Polymer particles capable of dynamic shape changes in response to light have received substantial attention in the development of intelligent multifunctional materials. In this study, we develop a light-responsive block copolymer (BCP) particle system that exhibits fast and reversible shape and color transitions. The key molecular design is the integration of spiropyran photoacid (SPPA) molecules into the BCP particle system, which enables fast and dynamic transformations of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) particles in response to light. The SPPA photoisomerization, induced by 420 nm light irradiation, lowers the pH of the aqueous surroundings from 5.5 to 3.3. The protonated P4VP block substantially increases in domain size from 14 to 39 nm, resulting in significant elongation of the BCP particles (i.e., an increase in the aspect ratio (AR) of the particles from 1.8 to 3.4). Moreover, SPPA adsorbed onto the P4VP surface induces significant changes in the luminescent properties of the BCP particles via photoisomerization of SPPA. Notably, the BCP particles undergo fast, dynamic shape and color transitions within a period of 10 min, maintaining high reversibility over multiple light exposures. Functional dyes are selectively incorporated into different domains of the light-responsive BCP particles to achieve different ranges of color responses. Thus, this study showcases a light-responsive hydrogel display capable of reversible and multicolor photopatterning.
Diblock copolymer (dBCP) particles capable of dynamic shape and color changes have gained significant attention due to their versatility in programmable shapes and intricate nanostructures. However, their application in photonic systems remains limited due to challenges in achieving a sufficient number of defect-free photonic layers over a tens-of-micrometer scale. In this study, we present a pioneering demonstration of photonic dBCP particles featuring over 300 axially stacked photonic layers with responsive color- and shape-transforming capabilities. Our approach leverages the complex interplay between the macrophase separation of multiple incompatible components and the microphase separation of dBCP from solvent-evaporative microemulsions. Specifically, continuous phase separation of silicone oil from polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP), triggered by solvent evaporation, promotes the anisotropic growth of PS-b-P2VP layers. This results in the formation of Janus colloids, where an oil droplet merges with a nanostructured polymer cone and lamellar structures align along the long axis of the cone. We highlight the capability to precisely adjust the particle morphology and the corresponding orientation, dispersion, and structural color window by modulating both the molecular weight of PS-b-P2VP and the volume ratio between PS-b-P2VP and silicone oil. Furthermore, reversible swelling/deswelling of photonic colloids is visualized and correlated with their structural colors. Finally, we demonstrate the potential of this study by presenting a multicolor-patterned array of photonic colloids, highlighting the possibilities for applications in smart photonic ink and devices.
The self-assembly of core/shell nanoparticles (NPs) at fluid interfaces is a rapidly evolving area with tremendous potential in various fields, including biomedicine, display devices, catalysts, and sensors. This review provides an in-depth exploration of the current state-of-the-art in the programmed design of stimuli-responsive NP assemblies, with a specific focus on inorganic core/organic shell NPs below 100 nm for their responsive adsorption properties at fluid and polymer interfaces. The interface properties, such as ligands, charge, and surface chemistry, play a significant role in dictating the forces and energies governing both NP-NP and NP-hosting matrix interactions. We highlight the fundamental principles governing the reversible surface chemistry of NPs and present detailed experimental examples in the following three key aspects of stimuli-responsive NP assembly: (i) stimuli-driven assembly of NPs at the air/liquid interface, (ii) reversible NP assembly at the liquid/liquid interface, including films and Pickering emulsions, and (iii) hybrid NP assemblies at the polymer/polymer and polymer/water interfaces that exhibit stimuli-responsive behaviors. Finally, we address current challenges in existing approaches and offer a new perspective on the advances in this field.
