Responsive Macroscopic Materials From Self‐Assembled Cross‐Linked SiO2‐PNIPAAm Core/Shell Structures

A way to obtain macroscopic responsive materials from silicon‐oxide polymer core/shell microstructures is presented. The microparticles are composed of a 60 nm SiO₂‐core with a random copolymer corona of the temperature responsive poly‐N‐isopropylacrylamide (PNIPAAm) and the UV‐cross‐linkable 2‐(dimethyl maleinimido)‐N‐ethyl‐acrylamide. The particles shrink upon heating and form a stable gel in both water and tetrahydrofuran (THF) at 3–5 wt% particle content. Cross‐linking the aqueous gel results in shrinkage when the temperature is increased above the lower critical solution temperature and it regains its original size upon cooling. By freeze drying with subsequent UV irradiation, thin stable layers are prepared. Stable fibers are produced by extruding a THF gel into water and subsequent UV irradiation, harnessing the cononsolvency effect of PNIPAAm in water/THF mixtures. The temperature responsiveness translates to the macroscopic materials as both films and fibers show the same collapsing behavior as the microcore/shell particle. The collapse and re‐swelling of the materials is related to the expelling and re‐uptake of water, which is used to incorporate gold nanoparticles into the materials by a simple heating/cooling cycle. This allows for future applications, as various functional particles (antibacterial, fluorescence, catalysis, etc.) can easily be incorporated in these systems.     

Bio‐Inspired Nanospiky Metal Particles Enable Thin,Flexible, and Thermo‐Responsive Polymer Nanocomposites for Thermal Regulation

Safety issues remain a major obstacle toward large‐scale applications of high‐energy lithium‐ion batteries. Embedding thermo‐responsive polymer switching materials (TRPS) into batteries is a potential strategy to prevent thermal runaway, which is a major cause of battery failures. Here, thin, flexible, highly responsive polymer nanocomposites enabled by bio‐inspired nanospiky metal (Ni) particles are reported. These unique Ni particles are synthesized by a simple aqueous reaction at gram‐scale with controlled surface morphology and composition to optimize electrical properties of the nanocomposites. The Ni particles provide TRPS films with a high room‐temperature conductivity of up to 300 S cm^?1. Such TRPS composite films also have a high rate (<1 s) of resistance switching within a narrow temperature range, good reversibility upon on/off switching, and a tunable switching temperature (T_s; 75 to 170 °C) that can be achieved by tailing their compositions. The small size (≈500 nm) of Ni particles enables ready fabrication of thin and flexible TPRS films with thickness approaching 5 µm or less. These features suggest the great potential of using this new type of responsive polymer composite for more effective battery thermal regulation without sacrificing cell performance.     

Mussel‐Inspired Approach to Constructing Robust Multilayered Alginate Films for Antibacterial Applications

The exceptional mechanical properties of the byssus—the fibrous holdfast of mussels that provides underwater adhesion—have potential applications in medicine and technology. The catechol–Fe³⁺–catechol interaction underlies the unique properties of mussel byssus and has emerged as a tool for developing functional hybrid materials such as pH‐responsive, self‐healing gels. Herein, the construction of functional alginate (Alg) film on a solid substrate inspired by mussel byssus is reported. The approach consists of spin‐coating‐assisted deposition of Alg catechols onto a solid substrate and their subsequent crosslinking via catechol–Fe³⁺–catechol interactions. This yields robust and multilayered Alg films that are resistant to protein adsorption and suppress bacterial adhesion. This method can be used to create antibacterial films for coating implanted medical devices.     

