Supramolecular self-assembly of lipid derivatives on carbon nanotubes

Images of the assembly of surfactants and synthetic lipids on the surface of carbon nanotubes were obtained by transmission electron microscopy. Above the critical micellar concentration, sodium dodecyl sulfate (SDS) forms supramolecular structures made of rolled-up half-cylinders on the nanotube surface. Depending on the symmetry and the diameter of the carbon nanotube, we observed rings, helices, or double helices. Similar self-assemblies were also obtained with several synthetic single-chain lipids designed for the immobilization of histidine-tagged proteins. At the nanotube-water interface, permanent assemblies were produced from mixed micelles of SDS and different water-insoluble double-chain lipids after dialysis of the surfactant. Such arrangements could be further exploited for the development of new biosensors and bioelectronic nanomaterials.     

Synthesis of macrocyclic copolymer brushes and their self-assembly into supramolecular tubes

We report on an efficient route to design large macrocyclic polymers of controlled molar mass and narrow dispersity. The strategy is based on the synthesis of a triblock copolymer ABC, in which the long central block B is extended by two short A and C sequences bearing reactive antagonist functions. When reacted under highly dilute conditions, this precursor produces the corresponding macrocycle by intramolecular coupling of the A and C blocks. Chloroethyl vinyl ether was selected as the monomer for the central block B, because it can be readily derivatized into brushlike polymers by a grafting process. The corresponding macrocyclic brushes were decorated with polystyrene or randomly distributed polystyrene and polyisoprene branches. In a selective solvent for the polyisoprene branches, the macrocyclic brushes self-assemble into cylindrical tubes of up to 700 nanometers.     

Quantum superposition of macroscopic persistent-current states

Microwave spectroscopy experiments have been performed on two quantum levels of a macroscopic superconducting loop with three Josephson junctions. Level repulsion of the ground state and first excited state is found where two classical persistent-current states with opposite polarity are degenerate, indicating symmetric and antisymmetric quantum superpositions of macroscopic states. The two classical states have persistent currents of 0.5 microampere and correspond to the center-of-mass motion of millions of Cooper pairs.     

Entangling macroscopic diamonds at room temperature

Quantum entanglement in the motion of macroscopic solid bodies has implications both for quantum technologies and foundational studies of the boundary between the quantum and classical worlds. Entanglement is usually fragile in room-temperature solids, owing to strong interactions both internally and with the noisy environment. We generated motional entanglement between vibrational states of two spatially separated, millimeter-sized diamonds at room temperature. By measuring strong nonclassical correlations between Raman-scattered photons, we showed that the quantum state of the diamonds has positive concurrence with 98% probability. Our results show that entanglement can persist in the classical context of moving macroscopic solids in ambient conditions.     

Supramolecular Materials: Self-Organized Nanostructures

Miniaturized triblock copolymers have been found to self-assemble into nanostructures that are highly regular in size and shape. Mushroom-shaped supramolecular structures of about 200 kilodaltons form by crystallization of the chemically identical blocks and self-organize into films containing 100 or more layers stacked in a polar arrangement. The polar supramolecular material exhibits spontaneous second-harmonic generation from infrared to green photons and has an adhesive tape-like character with nonadhesive-hydrophobic and hydrophilic-sticky opposite surfaces. The films also have reasonable shear strength and adhere tenaciously to glass surfaces on one side only. The regular and finite size of the supramolecular units is believed to be mediated by repulsive forces among some of the segments in the triblock molecules. A large diversity of multifunctional materials could be formed from regular supramolecular units weighing hundreds of kilodaltons.     

Predictive self-assembly of polyhedra into complex structures

Predicting structure from the attributes of a material's building blocks remains a challenge and central goal for materials science. Isolating the role of building block shape for self-assembly provides insight into the ordering of molecules and the crystallization of colloids, nanoparticles, proteins, and viruses. We investigated 145 convex polyhedra whose assembly arises solely from their anisotropic shape. Our results demonstrate a remarkably high propensity for thermodynamic self-assembly and structural diversity. We show that from simple measures of particle shape and local order in the fluid, the assembly of a given shape into a liquid crystal, plastic crystal, or crystal can be predicted.     

Cavitation and the interaction between macroscopic hydrophobic surfaces

The interaction in water of neutral hydrocarbon and fluorocarbon surfaces, prepared by Langmuir-Blodgett deposition of surfactant monolayers, has been investigated. The attraction between these hydrophobic surfaces can be measured at separations of 70 to 90 nanometers and thus is of considerably greater range than previously found. Spontaneous cavitation occurred as soon as the fluorocarbon surfaces were brought into contact but occurred between the hydrocarbon surfaces only after separation from contact. The very long range forces measured are a consequence of the metastability of water films between macroscopic hydrophobic surfaces. Thus the hydrophobic interaction between macroscopic surfaces may not be related to water structure in the same way that the hydrophobic effect between nonpolar molecules is related to water structure.     

Entangled macroscopic quantum States in two superconducting qubits

We present spectroscopic evidence for the creation of entangled macroscopic quantum states in two current-biased Josephson-junction qubits coupled by a capacitor. The individual junction bias currents are used to control the interaction between the qubits by tuning the energy level spacings of the junctions in and out of resonance with each other. Microwave spectroscopy in the 4 to 6 gigahertzrange at 20 millikelvin reveals energy levels that agree well with theoretical results for entangled states. The single qubits are spatially separate, and the entangled states extend over the 0.7-millimeter distance between the two qubits.     

Templating organic semiconductors via self-assembly of polymer colloids

A route for producing semiconducting polymer blends is demonstrated in which a doped pi-conjugated polymer is forced into a three-dimensionally continuous minor phase by the self-assembly of colloidal particles and block copolymers. The resulting cellular morphology can be viewed as a high-internal phase polymeric emulsion. Compared with traditional blending procedures, this process reduces the percolation threshold for electrical conductivity by a factor of 10, increases the conductivity by several orders of magnitude, and simultaneously improves thermal stability. Following this route, new applications can be envisaged for semiconducting polymer blends that require only minimal concentrations of doped pi-conjugated polymer.     

Functional materials based on self-assembly of polymeric supramolecules

Self-assembly of polymeric supramolecules is a powerful tool for producing functional materials that combine several properties and may respond to external conditions. We illustrate the concept using a comb-shaped architecture. Examples include the hexagonal self-organization of conjugated conducting polymers and the polarized luminance in solid-state films of rodlike polymers obtained by removing the hydrogen-bonded side chains from the aligned thermotropic smectic phase. Hierarchically structured materials obtained by applying different self-organization and recognition principles and directed assembly form a basis for tunable nanoporous materials, smart membranes, preparation of nano-objects, and anisotropic properties, such as proton conductivity.     

Living cells as test tubes

The combination of specific probes and advanced optical microscopy now allows quantitative probing of biochemical reactions in living cells. On selected systems, one can detect and track a particular protein with single-molecule sensitivity, nanometer spatial precision, and millisecond time resolution. Metabolites, usually difficult to detect, can be imaged and monitored in living cells with coherent anti-Stokes Raman scattering microscopy. Here, we describe the application of these techniques in studying gene expression, active transport, and lipid metabolism.