Highly anisotropic-shaped particles with well-ordered internal nanostructures have received significant attention due to their unique shape-dependent photonic, rheological, and electronic properties and packing structures. In this work, nanosheet particles with cylindrical block copolymer (BCP) arrays are achieved by utilizing collapsed emulsions as a scaffold for BCP self-assembly. Highly elongated structures with large surface areas are formed by employing crystallizable surfactants that significantly reduce the interfacial tension of BCP emulsions. Subsequently, the stabilized elongated emulsion structures lead to the formation of BCP nanosheets. Specifically, when polystyrene-block-polydimethylsiloxane (PS-b-PDMS) and 1-octadecanol (C18-OH) are co-assembled within an emulsion, C18-OH penetrates the surfactant layer at the emulsion interface, lowering the interfacial tension (i.e., below 1 mN m-1 ) and causing emulsion deformation. In addition, C18-OH crystallization allows for kinetic arrest of the collapsed emulsion shape during solvent evaporation. Consequently, PS-b-PDMS BCPs self-assemble into defect-free structures within nanosheet particles, exhibiting an exceptionally high aspect ratio of over 50. The particle formation mechanism is further investigated by controlling the alkyl chain length of the fatty alcohol. Finally, the coating behavior of nanosheet particles is investigated, revealing that the deposition pattern on a substrate is strongly influenced by the particle's shape anisotropy, thus highlighting their potential for advanced coating applications.
Owing to the rise in global population and living standards, waste treatment has inevitably become a critical issue for a sustainable environment. In particular, for an effective recycling process, it is vital to disassemble different types of materials by removing adhesives used in the packaging. However, this removal process requires harsh solvents (acidic and organic) that are unfriendly to nature and may cause additional pollution. To address this issue, functional adhesive materials that can be removed without the use of harsh solvents have drawn significant attention. One promising approach is to utilize the stimuli-responsive polymers to synthesize pressure sensitive adhesives (PSAs); however, it is technically challenging to simultaneously satisfy (i) strong initial adhesion (without stimulus), (ii) stimuli-responsive sufficient reduction of adhesion, and (iii) reversibility. In this study, thermo-switchable PSAs were synthesized by copolymerizing N-isopropylacrylamide (NIPAM), which possesses thermal-responsive properties; acrylic acid, which endows adhesive properties; and 2-ethylhexyl acrylate, which has a low glass transition temperature to attain sufficient flexibility. The synthesized NIPAM-based thermo-switchable PSAs exhibited significantly high peel strength at room temperature (â¼15.41 N/25 mm at 20 °C), which decreased by â¼97% upon heating (â¼0.46 N/25 mm at 80 °C). Importantly, no residues remained due to the cohesive nature of NIPAM at high temperature. The reversible adhesion behaviour of the thermo-switchable PSAs was retained during repeated heating and cooling cycles. Therefore, the developed thermo-switchable PSA can enhance the reusability and recyclability of valuable materials and minimize the use of toxic chemicals for adhesive removal, contributing to a more sustainable future.
Polymer particles that switch their shape and color in response to light are of great interest for the development of programmable smart materials. Herein, we report block copolymer (BCP) particles with reversible shapes and colors activated by irradiation with ultraviolet (UV) and visible lights. This shape transformation of the BCP particles is achieved by a spiropyran-dodecyltrimethylammoium bromide (SP-DTAB) surfactant that changes its amphiphilicity upon photoisomerization. Under UV light (365 nm) irradiation, the hydrophilic ring-opened merocyanine form of the SP-DTAB surfactant affords the formation of spherical, onion-like BCP particles. In contrast, when exposed to visible light, surfactants with the ring-closed form yield prolate or oblate BCP ellipsoids with axially stacked nanostructures. Importantly, the change in BCP particle morphology between spheres and ellipsoids is reversible over multiple UV and visible light irradiation cycles. In addition, the shape- and color-switchable BCP particles are integrated to form a composite hydrogel, demonstrating their potential as high-resolution displays with reversible patterning capabilities.