Adhesion and Surface Interactions of a Self‐Healing Polymer with Multiple Hydrogen‐Bonding Groups

The surface properties and self‐adhesion mechanism of self‐healing poly(butyl acrylate) (PBA) copolymers containing comonomers with 2‐ureido‐4[1H]‐pyrimidinone quadruple hydrogen bonding groups (UPy) are investigated using a surface forces apparatus (SFA) coupled with a top‐view optical microscope. The surface energies of PBA–UPy4.0 and PBA–UPy7.2 (with mole percentages of UPy 4.0% and 7.2%, respectively) are estimated to be 45–56 mJ m^?2 under dry condition by contact angle measurements using a three probe liquid method and also by contact and adhesion mechanics tests, as compared to the reported literature value of 31–34 mJ m^?2 for PBA, an increase that is attributed to the strong UPy–UPy H‐bonding interactions. The adhesion strengths of PBA–UPy polymers depend on the UPy content, contact time, temperature and humidity level. Fractured PBA–UPy films can fully recover their self‐adhesion strength to 40, 81, and 100% in 10 s, 3 h, and 50 h, respectively, under almost zero external load. The fracture patterns (i.e., viscous fingers and highly “self‐organized” parallel stripe patterns) have implications for fabricating patterned surfaces in materials science and nanotechnology. These results provide new insights into the fundamental understanding of adhesive mechanisms of multiple hydrogen‐bonding polymers and development of novel self‐healing and stimuli‐responsive materials.     

Reusable Cellulose‐Based Hydrogel Sticker Film Applied as Gate Dielectric in Paper Electrolyte‐Gated Transistors

A new concept for reusable eco‐friendly hydrogel electrolytes based on cellulose is introduced. The reported electrolytes are designed and engineered through a simple, fast, low‐cost, and eco‐friendly dissolution method of microcrystalline cellulose at low temperature using an aqueous LiOH/urea solvent system. The cellulose solution is combined with carboxymethyl cellulose, followed by the regeneration and simultaneous ion incorporation. The produced free standing cellulose‐based electrolyte films exhibit interesting properties for application in flexible electrochemical devices, such as biosensors or electrolyte‐gated transistors (EGTs), because of their high specific capacitances (4–5 µF cm^?2), transparency, and flexibility. Indium–gallium–zinc‐oxide EGTs on glass with laminated cellulose‐based hydrogel electrolytes (CHEs) as the gate dielectric are produced presenting a low working voltage (<2 V), showing an on–off current ratio (I _on/off) of 10⁶, a subthreshold swing lower than 0.2 V dec^?1, and saturation mobility (μ_Sat) reaching 26 cm² V^?1 s^?1. The flexible CHE‐gated transistors on paper are also demonstrated, which operate at switching frequencies up to 100 Hz. Combining the flexibility of the EGTs on paper with the reusability of the developed CHEs is a breakthrough toward biodegradable advanced functional materials allied with disposable/recyclable and low‐cost electronic devices.     

Layer‐by‐Layer Assembly of Light‐Responsive Polymeric Multilayer Systems

Layer‐by‐Layer (LbL) assembly is a simple and highly versatile method to modify surfaces and fabricate robust and highly‐ordered nanostructured coatings over almost any type of substrate. Such versatility enables the incorporation of a plethora of building blocks, including materials exhibiting switchable properties, in a single device through a multitude of complementary intermolecular interactions. Switchable materials may undergo reversible physicochemical changes in response to a variety of external triggers. Although most of the works in the literature have been focusing on stimuli‐responsive materials that are sensitive to common triggers such as pH, ionic strength, or temperature, much less has been discussed on LbL systems which are sensitive to non‐invasive and easily controlled light stimulus, despite its unique potential. This review provides a deep overview of the recent progresses achieved in the design and fabrication of light‐responsive LbL polymeric multilayer systems, their potential future challenges and opportunities, and possible applications. Many examples are given on light‐responsive polymeric multilayer assemblies built from metal nanoparticles, functional dyes, and metal oxides. Such stimuli‐responsive functional materials, and combinations among them, may lead to novel and highly promising nanostructured smart functional systems well‐suited for a wide range of research fields, including biomedicine and biotechnology.     

