Frank-Kasper phases in charge transfer complexes enable tunable photoelectronic properties.

Understanding how particles pack in space and the mechanisms underlying symmetry selection across soft matter is challenging. The Frank-Kasper (F-K) phase of complex spherical packing is amongst the most fascinating phases; however, it has not been observed in discotic liquid crystals until now. Herein, we report the first observation of F-K phases of charge transfer complexes (CTCs) obtained from triphenylene derivatives as donors and 2,4,7-trinitro-9-fluorenone as the acceptor. The CTCs were characterized using experimental and theoretical calculations, indicating that the F-K A15 cubic lattice possesses a unit cell containing 8 sphere-like supramolecules, each of which was self-assembled from 3 CTC complexes. The lattice constant was only 3.2 nm, which is by far the smallest for the A15 phase. Interestingly, the supramolecular assembly can be regarded as the molecular column splitting into isolated spherical fragments, impeding charge transfer and turning it into one insulator. This provides a simple and effective method for preparing asymmetric complex compounds for the design of unconventional self-assembled nanostructures.

Adsorption of triblock copolymers confined between two plates: An analytical approach.

We present an approximate analytical approach to the adsorption problem of ABA triblock copolymers confined between two parallel plates in a θ solvent and give the expression of the propagator q(x, t) as a piece-wise function by solving the modified diffusion equation. In this way, the role of separation between the two plates, adsorption energy and block lengths on segment concentration profile, chain conformations, and interaction potential is then investigated, which agrees well with the numerical results. It is demonstrated that there are parallels between lengthening adsorbing A blocks and increasing surface affinity: strong adsorption and long adsorbing blocks favor the formation of loops and bridges, whereas more tails and free chains exist in the case of weak adsorption and short A blocks at large separations. For moderate and strong adsorptions, the bridging fraction begins to plummet at a separation larger than the end-to-end distance of non-adsorbing B block RB and becomes negligible at above 2RB owing to the entropy effect. The depth of the potential well in the interaction potential profile depends on the adsorption energy and A block length, while the location of the potential minimum corresponds to the onset of the sharp decrease in bridges.

Precisely Controllable Artificial Muscle with Continuous Morphing based on "Breathing" of Supramolecular Columns.

Skeletal muscles are natural motors executing sophisticated work through precise control of linear contraction. Although various liquid crystal polymers based artificial muscles have been designed, the mechanism based on mainly the order-disorder transition usually leads to discrete shape morphing, leaving arbitrary and precise deformation a huge challenge. Here, one novel photoresponsive hemiphasmidic side-chain liquid crystal polymer with a unique "breathing" columnar phase that enables continuous morphing is presented. Due to confinement inside the supramolecular columnar assembly, the cooperative movements of side-chains and backbones generate a significant negative thermal expansion and lead to temperature-controllable muscle-like elongation/contraction in the oriented polymer strip. The irreversible isomerization of the photoresponsive mesogens results in the synergistic phototunable bending and high-contrast fluorescence change. Based on the orthogonal responses to heat and light, controllable arm-like bending motions of this material, which is applicable in constructing advanced artificial muscles or intelligent soft robotics, are further demonstrated.

Elastomers Grow into Actuators.

It is common knowledge that when an elastomer (rubber) is stretched, its length will be maintained if its two ends are fixed. Here, it is serendipitously found that when an elastomer is slowly elongated further to achieve buckling under such conditions, the final length is much longer than the pre-stretched length. This allows the design of untethered autonomous synthetic-material-based soft robots that do not need any other chemical or electrical energy sources or external stimuli after the pre-strain is installed. Once the growth starts, the elongation continues to proceed even when the applied force is removed. Moreover, the elastomer, after growing, eventually forms a robust soft actuator that can be reshaped for different purposes. Few synthetic materials can grow like this, so far. This investigation shows that the material has an uncommon liquid crystal phase. Contrary to normal liquid crystals, it becomes birefringent only at high temperatures. The formation and the reshaping of the resulting soft actuators relate to a usually unnoticed reversible reaction. The work is promising to promote further understanding of dynamic covalent chemistry and liquid crystal elastomers, as well as to foster new designs and high-impact applications of bioinspired sustainable soft actuators in areas other than soft robots.

