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[Katsuhiko Ariga](https://orcid.org/0000-0002-2445-2955)

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Responsive materials nanoarchitectonics at interfacesReceived: 21 March 2024 - Revised: 21 April 2024 - Accepted: 23 April 2024DOI: 10.1002/rpm.20240011REV I EW ART I CLEResponsive materials nanoarchitectonics at interfacesKatsuhiko Ariga1,21Research Center for Materials Nanoarchitectonics,National Institute for Materials Science (NIMS),Tsukuba, Japan2Graduate School of Frontier Sciences, TheUniversity of Tokyo, Kashiwa, JapanCorrespondenceKatsuhiko Ariga.Email: ARIGA.Katsuhiko@nims.go.jpAbstractAdvanced materials could perform functions in response to external stimuli. Theseare responsive materials. In order for us to develop advanced functional systemswith a good responsive nature, we need to create a methodology that goes one stepfurther. It is the artificial architecture of functional material systems based on theknowledge of nanotechnology. The task will be fulfilled by the new concept ofnanoarchitectonics. Nanoarchitectonics integrates nanotechnology with variousmaterial sciences, basic chemistry, microfabrication techniques, and biologicalprocesses to architect functional material systems from atomic, molecular, andnanomaterial units. This review will deal with the nanoarchitectonics of responsivematerials related with phenomena at interfaces. In order to demonstrate theeffectiveness of responsive materials nanoarchitectonics at interfaces for functionalsystems of various sizes, this review article is organized by size for variousfunctional systems. Specifically, this review has grouped them into (i) molecularlevel response, (ii) nanodevice level response, (iii) material level response, and (iv)living cell level response. If the social demand for these materials is fully recog-nized, such development is expected to efficiently progress. This review articlewould play a role in stimulating such development.Keywordsinterface, living cell, nanoarchitectonics, nanodevice, responsive materials1 | INTRODUCTIONThe development of humankind is heavily dependent on thedevelopment of materials. Since time immemorial, mankindhas extracted materials from nature and used them. Subse-quent developments in various sciences have made it possibleto create materials that perform desired functions. Many earlymaterials were used to form structures or for simple tasks.However, more advanced materials began to be created thatcould perform functions in response to external stimuli. Theseare responsive materials.[1–5] Various materials have beenshown to function as responsive materials with various pur-poses including sensing,[6–8] energy,[9–11] environment,[12–14]device,[15–17] and biomedical applications.[18–20] In the pro-cess, it has become clear that it is not thematerial itself, but theprecision of its precise structure that leads to more advancedfunctions.A major factor that has paved the way for such a path isinitiation of nanotechnology. Nanotechnology has made itpossible to observe and manipulate structures at the atomic,molecular, and nano-level.[21–23] It has alsomade it possible tocharacterize nano-level properties.[24–26] As a result, it hasbecome clear that there are unique phenomena such as quan-tum effects at the nanoscale that are different from macro-scopic phenomena.[27,28] It has been found that materialsexhibiting superior functionality have rational structures at thenano-level.[29,30] In particular, the structure of functionalsystems in the biological world has been found to be a superborganization of molecular units, exhibiting highly character-istic and highly efficient functions. In biological functionalThis is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the originalwork is properly cited.© 2024 The Authors. Responsive Materials published by John Wiley & Sons Australia, Ltd on behalf of Southeast University.Responsive Materials. 2024;2:e20240011. wileyonlinelibrary.com/journal/rpm2 - 1 of 16https://doi.org/10.1002/rpm.20240011https://doi.org/10.1002/rpm.20240011https://orcid.org/0000-0002-2445-2955mailto:ARIGA.Katsuhiko@nims.go.jphttps://orcid.org/0000-0002-2445-2955http://creativecommons.org/licenses/by/4.0/https://onlinelibrary.wiley.com/journal/28348966https://doi.org/10.1002/rpm.20240011http://crossmark.crossref.org/dialog/?doi=10.1002%2Frpm.20240011&domain=pdf&date_stamp=2024-05-11systems, functional molecules often line up to flow or accu-mulate information, energy, and electrons in specific di-rections in response to external stimuli. For example,photosynthesis[31] and signal transduction[32] can be regardedas extremely well designed responsive materials.In order for us to develop advanced functional systemslike those found in living organisms, we need to create amethodology that goes one step further. It is the artificialarchitecture of functional material systems based on theknowledge of nanotechnology. The task will be fulfilled bythe new concept of nanoarchitectonics (Figure 1).[33,34]While nanotechnology was originated by Richard Feynmanin the middle of the 20th century,[35,36] nanoarchitectonicswas proposed by Masakazu Aono in the beginning of the21st century.[37] Nanoarchitectonics can be considered apost-nanotechnology concept.[38]Rather than an entirely new concept, nanoarchitectonicscombines existing research fields. Nanoarchitectonics in-tegrates nanotechnology with various material sciences,basic chemistry, microfabrication techniques, and biologicalprocesses to architect functional material systems fromatomic, molecular, and nanomaterial units.[39,40] Materialsconstruction by nanoarchitectonics strategy includes atomicand molecular manipulation, physical and chemical con-version, self-assembly and self-organization, orientation andorganization by external fields, nano- and micro-levelfabrication, biochemical and biological processes, whichare selected and combined during the nanoarchitectonicsprocesses.[41–43] This methodology is independent of thesubstance and its application. It is used to construct a varietyof functional systems using a variety of substances includingmaterials synthesis,[44–46] structure fabrication,[47–49] basicphysics,[50–52] catalysis,[53–55] sensors,[56–58] devices,[59–61]energy,[62–64] environmental,[65–67] biochemistry,[68–70] andbiomedical issues.