Multivalent‐Ion‐Mediated Stabilization of Hydrogen‐Bonded Multilayers

Hydrogen‐bonding interactions are an important alternative to electrostatic interactions for assembling multilayer thin films of uncharged components. Herein, a new method is reported for rendering such films stable at pH values close to physiological conditions. Multilayer films based on hydrogen bonding are assembled by the alternate deposition of poly[(styrene sulfonic acid)‐co‐(maleic acid)] (PSSMA) and poly(N‐isopropylacrylamide) (PNiPAAm) at pH 2.5. The use of PSSMA results in multilayers that contain free styrene sulfonate groups, as these moieties do not interact with the PNiPAAm functional groups. Subsequent infiltration of a multivalent ion (Ce⁴⁺ or Fe³⁺) leads to an increase in the total film mass, with little impact on the film morphology, as determined by using atomic force microscopy. To examine the film stability, the resulting films have been exposed to elevated pH (7.1). While there is substantial swelling of the multilayers (25 % and 55 % for Ce⁴⁺‐ and Fe³⁺‐stabilized films, respectively), film loss is negligible. This provides a stark contrast with non‐stabilized films, which disassemble almost immediately upon exposure to pH 7.1. This method represents a simple and effective strategy for stabilizing hydrogen‐bonded structures non‐covalently. Further, the multivalent ions also render the films responsive to changes in the local redox environment, as demonstrated by film disassembly after exposure of Fe³⁺‐treated films to iodide solutions.     

Inkjet Printing of Self‐Assembled 2D Titanium Carbide and Protein Electrodes for Stimuli‐Responsive Electromagnetic Shielding

2D titanium carbides (MXene) possess significant characteristics including high conductivity and electromagnetic interference shielding efficiency (EMI SE) that are important for applications in printed and flexible electronics. However, MXene‐based ink formulations are yet to be demonstrated for proper inkjet printing of MXene patterns. Here, tandem repeat synthetic proteins based on squid ring teeth (SRT) are employed as templates of molecular self‐assembly to engineer MXene inks that can be printed as stimuli‐responsive electrodes on various substrates including cellulose paper, glass, and flexible polyethylene terephthalate (PET). MXene electrodes printed on PET substrates are able to display electrical conductivity values as high as 1080 ± 175 S cm^?1, which significantly exceeds electrical conductivity values of state‐of‐the‐art inkjet‐printed electrodes composed of other 2D materials including graphene (250 S cm^?1) and reduced graphene oxide (340 S cm^?1). Furthermore, this high electrical conductivity is sustained under excessive bending deformation. These flexible electrodes also exhibit effective EMI SE values reaching 50 dB at films with thicknesses of 1.35 µm, which mainly originate from their high electrical conductivity and layered structure.     

Nanodiamond‐Palladium Core–Shell Organohybrid Synthesis: A Mild Vapor‐Phase Procedure Enabling Nanolayering Metal onto Functionalized sp3‐Carbon

A novel approach for the bottom‐up construction of hybrid organic–inorganic nanocomposites with an intimate arrangement between sp³‐carbon 3D molecular‐size nanodiamonds (diamondoids) and a coated palladium surface as nanolayer is reported. The construction process is conducted stepwisely from the gas phase, using first controlled vapor‐phase self‐assembly of tailor‐made functionalized diamantane derivatives, followed by low‐temperature (45 °C) chemical vapor deposition of an organometallic complex in a reducing H₂ atmosphere over the self‐assembled diamondoid scaffold. The use of self‐assemblies of primary diamantane phosphine and phosphine oxide, which are produced with high structural uniformity and reproducibility, yields new hybrid diamondoid‐palladium materials incorporating Pd? O? PH? diamantane bonding motifs. Additional investigations provide evidence for a very challenging issue in the intimate construction of sp³‐C/metal scaffolds. Scanning electron microscopy and transmission electron microscopy microscopies combined with X‐ray photoelectron spectroscopy surface analysis and EDX bulk analysis confirm the formation of diamondoid‐palladium organohybrids with unique surface layering. The vapor phase‐controlled mild synthetic process allows excellent control over nanocomposite formation and morphology from molecular‐level modifications. As such, this bottom‐up composite building process bridges scales from the molecular (functionalized diamondoids) over nanoscopic (self‐assemblies) to microscopic regime (hybrids), in the challenging association of transition metals with an electronically saturated sp³‐carbon organic host material.     