The precise self-assembly of block copolymers (BCPs) and inorganic nanoparticles (NPs) under 3D confinement offers microparticles with programmable nanostructures and functionalities. Here, fluorescence-switchable hybrid microspheres are developed by forming doubly alternating arrays of Au NPs and CdSe/ZnS quantum dots (QDs) within polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) BCP domains. These doubly alternating arrays afford controlled nonradiative energy transfer (NRET) between the QDs and Au NPs that is dependent on the layer-to-layer distance. Solvent-selective swelling of the hybrid particles tunes the distance between layers, modulating their NRET behavior and affording switchable fluorescence. The particle fluorescence is "OFF" in water through strong NRET from the QDs to Au NPs, but is "ON" in alcohols due to the increased distance between the Au NP and QD arrays in the swollen P4VP domains. The experimentally observed NRET intensity as a function of interparticle distance shows larger quenching efficiencies than those theoretically predicted due to the enhanced quenching within a 3D-confined system. Finally, the robust and reversible fluorescence switching of the hybrid particles in different solvents is demonstrated, highlighting their potentials for bioimaging, sensing, and diagnostic applications.
Nanoparticles , Nanostructures , Quantum Dots , Fluorescence , Polymers
Multiphase microscale emulsions are a material platform that can be tuned and dynamically configured by a variety of chemical and physical phenomena, rendering them inexpensive and broadly programmable optical transducers. Interface engineering underpins many of these sensing schemes but typically focuses on manipulating a single interface, while engineering of the multiphase junctions of complex emulsions remains underexplored. Herein, multiphilic triblock copolymer surfactants are synthesized and assembled at the triphase junction of a dynamically reconfigurable biphasic emulsion. Tailoring the linear structure and composition of the polymer surfactants provides affinity to each phase of the complex emulsion (hydrocarbon, fluorocarbon, and continuous water phase), yielding selective localization of polymers around the triphase junction. Conjugation of these polymers with gold nanoparticles, forming structured rings, affords a dynamic reflected isotropic structural color that tracks with emulsion morphology, demonstrating the uniquely enabling nature of a functionalized triphase interface. This color is the result of interference of light along the internal hydrocarbon/fluorocarbon interface, with the gold nanoparticles scattering and redirecting light into total internal reflection competent paths. Thus, the functionalization of the triphase junction renders complex emulsions colorimetric sensors, a powerful tool toward sensitive and simple sensing platforms.
Gold , Metal Nanoparticles , Emulsions , Surface-Active Agents , Water
A chemiresistive sensor is described for the detection of methane (CH4), a potent greenhouse gas that also poses an explosion hazard in air. The chemiresistor allows for the low-power, low-cost, and distributed sensing of CH4 at room temperature in air with environmental implications for gas leak detection in homes, production facilities, and pipelines. Specifically, the chemiresistors are based on single-walled carbon nanotubes (SWCNTs) noncovalently functionalized with poly(4-vinylpyridine) (P4VP) that enables the incorporation of a platinum-polyoxometalate (Pt-POM) CH4 oxidation precatalyst into the sensor by P4VP coordination. The resulting SWCNT-P4VP-Pt-POM composite showed ppm-level sensitivity to CH4 and good stability to air as well as time, wherein the generation of a high-valent platinum intermediate during CH4 oxidation is proposed as the origin of the observed chemiresistive response. The chemiresistor was found to exhibit selectivity for CH4 over heavier hydrocarbons such as n-hexane, benzene, toluene, and o-xylene, as well as gases, including carbon dioxide and hydrogen. The utility of the sensor in detecting CH4 using a simple handheld multimeter was also demonstrated.
Responsive polymer particles with switchable properties are of great importance for designing smart materials in various applications. Recently, the self-assembly of block copolymers (BCPs) and polymer blends within evaporative emulsions has led to advances in the shape-controlled synthesis of polymer particles. Despite extensive recent progress on BCP particles, the responsive shape tuning of BCP particles and their applications have received little attention. This review provides a brief overview of recent approaches to developing non-spherical polymer particles from soft evaporative emulsions based on the physical principles affecting both particle shape and inner structure. Special attention is paid to the stimuli-responsive, shape-changing nanostructured polymer particles, i.e., design of polymers and surfactant pairs, detailed experimental results, and their applications, including the state-of-the-art progress in this field. Finally, the perspectives on current challenges and future directions in this research field are presented, including the development of surfactants with higher reversibility to multiple stimuli and polymers with unique structural functionality, and diversification of polymer architectures.