[71–73] Originally, materials are composedof atoms and molecules. Therefore, the concept of nano-architectonics can be considered to lead to the creation of allmatter. It is considered to be regarded as the method foreverything in materials science,[74,75] which corresponds tothe theory of everything in physics.[76]The creation possibilities of responsive materials bynanoarchitectonics would expand to a very large area.Therefore, it is impossible to discuss all of them here.Therefore, this review will deal with the nanoarchitectonicsof responsive materials related with phenomena at interfaces.At solid interfaces, atoms and molecules can be preciselyobserved and evaluated.[77,78] At liquid interfaces, moleculesand materials can move and accumulate.[79,80] In some as-pects, it is easier to approach the consideration of a materialsystem trapped in a two-dimensional system than to examinea material system spread out in three-dimensional space. Inorder to demonstrate the effectiveness of responsive mate-rials nanoarchitectonics (MANA) at interfaces for functionalsystems of various sizes, the following sections are orga-nized by size for various functional systems. Specifically,this review has grouped them into (i) molecular levelresponse, (ii) nanodevice level response, (iii) material levelresponse, and (iv) living cell level response. The examplesdiscussed are not necessarily the most advanced or repre-sentative of the fields. Some typical examples are discussedto show that they can be applied from the atomic/molecularlevel to the living cell level.2 | MOLECULAR LEVEL RESPONSEConsider building a stimulus-response system at the smallestlevel of structure. This would be a molecular machine inwhich each molecule moves like a machine in response tostimuli.[81–83] However, in the early days of molecular ma-chine research, the behavior of a molecular machine dis-solved in solution was mainly evaluated as the sum of itshuge molecules. Later, with the advancement of nanotech-nology, it became possible to actually observe and evaluatethe movement of molecular machines. Successful examplesof this realization are the development of nanocars[84,85] andnanocar race.[86,87] From the viewpoint of nano-architectonics, it is significant to examine a system in whichseveral molecules work together, rather than the movementof a single molecule.One such example was reported by Moresco and co-workers who demonstrated collective rotational transmissionbetween three molecular gears.[88] Thus, the transmission ofrotation along a row of molecular gears is an essential elementin the construction of molecular mechanical machines. First,an important condition is that the molecular gears must movestably. In order to stably drive themolecular gear train at the tipof a scanning tunneling microscope (STM), each gear mole-culemust be stably anchored to ametal surface. The anchoringrequired for immobilization is facilitated by the radical state ofthe molecules induced by dissociation reactions. That such anopen radical state in the nucleus of star-shaped pentaphe-nylcyclopentadiene is favorable for anchoring was alsodemonstrated by density functional theory calculations. ToF I GURE 1 Outline of nanoarchitectonics concept.2 of 16 - RESPONSIVE MATERIALS 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licenseenable the transmission of motion by STM manipulation, themolecular gear requires a functional group to ensure interac-tion with the tip. In the reported system, it was found to beeffective to place a tert-butyl group on one tooth end of thegear. The presence of a tert-butyl group is not only advanta-geous for molecular manipulation by the tip, but also formonitoring gear rotation. By manipulating it as a screwdriver,a step was created in the rotational transmission between thethree meshing gears (Figure 2). When rotated counterclock-wise from the driver (green), follower 1 (blue) rotated clock-wise, while follower 2 (yellow) rotated counterclockwise atthe same time. The series of behaviors and their observationrequire a very specific energy pathway on the ground statepotential energy surface. Furthermore, the effects are inter-dependent. The steric tert-butyl tag is advantageous formanipulation by the tip and stabilizes the gear. At the sametime, however, it prevents further transmission of rotation. Forthe development of molecular mechanical machines such asmechanical calculators, the controllability of the rotation of alarge number of gears in a train is particularly important.The electron beam can also be used as a stimulus toinduce chemical reactions in molecules, which can then beprecisely observed. Lungerich and coworkers demonstratedthat electron beams can be used for synthesis.[89] The for-mation of double-hole fullerene-porphyrin cage structuresfrom benzoporphyrin precursors deposited on graphene wasobserved and studied in detail using single molecule, atomicresolution, time-resolved transmission electron microscopy(Figure 3). The ability of the hybrid to host up to two leadatoms was demonstrated through real-time imaging analysis.The dynamics of the lead-lead bonding motif in this exoticorganometallic cage structure was also analyzed and subse-quently examined. After discussion, including a simulationstudy, it was concluded that the secondary electrons thataccumulate around the irradiated region may also beresponsible for the chemical reaction. This means that notonly the fast primary electrons, but also the much slowersecondary electrons in the beam shadow must be taken intoaccount in the chemical transformation. Although under-standing of fast electron-induced molecular reactions is stillin its infancy, cinematic observations such as these canreveal a great deal. Single-molecule atomic-resolution time-resolved electron microscopy is a powerful tool for thispurpose. It will also provide information on the kind ofsynthetic reactions that can be expected from focused elec-tron beam-induced reactions. In addition, understanding ra-diation chemistry at the molecular level will have a profoundimpact on the design and fabrication of well-defined topo-logical nanostructures using electron beam lithographytechniques. It will also make a significant contribution tonanoarchitectonics at the molecular level.In terms of the induction of organic reactions by externalstimuli and detailed observation, reactions can be controlledby stimuli such as the application of local voltage from the tipof a probe microscope. This is also called local probe chem-istry.