Ligand-Directed Shape Reconfiguration in Inorganic Materials.

Polymer elastomers with reversible shape-changing capability have led to significant development of artificial muscles, functional devices, and soft robots. By contrast, reversible shape transformation of inorganic nanoparticles is notoriously challenging due to their relatively rigid lattice structure. Here, the authors demonstrate the synthesis of shape-changing nanoparticles via an asymmetrical surface functionalization process. Various ligands are investigated, revealing the essential role of steric hindrance from the functional groups. By controlling the unbalanced structural hindrance on the surface, the as-prepared clay nanoparticles can transform their shape in a fast, facile, and reversible manner. In addition, such flexible morphology-controlled mechanism provides a platform for developing self-propelled shape-shifting nanocollectors. Owing to the ion-exchanging capability of clay, these self-propelled nanoswimmers (NS) are able to autonomously adsorb rare earth elements with ultralow concentration, indicating the feasibility of using naturally occurring materials for self-powered nanomachine.

Iridescence in nematics: Photonic liquid crystals of nanoplates in absence of long-range periodicity.

Photonic materials with positionally ordered structure can interact strongly with light to produce brilliant structural colors. Here, we found that the nonperiodic nematic liquid crystals of nanoplates can also display structural color with only significant orientational order. Owing to the loose stacking of the nematic nanodiscs, such colloidal dispersion is able to reflect a broad-spectrum wavelength, of which the reflection color can be further enhanced by adding carbon nanoparticles to reduce background scattering. Upon the addition of electrolytes, such vivid colors of nematic dispersion can be fine-tuned via electrostatic forces. Furthermore, we took advantage of the fluidity of the nematic structure to create a variety of colorful arts. It was expected that the concept of implanting nematic features in photonic structure of lyotropic nanoparticles may open opportunities for developing advanced photonic materials for display, sensing, and art applications.

Computational ghost imaging via adaptive deep dictionary learning.

Ghost imaging has gone through from quantum to classical pseudothermal to computational field over the last two decades. As a kernel part in computational ghost imaging (CGI), the reconstruction algorithm plays a decisive role in imaging quality and system practicality. In order to introduce more prior knowledge into the reconstruction algorithm, existing research adds image patch prior into CGI and improves the imaging efficiency. In this paper, the total variation minimization algorithm via adaptive deep dictionary learning (TVADDL) is proposed to update an adaptive deep dictionary through the CGI reconstruction process. The proposed algorithm framework is able to capture more precise texture features with a multi-layer architecture dictionary and adapt the learned dictionary by gradient descent on CGI reconstruction loss value. The results of simulation and experiment show that TVADDL can achieve higher peak signal-to-noise ratio than the algorithms without patch prior and the algorithms using the shallow dictionary or non-adaptive deep dictionary.

Facile one-step microwave-assisted modification of kaolinite and performance evaluation of pickering emulsion stabilization for oil recovery application.

A facile one-step microwave-assisted method was proposed for kaolinite intercalation and grafting. The structure, morphology, composition, and size distribution of kaolinite sheets were investigated using various methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric (TG) analysis. The potential application of the modified kaolinite as an oil/water emulsion stabilizer was studied. The results verified that intact kaolinite sheets were obtained. The dodecane/water emulsion stabilized by the modified kaolinite remained stable for more than 60 days. The effective performance suggests that the effectiveness of the proposed kaolinite modification method may be useful for Pickering emulsion stabilization in oil recovery applications.

AC Electrodeposition of PEDOT Films in Protic Ionic Liquids for Long-Term Stable Organic Electrochemical Transistors.

Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)-based organic electrochemical transistors (OECTs) are widely utilized to construct highly sensitive biosensors. However, the PSS phase exhibits insulation, weak acidity, and aqueous instability. In this work, we fabricated PEDOT OECT by alternating current electrodeposition in protic ionic liquids. The steady-state characteristics were demonstrated to be stable in long-term tests. In detail, the maximum transconductance, the on/off current ratio, and the hysteresis were stable at 2.79 mS, 504, and 0.12 V, respectively. Though the transient behavior was also stable, the time constant could reach 218.6 ms. Thus, the trade-off between switching speed and stability needs to be considered in applications that require a rapid response.

All-inorganic perovskite quantum dots stabilized blue phase liquid crystals.