Highly Porous Polymer Aerogel Film‐Based Triboelectric Nanogenerators

A novel class of high performance polymer porous aerogel film‐based triboelectric nanogenerators (A‐NGs) is demonstrated. The A‐NGs, made of a pair of highly porous polymer films, exhibit much higher triboelectric outputs than the corresponding dense polymer film‐based triboelectric nanogenerators (D‐NGs) under the same mechanical stress. The triboelectric outputs of the A‐NGs increase significantly with increasing porosity, which can be attributed to the increase in contact area and the electrostatic induction in the porous structure, thereby leading to additional charges on the porous surface. Remarkably, the A‐NG fabricated using porous chitosan aerogel film paired with the most porous polyimide (with a porosity of 92%) aerogel film demonstrates a very high voltage of 60.6 V and current of 7.7 µA, corresponding to a power density of 2.33 W m^?2, which is sufficient to power 22 blue light‐emitting‐diodes (LEDs). This is the first report on triboelectric nanogenerators (TENGs) employing porous polymer aerogel films as both positive and negative materials to enhance triboelectric outputs. Furthermore, enhancing the tribopositive polarity of the cellulose aerogel film via silanization using aminosilane can dramatically improve the triboelectric performance. Therefore, this study provides new insights into investigating porous materials with tunable triboelectric polarities for high performance TENGs.     

A Controllable Self‐Assembly Method for Large‐Scale Synthesis of Graphene Sponges and Free‐Standing Graphene Films

A simple method to prepare large‐scale graphene sponges and free‐standing graphene films using a speed vacuum concentrator is presented. During the centrifugal evaporation process, the graphene oxide (GO) sheets in the aqueous suspension are assembled to generate network‐linked GO sponges or a series of multilayer GO films, depending on the temperature of a centrifugal vacuum chamber. While sponge‐like bulk GO materials (GO sponges) are produced at 40 °C, uniform free‐standing GO films of size up to 9 cm² are generated at 80 °C. The thickness of GO films can be controlled from 200 nm to 1 µm based on the concentration of the GO colloidal suspension and evaporation temperature. The synthesized GO films exhibit excellent transparency, typical fluorescent emission signal, and high flexibility with a smooth surface and condensed density. Reduced GO sponges and films with less than 5 wt% oxygen are produced through a thermal annealing process at 800 °C with H₂/Ar flow. The structural flexibility of the reduced GO sponges, which have a highly porous, interconnected, 3D network, as well as excellent electrochemical properties of the reduced GO film with respect to electrode kinetics for the [Fe(CN)₆]^3?/4? redox system, are demonstrated.     

Third‐Order Nonlinear Optical Response of Gold‐Island Films

Films of gold nanoscaled islands with thicknesses ranging between 0.5 and 15 nm were prepared by thermal evaporation onto untreated and aminosilane‐pretreated glass substrates. Post‐deposition annealing was found to modify the morphological characteristics of the islands (e.g., average island area and height, inter‐island distance, etc.), resulting in changes of the localized surface plasmon resonance (SPR) characteristics and, therefore, modifying the nonlinear optical (NLO) response of the films. The NLO response of both unannealed and annealed (20 h at 200 °C) films was studied by means of the optical Kerr effect (OKE), using 35 ps, 532 nm laser excitation, while measurements performed by means of the Z‐scan technique allowed for the determination of both the nonlinear refraction and absorption characteristics of the films. The results are discussed and compared with other reports.     

Tessellation of Chiral‐Nematic Cellulose Nanocrystal Films by Microtemplating

In biological architectures, material properties are optimized by the hierarchical structuring of components with a multiscaled order, from the nano‐ to the macroscales. Such designs enable, for instance, programmed yield points that maximize toughness. However, research efforts in biomimetic materials have focused on the assembly of nano‐ or macrostructures individually. In this study, high strength cellulose nanocrystals (CNCs), assembled into chiral‐nematically ordered structures, are tiled into a higher level, macro‐sized, architecture by topographical templating. As templates, two meshed architectures with distinct feature sizes are evaluated, and the optomechanical properties of the resulting films are compared to featureless, flat, CNC films. Controlling capillary stresses arising during CNC assembly is shown to enable control over the orientation of the chiral‐nematic director across the topography of the template. Tuning the specific reflections and multiscaled fracture propagation is demonstrated for the microtemplated CNC films. The latter phenomenon contributed to enhancing the toughness of the material through a high tortuosity of fracture propagation in all (x, y, z) directions. The presented findings are expected to pave the way towards the incorporation of current research in cellular metamaterials with the research focusing on the generation of nanoscaled biomimetic constructs.     