The capping reagent plays an essential role in the functional properties of gold nanoparticles (AuNPs). Multiple stimuli-responsive materials are generated via diverse surface modification. The ability of the organic ligand shell on a gold surface to create a porous shell capable of binding small molecules is demonstrated as an approach to detect molecules, such as methane, that would be otherwise difficult to sense. Thiols are the most studied capping ligands of AuNPs used in chemiresistors. Phosphine capping groups are usually seen as stabilizers in synthesis and catalysis. However, by virtue of the pyramidal shape of triarylphosphines, they are natural candidates to create intrinsic voids within the ligand shell of AuNPs. In this work, surface-functionalized (capped) AuNPs with chelating phosphine ligands are synthesized via two synthetic routes, enabling chemiresistive methane gas detection at sub-100 ppm levels. These AuNPs are compared to thiol-capped AuNPs, and studies were undertaken to evaluate structure-property relationships for their performance in the detection of hydrocarbons. Polymer overcoatings applied to the conductive networks of the functionalized AuNP arrays were shown to reduce resistivity by promoting the formation of conduction pathways with decreased core-core distance between nanoparticles. Observations made in the context of developing methane sensors provide insight relevant to applications of phosphine or phosphine-containing surface groups in functional AuNP materials.
Photothermal heating with accurate monitoring of local temperature in complex biological fluids is crucial for therapeutic accuracy. Herein, photothermal microgels are developed to heat microscopic volumes through photothermal conversion and report the local temperature with a colorimetric response. The microgels consist of poly(ethylene glycol)-based hydrogels, which integrate temperature-responsive block-copolymer-grafted MoS2 nanosheets (BCP-grafted MoS2 NSs). The MoS2 NSs are used as a fluorescence quencher as well as an efficient photothermal agent, with their surface decorated with three distinct temperature-responsive BCPs containing blue-, green-, and red-fluorescent dyes. Upon irradiation of near-infrared light, MoS2 NSs convert the radiation into heat, and the BCPs change their conformation depending on the local temperature, selectively activating Förster resonance energy transfer of the three dyes. The use of three distinct BCPs and dyes enables the measurement of temperature in a wide range (i.e., from 25 to 50 °C). Importantly, the hydrogel matrix excludes molecules larger than the limiting mesh size so that BCP-grafted MoS2 NSs remain free from contamination against large adhesive proteins such as albumin, thus maintaining their sensitivity even in complex fluids.
Colorimetry , Disulfides/chemistry , Fluorescent Dyes/chemistry , Heating , Microgels/chemistry , Molybdenum/chemistry , Molecular Structure , Particle Size , Photochemical Processes
We report the dispersion of single-walled carbon nanotubes (SWCNTs) using pentiptycene polymers and their use in chemiresistance-based and QCM-D sensors. Poly(p-phenylene ethynylene)s (PPEs) incorporating pentiptycene moieties present a concave surface that promotes π-π interactions and van der Waals interactions with SWCNTs. In contrast to more common polymer-dispersing mechanisms that involve the wrapping of polymers around the SWCNTs, we conclude that the H-shape of pentiptycene groups and the linear rigid-rod structure creates a slot for nanotube binding. UV-vis-NIR, Raman, and fluorescence spectra and TEM images of polymer/SWCNTs support this dispersion model, which shows size selectivity to SWCNTs with diameters of 0.8-0.9 nm. Steric bulk on the channels is problematic, and tert-butylated pentiptycenes do not form stable dispersions with SWCNTs. This result, along with the diameter preference, supports the model in which the SWCNTs are bound to the concave clefts of the pentiptycenes. The binding model suggests that the polymer/SWCNTs complex creates galleries, and we have demonstrated the binding of benzene, toluene, and o-xylene (BTX) vapors as the basis for a robust, sensitive, and selective sensing platform for BTX detection. The utility of our sensors is demonstrated by the detection of benzene at the OSHA short-term exposure limit of 5 ppm in air.
