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.

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.

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.

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.

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.

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.

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.

Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering.

The engineering of structures across different length scales is central to the design of novel materials with controlled macroscopic properties. Herein, we introduce a unique class of self-assembling materials, which are built upon shape- and volume-persistent molecular nanoparticles and other structural motifs, such as polymers, and can be viewed as a size-amplified version of the corresponding small-molecule counterparts. Among them, "giant surfactants" with precise molecular structures have been synthesized by "clicking" compact and polar molecular nanoparticles to flexible polymer tails of various composition and architecture at specific sites. Capturing the structural features of small-molecule surfactants but possessing much larger sizes, giant surfactants bridge the gap between small-molecule surfactants and block copolymers and demonstrate a duality of both materials in terms of their self-assembly behaviors. The controlled structural variations of these giant surfactants through precision synthesis further reveal that their self-assemblies are remarkably sensitive to primary chemical structures, leading to highly diverse, thermodynamically stable nanostructures with feature sizes around 10 nm or smaller in the bulk, thin-film, and solution states, as dictated by the collective physical interactions and geometric constraints. The results suggest that this class of materials provides a versatile platform for engineering nanostructures with sub-10-nm feature sizes. These findings are not only scientifically intriguing in understanding the chemical and physical principles of the self-assembly, but also technologically relevant, such as in nanopatterning technology and microelectronics.

Membrane rigidity induced by grafted polymer brush.

The contribution of neutral polymer brush to the curvature elasticity of the grafting surface is investigated theoretically. Using self-consistent field theory, we accurately evaluate the dependence of bending modulus on parameters including chain length, Flory-Huggins parameter and grafting density and reveal the importance of solvent. The results show that the brush-induced bending modulus follows a complex dependence on grafting density and Flory-Huggins parameter, while it obeys a simple power law with chain length as N(3). The method is further applied to calculate the polymer brush's contribution to the elastic properties of PEG-grafted lipid monolayers.

Regulating block copolymer phases via selective homopolymers.

The phase behavior of strongly segregated AB diblock copolymer and selective C homopolymer blends is examined theoretically using a combination of strong stretching theory (SST) and self-consistent field theory (SCFT). The C-homopolymer is immiscible with the B-blocks but strongly attractive with the A-blocks. The effect of homopolymer content on the order-order phase transitions is analyzed. It is observed that, for AB diblock copolymers with majority A-blocks, the addition of the C-homopolymers results in lamellar to cylindrical to spherical phase transitions because of the A/C complexation. For diblock copolymers with minor A-blocks, adding C-homopolymers leads to transitions from spherical or cylindrical morphology with A-rich core to lamellae to inverted cylindrical and spherical morphologies with B-rich core. The results from analytical SST and numerical SCFT are in good agreement within most regions of the phase diagram. But the deviation becomes more obvious when the composition of A-blocks is too small and the content of added C-homopolymers is large enough, where the SCFT predicts a narrow co-existence region between different ordered phases. Furthermore, it is found that the phase behavior of the system is insensitive to the molecular weight of C-homopolymer.

Supramolecular [60]fullerene liquid crystals formed by self-organized two-dimensional crystals.

Fullerene-based liquid crystalline materials have both the excellent optical and electrical properties of fullerene and the self-organization and external-field-responsive properties of liquid crystals (LCs). Herein, we demonstrate a new family of thermotropic [60]fullerene supramolecular LCs with hierarchical structures. The [60]fullerene dyads undergo self-organization driven by π-π interactions to form triple-layer two-dimensional (2D) fullerene crystals sandwiched between layers of alkyl chains. The lamellar packing of 2D crystals gives rise to the formation of supramolecular LCs. This design strategy should be applicable to other molecules and lead to an enlarged family of 2D crystals and supramolecular liquid crystals.

Incorporating headgroup structure into the Poisson-Boltzmann model of charged lipid membranes.