[90,91] Kawai, Kubo, Foster, and co-workers have com-bined low-temperature scanning tunneling microscopy withdensity functional theory calculations to study dehy-droazulene units in three-dimensional organometallic com-pounds on Ag(111).[92] Target compounds on Ag(111) using acombination of low-temperature scanning tunneling micro-scopy and density functional theory calculations. In this sys-tem, a reversible chiral switch of dehydroazulene units isinduced by the application of a local probe-induced structuralisomerization large bias voltage. The application of a tip-induced voltage pulse results in the formation of diradicalspecies by successive homolysis of the two C-Br bonds of thenaphthyl group (Figure 4). It is then converted to the chiraldehydroazulene moiety. The delicate balance of the reactionrate between the diradical and the two stereoisomers can becontrolled by the in-line arrangement of the tip and molecularunit. The result is a controlled local probe structural isomeri-zation of the azulene to azulene and azulene to diradical. Thediradical moiety hosts an open-shell singlet that can undergoan inelastic spin transition from antiferromagnetic to ferro-magnetic. Theoretical calculations suggest that the singletundergoes an inelastic spin transition to a ferromagneticallycoupled triplet state. Calculations of the energy barrier toisomerization also prove that isomerization does not occur atlow temperatures without the influence of the tip. The highdegree of chiral control of the dehydroazulene sequence bytip-induced isomerization was also demonstrated. Molecularnanoarchitectonics with such detailed structural observationsprovides a means by which the structure of units of moleculararrays can be rationally controlled. The structural control ofsuch localized molecular arrays and the analysis of theirfunctional properties will greatly contribute to the develop-ment of molecular optical, electronic, and magnetic devicesF I GURE 2 Rotational transmission between the meshing gears inwhich the driver (green) rotated counterclockwise, follower 1 (blue)rotated clockwise, while follower 2 (yellow) rotated counterclockwise atthe same time. Reproduced with permission.[88] 2020, AmericanChemical Society.RESPONSIVE MATERIALS - 3 of 16 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensebased on localized molecular array structures. In addition, tip-based vertical systematic isomerization is important for ad-vances in nanochemistry and molecular nanoarchitectonics,where molecular systems are fabricated molecule bymolecule.The stimulus of atomic manipulation by the tip of a probemicroscope can control the physical properties of nano-materials. For example, the control of magnetic topologicalstates by spin polarization in extended π-carbon systems hasgreat potential for spintronics applications. Foster, Kawai, andco-workers used low-temperature scanning tunneling micro-scopy to observe and manipulate the spin polarization in realspace in a heteroatom-substituted system.[93] Because Siatoms are strongly bound to the B site, resulting in largecorrugation amplitudes, their atomic manipulation can causesignificant changes in the electronic properties of boron-substituted graphene nanoribbons. Therefore, they attemptedto remove Si atoms by vertical manipulation with a tipF I GURE 3 The double-hole fullerene-porphyrin cage structures with ability of the hybrid to host up to two lead atoms observed using single molecule,atomic resolution, time-resolved transmission electron microscopy. Reproduced with permission.[89] 2023, Springer-Nature.4 of 16 - RESPONSIVE MATERIALS 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License(Figure 5). First, after positioning the tip at the Si site, the Zfeedback of the tunnel junction was deactivated. Then, the tipwas moved close enough to obtain a single-atom conductancegap and then retracted. After removal of Si atoms, a brick-likecontrast appeared around the boron sites in the STM topog-raphy. This image was very different from boron-substitutedgraphene nanoribbons formed directly on Au(111) or onAuSiX layers without adsorbed Si atoms. A clear Kondoresonance peak appeared, which was further split by applyinga 12 Tmagnetic field. Thismagnetic state can be relayed alongthe longitudinal axis of the graphene nanoribbon by sequentialremoval of Si atoms. In otherwords, thismanipulation processcan be repeated while effectively moving spin sites along thelongitudinal axis of boron-substituted graphene nanoribbon.The result is local-probe spin engineering. This demonstrationmay point the way to the control of spin states in quantummaterials.3 | NANODEVICE LEVEL RESPONSEVarious devices consist of a mechanism in which theresponse such as the current flowing in a circuit changes inresponse to a signal. Molecular switches, in which moleculesplay the role of the switch part, continue to be studied asideal systems for ultra-small devices.[94,95] The switch partof the circuit, in which clusters of atoms are formed, is beingstudied as an atomic switch.[96,97] In any case, attempts arebeing made to develop stimulus-responsive devices throughatomic and molecular nanoarchitectonics. Typical examplesare given below.Tsuruoka and co-workers investigated resistance changememory using silver ion-conducting solid polymer electro-lytes.[98] This is the first report of an electrochemical atomicswitch realized using organic materials. A simple Ag/solid-state polyelectrolyte/Pt structure containing a polyethyleneoxide-silver perchlorate complex exhibited bipolar resistanceswitching under bias voltage sweep (Figure 6). The behaviorwas analyzed by electrical conductivity, glass transitiontemperature, transport number, and cyclic voltammetrymeasurements. The results show that the observed switchingbehavior is the result of the formation and dissolution of AgF I GURE 4 Formation of diradical species by successive homolysis of the two C-Br bonds of the naphthyl group though the application of a tip-induced voltage pulse. Reproduced under terms of the CC-BY license.