The effect of ion pairs on coacervate-driven self-assembly of block polyelectrolytes.

The incorporation of oppositely charged polyelectrolytes into a block copolymer system can lead to formation of microphase separated nanostructures driven by the electrostatic complex between two oppositely charged blocks. It is a theoretical challenge to build an appropriate model to handle such coacervate-driven self-assembly, which should capture the strong electrostatic correlations for highly charged polymers. In this paper, we develop the self-consistent field theory considering the ion paring effect to predict the phase behavior of block polyelectrolytes. In our model, two types of ion pairs, the binding between two oppositely charged monomers and the binding between charged monomers and counterions, are included. Their strength of formation is controlled by two parameters Kaa and Kac, respectively. We give a detailed analysis about how the binding strength Kac and Kaa and salt concentration affect the self-assembled nanostructure of diblock polyelectrolyte systems. The results show that the binding between two oppositely charged blocks provides driven force for microphase separation, while the binding between charged monomers and counterions competes with the polyion pairing and thus suppresses the microphase separation. The addition of salt has a shielding effect on the charges of polymers, which is a disadvantage to microphase separation. The phase diagrams as a function of polymer concentration and salt concentration at different situations are constructed, and the influence of Kaa, Kac, and charged block composition fa is analyzed in depth. The obtained phase diagrams are in good agreement with currently existing experimental and theoretical results.

Multiphase Coacervates Driven by Electrostatic Correlations.

The liquid-liquid phase separation of a polyelectrolyte solution containing one type of negatively and two types of positively charged polymers with different charge densities is studied theoretically by random phase approximation (RPA). It is predicted that multicoacervate phases could coexist, driven purely by electrostatic correlations. The asymmetry of the linear charge density could induce an effective immiscibility between two positively charged polyelectrolytes, leading to the multiphase separation. Adding salt will induce the disappearance of the dilute phase, forming two coexisting complex phases, instead of fusion between coacervates. Raising temperature could either induce a two coexisting complex phase, or a dilute phase coexisting with a coacervate phase, depending on the bulk concentration. Our predictions are in good agreement with experiments and provide insights in the further designing of the multiphase coacervation system.

The size and affinity effect of counterions on self-assembly of charged block copolymers.

The effect of counterions' size and affinity on the microphase separated morphologies of neutral-charged diblock copolymers is investigated systematically using a random phase approximation (RPA) and self-consistent field theory (SCFT). The phase diagrams as a function of χAB and fA at different counterion sizes and different affinities to neutral blocks are constructed, respectively. Stability limits calculated using the RPA are in good agreement with the disorder-body-centered cubic phase boundaries from SCFT calculations. It was found that increasing the size of counterions causes the phase diagram to shift upward and leftward, which is attributed to electrostatic interactions and the intrinsic volume of counterions. The domain size of the ordered phase shows an unexpected tendency that it decreases with increasing counterions' size. The counterions' distributions in H and G phases demonstrate that it is electrostatic interaction, instead of packing frustration, that plays a leading role in such systems. For finite size counterions, with the increase in affinity between counterions and neutral blocks, the phase diagram shifts upward, indicating the improved compatibility between different blocks. Furthermore, the affinity effect between counterions and neutral blocks can be mapped into an effective Flory parameter χAB ' = χAB + 0.27χBC.

Multivalent counterions induced attraction between DNA polyelectrolytes.

In this paper we study the electrostatic attraction between two parallel rodlike DNA polyelectrolytes induced by neutralizing multivalent counterions at the zero temperature limit. The counterions crystallize on the charged surfaces of DNA so that we can handle the system by using the Wigner crystal lattice model. We derived the 3D ground state configuration of counterions with minimized energy by use of the gradient descent method, and calculated the interaction between two DNA cylinders with divalent or trivalent counterions when they approach. The results show that the complex ground state configuration of counterions plays a key role in determining the caused attraction. The counterions form three-dimensional Wigner crystals on each cylinder at large separation. When the cylinders are brought together, some counterion lines will move towards the inner region and lead to strong attraction. The calculated interaction from our model is in good agreement with the simulation result, however, the single particle approximation considerably overestimates the attraction.