Charged lipids often possess a complex headgroup structure with several spatially separated charges and internal conformational degrees of freedom. We propose a headgroup model consisting of two rod-like segments of the same length that form a flexible joint, with three charges of arbitrary sign and valence located at the joint and the two terminal positions. One terminal charge is firmly anchored at the polar-apolar interface of the lipid layer whereas the other two benefit from the orientational degrees of freedom of the two headgroup segments. This headgroup model is incorporated into the mean-field continuum Poisson-Boltzmann formalism of the electric double layer. For sufficiently small lengths of the two rod-like segments a closed-form expression of the charging free energy is calculated. For three specific examples--a zwitterionic headgroup with conformational freedom and two headgroups that carry an excess charge--we analyze and discuss conformational properties and electrostatic free energies.

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.

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.

Mesogen-jacketed liquid crystalline polymers.

This critical review covers the recent progress in the research of mesogen-jacketed liquid crystalline polymers (MJLCPs), special side-on side-chain liquid crystalline polymers with very short spacers or without spacers. MJLCPs can self-organize into supramolecular columnar phases with the polymer chains aligned parallel to one another or smectic phases with the backbones embedded in the smectic layers. The semi-rigid rod-like MJLCP with a tunable rod shape in both length and diameter provides an excellent building block in designing novel rod-coil liquid crystalline block copolymers which can self-assemble into hierarchical supramolecular nanostructures depending on the competition between liquid crystal formation and microphase separation (229 references).

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.

Hierarchical supramolecular ordering with biaxial orientation of a combined main-chain/side-chain liquid-crystalline polymer obtained from radical polymerization of 2-vinylterephthalate.

The liquid-crystalline (LC) phase structures and transitions of a combined main-chain/side-chain LC polymer (MCSCLCP) 1 obtained from radical polymerization of a 2-vinylterephthalate, poly(2,5-bis{[6-(4-butoxy-4'-oxybiphenyl) hexyl]oxycarbonyl}styrene), were studied using differential scanning calorimetry, one- and two-dimensional wide-angle X-ray diffraction (1D and 2D WAXD), and polarized light microscopy. We have found that 1 with sufficiently high molecular weight can self-assemble into a hierarchical structure with double orderings on the nanometer and subnanometer scales at low temperatures. The main chains of 1, which are rodlike as a result of the "jacketing" effect generated by the central rigid portion of the side chains laterally attached to every second carbon atom along the polyethylene backbone, form a 2D centered rectangular scaffold. The biphenyl-containing side chains fill the space between the main chains, forming a smectic E (SmE)-like structure with the side-chain axis perpendicular to that of the main chain. This biaxial orientation of 1 was confirmed by our 2D WAXD experiments through three orthogonal directions. The main-chain scaffold remains when the SmE-like packing is melted at elevated temperatures. Further heating leads to a normal smectic A (SmA) structure followed by the isotropic state. We found that when an external electric field was applied, the main-chain scaffold greatly inhibited the motion of the biphenyls. While the main chains gain a sufficiently high mobility in the SmA phase, macroscopic orientation of 1 can be achieved using a rather weak electric field, implying that the main and side chains with orthogonal directions can move cooperatively. Our work demonstrates that when two separate components, one offering the "jacketing" effect to the normally flexible backbone and the other with mesogens that form surrounding LC phases, are introduced simultaneously into the side chains, the polymer obtained can be described as an MCSCLCP with a fascinating hierarchically ordered structure.

Enhancing the toughness of regenerated silk fibroin film through uniaxial extension.

Films of regenerated silk fibroin (RSF) are usually brittle and weak, which prevents its wide application as a structural material. To improve the mechanical properties of RSF film, uniaxial extension under swollen conditions was employed to introduce preferred orientation of molecular chains of silk fibroin. Such a prestretching treatment resulted in the strain at break, ultimate stress, Young's modulus, and energy to break along the predrawn direction of the RSF film increasing from approximate 5%, 90 MPa, 2.7 GPa, and 2.1 kJ/kg to 35%, 169 MPa, 3.5 GPa, and 38.9 kJ/kg, respectively, which is an attractive combination of strength and toughness. The mechanism of these property enhancements was investigated using techniques such as small-angle X-ray scattering, wide-angle X-ray diffraction, atomic force microscopy, and dynamic mechanical analysis.