[92] 2023, Springer-Nature.F I GURE 5 Removal of Si atoms by vertical manipulation with a tipform boron-substituted graphene nanoribbons formed directly onAu(111)/AuSiX layers resulting in clear Kondo resonance peak.Reproduced with permission.[93] 2022, American Chemical Society.RESPONSIVE MATERIALS - 5 of 16 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensemetal filaments in the polymer electrolyte membrane byelectrochemical reactions. When a positive bias is applied tothe Ag electrode in the first sweep cycle, the Agþ and ClO4−ions in the electrolyte membrane move toward the Pt and Agelectrodes, respectively. In addition, some of the Ag atoms atthe Ag-electrolyte interface are oxidized to Agþ ions by theanodic dissolution reaction Ag → Agþ þ e−. Ag nuclei thengrow preferentially toward the opposite electrode. Eventu-ally, a metal filament is formed between the two electrodes.This filament formation leads to a low-resistance (ON) stateof the cell. At this point, it is inferred that the thinnest part ofthe metal filament is only a few nanometers in diameter, asthe cell exhibits an ON resistance on the order of kΩ. Thedevice exhibits an ON/OFF resistance ratio in excess of 105.It also exhibits a programming speed in excess of 1 μs and aretention time in excess of 1 week. Such polymer electrolyte-based electrochemical devices are expected to be particularlysuitable for flexible switch and memory applications.Mallik, Tsuruoka, Nayak, and co-workers studied trip-tycene azo-polymers as switch materials for atomic switches(Figure 7).[99] The noncompliant structure of the triptycenemotif in polymers causes inefficient packing of the polymerchain. This results in microporosity in the polymer matrix,which is favorable for metal filament development. Theresistive switching properties of triptycene azo-polymerswere investigated by current-voltage measurements basedon current atomic force microscopy. In particular, volatileand nonvolatile switching was demonstrated depending onthe amplitude of the bias voltage and the sweep cycle.Repeated voltage sweeps with varying voltage applicationinterval time resulted in a transition in switching behaviorfrom volatile to nonvolatile. In other words, repeated voltagesweeps lead to a short-term memory to long-term memorytransition. This behavior is supposed to mimic the learningprocess of the human brain. The low-resistance state is foundto result from the quantization of conductance by an integerfactor of a single atomic point contact in the Ag filamentformed between the current atomic force microscope tip andthe Ag electrode. The switching time from the high-resistance state to the low-resistance state decreases expo-nentially as the amplitude of the voltage pulse increases.This suggests that the nucleation of metal atoms is likely arate-limiting process. These results indicate that atomicswitches based on triptycene azo polymers have great po-tential for organic neuromorphic electronics.Field-mediated neurotransmission due solely to extracel-lular field effects has been postulated in biological synapticsystems. Mimicking this, Mishra, Nayak, and co-workersdemonstrated field-mediated signal transduction to low-biasstimuli using an Ag2S gap-type atomic switch(Figure 8).[100] In other words, they demonstrated ephaptictransmission solely by electric field effects in an AgS-gapatomic switch. The gap structure, which mimics a synapticgap, is realized by placing a Pt-coated atomic force micro-scope tip on the AgS thin film with controlled contact forces.The hysteresis increase corresponding to input energies fromF I GURE 6 An electrochemical atomic switch with Ag/solid-state polyelectrolyte/Pt structure containing a polyethylene oxide-silver perchloratecomplex where a metal filament can be formed between the two electrodes. Reproduced with permission.[98] 2010, Wiley-VCH.6 of 16 - RESPONSIVE MATERIALS 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License10 to 1000 pJ was observed. Signal transduction at biologicalsynapses can occur when local electric fields generated atpresynaptic terminals induce depolarization and hyperpolar-ization of postsynaptic terminals. Although not strong enoughto mediate synaptic activation, they can affect neighboringcells and create waves of activation throughout the network.Similarly, at an atomically switched synapse, the subthresholdpotential before electrochemical precipitation causes currentflow solely due to field effects through the high-resistancetunnel gap. In systems under weak activation, the current isF I GURE 7 An atomic switch with triptycene azo-polymers as switching media with favorable development of metal filament development uponinefficient packing of the polymer chain. Reproduced with permission.[99] 2022, Royal Society of Chemistry.F I GURE 8 Field-mediated neurotransmission due solely to extracellular field in biological synaptic systems (left) and field-mediated signaltransduction to low-bias stimuli using an Ag2S gap-type atomic switch (right). Reproduced with permission.