Liquid Crystal Promoted Self-Assembly of Statistical Copolymers into Diverse Nanostructures with Precise Dimensions.

In both natural and synthetic systems, the segregation of multicomponent entities is vital for regulating functions and the ultimate usage of materials. To accomplish the desired properties via nanosegregation or microphase separation, great effort is usually demanded in the synthesis. For example, microphase-separated block copolymers rely on the delicate controlled/living polymerization of different monomers in sequence.

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.

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.

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.

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.

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 χ and f 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.

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.

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.

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.

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.

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.

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.

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

A novel tetraphenylethylene complex composed of 4',4'',4''',4''''-(ethene-1,1,2,2-tetrayl)tetrabiphenyl-4-carboxylic acid (H 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.

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.

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 (Φ ) 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 Φ , the multichain columns in P1 act as robust physical crosslinks.

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.

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.

Homeotropically-aligned main-chain and side-on liquid crystalline elastomer films with high anisotropic thermal conductivities.

Homeotropically-aligned main-chain and side-on liquid crystalline elastomer films are prepared by using LC thiol-ene and acrylate systems respectively. Evaluated by laser flash analysis, the room temperature thermal conductivities of these two LCP films in the film normal direction are both dramatically higher than those along the horizontal direction.

Curvature elasticity of a grafted polyelectrolyte brush.

The curvature elasticity of a polyelectrolyte brush monolayer attached to curved surface is investigated theoretically. An analytical method based on the strong-stretching theory for a Gaussian chain is developed to calculate the elastic modulus induced by a polyelectrolyte brush. In particular, the scaling relations for the bending or Gaussian modulus with respect to system parameters related to the electrostatic interaction (degree of ionization and salt concentration) are derived.

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.

"Brill Transition" Shown by Green Material Poly(octamethylene carbonate).

Poly(octamethylene carbonate) (POMC), as the eighth member of the newly developed biodegradable aliphatic polycarbonate family, demonstrates a reversible crystal-crystal transition, which is highly similar to Brill transition extensively studied in the nylon family. With the dipole-dipole interaction in POMC much weaker than the hydrogen bonding, POMC exhibits its "Brill transition" temperature at around 42 °C, much lower than nylons. The two crystalline structures of POMC at below and above the transition temperature can be identified.

Liquid crystalline macrocyclic azacalix[4]pyridine and its complexes with the zinc ion: conformational change from the saddle to flattened shape.

Substituted with four 3,4,5-tris(alkoxy)benzyl mini-dendrons, azacalix[4]pyridine (1) with the saddle-shaped core is the first liquid crystal (LC) of heteracalixaromatics. Conformational regulation of azacalix[4]pyridine by complexing with the zinc ion leads to a significant change in LC properties.

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).

Self-Organized Columnar Phase of Side-Chain Liquid Crystalline Polymers: To Precisely Control the Number of Chains Bundled in a Supramolecular Column.

Self-organization of liquid crystalline (LC) polyacetylene derivatives (PAs) bearing hemiphasmid side-chains was investigated. The synthesized PAs can form smectic and columnar phases, depending on the constitutions of side chains. With a nanosegregation structure, the columnar phase of PAs takes a bundle of chains as its building block, of which the chain number is precisely determined by the volume fraction of the rigid component in PAs.