All-inorganic perovskite quantum dots (PQDs) have been effectively incorporated in the three-dimensional ordered structure of blue phase liquid crystals (BPLCs) to stabilize the BPLCs. Uniform dispersion, reduced phase transition temperature, widened BP temperature range, dynamic and fast electro-optical response and static optical display of selective reflection mode and photoluminescence mode have been confirmed with a given concentration of PQDs. Such a novel strategy of assembling all-inorganic PQDs in BPLCs shows favorable prospects for wide-range and near room temperature BPLCs, responsive BPLCs, multifunctional display materials and tunable bandgap lasers.

Assembly and Chiral Memory Effects of Dynamic Macroscopic Supramolecular Helices.

Macroscopic enantiomerically pure helical supramolecular fibers are bottom-up assembled in aqueous media from a chiral π-electron donor template and an achiral π-electron acceptor. The helices can be assembled to the sub-millimeter scale with controlled handedness. These dynamic supramolecular architectures allow for a quantitative exchange of the chiral donor template with achiral analogues. During this process, a chiral memory effect was observed, affording enantiomerically pure helices composed entirely of achiral components.

Self-assembly of anisotropic red blood cell (RBC)-like colloidal particles.

Non-spherical colloidal particles, as basic building blocks, exhibit special capability in constructing novel materials. In this work, red blood cell (RBC)-like, anisotropic particles were synthesized and the self-assembly of the RBC-like particles was then carried out at the air-water interface. Subsequently, multilayer 3D structured colloidal crystals were also fabricated. The as-prepared colloidal crystal film displays beautiful Bragg diffraction, which can be used to construct a photonic crystal. After that, the self-assembly of binary colloidal particles was explored to design well-patterned binary colloidal crystals. This facile self-assembly approach to prepare colloidal crystals may extend to other anisotropic building blocks, providing guidance for the fabrication of more complex and flexible materials.

Electrostatic-Driven Dynamic Jamming of 2D Nanoparticles at Interfaces for Controlled Molecular Diffusion.

Dynamically engineering the interfacial interaction of nanoparticles has emerged as a new approach for bottom-up fabrication of smart systems to tailor molecular diffusion and controlled release. Janus zwitterionic nanoplates are reported that can be switched between a locked and unlocked state at interfaces upon changing surface charge, allowing manipulation of interfacial properties in a fast, flexible, and switchable manner. Combining experimental and modeling studies, an unambiguous correlation is established among the electrostatic energy, the interface geometry, and the interfacial jamming states. As a proof-of-concept, the well-controlled interfacial jamming of nanoplates enabled the switchable molecular diffusion through liquid-liquid interfaces, confirming the feasibility of using nanoparticle-based surfactants for advanced controlled release.

Staged phase separation in the I-I-N tri-phase region of platelet-sphere mixtures.

Mixtures of colloids with different sizes or shapes are ubiquitous in nature and extensively applied in industries. Phase transition pathways and kinetics in this model system should be investigated because of the difficulty in observing tri-phase coexistence in colloidal platelet-sphere mixtures. Similar to the polymer-sphere mixtures, the phase transition pathway has three main categories. Analytical results show a staged phase transition process in which the mixture first separates into one or two metastable phases, then further separates, and subsequently reaches tri-phase equilibrium. Unique to our system, and different from the gas-liquid-crystal coexistence in colloid-polymer mixtures, the platelet-sphere mixture reached a gas-liquid-liquid crystal (nematic) coexistence. Thus, the different phases are easy to distinguish using the birefringence of the liquid crystals. In addition, the volume fraction of the liquid crystal formation in the ZrP platelet suspensions is much lower than for the crystal formation in hard spheres.

Polydispersity reduction of colloidal plates via size fractionation of the isotropic-nematic phase transition.

Controlling the size polydispersity of colloidal particles is important for their phase transitions, resulting structures, and properties. In this study, a fractionation method was established to control the polydispersity of colloidal plates based on the isotropic-nematic (I-N) phase transition. The size ratio of nanoplates between the N phase and the I phase (DN/DI) was relatively large, whereas the size polydispersities in both the N phase and the I phase were smaller than that of the original sample before fractionation. The degree of fractionation was dependent on the time since the phase transition began and the polydispersity of the original sample. A long time resulted in a small DN/DI and a small degree of polydispersity reduction. The experimental data confirmed a quadratic scaling of DN/DI with polydispersity that was predicted by simulations. Large to small particles were segregated sequentially by sedimentation because of self-assembly and gravity. The polydispersity reduction based on the I-N phase transition can be utilized to select nanoplates with a certain size with improved size monodispersity.

Magnetically-active Pickering emulsions stabilized by hybrid inorganic/organic networks.