[100] 2024, Elsevier.RESPONSIVE MATERIALS - 7 of 16 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensesmall, but indicates that there is communication between thetwo terminals that has the potential to modulate the next signalresponse. This can modulate the spike timing activity of theneural network by synchronizing spatially distant sites. This isthe basic synaptic behavior for all neurotransmission. Thecomplex transmissions and interactions that occur in thesynaptic cleft design the memory patterns of the human brainand create perceptions unique to each individual. This systemis an important exemplar for the development of artificialneural networks that can mimic the communication via elec-tric fields found in the cerebellum, heart, retina, and olfactorysystem.Thin films of organic semiconductors and other materialsare also used to carry the electrical properties of devicefunctions. Ishii, Yamashita, and co-workers focused onproton-coupled electron transfer reactions,[101] which arewidely used in biochemical processes, and developed achemical doping process controlled by an unconventionalparameter called proton activity (Figure 9). First, a p-typeorganic semiconductor thin film was immersed in anaqueous solution containing the redox pair of the protoncoupled electron transfer reaction and hydrophobic molecularions. Here, a benzoquinone/hydroquinone pair was used forthe two-electron two-proton proton coupled electron transferreaction. The synergistic reaction of proton coupled electrontransfer reaction and ion intercalation resulted in efficientchemical doping of crystalline organic semiconductor thinfilms under room temperature conditions. According to theNernst equation, the redox potential of the redox pair and theFermi level of the organic semiconductor thin film werereproducibly tunedwith high accuracy depending on the pH ofthe doping solution. Thismethod has significant advantages inits ease and versatility over conventional chemical dopingmethods, which are performed in aqueous solution understandby and in an inert atmosphere in vacuum or in organicsolvents. In other words, it has superior controllability, sta-bility, and scalability. The ease of solution processing makesthis method applicable to a wide variety of structures. Thisdoping nanoarchitectonics is expected to contribute signifi-cantly to the fabrication of advanced and reliable organicsemiconductor-based devices and bioelectronics, includingsensors. The concept of this method will also link semi-conductor doping with any chemical or biochemical processthat can alter proton activity. It could thereby serve as a plat-form for environmental semiconductor processes and bio-molecular electronics.The structure of a few molecular layers can be created bycrystallization of organic semiconductors. Transistor deviceswith gate structures on both sides can be created. Kumagai,Kasuya, Takeya, and co-workers have created solid and ionicgel gate dielectrics on the bottom and top surfaces, respec-tively, of bimolecular-thick single crystals of p-type organicF I GURE 9 Chemical doping of crystalline organic semiconductor thin film upon the synergistic reaction of proton coupled electron transfer reactionand ion intercalation using the redox pair of the proton coupled electron transfer reaction and hydrophobic molecular ions. Reproduced withpermission.[101] 2023, Springer-Nature.8 of 16 - RESPONSIVE MATERIALS 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensethin-film transistors (Figure 10).[102] The charge transportproperties at individual interfaces between the morphologi-cally compatible organic thin-film transistor surfaces anddifferent gate dielectrics were investigated. The resultsreveal the important influence of the gate dielectric materialon the interfacial charge transport. Gate bias was appliedthrough both dielectrics. In other words, a solid-state/ion-geldual-gate transistor was operated. In this case, the holemobility at the solid gate interface was 1.5 times higher. It isthought that the electric double layer formed on the ion-gel/homogeneous crystal surface provided a near-ideal chargetransport interface due to dramatic trap filling. Thus, thisdual-gate organic thin-film transistor geometry may besuitable for studying the inherent charge-carrier mobility ofvarious organic semiconductors with high ionization poten-tials and large organic thin-film transistor threshold voltages.4 | MATERIAL LEVEL RESPONSENanoarchitectonics of diverse components is useful not onlyfor phenomena at the atomic and molecular level, but alsofor the construction of stimulus-response systems at thematerial level. For example, controlling material orientationand properties through light stimulation is a common prac-tice. In a recent review, Seki summarized the photoinducedstructural control of azobenzene derivatives and azobenzenepolymers with nanoarchitectonics on their surfaces.[103]Azobenzene is a simple rod-shaped photochromic moleculethat has been widely studied. Nevertheless, new applicationsof photoswitching molecules and polymer systems are stillbeing actively proposed. In particular, many attractive newkinetic functions have been realized by linking azobenzenemolecules to liquid crystals and polymer systems. Theseuseful functions are manifested by nanoarchitectonics at theinterface. Azobenzene-containing monolayers and liquidcrystalline polymer films created at the interface can beendowed with a variety of functions. Surface photo-orientation of liquid crystals, photoorientation of hierarchicalstructures, photodynamic motion and morphologicalswitching in block copolymer monolayers, high-densitybrush and photo-triggered mass transfer of azobenzene sidechain liquid crystal polymers, and polymer motion byMarangoni flow are examples. Stimulation of matter by lighthas the advantage of generating several types of informationat once in a non-contact manner. When light is irradiated to aphotoreactive molecular layer or polymer film layer withlinearly polarized light or oblique irradiation, angle-selectivephotoreactions occur in the in-plane direction. Especiallywhen liquid crystal materials are used, strong molecularcooperativity leads to obvious molecular orientation andprovides a large orientation order. Such diverse methodolo-gies can be applied to other photochromic moleculesand polymers. It will be a useful tool for photo-stimuli-F I GURE 1 0 Device structure with solid gate and ionic gel gate on the bottom and top surfaces, respectively, of bimolecular-thick single crystals ofp-type organic thin-film transistors. Reproduced with permission.[102] 2023, Royal Society of Chemistry.RESPONSIVE MATERIALS - 9 of 16 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licenseresponsive dynamic processes for smart molecular systemsand devices.Nanoarchitectonics of surfaces allows the developmentof materials that combine versatile functions. Tao and co-workers have created fluorine-free UV-responsive materialsfor oil/water separation materials and dye degradation(Figure 11).