Programmable 3D Shape-Change Liquid Crystalline Elastomer Based on a Vertically Aligned Monodomain with Cross-link Gradient.

A liquid crystalline elastomer (LCE) as a kind of stimuli-responsive materials, which can be fabricated to present the three-dimensional (3D) change in shape, shows a wide range of applications. Herein, we propose a simple and robust way to prepare a 3D shape-change actuator based on gradient cross-linking of the vertically aligned monodomain of liquid crystals (LCs). First, gold nanoparticles grafted by liquid crystalline polymers (LCPs) are used to induce the homeotropic orientation of the LC monomer and cross-linkers. Then, photopolymerization under UV irradiation is carried out, which can result in the LCE film with a cross-link gradient. Different from the typical LCEs with homogenous alignment that usually show the shape change of extension/contraction, the obtained vertically aligned LCE film exhibits excellent bendability under a thermal stimulus. The nanoindentation experiment demonstrates that the deformation of LCE films comes from the difference in Young's modulus on two sides of the thin film. Simply scissoring the thin film can prepare the samples with different bending angles under the fixed length. Moreover, using a photomask to pattern the film during photopolymerization can realize the complex 3D deformation, such as bend, fold, and buckling. Further, the patterned LCE film doped with multiwalled carbon nanotubes modified by LCPs (CNT-PDB) can act as a light-fueled microwalker with fast crawl behavior.

Polyhedral oligosilsesquioxane tethered perylene diimide for application in optical limiting and rapid detection of fluoride ions.

A novel perylene diimide derivative equipped with polyhedral oligosilsesquioxane nanocages (POSS-AMPDI) was designed and synthesized for application in optical limiting. Moreover, due to the dual mechanisms of POSS collapse and intermolecular proton transfer, POSS-AMPDI exhibits high sensitivity and rapid selectivity to fluoride ions, with a detection limit as low as 1.64 × 10-8 M.

Depletion driven self-assembly of block copolymer solutions by homopolymers.

The addition of a non-adsorbing homopolymer to a block copolymer solution provides a convenient strategy for regulating its self-assembly. We systematically investigate the depletion effect from a homopolymer on the morphologies of AB diblock and BAB triblock copolymers in selective solvents. Increasing the homopolymer content results in larger spherical micelles, and the curvature of micelles is proportional to the square of homopolymer concentrations. A high enough homopolymer concentration may transfer micelles into vesicles. A deep analysis shows that the depletion effect produces attractive interaction between hydrophilic B blocks as well as their contraction on the micellar surface. The size of triblock copolymer micelles is not affected by homopolymers significantly, and spherical-to-wormlike micelle transition occurs at high homopolymer contents. These results have important applications for the precise design of self-assembled nanostructures of copolymer systems.

Highly Efficient Luminescent Liquid Crystal with Aggregation-Induced Energy Transfer.

A luminescent liquid crystal molecule (TPEMes) with efficient solid-state emission is rationally constructed via the chemical conjugation of blue-emitting tetraphenylethene cores and luminescent mesogenic tolane moieties, which are both featured with aggregation-induced emission properties. As for this fluorophore, aggregation-induced energy transfer from the emissive tolane mesogens to the lighting-up tetraphenylethene units endows the molecule pure blue emission in the suspension and bulk state. Combining differential scanning calorimetry, polarized optical microscope, and one-dimensional X-ray diffraction (1D XRD) experiments, the compound TPEMes is deduced to adapt thermodynamically more stable layered crystalline phase and can be "frozen" into a monotropic smectic mesophase due to kinetic reasons. As a result of more dense packing of TPEMes in the crystalline phase indicated by 1D XRD, the luminescence of TPEMes in crystalline phase blue-shifted by 17 nm relative to the metastable mesophase.

Surface morphologies of spherical polyelectrolyte brushes induced by trivalent salt ions.

