constants, discuss how to obtain other valences and analyze the thermal distortions of ground state configurations of defects on the sphere.Comment: Replaced to improve figures. 4 figures Nano Letter

Avoided Critical Behavior in O(n) Systems

Long-range frustrating interactions, even if their strength is infinitesimal, can give rise to a dramatic proliferations of ground or near-ground states. As a consequence, the ordering temperature can exhibit a discontinuous drop as a function of the frustration. A simple model of the doped Mott insulator, where the short-range tendency of the holes to phase separate competes with long-range Coulomb effects, exhibits this "avoided critical" behavior. This model may serve as a paradigm for many other systems.Comment: 4 pages, 2 figure

Hexatic Order and Surface Ripples in Spherical Geometries

In flat geometries, two dimensional hexatic order has only a minor effect on capillary waves on a liquid substrate and on undulation modes in lipid bilayers. However, extended bond orientational order alters the long wavelength spectrum of these ripples in spherical geometries. We calculate this frequency shift and suggest that it might be detectable in lipid bilayer vesicles, at the surface of liquid metals and in multielectron bubbles in liquid helium at low temperatures. Hexatic order also leads to a shift in the threshold for the fission instability induced in the later two systems by an excess of electric charge.Comment: 5 pages, 1 figure; revised version; to appear in Phys. Rev. Let