[104] Cellulose, silicon dioxide, titanium dioxide,and stearic acid were used to create the superhydrophobiccoatings. An environmentally friendly fluorine-free super-hydrophobic coating was created. In addition, 3-aminopropyltrimethoxysilane was used to provide adhesiveproperties. These nanoarchitectonics products can be coatedon cotton fabrics by a simple dip coating method. The coatedcotton fabrics exhibited excellent superhydrophobicity andself-cleaning properties. They were able to withstand me-chanical performance tests such as scrubbing and immersionin boiling water. The coated cotton cloth was used not onlyfor separating heavy oil and light water mixtures, but also forseparating surfactant-stabilized oil-in-water and oil-in-wateremulsions. Wettability changes from superhydrophobic tosuperhydrophilic under UV irradiation. In addition, after UVirradiation, methyl blue can be decomposed. This approachwill contribute to the development of intelligent materialsthat perform multiple functions. It is also expected to havehigh potential in its industrial production.By intentionally nanoarchitectonizing complex structureson surfaces, materials can be developed that have a combi-nation of incompatible properties. For example, stretchable,self-powered sensors are of great interest in the next gen-eration of wearable electronics, but they must combine theproperties of several materials. Zhang, Bowen, and co-workers have developed a biomimetic soft rigid hybridstrategy to construct a new form of piezoelectric sensor withhigh flexibility, high performance, and stretchability(Figure 12).[105] Droplet-shaped hierarchical ceramics werefabricated by freeze casting on superhydrophobic surfaces.This hierarchical droplet-shaped ceramic structure effec-tively provides a rigid element. The unique arched surfaceand rounded corners of the unique droplet shape can relievestress concentration. To ensure electrical connection of thepiezoelectric phases during stretching, the patterned liquidmetal acts as a soft circuit. In addition, silicone polymersF I GURE 11 UV-responsive materials for oil/water separation materials fabricated with cellulose, silicon dioxide, titanium dioxide, stearic acid, and3-aminopropyltrimethoxysilane. Reproduced with permission.[104] 2022, Oxford University Press.F I GURE 1 2 Fabrication of droplet-shaped hierarchical ceramics with unique arched surface and rounded corners. Reproduced under terms of the CC-BY license.[105] 2024, Wiley-VCH.10 of 16 - RESPONSIVE MATERIALS 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensewith optimized wettability and extensibility are introducedas soft components. This structure forms a strong mechanicalinterlock with hierarchical ceramics. Nanoarchitectedstretchable sensors can be used for healthcare applications.For example, they were used for wireless gesture recognitionand to assess the progression of knee osteoarthritis. The highpotential in the field of stretchable and flexible sensors forhealthcare, e-skin, and wearables was demonstrated. Thistactic breaks the current trade-off between piezoelectric ac-tivity and stretchability, which has been difficult to achievewith traditional processing strategies. It will provide usefulhints for the development of future stretchable devices forsoft robotics and healthcare.With rapid advances in human-machine interaction andvoice biometrics, soft mechanical sensors that can detectcomplex dynamic signals are desired. Lu and co-workersproposed a hydrogel-based soft mechanical sensor thatskillfully utilizes layered nanoarchitectonics to record a widerange of human-related dynamic signals (Figure 13).[106]Mechanical acoustic signals play an important role inhuman-machine interaction and human health diagnostics.Iontronic dynamic sensors are intended to monitor a widerange of human-related dynamic signals, including complexfrequency sound signals such as the human voice and thesound of musical instruments. The nanoarchitectonics com-bines a preloaded design strategy with an iontronic sensingmechanism. The sensing module is a multilayered structuremade of a polyethylene terephthalate film coated with asilver electrode film, a resin/elastomer ring frame, a micro-structured hydrogel film, and an elastomer base coated with agold electrode film. By adjusting the parameters of thepreload and microstructure hydrogel, it can be preciselytuned to meet the desired requirements. The sensor canrecord instrumental sounds with high fidelity, from simplepure tones to melodic tunes. The skin-wearable sensor canalso be used for voice-activated remote control of toy cars.This demonstration could make a significant contribution tovoice user interface applications in human-machineinteraction.5 | LIVING CELL LEVEL RESPONSEOne application of surface nanoarchitectonics to morecomplex functional systems is the determination of cell fateby spontaneous stimulation of the interface. In many cases,mechanical stimuli transmitted to cells are modulated bycoating solid substrates with various mechanical propertiesor by creating nanostructures.[107–109] A recent advancedtopic is the use of weak forces from spontaneously generatednanostructures at the liquid–liquid interface to controlcells.[110,111] The last section discusses such examples.Jia et al. have studied the behavior of stem cells at theliquid–liquid interface between water and fluorocar-bons.[112,113] Adaptive biomaterials containing fibronectininserted into protein nanosheets at the liquid interface havebeen found to promote neuronal differentiation of humanmesenchymal stem cells. Stem cells and the microenvi-ronment interact cooperatively to determine cell fate. Bio-materials are dynamically remodeled by stem cells.Furthermore, stem cells sense the changes and reflect themin cell fate decisions. Recently, Jia, Nakanishi, and co-workers investigated the effect of adaptive biomaterialsbased on two-dimensional networks of protein nanofibrils atthe liquid–liquid interface.[114] Compared to flat proteinnanosheets, networked biomaterials promote neuralF I GURE 1 3 A hydrogel-based soft mechanical sensor with layered nanoarchitectonics for a wide range of human-related dynamic signals.Reproduced with permission.