A concept for molecular electronics exploiting carbon nanotubes as both molecular device elements and molecular wires for reading and writing information was developed. Each device element is based on a suspended, crossed nanotube geometry that leads to bistable, electrostatically switchable ON/OFF states. The device elements are naturally addressable in large arrays by the carbon nanotube molecular wires making up the devices. These reversible, bistable device elements could be used to construct nonvolatile random access memory and logic function tables at an integration level approaching 10 12 elements per square centimeter and an element operation frequency in excess of 100 gigahertz. The viability of this concept is demonstrated by detailed calculations and by the experimental realization of a reversible, bistable nanotube-based bit.

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Carbon nanotube-based nonvolatile random access memory for molecular computing

Finding a synthetic pathway to artificial analogs of nacre and bones represents a fundamental milestone in the development of composite materials. The ordered brick-and-mortar arrangement of organic and inorganic layers is believed to be the most essential strength- and toughness-determining structural feature of nacre. It has also been found that the ionic crosslinking of tightly folded macromolecules is equally important. Here, we demonstrate that both structural features can be reproduced by sequential deposition of polyelectrolytes and clays. This simple process results in a nanoscale version of nacre with alternating organic and inorganic layers. The macromolecular folding effect reveals itself in the unique saw-tooth pattern of differential stretching curves attributed to the gradual breakage of ionic crosslinks in polyelectrolyte chains. The tensile strength of the prepared multilayers approached that of nacre, whereas their ultimate Young modulus was similar to that of lamellar bones. Structural and functional resemblance makes clay– polyelectrolyte multilayers a close replica of natural biocomposites. Their nanoscale nature enables elucidation of molecular processes occurring under stress.

Nanostructured artificial nacre

Materials found in nature combine many inspiring properties such as sophistication, miniaturization, hierarchical organizations, hybridation, resistance and adaptability. Elucidating the basic components and building principles selected by evolution to propose more reliable, efficient and environment-respecting materials requires a multidisciplinary approach.

Biomimetism and bioinspiration as tools for the design of innovative materials and systems.

We combined photoactivated localization microscopy (PALM) with live-cell single-particle tracking to create a new method termed sptPALM. We created spatially resolved maps of single-molecule motions by imaging the membrane proteins Gag and VSVG, and obtained several orders of magnitude more trajectories per cell than traditional single-particle tracking enables. By probing distinct subsets of molecules, sptPALM can provide insight into the origins of spatial and temporal heterogeneities in membranes.

/pdf/high-density-mapping-of-single-molecule-trajectories-with-3bwbyt9o9u.pdf

High-density mapping of single-molecule trajectories with photoactivated localization microscopy

Ten years ago, we wrote a Review on lipid rafts and signalling in the launch issue of Nature Reviews Molecular Cell Biology. At the time, this field was suffering from ambiguous methodology and imprecise nomenclature. Now, new techniques are deepening our insight into the dynamics of membrane organization. Here, we discuss how the field has matured and present an evolving model in which membranes are occupied by fluctuating nanoscale assemblies of sphingolipids, cholesterol and proteins that can be stabilized into platforms that are important in signalling, viral infection and membrane trafficking.

Revitalizing membrane rafts: new tools and insights

Nature abounds with intricate composite architectures composed of hard and soft materials synergistically intertwined to provide both useful functionality and mechanical integrity. Recent synthetic efforts to mimic such natural designs have focused on nanocomposites, prepared mainly by slow procedures like monomer or polymer infiltration of inorganic nanostructures or sequential deposition. Here we report the self-assembly of conjugated polymer/silica nanocomposite films with hexagonal, cubic or lamellar mesoscopic order using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. Polymerization results in polydiacetylene/silica nanocomposites that are optically transparent and mechanically robust. Compared to ordered diacetylene-containing films prepared as Langmuir monolayers or by Langmuir-Blodgett deposition, the nanostructured inorganic host alters the diacetylene polymerization behaviour, and the resulting nanocomposite exhibits unusual chromatic changes in response to thermal, mechanical and chemical stimuli. The inorganic framework serves to protect, stabilize, and orient the polymer, and to mediate its function. The nanocomposite architecture also provides sufficient mechanical integrity to enable integration into devices and microsystems.

Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites

The actin cytoskeleton has been implicated in restricting diffusion of plasma membrane components. Here, simultaneous observations of quantum dot-labelled FcepsilonRI motion and GFP-tagged actin dynamics provide direct evidence that actin filament bundles define micron-sized domains that confine mobile receptors. Dynamic reorganization of actin structures occurs over seconds, making the location and dimensions of actin-defined domains time-dependent. Multiple FcepsilonRI often maintain extended close proximity without detectable correlated motion, suggesting that they are co-confined within membrane domains. FcepsilonRI signalling is activated by crosslinking with multivalent antigen. We show that receptors become immobilized within seconds of crosslinking. Disruption of the actin cytoskeleton results in delayed immobilization kinetics and increased diffusion of crosslinked clusters. These results implicate actin in membrane partitioning that not only restricts diffusion of membrane proteins, but also dynamically influences their long-range mobility, sequestration and response to ligand binding.

/pdf/actin-restricts-fcepsilonri-diffusion-and-facilitates-1twfe5sx22.pdf

Actin restricts FcepsilonRI diffusion and facilitates antigen-induced receptor immobilization.

A mechanically-induced color transition (''mechanochromism'') in polydiacetylene thin films has been generated at the nanometer scale using the tips of two different scanning probe microscopes. A blue-to-red chromatic transition in polydiacetylene molecular trilayer films, polymerized from 10,12-pentacosadiynoic acid (poly-PCDA), was found to result from shear forces acting between the tip and the poly-PCDA molecules, as independently observed with near-field scanning optical microscopy and atomic force microscopy (AFM). Red domains were identified by a fluorescence emission signature. Transformed regions as small as 30 nm in width were observed with AFM. The irreversibly transformed domains preferentially grow along the polymer backbone direction. Significant rearrangement of poly-PCDA bilayer segments is observed by AFM in transformed regions. The removal of these segments appears to be a characteristic feature of the transition. To our knowledge, this is the first observation of nanometer-scale mechanochromism in any material.

/pdf/first-observation-of-mechanochromism-at-the-nanometer-scale-4mbbnfnji4.pdf

First observation of mechanochromism at the nanometer scale

Polydiacetylenes (PDAs) form a unique class of polymeric materials that couple highly aligned and conjugated backbones with tailorable pendant sidegroups and terminal functionalities. They can be structured in the form of bulk materials, multilayer and monolayer films, polymerized vesicles, and even incorporated into inorganic host matrices to form nanocomposites. The resulting materials exhibit an array of spectacular properties, beginning most notably with dramatic chromogenic transitions that can be activated optically, thermally, chemically, and mechanically. Recent studies have shown that these transitions can even be controlled and observed at the nanometre scale. These transitions have been harnessed for the purpose of chemical and biomolecular sensors, and on a more fundamental level have led to new insights regarding chromogenic phenomena in polymers. Other recent studies have explored how the strong structural anisotropy that thes em aterials possess leads to anisotropic nanomechanical behaviour. These recen ta dvances suggest that PDAs could be considered as a potential component in nanostructured devices due to the large number of tunable properties. In this paper, we provide a succinct review of the latest insights and applications involving PDA. We then focus in more detail on our work concerning ultrathin films, specifically structural properties, mechanochromism, thermochromism, and in-plane mechanical anisotropy of PDA monolayers. Atomic force microscopy (AFM) and fluorescence microscopy confirm that films 1–3 monolayers thick can be organized into highly ordered domains,with the conjugated backbones parallel to the substrate. The number of stable layers is controlled by the head-group functionality. Local mechanical stress applied by AFM an dn ear-field optical probes induces the chromogenic transition in the film at the nanometre scale. The transition

https://alliance.seas.upenn.edu/~carpickg/dynamic/wordpress/wp-content/uploads/2014/01/Carpick_JCondMat_2004.pdf

Polydiacetylene films: a review of recent investigations into chromogenic transitions and nanomechanical properties

Time-of-flight laser resonance ionization is used to measure state-selective translational energies of neutral NO, CO, and metastable CO (${\mathrm{a}}^{3}$\ensuremath{\Pi}) desorbed from Pt(111) upon electron impact. A novel and dominant NO channel has a threshold of \ensuremath{\sim}6 eV and a peak translational energy of 0.05 eV. Lifetime calculations reveal a long-lived simple excitation (5${\mathrm{\ensuremath{\sigma}}}^{\mathrm{\ensuremath{-}}1}$). Dynamical calculations reproduce translational and rotational energy distributions and suggest that the excitation frees the hindered rotation of NO.

Alan R. Burns

Papers

Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites

Actin restricts FcepsilonRI diffusion and facilitates antigen-induced receptor immobilization.

First observation of mechanochromism at the nanometer scale

Polydiacetylene films: a review of recent investigations into chromogenic transitions and nanomechanical properties

Desorption by electronically stimulated adsorbate rotation