Intercalation‐Induced Tunable Stimuli‐Responsive Color‐Change Properties of Crystalline Organic Layered Compound

Layered structures accommodate guest molecules and ions in the interlayer space through intercalation. Organic layered compounds, such as layered polymers, have both intercalation and dynamic properties. Here intercalation‐induced tunable temperature‐ and mechanical‐stress‐responsive color‐change properties of crystalline layered polydiacetylene (PDA) as an organic layered compound are reported. In general, organic materials with stimuli responsivity are developed by molecular design and synthesis. In the present work, intercalation of guest metal cations in the layered PDA directs tuning of the stimuli‐responsive color‐change properties, such as color, responsivity, and reversibility. Whereas PDA without intercalation of metal ions distinctly changes the color from blue to red at the threshold temperature, the PDA with intercalation of the divalent metal ions (PDA‐M²⁺) shows a variety of color‐change properties. The present study indicates that intercalation has versatile potentials for functionalization of organic layered compounds.     

Color Tunable Poly (N‐Isopropylacrylamide)‐co‐Acrylic Acid Microgel–Au Hybrid Assemblies

A new class of materials that are capable of color tunability over 300 nm with a 15 °C temperature change is introduced. The materials are assembled from thermoresponsive poly (N‐isopropylacrylamide)‐co‐acrylic acid (pNIPAm‐co‐AAc) microgels, which are deposited on Au coated glass substrates. The films are also pH responsive; the temperature‐induced color change was suppressed at high pH and is consistent with the behavior of a solution of suspended microgels. The mechanism proposed to account for the observed optical properties suggests that they result from the two Au layers being separated from each other by the “monolithic” microgel film, much like a Fabry‐Pérot etalon or interferometer. It is the modulation of the distance between these two layers, facilitated by the microgel collapse transition at high temperature, that allows the color to be tuned. The sensitivity of the system presented here will be used for future sensing and biosensing applications, as well as for light filtering applications.     

Hybrid Improper Ferroelectricity in Multiferroic Superlattices: Finite‐Temperature Properties and Electric‐Field‐Driven Switching of Polarization and Magnetization

The so‐called hybrid improper ferroelectricity (HIF) mechanism allows to create an electrical polarization by assembling two nonpolar materials within a superlattice. It may also lead to the control of the magnetization by an electric field when these two nonpolar materials are magnetic in nature, which is promising for the design of novel magneto‐electric devices. However, several issues of fundamental and technological importance are presently unknown in these hybrid improper ferroelectrics. Examples include the behaviors of its polarization and dielectric response with temperature, and the paths to switch both the polarization and magnetization under electric fields. Here, an effective Hamiltonian scheme is used to study the multiferroic properties of the model superlattice (BiFeO₃)₁/(NdFeO₃)₁. Along with the development of a novel Landau‐type potential, this approach allows to answer and understand all the aforementioned issues at both microscopic and macroscopic levels. In particular, the polarization and dielectric response are both found to adopt temperature dependences, close to the phase transition, that agree with the behavior expected for first‐order improper ferroelectrics. And most importantly, a five‐state path resulting in the switching of polarization and magnetization under an electric field, via the reversal of antiphase octahedral tiltings, is also identified.     