[106] 2024, American Chemical Society.RESPONSIVE MATERIALS - 11 of 16 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensedifferentiation of human mesenchymal stem cells through asignaling mechanism involving focal adhesion kinases. Inparticular, lipid raft microdomains in the plasma membraneplay a central role in the rapid adaptation of humanmesenchymal stem cells to the dynamic microenvironmentat the liquid interface (Figure 14). Lipid rafts internalizecell adhesion molecules and are involved in the process ofmobilizing them to different cell membranes. Lipid raftsalso function as enrichment platforms and support theintegration of large signaling complexes. This role withlipid rafts allows cells to rapidly adapt to a constantlychanging microenvironment. It is also suggested that focaladhesion kinase is one of the key mechanosensors at theadaptive liquid interface. Spatio-temporal regulation offocal adhesion kinase phosphorylation results in neuraldifferentiation of human mesenchymal stem cells. Thesefindings have major implications for regenerative medicineand tissue engineering. In particular, they provide the basisfor dynamic interactions between cells and extracellularmatrices and for understanding the biophysics underlyingmechanotransduction. A variety of stimulus responsivenesscould be incorporated into such systems by incorporatingbioactive proteins and responsive polymers. The liquid–liquid interface will provide a valuable venue to guide thedesign of new adaptive biomaterials for applications inregenerative medicine and tissue engineering.Perfluorocarbons and silicones, for example, form aninsoluble interface with water, where they allow cell adhesionthrough protein nanolayers. However, these liquids could onlycontrol a narrow range of physicochemical parameters. Thus,they could not provide a variety of cell culture environments.To overcome such difficulties, Ueki, Nakanishi, and co-workers investigated cell culture at the liquid–liquid inter-face using water-immiscible ionic liquids (Figure 15).[115]Ionic liquids have tunable physicochemical properties andhigh solvation capacity. The tetraalkylphosphonium-basedionic liquid used is a non-cytotoxic ionic liquid. Humanmesenchymal stem cells were successfully cultured at theinterface betweenwater and this ionic liquid. Elongation of thealkyl chains reduces the charge distribution of the cations, thatF I GURE 1 4 Neural differentiation of human mesenchymal stem cells promoted with networked biomaterials through a signaling mechanisminvolving focal adhesion kinases where lipid raft microdomains in the plasma membrane play a central role in the rapid adaptation of human mesenchymalstem cells to the dynamic microenvironment at the liquid interface. Reproduced under terms of the CC-BY license.[114] 2022, Springer-Nature.12 of 16 - RESPONSIVE MATERIALS 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licenseis, their ionicity, and the interface allows cell diffusion with amature focal contact. Unlike fluorocarbons, ionic liquids candissolve a wide variety of substrates and are therefore alsosuitable for altering the bulk mechanics of hydrophobic pha-ses. The van der Waals interactions of the constituent ions ofionic liquids and the charge distribution of cations were tunedand their effects on protein nanolayer formation and celladhesion were investigated in detail. It also has significantpractical advantages. Compared to the conventional two-dimensional culture method using plastic dishes, its cultureefficiency is much higher. Since the liquid can deform freely,cell resources can be recovered by a filtration process that doesnot require trypsin enzyme treatment. If this becomes possible,it will also lead to the complete automation of the cell cultureprocess. Finally, it is expected to lead to the realization of anenvironmentally friendly cell culture method that does notproduce plastic waste.6 | SHORT SUMMARY ANDPERSPECTIVESIn this review article, we summarize stimulus-response sys-tems from the atomic and molecular level to the living celllevel in terms of nanoarchitectonics at interfaces. For example,a stimulus-response system at the molecular level is a mo-lecular machine. From the viewpoint of nanoarchitectonics, asystem inwhich severalmolecular elements work in concert isattractive. When such a system is organized on a surface, theinterlocking behavior can be observed. For example, a probemicroscope stimulus can move several molecular gears intandem. In terms of converting molecules, synthetic methodsthat are not possible with conventional organic chemistry,where the chemistry of molecules present on the surface isunder an electron beam, can become possible. An example isthe control of reactions by stimuli such as the application oflocal voltage from the tip of a probe microscope. Atomicmanipulation with the tip of a probe microscope can alsocontrol magnetic topological states through spin polarization.In nanodevices, there are molecular switches in which theswitch part is a molecule and atomic switches in which theswitch part is an atomic cluster. Examples have been reportedin which device functions can be expressed by such dynamicnanoarchitectonics of atoms and molecules. Resistancechange memory using silver ion conductive solid polymerelectrolytes is an electrochemical atomic switch realized usingorganic materials. In atomic switches using porous polymers,the switching behavior transitions from volatile to nonvolatilein response to metal filament development. This can bechanged from short-term memory to long-term memory byrepeated voltage sweeps. In addition, quantization ofconductance by an integer factor of single-atom point contactsis achieved in response to growth in Ag filaments in thepolymer matrix. Atomic cluster architectonics makes devicequantization possible. Field-mediated atomic switches for lowbias stimuli have also been achieved. This mimics the field-F I GURE 1 5 Cell culture at the liquid–liquid interface using water-immiscible ionic liquids. Reproduced with permission.