The surface morphologies of spherical polyelectrolyte brushes in salt solutions with opposite trivalent ions are studied using molecular dynamics (MD) simulations. The impact of salt concentration, grafting density, and charge fraction on brush morphologies is investigated systematically. A variety of surface patterns are predicted and the phase diagrams are presented. Both lateral and radial microphase separated structures in the brushes are observed upon varying the salt concentration. With low grafting density the spherical brush is separated into several patches, the number of which decreases with the addition of salt. At high grafting density, the polymer brush changes its morphology from an extended micelle to a 'carpet + brush' to the collapsed state upon increasing the salt concentration. Especially, the 'carpet + brush' structure consists of a core formed by partially collapsed brush chains and a corona formed by other stretched chains. The inter-chain 'bridging' interactions mediated by trivalent ions and the curvature effect play important roles in determining the chain conformations and brush structures.

Alignment Control of Nematic Liquid Crystal using Gold Nanoparticles Grafted by the Liquid Crystalline Polymer with Azobenzene Mesogens as the Side Chains.

The gold nanoparticles highly grafted by a liquid crystalline polymer (LCP) with azobenzene mesogens as the side chain (denoted as Au@TE-PAzo NPs) are successfully designed and synthesized by the two-phase Brust-Schiffrin method. The chemical structures of the monomer and polymer ligands have been confirmed by nuclear magnetic resonance, and the molecular weight of the polymer is determined by gel permeation chromatography. The combined analysis of transmission electron microscopy and thermogravimetric analysis shows that the size of the nanoparticles is 2.5(±0.4) nm and the content of the gold in the Au@TE-PAzo NPs is ca. 17.58%. The resultant Au@TE-PAzo NPs can well disperse in the nematic LC of 5CB. The well-dispersed mixture with appropriate doping concentrations can automatically form a perfect homeotropic alignment in the LC cell. The homeotropic alignment is attributed to the brush formed by Au@TE-PAzo NPs on the substrate, wherein the Au@TE-PAzo NPs gradually diffuse onto the substrate from the mixture. On the contrary, the pure side chain LCPs cannot yield vertical alignment of 5CB, which indicates that the alignment of 5CB is ascribed to the synergistic interaction of the nanoparticles and the grafted LCPs. Moreover, Au@TE-PAzo NPs show excellent film-forming property on account of their periphery of high densely grafted LCPs, which can form uniform thin film by spin-coating. The resultant thin film also can prompt the automatical vertical alignment of the nematic 5CB. Further, upon alternative irradiation of UV and visible light, the alignment of 5CB reversibly switches between vertical and random orientation because of the trans-cis photoisomerization of the azobenzene group on the periphery of Au@TE-PAzo NPs. These experimental results suggest that this kind of nanoparticles can be potentially applied in constructing the remote-controllable optical devices.

Ionic Self-Assembled Derivative of Tetraphenylethylene: Synthesis, Enhanced Solid-State Emission, Liquid-Crystalline Structure, and Cu2+ Detection Ability.

A novel tetraphenylethylene complex composed of 4',4'',4''',4''''-(ethene-1,1,2,2-tetrayl)tetrabiphenyl-4-carboxylic acid (H4 ETTC) and dimethyldioctadecylammonium bromide (DOAB) with enhanced solid-state emission is designed and synthesized through an ionic self-assembly (ISA) strategy. The aggregation-induced emission property, phase behavior, and supramolecular structure of the complex are characterized by a combination of experimental measurements. The experimental results reveal that the ISA complex can self-assemble into an ordered helical supramolecular structure with enhanced luminescent properties, although the ETTC cores possess extensive conjugation and high rigidity. Due to the prolonged conjugation length, the fluorescence quantum yield of ETTC-DOAB is boosted to 66 %. Moreover, it is demonstrated that assemblies of the ISA complex are an effective sensor for Cu2+ . Owing to the disassembly modulation of ETTC-DOAB aggregations, the fluorescence emission of the assemblies can be selectively and sensitively quenched by Cu2+ , with a detection limit as low as 12.6 nm. The enhanced emission efficiency, in combination with the liquid crystallinity and superior sensing performance to Cu2+ , make the ETTC-DOAB complex a potential candidate for the fabrication of a luminescent device and chemosensor for Cu2+ detection.

