The Role of the 1,2,3-Triazolyl Heterocycle in the Helical Columnar Assembly and Electric Field Response.

Here, we have proven the role of the 1,2,3-triazolyl group in the helical assembly and electric field (E-field) response upon comparing liquid crystal analogs 1 and 2 based on 1,2,3-triazolyl and 1,3,4-oxadiazolyl linkers, respectively. An ordered helical column was only observed in 1, driven by the hydrogen-bonding interactions between the adjacent triazolyl nitrogen and hydrogen atoms. X-ray diffraction and energy simulations indicate that the helical column is a 112 helix and the helical axis does not coincide with the center of the molecular long axis. The key for the formation of the helical column is the tilted conformation of 1 originating from the steric repulsion between the triazolyl C-H and C-H of the aromatic core. Analysis of the dynamics in the simple hexagonal columnar phase revealed that the in-plane rotational motion of the triazolyl linker (1) is allowed, while the oxadiazolyl linker of 2 has limited conformational flexibility. A uniform alignment under an E-field only occurs in 1, demonstrating the requirement for conformational flexibility in the polar linker. This alignment enhances the electric conductance of 1 by approximately two-fold.

Ferroelectrically Switchable Axial Polarization in Columnar Liquid Crystalline Phases.

Recently, ferroelectrically switchable columnar LCs have drawn a great deal of attention for their generation of rich polarization domains. Because of their unique dielectric and self-assembly properties, they are considered to be a promising material for the design of sensors and ultra-high memory devices. Herein, ferroelectrically switchable LCs by using ester, amide, and 1,2,3-triazole groups are reviewed. Most of them do not exhibit genuine ferroelectricity owing to the low energy barrier between the two polar states. The intermolecular interactions between polar groups strongly affect the switchability and stability of polarization. Therefore, it is challenging to balance these two competing factors to improve the ferroelectric function in columnar LCs. Overall, additional effort, including LC design and device fabrication, should be made to optimize the material performance for practical applications in the future.

Ferroelectrically Switching Helical Columnar Assembly Comprising Cisoid Conformers of a 1,2,3-Triazole-based Liquid Crystal.

The 1,2,3-triazole molecule, which is a product of click chemistry, possesses a high dipole moment and can be a useful polar motif for ferroelectric columnar liquid crystal (LC) materials-though it has not been used to date. Herein, we report the helical assembly and ferroelectric switching properties of a columnar liquid crystal comprising a naphthalene core and 1,2,3-triazolyl linkages. The molecule assembles into a double-stranded helical columnar LC structure (Colhel ). The X-ray simulations of cisoid and transoid columnar models suggest that the helical assembly comprises cisoid conformers with a non-zero dipole moment. The helical columns in the Colhel phase are aligned homeotropically under an electric field. The ferroelectric switching of the axial polarization can be observed in the temperature range of 105-115 °C in the Colhel phase, wherein the triazolyl hydrogen bonding along the column axis is weakened. The ferroelectric switching event is attributed to the rotation of the polar triazolyl units in response to the electric field.

Development of Gallic Acid-Modified Hydrogels Using Interpenetrating Chitosan Network and Evaluation of Their Antioxidant Activity.

In this work, antioxidant hydrogels were prepared by the construction of an interpenetrating chitosan network and functionalization with gallic acid. The poly(2-hydroxyethyl methacrylate) p(HEMA)-based hydrogels were first synthesized and subsequently surface-modified with an interpenetrating polymer network (IPN) structure prepared with methacrylamide chitosan via free radical polymerization. The resulting chitosan-IPN hydrogels were surface-functionalized with gallic acid through an amide coupling reaction, which afforded the antioxidant hydrogels. Notably, gallic-acid-modified hydrogels based on a longer chitosan backbone exhibited superior antioxidant activity than their counterpart with a shorter chitosan moiety; this correlated to the amount of gallic acid attached to the chitosan backbone. Moreover, the surface contact angles of the chitosan-modified hydrogels decreased, indicating that surface functionalization of the hydrogels with chitosan-IPN increased the wettability because of the presence of the hydrophilic chitosan network chain. Our study indicates that chitosan-IPN hydrogels may facilitate the development of applications in biomedical devices and ophthalmic materials.