Phototunable Underwater Oil Adhesion of Micro/Nanoscale Hierarchical‐Structured ZnO Mesh Films with Switchable Contact Mode

Controllable surface adhesion of solid substrates has aroused great interest both in air and underwater in solving many challenging interfacial science problems such as robust antifouling, oil‐repellent, and highly efficient oil/water separation materials. Recently, responsive surface adhesion, especially switchable adhesion, under external stimulus in air has been paid more and more attention in fundamental research and industrial applications. However, phototunable underwater oil adhesion is still a challenge. Here, an approach to realize phototunable underwater oil adhesion on aligned ZnO nanorod array‐coated films is reported, via a special switchable contact mode between an unstable liquid/gas/solid tri‐phase contact mode and stable liquid/liquid/solid tri‐phase contact mode. The photo‐induced wettability transition to water and air exists (or does not) in the micro/nanoscale hierarchical structure of the mesh films, playing important role in controlling the underwater oil adhesion behavior. This work is promising in the design of novel interfacial materials and functional devices for practical applications such as photo‐induced underwater oil manipulation and release, with loss‐free oil droplet transportation.     

Double Stimuli‐Responsive Isoporous Membranes via Post‐Modification of pH‐Sensitive Self‐Assembled Diblock Copolymer Membranes

Double stimuli‐responsive membranes are prepared by modification of pH‐sensitive integral asymmetric polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer membranes with temperature‐responsive poly(N‐isopropylacrylamide) (pNIPAM) by a surface linking reaction. PS‐b‐P4VP membranes are first functionalized with a mild mussel‐inspired polydopamine coating and then reacted via Michael addition with an amine‐terminated pNIPAM‐NH₂ under slightly basic conditions. The membranes are thoroughly characterized by nuclear magnetic resonance (¹H‐NMR), Fourier transform infrared spectroscopy and X‐ray‐induced photoelectron spectroscopy. Additionally dynamic contact angle measurements are performed comparing the sinking rate of water droplets at different temperatures. The pH‐ and thermo‐double sensitivities of the modified membranes are proven by determining the water flux under different temperature and pH conditions.     

Construction of White‐Light‐Emitting Silk Protein Hybrid Films by Molecular Recognized Assembly among Hierarchical Structures

The fabrication of bio‐hybrid functional films is demonstrated by applying a materials assembly technique. Based on the hierarchical structures of silk fibroin materials, functional molecular/materials, i.e., quantum dots (QDs), can be fixed to amino acid groups in silk fibroin films. It follows that white‐light‐emitting QD silk hybrid films are obtained by hydrogen bond molecular recognition to the –COO^– groups functionalized to blue luminescent ZnSe (5.2 nm) and yellow luminescent CdTe (4.1 nm) QDs in a molar ratio of 30:1 of ZnSe to CdTe QDs. Simultaneously, a systematic blue shift in the emission peak is observed from the QD solution to QDs silk fibroin films. The significant blue shift hints the appearance of the strong interaction between QDs and silk fibroins, which causes strong white‐light‐emitting uniform silk films. The molecular recognized interactions are confirmed by high resolution transmission electron microscopy, field scanning electron microscope, and attenuated total internal reflectance Fourier transform infrared spectroscopy. The QD silk films show unique advantages, including simple preparation, tunable white‐light emission, easy manipulation, and low fabrication costs, which make it a promising candidate for multicomponent optodevices.     

Humidity‐Driven Mechanical and Electrical Response of Graphene/Cloisite Hybrid Films

Humidity‐driven and electrically responsive graphene/cloisite hybrid films are obtained by casting water dispersions of graphene oxide and cloisite Na⁺. Coupling hydrophilicity and a high water vapor barrier in a homogenous film enables to realize humidity‐driven actuators which exploit the water gradient generated across the film section under asymmetric exposure to humidity. The hybrid films are self‐standing, flexible, and exhibit fast humidity‐triggered bidirectional bending up to 75°, which is tuned by varying the relative amount of the two components. Up to 60% of the bending angle can be preserved at the steady state, providing a large and reliable response to humidity. Moreover, thermal treatment results in the reduction of graphene oxide, endowing the films with humidity‐dependent electrical conductivity, which increases from 1.5 × 10^?6 S at 20% relative humidity (RH) up to 2.7 × 10^?5 S at 90% RH. The films are used to realize a humidity‐sensitive electrical switching system in which the reversible actuation is due to water desorption induced by the Joule effect. Due to their ease of preparation and tunable properties, this new class of graphene‐based materials is suitable for the realization of humidity‐driven and electrically responsive actuators and sensors.