Nanoarchitectonics Revolution and Evolution: From Small Science to Big Technology

Abstract

Along with the progresses of material syntheses, the importance of structural regulation is realized to rationally improve the efficiencies and specificities in target functions. Small science is necessary for advanced material systems. A novel concept, nanoarchitectonics, to combine nanotechnology with the other scientific disciplines to synthesize a functional material system with contributions of small objects, nano-units, is recently proposed. Based on facts and knowledge in nanoscale objects explored by nanotechnology, functional material systems are constructed using nano-units with the aid of the other research fields, such as organic chemistry, supramolecular chemistry, materials science, and biology. The introduction of nanoarchitectonics essences to material construction can produce unusual functional systems, such as brain-like information processing based on atomic-level reactions, diffusions, and aggregations. Probe-tip-mediated organic reactions are also possible with precise site selectivity. The coupling of equilibrium self-assemblies and non-equilibrium fabrication processes results in variously structured and hierarchical functional structures even from simple 0D nano-units such as fullerenes. Especially, interfacial nanoarchitectonics directly bridge nanoscopic functions and macroscopic actions, including facile contact with nanostructures and living cells. This review article overviews nanoarchitectonics from origin to future, from atoms to materials, and from small science to big technology.

Keywords: interfaces; living cells; molecular machines; nanoarchitectonics; nanotechnology; self-assembly.

Figure 1

The nanoarchitectonics approaches to produce the functional material system upon structural construction from nano‐units through combining nanotechnology concept and the other research fields, such as organic chemistry, supramolecular chemistry, materials science, and bio‐related technology.

Figure 2

Historical background on paradigm shifts from nanotechnology to nanoarchitectonics.

Figure 3

Nanoarchitectonics procedures including various energy consuming processes in step‐wise orders and/or harmonizing fashions as well as self‐assembly at equilibrium.

Figure 4

Major working size region for nanoarchitectonics similar to conversion point from non‐living entities to living creatures.

Figure 5

Basic design of typical atomic switch with Ag₂S electrode and a Pt electrode separated with a gap of about 1 nm where the formation of ten atom‐level silver cluster through diffusion and rearrangement of silver atoms leads to electrical bridging between two electrodes to make the device switching on.

Figure 6

Inorganic synaptic devices with short‐term plasticity and long‐term potentiation capabilities upon electrochemical reactions and atom diffusion/aggregation in atomic switch.

Figure 7

Site‐specific substitution of Br atoms by a fullerene molecule with an SPM tip at a graphene 3D nanotape on a Au(111) surface.

Figure 8

Synthesis of Sondheimer–Wong diyne from 6,13‐dibromopentaleno[1,2‐b:4,5‐b′]dinaphthalene using a probe tip on a Cu(111) surface covered with NaCl ultra‐thin film at 4.3 K.

Figure 9

Precipitation of 0D single‐element molecular units, fullerenes (C₇₀), at liquid–liquid interface to give integral structures, such as hole on cubes.

Figure 10

Hierarchic pore‐rod‐cube structures nanoarchitected through crystallization of C₇₀ molecules at the interface between tert‐butyl alcohol and mesitylene, and the collected cubes followed by exposure to isopropanol at 25 °C.

Figure 11

Transformation from fullerene (C₆₀ and C₇₀ mixture) microtubs to fullerene microhorns upon solvent evaporation and their particle trap capability.

Figure 12

Bio‐like metamorphosis and differentiation from simple chemical objects, fullerene derivatives, pentakis(4‐dodecylphenyl)fullerene), and pentakis(phenyl)fullerene, at isopropyl alcohol/toluene interface, upon the addition of non‐equilibrium event of temporal irradiation of ultrasonic to self‐assembling process.

Figure 13

Significantly extended catenane linkages from hydrogen‐bond‐capable molecular units where supramolecular rosettes were assembled into supramolecular ring structures of toroids and were further entangled into catenane motif.

Figure 14

Hierarchical integration of conductive polymers with MOF structures using LbL assembly of two kinds of colloidal assemblies: anionic PANI/PSS colloidal particles and ZIF‐8 colloidal particles modified with cationic PAH.

Figure 15

Multi‐dimensional nanoarchitectonics PtNi multicube structures through autocatalytic effect to form PtNi bimetallic nuclei, epitaxial growth, and assembly.

Figure 16

Cage‐bell nanoarchitectonics for efficient Pt catalysis in oxygen reduction reaction.

Figure 17

Dynamic changes of DNA‐based complex structures for sensitive mercury detections through quick transformation of the original co‐assemblies with organic semiconductor into a metallo‐DNA duplex with mercury.

Figure 18

Accumulation of nano‐actions at interfaces as effective ways to induce macroscopic motions: A) motional control of liquid droplet by isomerization of monomolecular layer of photo‐active molecules and B) deformation of cantilever upon group actions of molecular machines.

Figure 19

Mechanical compression and expansion of a Langmuir monolayer of molecular machines (steroid cyclophane molecules) embedded at the air–water interface for reversible capture and release of guest molecules from water subphase, respectively.

Figure 20

Submarine emission mechanism upon orientational changes of coordination complex molecules embedded on water as a Langmuir monolayer by external macroscopic forces.

Figure 21

Investigations on conformational changes of a bisbinaphthyldurene molecule having two binaphthyl groups connected through a central durene moiety theoretically and experimentally at various environments including air–solid interface at low temperature under high vacuum and the air–water interface under ambient conditions.

Figure 22

Required forces estimated for various molecular events.

Figure 23

Application of macroscopic mechanical forces laterally to a Langmuir monolayer of N‐substituted cyclen, containing a 1,4,7,10‐tetraazacyclododecane core with four cholesteric side arms as molecular receptor, for pressure‐dependent chiral recognition of amino acids in aqueous subphase.

Figure 24

Three major modes of molecular recognition: A) one state mode, B) switching more, and C) tuning mode.

Figure 25

Interfacial culture system to human mesenchymal stem cells using perfluorooctane as organic phase where neural differentiation was promoted upon delicate interaction with the formed protein assembly.

Figure 26

Culture system for human mesenchymal stem cells both capable of enhanced self‐renewal properties and retained multipotency using a solid interface covered with aligned fullerene nanowhiskers by the LB method.

Figure 27

Soft nanoarchitectonics approach using polymer brush grown from TiO₂ surface for promoted osseointegration upon slow delivery of Sr²⁺ ions.

Figure 28

Fabrication of cell‐recognizing materials using HeLa cells as sacrificial template using silica/halloysite composites.

Figure 29

Layered hybrid systems with lipid bilayer membrane including motor protein adenosine triphosphate (ATP) synthase and thin film of gold nanoparticles on a glass substrate for conversion from adenosine diphosphate (ADP) to ATP upon formation of SAM on the surface of the gold nanoparticles accompanied with proton generation.

Figure 30

Summary and possible future directions of nanoarchitectonics.