Michael V. Lee

Challenges and breakthroughs in recent research on self-assembly

Abstract The controlled fabrication of nanometer-scale objects is without doubt one of the central issues in current science and technology. However, existing fabrication techniques suffer from several disadvantages including size-restrictions and a general paucity of applicable materials. Because of this, the development of alternative approaches based on supramolecular self-assembly processes is anticipated as a breakthrough methodology. This review article aims to comprehensively summarize the salient aspects of self-assembly through the introduction of the recent challenges and breakthroughs in three categories: (i) types of self-assembly in bulk media; (ii) types of components for self-assembly in bulk media; and (iii) self-assembly at interfaces.

Two-dimensional nanoarchitectonics based on self-assembly.

Top-down nanofabrication techniques, especially photolithography, have advanced nanotechnology to a point where system-process integration with bottom-up self-assembly is now required. Because most lithographic techniques are constrained to two-dimensional planes, investigation of integrated self-assembly systems should focus on two-dimensional organization. In this review, research on two-dimensional nanoartchitectonics is classified and summarized according to the type of interface used. Pattern formation following deposition of vaporized molecules onto a solid surface can be analyzed with high structural precision using scanning probe microscopy under ultra high vacuum. Transitions of adsorbed phases and adjustment of pattern mismatch by conformational changes of adsorbed molecules are discussed, in addition to the forces constraining pattern formation, i.e., two-dimensional hydrogen bond networks, van der Waals forces, and molecule-surface interactions. Molecular deposition at a liquid-solid interface broadens the range of molecules that can be investigated. The more complex molecules discussed in this work are C(60)-fullerene derivatives and designer DNA strands. Gas-liquid interfaces, e.g. between air and water, allow dynamic formations that can adjust to molecular conformational changes. In this case, any resulting patterns can be modulated by varying conditions macroscopically. Using flexible molecules at the fluid air-water interface also permits dynamic operation of molecular machines by macroscopic mechanical motion, thus enabling, hand-operated nanotechnology.

Langmuir Nanoarchitectonics: One-Touch Fabrication of Regularly Sized Nanodisks at the Air–Water Interface

In this article, we propose a novel methodology for the formation of monodisperse regularly sized disks of several nanometer thickness and with diameters of less than 100 nm using Langmuir monolayers as fabrication media. An amphiphilic triimide, tri-n-dodecylmellitic triimide (1), was spread as a monolayer at the air-water interface with a water-soluble macrocyclic oligoamine, 1,4,7,10-tetraazacyclododecane (cyclen), in the subphase. The imide moieties of 1 act as hydrogen bond acceptors and can interact weakly with the secondary amine moieties of cyclen as hydrogen bond donors. The monolayer behavior of 1 was investigated through π-A isotherm measurements and Brewster angle microscopy (BAM). The presence of cyclen in the subphase significantly shifted isotherms and induced the formation of starfish-like microstructures. Transferred monolayers on solid supports were analyzed by reflection absorption FT-IR (FT-IR-RAS) spectroscopy and atomic force microscopy (AFM). The Langmuir monolayer transferred onto freshly cleaved mica by a surface touching (i.e., Langmuir-Schaefer) method contained disk-shaped objects with a defined height of ca. 3 nm and tunable diameter in the tens of nanometers range. Several structural parameters such as the disk height, molecular aggregation numbers in disk units, and 2D disk density per unit surface area are further discussed on the basis of AFM observations together with aggregate structure estimation and thermodynamic calculations. It should be emphasized that these well-defined structures are produced through simple routine procedures such as solution spreading, mechanical compression, and touching a substrate at the surface. The controlled formation of defined nanostructures through easy macroscopic processes should lead to unique approaches for economical, energy-efficient nanofabrication.

Studies on Langmuir monolayers of polyprenyl phosphates towards a possible scenario for origin of life.

Although some biological components such as RNA are believed to play a crucial role in the processes which led to the formation of the first living systems, we cannot ignore the importance of lipids in the genesis of cell membranes. To answer the fundamental question of what the oldest cell-forming components were the Ourisson/Nakatani group has extensively investigated the origin of lipids and they have proposed polyprenyl phosphates and related molecules as plausible candidates for precursors of modern lipids. These molecules have been demonstrated as being capable of forming vesicle structures, and this feature has been extended to preparation of Langmuir monolayers of polyprenyl phosphates in collaboration with the Ourisson/Nakatani group. In this review, after a brief outline of chemical evolution of cell components, we summarize research on Langmuir monolayers of polyprenyl phosphates and related molecules. Two topics are described: the evaluation of any reinforcing effects and the determination of interfacial acid dissociation. Rules governing reinforcing effects in molecular structures and unusual shifts of acid dissociation constants at interfaces were established. Finally, we propose a revised possible scenario of how the first cell-like membranes formed based on the former results.

Characteristic IR C=C stretch enhancement in monolayers by nonconjugated, noncumulated unsaturated bonds.

Control over and understanding of single-molecule covalent coatings becomes increasingly important in tailoring surfaces during the fabrication of nanoscale electrical or optical elements, such as organic field-effect transistors and light-emitting devices as well as microelectromechanical systems as the relevant feature sizes decrease. In this work, we develop a model based on IR spectra from public databases and DFT calculations that can be used to semiquantitatively assess the level of double bonds in monolayer coatings. We use the model to show the enhancement of the C=C vibrational mode due to silicon substitution and also from additional unsaturated bonds. Simple models for other functional groups in organic monolayers could be produced similarly.