Magnetically-active hybrid networks (MHNs) are complex inorganic/organic composite materials that have been synthesized from the coupling of amine-functionalized iron oxide nanoparticles (amine-IONs) and pre-assembled shell crosslinked knedel-like (SCK) polymeric nanoconstructs. The intricate structure of these materials is composed of several inter-connected bundles of SCKs covalently bound to amine-IONs, which afford them magnetic responsivity. The MHNs were originally designed to sequester complex hydrocarbons from water; however, they have displayed a remarkable ability to form stable Pickering emulsions between organic solvents and water, upon mechanical stimulus. Two methods of emulsification, vortex and probe sonication, have been utilized to yield magnetically-active toluene-in-water and dodecane-in-water emulsions, which are stable for up to two months in the presence of the MHNs. A detailed study of the effect of the water-to-oil (W : O) volume ratio and the MHN concentration on the droplet size of the emulsions revealed that the smallest droplet size, and narrowest dispersity were obtained at a W : O = 3 : 1, for all conditions tested. Additionally, concentrations of MHNs as low as 1 mg mL-1 and 1.5 mg mL-1, for emulsions prepared via vortex and probe sonication, respectively, were sufficient to yield the smallest droplets and narrowest distributions. Furthermore, the oil droplets stabilized by the MHNs exhibited magnetic character, and could be manipulated with an external magnetic field.

Observation of isotropic-isotropic demixing in colloidal platelet-sphere mixtures.

Mixtures of colloids with different sizes and shapes are ubiquitous in nature and industry. The possible existence of isotropic-isotropic (I1-I2) demixing of platelets and spheres remains an open question. Here we present direct experimental evidence of I1-I2 demixing using platelets with a very small thickness-to-diameter ratio mixed with silica spheres at the size ratio q = R(sphere)/R(disk) = 0.0901 ± 0.0004. The platelets cause the isotropic-to-nematic phase transition at a very low volume fraction because of their highly anisometric shape. The presence of silica spheres in the suspension accelerates the phase transition and packs the nematic phase more densely via depletion interaction. Increasing the sphere volume fraction to 0.0014, a tri-phase region emerges. This direct observation of I1-I2 demixing seems to validate the free-volume scaled particle theory and indicates the need for refinement of the fundamental measure density functional theory.

Thermo-sensitive discotic colloidal liquid crystals.

We fabricated for the first time thermo-sensitive discotic liquid crystals by grafting poly(N-isopropylacrylamide) (PNIPAM) onto zirconium phosphate (ZrP) platelets using pre-irradiated polymerization. The I-N transition was investigated by adjusting the temperature for a single set of samples. We found that soft disks self-assemble into nematic liquid crystals in a wider thickness-over-diameter ratio than do hard disks.

Observation of the photorefractive effects in bent-core liquid crystals.

We present a new observation of photorefractive (PR) effects in bent-core nematic (BCN) liquid crystal (LC) materials, where two kinds of optical-induced gratings are demonstrated and compared in pure and surface-doped BCN systems. The experimental results showed that these two kinds of gratings exhibit distinctive different polarization-dependent and angular-dependent behaviors, respectively. Furthermore, we supplied the pure and surface-doped rodlike LC systems for comparison, which revealed that V shape molecular structure of BCN can produce charge carrier more efficiently than rodlike molecular structure does. Thus BCN materials can offer an exciting potential for optical information processing.

Gelation via ion exchange in discotic suspensions.

The phase behavior of charged disk suspensions displays a strong dependence on ionic strengths, as the interplay between excluded volume and electrostatic interactions determines the formation of glasses, gels, and liquid crystal states. The various ions in natural soil or brine, however, could present additional effects, especially considering that most platelet structures bear a momentous ion-exchange capacity. Here we observed how ion exchange modulates and controls the interaction between individual disks and leads to unconventional phase transitions from isotropic gel to nematic gel and finally to nematic liquid crystals.

Signatures of structural recovery in colloidal glasses.

Colloids near the glass concentration are often taken as models for molecular glasses. Yet, an important aspect of the dynamics of molecular glasses, structural recovery, has not been elucidated in colloids. We take advantage of a thermosensitive colloidal suspension to study the structural recovery after concentration jumps by using diffusing wave spectroscopy. The three classical aging signatures observed in molecular glasses are studied and the results are compared with those typical of molecular glasses. For the intrinsic isotherms, unlike molecular glasses, the colloid shows huge changes in relaxation time at equilibrium while the times required to reach the equilibrium state are nearly constant. For asymmetry of approach, we find a similar nonlinearity to that observed in the molecular glasses. For the memory experiment, while a memory effect is seen, the response is qualitatively different from that in molecular glasses.