[115] 2024, Wiley.RESPONSIVE MATERIALS - 13 of 16 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensemediated communication found in the cerebellum, heart,retina, and olfactory system. Nanoarchitectonics, whichbrings doping to thin films of organic semiconductors, alsoallows precise control of conductivity in conjunction withproton coupled electron transfer reactions widely used inbiochemical processes. Molecular-level device design is alsopossible, in which gate functions are provided at both in-terfaces of crystalline sheets of organic semiconductors a fewmolecules thick.Interfacial nanoarchitectonics with diverse components isuseful for the construction of material-level stimulus-responsive systems. Photo-induced structural control of azo-benzene derivatives and azobenzene polymers nano-architectonized on surfaces can be applied to photo-stimuli-responsive dynamic processes for smart molecular systemsand devices. Nanoarchitectonics of surfaces can developmaterials that combine a wide variety of functions. UV-responsive materials for oil/water separation and dye degra-dation have been developed. By intentionally nano-architectonizing complex structures on surfaces, materials canbe developed that have a combination of incompatible prop-erties. Hybrid strategies can also be used to create new formsof piezoelectric sensors that are flexible, high performance,and stretchable. There is an example of a hydrogel-based softmechanical sensor made with layered nanoarchitectonics.This could contribute significantly to applications in voiceuser interfaces in human-machine interaction.An application of surface nanoarchitectonics to morecomplex functional systems is the determination of cell fate byspontaneous stimulation of the interface. Cells are controlledusing weak forces from spontaneously generated nano-structures at the liquid–liquid interface. Adaptive biomaterialsbased on two-dimensional networks of protein nanofibrils atthe liquid–liquid interface promote neural differentiation ofhuman mesenchymal stem cells through signaling mecha-nisms. Water immiscible ionic liquids can also be used toculture cells at the liquid–liquid interface. These nano-architectonics at the liquid–liquid interface will provideguidelines for designing new adaptive biomaterials for ap-plications in regenerative medicine and tissue engineering. Itwill also lead to the realization of environmentally friendlycell culture methods that do not produce plastic waste.As described above, a wide range of stimulus-responsivesystems, from devices based on atomic and molecularmovements to differentiation control by signal transductionin living cells, can be created by interfacial nano-architectonics. The abundance of choices should also makeit possible to construct responsive material systems bycombining them. Rather, the development of materials thatcan control such complex systems will be useful for thedevelopment of highly functional responsive material sys-tems, such as those in living organisms. However, the morediverse the components and the more complex the structure,the more difficult the approach becomes. The experienceand intuition of the experimenter, or the principled pre-dictions of academia, may not be sufficient. Fortunately,mankind has rapidly developed artificial intelligence. Theuse of machine learning for materials design[116,117] and theconcept of materials informatics[118–120] have become pop-ular. The need to integrate nanoarchitectonics and materialsinformatics has also been proposed.[121] Such new infor-mation technologies will strongly support the developmentof responsive materials systems through nanoarchitectonics.Another problem to be solved is the conversion to in-dustrial applications. As we have shown in several exam-ples, many of the interface stimulating materials fromMANA have strong practical potential. It will also beimportant to determine how to translate the methodology ofmaterial creation by nanoarchitectonics into mass produc-tion. If the social demand for these materials is fullyrecognized, such development is expected to progress. Ihope that this review article will play a role in stimulatingsuch development.AUTHOR CONTRIBUTIONSKatsuhiko Ariga: Conceptualization (lead); funding acqui-sition (lead); writing—original draft (lead); writing—reviewand editing (lead).ACKNOWLEDGMENTSThis study was partially supported by the Japan Society forthe Promotion of Science KAKENHI (Grant NumbersJP20H00392 and JP23H05459).CONFLICT OF INTEREST STATEMENTThe authors declare no conflicts of interest.ORCIDKatsuhiko Ariga https://orcid.org/0000-0002-2445-2955REFERENCES1. W.-C. Gao, J. Qiao, J. Hu, Y.-S. Guan, Q. Li, Responsive Mater. 2024,2, e20230022.2. D.-H. Tuo, T.-H. Shi, S. Ohtani, T. Ogoshi, Responsive Mater. 2024,2, e20230024.3. S. Ma, P. Xue, Y. Tang, R. Bi, X. Xu, L. Wang, Q. Li, ResponsiveMater. 2024, 2, e20230026.4. Y. Zhang, Z.-G. Zheng, Q. Li, Responsive Mater. 2024, 2, e20230029.5. J. Jeon, D. Bukharina, M. Kim, S. Kang, J. Kim, Y. Zhang, V.Tsukruk, Responsive Mater. 2024, 2, e20230032.6. K.-H. Liu, M. Liu, Z. 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Chaikittisilp, Y. Yamauchi, K. Ariga, Adv. Mater. 2022, 34,2107212.AUTHOR BIOGRAPHYKatsuhiko Ariga received his Ph.D.degree from the Tokyo Institute ofTechnology in 1990. He joined theNational Institute for Materials Science(NIMS) in 2004 and is currently agroup leader of the SupermoleculesGroup and a principal investigator ofthe World Premier International (WPI) Research Centerfor Materials Nanoarchitectonics (MANA). He is alsoappointed as a professor at The University of Tokyo. Hisexpertise is in supramolecular chemistry and materialnanoarchitectonics.How to cite this article: K. Ariga, Responsive Mater.2024, 2, e20240011. https://doi.org/10.1002/rpm.2024001116 of 16 - RESPONSIVE MATERIALS 28348966, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/rpm.20240011 by Cochrane Japan, Wiley Online Library on [31/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttps://doi.org/10.1002/rpm.20240011https://doi.org/10.1002/rpm.20240011 Responsive materials nanoarchitectonics at interfaces 1 | INTRODUCTION 2 | MOLECULAR LEVEL RESPONSE 3 | NANODEVICE LEVEL RESPONSE 4 | MATERIAL LEVEL RESPONSE 5 | LIVING CELL LEVEL RESPONSE 6 | SHORT SUMMARY AND PERSPECTIVES AUTHOR CONTRIBUTIONS ACKNOWLEDGMENTS CONFLICT OF INTEREST STATEMENT