Capillary-force-induced collapse lithography for controlled plasmonic nanogap structures.

The capillary force effect is one of the most important fabrication parameters that must be considered at the micro/nanoscale because it is strong enough to deform micro/nanostructures. However, the deformation of micro/nanostructures due to such capillary forces (e.g., stiction and collapse) has been regarded as an undesirable and uncontrollable obstacle to be avoided during fabrication. Here, we present a capillary-force-induced collapse lithography (CCL) technique, which exploits the capillary force to precisely control the collapse of micro/nanostructures. CCL uses electron-beam lithography, so nanopillars with various shapes can be fabricated by precisely controlling the capillary-force-dominant cohesion process and the nanopillar-geometry-dominant collapse process by adjusting the fabrication parameters such as the development time, electron dose, and shape of the nanopillars. CCL aims to achieve sub-10-nm plasmonic nanogap structures that promote extremely strong focusing of light. CCL is a simple and straightforward method to realize such nanogap structures that are needed for further research such as on plasmonic nanosensors.

Hierarchical Self-Assembly of Poly-Pseudorotaxanes into Artificial Microtubules.

Hierarchical self-assembly of building blocks over multiple length scales is ubiquitous in living organisms. Microtubules are one of the principal cellular components formed by hierarchical self-assembly of nanometer-sized tubulin heterodimers into protofilaments, which then associate to form micron-length-scale, multi-stranded tubes. This peculiar biological process is now mimicked with a fully synthetic molecule, which forms a 1:1 host-guest complex with cucurbit[7]uril as a globular building block, and then polymerizes into linear poly-pseudorotaxanes that associate laterally with each other in a self-shape-complementary manner to form a tubular structure with a length over tens of micrometers. Molecular dynamic simulations suggest that the tubular assembly consists of eight poly-pseudorotaxanes that wind together to form a 4.5 nm wide multi-stranded tubule.

Fuel-Driven Transient Crystallization of a Cucurbit[8]uril-Based Host-Guest Complex.

Transient self-assembling systems often suffer from accumulation of chemical wastes that interfere with the formation of pristine self-assembled products in subsequent cycles. Herein, we report the transient crystallization of a cucurbit[8]uril-based host-guest complex, preventing the accumulation of chemical wastes. Base-catalyzed thermal decarboxylation of trichloroacetic acid that chemically fuels the crystallization process dissolves the crystals, and produces volatile chemical wastes that are spontaneously removed from the solution. With such self-clearance process, no significant damping in the formation of the crystals was observed. The morphology and structural integrity of the crystals was also maintained in subsequent cycles. The concept may be further extended to obtain other temporally functional materials, quasicrystals, etc., based on stimuli-responsive guest molecules.

Smart SERS Hot Spots: Single Molecules Can Be Positioned in a Plasmonic Nanojunction Using Host-Guest Chemistry.

Single-molecule surface-enhanced Raman spectroscopy (SERS) offers new opportunities for exploring the complex chemical and biological processes that cannot be easily probed using ensemble techniques. However, the ability to place the single molecule of interest reliably within a hot spot, to enable its analysis at the single-molecule level, remains challenging. Here we describe a novel strategy for locating and securing a single target analyte in a SERS hot spot at a plasmonic nanojunction. The "smart" hot spot was generated by employing a thiol-functionalized cucurbit[6]uril (CB[6]) as a molecular spacer linking a silver nanoparticle to a metal substrate. This approach also permits one to study molecules chemically reluctant to enter the hot spot, by conjugating them to a moiety, such as spermine, that has a high affinity for CB[6]. The hot spot can accommodate at most a few, and often only a single, analyte molecule. Bianalyte experiments revealed that one can reproducibly treat the SERS substrate such that 96% of the hot spots contain a single analyte molecule. Furthermore, by utilizing a series of molecules each consisting of spermine bound to perylene bisimide, a bright SERS molecule, with polymethylene linkers of varying lengths, the SERS intensity as a function of distance from the center of the hot spot could be measured. The SERS enhancement was found to decrease as 1 over the square of the distance from the center of the hot spot, and the single-molecule SERS cross sections were found to increase with AgNP diameter.

Solid lithium electrolytes based on an organic molecular porous solid.

A new type of solid lithium-ion conducting electrolytes prepared by incorporation of Li(+) ions into a cucurbit[6]uril (CB[6])-based organic molecular porous solid shows high Li(+) ion conductivity (∼10(-4) S cm(-1)) and mobility (transference numbers, tLi(+) = 0.7-0.8). In addition, the solid electrolytes show excellent, thermally stable performance even after several temperature cycles.