Sequential phase transformation of propeller-like C3-symmetric liquid crystals from a helical to ordered to disordered hexagonal columnar structure.

In this paper, we report thermally induced intercolumnar phase transitions of C3-symmetric liquid crystals (LCs) bearing a triazole-based propeller-like aromatic mesogen. Since the constituting aromatic rings are conjugated through rotatable single bonds, the mesogenic shape is tuneable depending on the degree of conformational motion. Molecule 1 with ninefold octyl peripheries shows a hexagonal columnar liquid crystalline phase transition from ordered mesogenic stacking to disordered mesogenic stacking upon heating. On the other hand, molecule 2 with sixfold octyl peripheries displays a helical hexagonal columnar phase with the P6/mmm space group at ambient temperature as well as the ordered and disordered hexagonal columnar phases at higher temperatures. The intracolumnar helical order can be understood by an interdigitated stacking of the propeller-like mesogens along the columnar axis and the optimized space-filling. Notably, all the intercolumnar phase transformations in this study are revealed as second-order transitions. The thermodynamic nature agrees well with the fact that the conformational motions of the C3-symmetric aromatic mesogen change abruptly with each columnar transition.

Micellar and vesicular nanoassemblies of triazole-based amphiphilic probes triggered by mercury(II) ions in a 100% aqueous medium.

ABA-type amphiphiles bearing a triazole-based aromatic block were easily synthesized using click chemistry, which act as fluorescent turn-off Hg(2+)-chemoprobes in an aqueous solution. Interestingly, the metal-binding process of amphiphiles induced nanoassemblies even below the CMCs, and the binding stoichiometry affected the morphologies of the resultant nanostructures.

Monoclinic to two-dimensional hexagonal transformation in hexacatenar molecules with a 1,2,3-triazole-based conjugated rod: morphology-dependent thermochromic behavior.

Novel hexacatenar molecules based on a 1,2,3-triazole-extended aromatic rod self-assemble into crystalline monoclinic and liquid crystalline hexagonal columnar structures depending on temperature. The phase transition may involve a conformational change from an anisotropic transoid to a half-disk cisoid conformer upon melting. In a hexacatenar molecule with sixfold octyl chains, the crystal-to-LC transition accompanies a photoluminescence color change from sky blue to dark blue, which is attributed to the formation of higher-order aggregates in the crystalline state.

An unusual stacking transformation in liquid-crystalline columnar assemblies of clicked molecular propellers with tunable light emissions.

The columnar liquid-crystalline (LC) and fluorescence properties of three-dimensional molecular propellers based on tetraphenylethylene is reported. X-ray scattering studies reveal an unusual transition from a rectangular (Colrec ) to a hexagonal columnar (Colhex ) phase. In contrast to second-order intercolumnar transitions based on a common tilt mechanism, the transition is first order and involves an unprecedented zigzag stacking of aromatic propellers in the Colrec phase. A sudden change in emission color from sky blue to green occurs rapidly and reversibly at this transition, which is due to the planarization of the propeller mesogen.

Smectic assemblies in C3-symmetric hexa-alkylated liquid crystals: transformation from smectogen to discogen via hydrogen bonding.

In this paper, we report a C3-symmetric liquid crystal (LC) with sixfold alkyl peripheries exhibiting an unusual smectic E-like organization in the LC state. Based on conformational considerations, the smectic assembly is attributed to the formation of an endo-type Y conformer of asymmetric triazolyl and benzylic groups that cannot be accessed in other C3-symmetric molecules exclusively showing columnar assemblies. The Y conformers form a two-dimensional oblique lattice in the aromatic layers of the ordered smectic phase. In addition, the Y-shaped molecule in the smectic phases can change into a circular shape by the 1 : 1 hydrogen-bonding interaction with a gallic acid derivative, which leads to a hexagonal columnar LC phase. The triazole-based LC design concept proves the smectic LC assembly in the C3-symmetric system, and provides the supramolecular manipulation of LC morphologies.