Full-color reflective photonic ellipsoidal polymer particles, capable of a dynamic color change, are created from dendronized brush block copolymers (den-BBCPs) self-assembled by solvent-evaporation from an emulsion. Surfactants composed of dendritic monomer units allow for the precise modulation of the interfacial properties of den-BBCP particles to transition in shape from spheres to striped ellipsoids. Strong steric repulsions between wedge-type monomers promote rapid self-assembly of polymers into large domains (i.e., 153 nm ≤ D ≤ 298 nm). Of note, highly ordered axially stacked lamellae (i.e., number of layers >100) within an ellipsoid give rise to a near-perfect photonic multilayer. The reflecting color is readily tunable across the entire visible spectrum by alteration of the molecular weight from 477 to 1144 kDa. Finally, the photonic ellipsoids are functionalized with magnetic nanoparticles organized into bands on the particle surface to produce real-time on/off coloration by magnetic field-assisted activation. In total, the reported photonic ellipsoidal particles represent a new class of switchable photonic materials.
Confined assembly of block copolymers (BCPs) is receiving increasing attention due to the ability to create unconventional morphologies that cannot be observed in the corresponding bulk systems. This effect is further driven by the simplicity and versatility of these procedures for controlling the shape of particles prepared by 3D soft confinement of BCPs in emulsions. By taking advantage of a mobile emulsion interface, the one-step formation of nonspherical BCP particles through spontaneous deformation is possible with design principles and theoretical models for controlling shape/nanostructure now being established. This Viewpoint highlights strategies for shape tuning of BCP particles, currently accessible shapes, their controllability, and potential application. The emergence of 3D soft confinement of BCPs and related theory is overviewed with a focus on current strategies, types of nonspherical shapes achieved, and structure-property relationships for nonspherical BCP particles. Finally, the applications and future perspectives for these materials are discussed.
Dynamically reconfigurable oil-in-water (o/w) Pickering emulsions are developed, wherein the assembly of particles (i.e., platinum-on-carbon and iron-on-carbon particles) can be actively controlled by adjusting interfacial tensions. A balanced adsorption of particles and surfactants at the o/w interface allows for the creation of inhomogeneity of the particle distribution on the emulsion surface. Complex Pickering emulsions with highly controllable and reconfigurable morphologies are produced in a single step by exploiting the temperature-sensitive miscibility of hydrocarbon and fluorocarbon liquids. Dynamic adsorption/desorption of (polymer) surfactants afford both shape and configuration transitions of multiple Pickering emulsions and encapsulated core/shell structured can be transformed into a Janus configuration. Finally, to demonstrate the intrinsic catalytic or magnetic properties of the particles provided by carbon bound Pt and Fe nanoparticles, two different systems are investigated. Specifically, the creation of a bimetallic microcapsule with controlled payload release and precise modulation of translational and rotational motions of magnetic emulsions are demonstrated, suggesting potential applications for sensing and smart payload delivery.
A robust strategy is developed for preparing light-responsive block copolymer (BCP) particles in which shape and color can be actively controlled with high spatial and temporal resolution. The key to achieving light-responsive shape transitions of BCP particles is the design and synthesis of surfactants containing light-active groups (i.e., nitrobenzyl esters and coumarin esters) that modulate the amphiphilicity and interfacial activity of the surfactants in response to light of a specific wavelength. These light-induced changes in surfactant structure modify the surface and wetting properties of BCP particles, affording both shape and morphological transitions of the particles, for example from spheres with an onion-like inner morphology to prolate or oblate ellipsoids with axially stacked nanostructures. In particular, wavelength-selective shape transformation of the BCP particles can be achieved with a mixture of two light-active surfactants that respond to different wavelengths of light (i.e., 254 and 420 nm). Through the use of light-emitting, photoresponsive surfactants, light-induced changes in both color and shape are further demonstrated. Finally, to demonstrate the potential of the light-triggered shape control of BCP particles in patterning features with microscale resolution, the shape-switchable BCP particles are successfully integrated into a patterned, free-standing hydrogel film, which can be used as a portable, high-resolution display.
