Eye patches: Protein assembly of index-gradient squid lenses.

A parabolic relationship between lens radius and refractive index allows spherical lenses to avoid spherical aberration. We show that in squid, patchy colloidal physics resulted from an evolutionary radiation of globular S-crystallin proteins. Small-angle x-ray scattering experiments on lens tissue show colloidal gels of S-crystallins at all radial positions. Sparse lens materials form via low-valence linkages between disordered loops protruding from the protein surface. The loops are polydisperse and bind via a set of hydrogen bonds between disordered side chains. Peripheral lens regions with low particle valence form stable, volume-spanning gels at low density, whereas central regions with higher average valence gel at higher densities. The proteins demonstrate an evolved set of linkers for self-assembly of nanoparticles into volumetric materials.

Structure of semidilute single-wall carbon nanotube suspensions and gels.

The microscopic network structure of surfactant-stabilized single-wall carbon nanotubes (SWNTs) in water was investigated as a function of SWNT concentration in the semidilute (overlapping) regime using small-angle neutron scattering (SANS). Most of the samples exhibit rigid rod behavior (i.e., Q(-1) intensity variation) at large scattering wavevector, Q, and a crossover to network behavior (i.e., approximately Q(-2) intensity variation) at low Q. The mesh size, xi, of the network was determined from the crossover of rigid rod to network behavior in the SANS intensity profile and was found to decrease with increasing SWNT concentration. When the dispersion quality of these associating rigid rods was degraded, only approximately Q(-2) intensity variation was observed at both high and low Q. Small-angle X-ray scattering measurements of the same stable dispersions were relatively insensitive to network structure because of poor contrast between SWNTs and surfactant.

Self-organization of supramolecular helical dendrimers into complex electronic materials.

The discovery of electrically conducting organic crystals and polymers has widened the range of potential optoelectronic materials, provided these exhibit sufficiently high charge carrier mobilities and are easy to make and process. Organic single crystals have high charge carrier mobilities but are usually impractical, whereas polymers have good processability but low mobilities. Liquid crystals exhibit mobilities approaching those of single crystals and are suitable for applications, but demanding fabrication and processing methods limit their use. Here we show that the self-assembly of fluorinated tapered dendrons can drive the formation of supramolecular liquid crystals with promising optoelectronic properties from a wide range of organic materials. We find that attaching conducting organic donor or acceptor groups to the apex of the dendrons leads to supramolecular nanometre-scale columns that contain in their cores pi-stacks of donors, acceptors or donor-acceptor complexes exhibiting high charge carrier mobilities. When we use functionalized dendrons and amorphous polymers carrying compatible side groups, these co-assemble so that the polymer is incorporated in the centre of the columns through donor-acceptor interactions and exhibits enhanced charge carrier mobilities. We anticipate that this simple and versatile strategy for producing conductive pi-stacks of aromatic groups, surrounded by helical dendrons, will lead to a new class of supramolecular materials suitable for electronic and optoelectronic applications.

Unexpected square symmetry seen by atomic force microscopy in bilayer films of disk-like molecules.

Thin films of disk-shaped molecules are expected to display anisotropic optical and transport properties, leading to applications in optical display or sensor technologies. Bilayer Langmuir-Blodgett films of monomeric triphenylene mesogens have been studied by atomic force microscopy. The triphenylene cores of the constituent molecules tend to promote the formation of columnar structures in the plane of the substrate and along the direction of deposition of the film. Atomic force microscopy images of bilayer Langmuir-Blodgett films revealed two types of structure, one corresponding to an aligned columnar structure and the other to an unusual square lattice, which may result from the superposition of columnar structures in adjacent layers that intersect at near right angles. Annealing such bilayers near the melting point of the bulk compound improved the structural ordering by reducing the angular spread of orientations associated with the well-developed columnar structure in some areas and by producing a more distinct square lattice in other areas of the sample.

Structure of langmuir-blodgett films of disk-shaped molecules determined by atomic force microscopy.

Monolayer Langmuir-Blodgett films of a discotic mesogen have been studied with atomic force microscopy (AFM). These measurements confirm the "edge on" arrangement for the disk-shaped molecules suggested by surface pressure-area isotherms and show that the molecules form columns that are separated by 17.7 angstroms +/- 10 percent. Column alignment is found to be predominantly along the film deposition direction, with an angular spread of 35 degrees . The AFM images also show that the mean disk separation within the columns is 5.1 +/- 1.3 angstroms, in good agreement with x-ray diffraction (XRD) results. Roomtemperature XRD measurements on bulk samples of the same material indicate a disordered-hexagonal liquid crystalline mesophase, with a column-to-column spacing of 19.9 +/- 0.2 angstroms.

Compressibility of M3C60 Fullerene Superconductors: Relation Between Tc and Lattice Parameter.

X-ray diffraction and diamond anvil techniques were used to measure the isothermal compressibility of K(3)C(60) and Rb(3)C(60), the superconducting, binary alkali-metal intercalation compounds of solid buckminsterfullerene. These results, combined with the pressure dependence of the superconducting onset temperature T(c) measured by other groups, establish a universal first-order relation between T(c) and the lattice parameter a over a broad range, between 13.9 and 14.5 angstroms. A small secondorder intercalate-specific effect was observed that appears to rule out the participation of intercalate-fullerene optic modes in the pairing interaction.

Compressibility of solid c60.

Room-temperature powder x-ray diffraction profiles have been obtained at hydrostatic pressures P = 0 and 1.2 gigapascals on the solid phase of cubic C(60) ("fullerite"). Within experimental error, the linear compressibility d(ln a)/dP is the same as the interlayer compressibility d(ln c)/dP of hexagonal graphite, consistent with van der Waals intermolecular bonding. The volume compressibility -d(ln V)/dP is 7.0 +/- 1 x 10(-12) square centimeter per dyne, 3 and 40 times the values for graphite and diamond, respectively.

Disorder in Al-li-cu and Al-mn-si icosahedral alloys.

Faceted dendrites of icosahedral AL(6)Li(3)Cu have been studied by high-resolution x-ray scattering. The samples display long-range icosahedral symmetry both in their diffraction patterns and in their macroscopic morphology. Despite the appearance of well-defined facets, the samples have a high degree of atomic disorder. The Bragg peaks have symmetry-dependent shapes and widths that scale linearly with G perpendicular (phason momentum). The peak widths are surprisingly similar to those found in icosahedral Al-Mn-Si alloys in both their absolute magnitude and their dependence on G perpendicular. The origin of these features in models for the icosahedral phase is discussed.