Amphiphilicity-adaptable graphene quantum dots to stabilize pH-responsive pickering emulsions at a very low concentration.

HYPOTHESIS: Stimuli-responsive Pickering emulsions have attracted considerable interest due to their widespread potential applications. Especially pH-responsive behavior could be easily implemented. In this work, we reported a pH-responsive Pickering emulsion based on amphiphilic graphene quantum dots at a low concentration which shows a great potential from the environmental and economic perspective. The stimuli responsive properties would make the smart Pickering emulsifiers recyclable and reusable. EXPERIMENTS: The amphiphilic-adaptable graphene quantum dots functionalized by alkyl groups (C-GQDs) were synthesized by a facile one-step pyrolysis method. The pH-responsive emulsion performances were investigated, and the mechanism of pH-responsive of C-GQDs was studied by dynamic light scattering. FINDINGS: The amphiphilicity of C-GQDs could be acquired controllably and effectively by this facile one-step pyrolysis method, which are able to stabilize Pickering emulsion at a very low concentration (0.001%). The amphiphilicity of C-GQDs are capable of changing in response to environmental stimuli. When the pH value of aqueous solution adjusts to 2, these C-GQDs aggregate in contrast to their stability in neutral condition due to the alternation of surface charges. The pH-responsive aggregation/ dispersion behavior of C-GQDs allows us to tune the interactions between oil-in-water emulsion droplets without introduction of destabilization agents. This will provide huge economic benefits in industrial applications in the future.

Engineered two-dimensional nanomaterials: an emerging paradigm for water purification and monitoring.

Water scarcity has become an increasingly complex challenge with the growth of the global population, economic expansion, and climate change, highlighting the demand for advanced water treatment technologies that can provide clean water in a scalable, reliable, affordable, and sustainable manner. Recent advancements on 2D nanomaterials (2DM) open a new pathway for addressing the grand challenge of water treatment owing to their unique structures and superior properties. Emerging 2D nanostructures such as graphene, MoS2, MXene, h-BN, g-C3N4, and black phosphorus have demonstrated an unprecedented surface-to-volume ratio, which promises ultralow material use, ultrafast processing time, and ultrahigh treatment efficiency for water cleaning/monitoring. In this review, we provide a state-of-the-art account on engineered 2D nanomaterials and their applications in emerging water technologies, involving separation, adsorption, photocatalysis, and pollutant detection. The fundamental design strategies of 2DM are discussed with emphasis on their physicochemical properties, underlying mechanism and targeted applications in different scenarios. This review concludes with a perspective on the pressing challenges and emerging opportunities in 2DM-enabled wastewater treatment and water-quality monitoring. This review can help to elaborate the structure-processing-property relationship of 2DM, and aims to guide the design of next-generation 2DM systems for the development of selective, multifunctional, programmable, and even intelligent water technologies. The global significance of clean water for future generations sheds new light and much inspiration in this rising field to enhance the efficiency and affordability of water treatment and secure a global water supply in a growing portion of the world.

Bioinspired Multiple Stimuli-Responsive Optical Microcapsules Enabled by Microfluidics.

Optical microcapsules encapsulating optical materials inside a symmetric spherical confinement are significant elements for the construction of optical units and the integration of optical arrays. However, the multiple stimuli-responsive characteristic of optical microcapsules still remains a challenge due to the insuperable physical barrier between the optical material core and the outside shell and the lack of effective mechanisms to trigger the dynamic switch of the encapsulated optical materials. Inspired by the dual-mode optical modulation of chameleon skins, a novel biomimetic binary optical microcapsule that combines the visible light reflection of chiral nematic liquid crystals and photoluminescence emission of rare-earth complexes is assembled by microfluidic emulsification and interfacial polymerization. The reflected color, fluorescent intensity, and size of the optical microcapsules are facilely controlled in the microfluidic chip by adjusting the composition and flow rate of the injected fluids. Most importantly, the biomimetic binary optical microcapsules demonstrate three reversible responsive behaviors, thermotropic reflection evolution, temperature-dependent fluorescence emission, and Fredericks electro-optical response. The bioinspired multiple stimuli-responsive optical microcapsules enabled by microfluidics provide a templated strategy to manufacture the next generation of intelligent optical units and to achieve the dynamic response of hybrid photonic devices.