Herein, we report a simple and robust strategy for preparing dual-responsive shape-switchable block copolymer (BCP) particles, which respond to subtle temperature and pH changes near physiological conditions (i.e., human body temperature and neutral pH). The shape transition of polystyrene- b-poly(4-vinylpyridine) BCP particles between lens and football shapes occurs in very narrow temperature and pH ranges: no temperature-based transition for pH 6.0, 40-50 °C transition for pH 6.5, and 25-35 °C for pH 7.0. To achieve these shape transitions, temperature/pH-responsive polymer surfactants of poly( N-(2-(diethylamino)ethyl)acrylamide- r- N-isopropylacrylamide) are designed to induce dramatic changes in relative solubility and their location in response to temperature and pH changes near physiological conditions. In addition, the BCP particles exhibit reversible shape-transforming behavior according to orthogonal temperature and pH changes. Colorimetric measurements of temperature and pH changes are enabled by shape-transforming properties combined with selective positioning of dyes, suggesting promising potential for these particles in clinical and biomedical applications.
Coloring Agents/chemistry , Polystyrenes/chemistry , Polyvinyls/chemistry , Pyridines/chemistry , Surface-Active Agents/chemistry , Body Temperature , Humans , Hydrogen-Ion Concentration , Temperature , Transition Temperature
Development of particles that change shape in response to external stimuli has been a long-thought goal for producing bioinspired, smart materials. Herein, the temperature-driven transformation of the shape and morphology of polymer particles composed of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymers (BCPs) and temperature-responsive poly(N-isopropylacrylamide) (PNIPAM) surfactants is reported. PNIPAM acts as a temperature-responsive surfactant with two important roles. First, PNIPAM stabilizes oil-in-water droplets as a P4VP-selective surfactant, creating a nearly neutral interface between the PS and P4VP domains together with cetyltrimethylammonium bromide, a PS-selective surfactant, to form anisotropic PS-b-P4VP particles (i.e., convex lenses and ellipsoids). More importantly, the temperature-directed positioning of PNIPAM depending on its solubility determines the overall particle shape. Ellipsoidal particles are produced above the critical temperature, whereas convex lens-shaped particles are obtained below the critical temperature. Interestingly, given that the temperature at which particle shape change occurs depends solely on the lower critical solution temperature (LCST) of the polymer surfactants, facile tuning of the transition temperature is realized by employing other PNIPAM derivatives with different LCSTs. Furthermore, reversible transformations between different shapes of PS-b-P4VP particles are successfully demonstrated using a solvent-adsorption annealing with chloroform, suggesting great promise of these particles for sensing, smart coating, and drug delivery applications.
Nanostructures/chemistry , Acrylic Resins/chemistry , Cetrimonium , Cetrimonium Compounds/chemistry , Microscopy, Electron, Transmission , Particle Size , Polystyrenes/chemistry , Polyvinyls/chemistry , Surface-Active Agents/chemistry , Temperature
A series of porous block copolymer (BCP) particles with controllable morphology and pore sizes was fabricated by tuning the interfacial behavior of BCP droplets in oil-in-water emulsions. A synergistic adsorption of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) BCPs and sodium dodecyl sulfate (SDS) to the surface of the emulsion droplet induced a dramatic decrease in the interfacial tension and generated interfacial instability at the particle surface. In particular, the SDS concentration and the P4VP volume fraction of PS-b-P4VP were key parameters in determining the degree of interfacial instability, leading to different types of particles including micelles, capsules, closed-porosity particles, and open-porosity particles with tunable pore sizes ranging from 10 to 500 nm. The particles with open-porosity could be used as pH-responsive, high capacity delivery systems where the uptake and release of multiple dyes could be achieved.