A homeotropic main-chain tolane-type liquid crystal elastomer film exhibiting high anisotropic thermal conductivity.

The development of pure polymeric films with anisotropic thermal conductivities for electronic device packaging applications has attracted intense scientific attention. In order to enhance the polymeric film's normal-direction thermal conductivity, homeotropic alignment of macromolecular chains is the primary concern. One of the promising preparation strategies is to perform in situ photopolymerization of homeotropic-oriented liquid crystal monomers. In this work, we design and synthesize a novel tolane-core thiol-ene-tailed liquid crystal monomer. Benefitting from the conjugated and extended tolane π-system of the mesogenic core and length extension of the terminal aliphatic tails, the normal-to-plane thermal conductivity value and the thermal conductivity anisotropy value of the corresponding cross-linked main-chain end-on liquid crystal polymer (xMELCP) film reach 3.56 W m-1 K-1 and 15.0, respectively. Compared with the data of a previously reported ester-type thiol-ene xMELCP film, the two primary values of this novel tolane-type thiol-ene xMELCP material are increased dramatically by 46% and 29%, respectively.

Thermoplastic High Strain Multishape Memory Polymer: Side-Chain Polynorbornene with Columnar Liquid Crystalline Phase.

A thermoplastic high strain multishape memory polymer can be fabricated using a hemiphasmid side-chain polynorbornene (P1) with hexagonal columnar liquid crystalline (ΦH ) phase. Without any chemical crosslinks, P1 can memorize multiple temporary shapes with high strain and exhibit excellent shape fixity and shape recovery. As the building blocks of ΦH , the multichain columns in P1 act as robust physical crosslinks.

Photocontrol of fluid slugs in liquid crystal polymer microactuators.

The manipulation of small amounts of liquids has applications ranging from biomedical devices to liquid transfer. Direct light-driven manipulation of liquids, especially when triggered by light-induced capillary forces, is of particular interest because light can provide contactless spatial and temporal control. However, existing light-driven technologies suffer from an inherent limitation in that liquid motion is strongly resisted by the effect of contact-line pinning. Here we report a strategy to manipulate fluid slugs by photo-induced asymmetric deformation of tubular microactuators, which induces capillary forces for liquid propulsion. Microactuators with various shapes (straight, 'Y'-shaped, serpentine and helical) are fabricated from a mechanically robust linear liquid crystal polymer. These microactuators are able to exert photocontrol of a wide diversity of liquids over a long distance with controllable velocity and direction, and hence to mix multiphase liquids, to combine liquids and even to make liquids run uphill. We anticipate that this photodeformable microactuator will find use in micro-reactors, in laboratory-on-a-chip settings and in micro-optomechanical systems.

Helical Polyacetylene-Based Switchable Chiral Columnar Phases: Frustrated Chain Packing and Two-Way Shape Actuator.

Chiral columns formed by a helical cis-polyphenylacetylene (PPA) derivative P1 are reversibly switched during a phase transition between two chiral columnar phases: the frustrated Φh (3D-SL) phase containing four chains at low temperature and a hexagonal columnar phase Φh at high temperature, accompanied by a simultaneous conformational change. The helix-helix transition along the PPA backbone during the Φh (3D-SL) -Φh transition makes the uniaxially oriented P1 capable of reversibly and reproducibly elongating (132 %) upon heating and contracting upon cooling, exhibiting the behavior of a two-way shape actuator.

A self-healing photoinduced-deformable material fabricated by liquid crystalline elastomers using multivalent hydrogen bonds as cross-linkers.

Liquid crystalline elastomers (LCEs) using multivalent hydrogen bonds as cross-linkers were successfully fabricated, which showed both self-healing and photoinduced-deformable properties. More interestingly, this LCE could be readily molded into different shapes through a versatile and efficient procedure, and the fibrous and filmy samples showed different photoinduced-deformable behavior originating from the difference in molecular orientations.