Supramolecular transformation from ordered columnar to disordered columnar to tetragonal micellar structures in clicked dodeca-alkylated discotic triphenylene liquid crystals.

We prepared three discotic liquid crystals (DLCs) based on a triphenylene (TP) disc functionalized with twelve alkyl peripheries. The synthesis of the discogens was performed by a click reaction using Cu(OAc)2 as the catalyst, with six triazolyl groups connecting the TP core with twelve alkyl chains. According to thermal data from differential scanning calorimetry (DSC), discogen , which has the shortest hexyl peripheries, exhibited two LC phases, and and , with decyl and tetradecyl peripheries, respectively, displayed three LC phases as a function of the temperature. Structural analyses using small- and wide-angle X-ray scattering (SAXS and WAXS) techniques revealed ordered and disordered hexagonal columnar LC phases in all the discogens. On the other hand, an unconventional micellar phase with P42/mnm symmetry consisting of thirty micelles was found only in and , when the temperature increased. The thermally induced transformation from the columnar to the micellar phase can be explained by increased chain entropy at higher temperatures. The complex micellar packing in the noncubic phase is attributed to the softness of the DLC micelles because the micellar corona consists of flexible alkyl chains. The discogen design concept in this study (i.e., the introduction of multibranched alkyl peripheries to the discotic mesogens via click chemistry) resulted in unconventional columnar-to-micellar transformation in conventional TP DLCs.

Organic-inorganic vesicular hybrids driven by assembly of dendritic amphiphiles: site-selective encapsulation of nanoparticles.

The amphiphilic block codendrimer self-assembled into supramolecular vesicles with a bilayer membrane in both hydrophilic and hydrophobic solvents. Surface-modified quantum dots (QDs) were successfully entrapped within the wall of vesicles through a simple self-assembly process without any structural disruption.

Non-tortuous ionic transport in robust micellar liquid crystalline phases with cubic symmetry.

A micellar cubic LC phase consisting of a hydrophilic matrix exhibited enhanced ionic transport and mechanical properties without macroscopic orientation, which are attributed to the non-tortuous ionic transport and highly symmetric cubic lattice, respectively.

Thickness-dependent morphological behavior of dendritic (PS)2-b-PLA copolymer thin films on a SiO2 substrate.

In contrast to the known perpendicular ordering of conventional PS-b-PLA thin films, branched (PS)(2)-b-PLA thin films showed two different parallel orientations whose locations are strongly dependent upon film thickness.

Functionality- and Size-Dependent Target-Differentiation of Nanoporous Carboxylated Polystyrenes in Polar Protic Solvents.

In this study, we investigated the functionality- and size-dependent differentiation capability of bulk nanoporous polystyrene (PS) materials in aqueous environments. A three-arm star block copolymer (consisting of dibranched PS and linear polylactide (PLA) blocks) was employed to prepare PS nanochannels with the average pore diameter of 14.2 nm. Due to the ester group at the junction of the PS and PLA blocks, a negatively charged carboxylate group could be placed as the wall functional group automatically after the PLA etching. Based on specific electrostatic interactions, the bulk PS channels with the carboxylated wall could selectively capture a water-soluble cationic dye (rhodamine 6G) in the aqueous and methanolic solutions. Furthermore, the well-defined porous PS displayed excellent size-dependent selectivity, which was proved by a fluorescence quenching experiment using differently sized gold nanoparticles (AuNPs). Rhodamine 6G dyes on the pore wall were effectively quenched by 2 nm AuNPs. In contrast, the 16 nm AuNPs (larger than the pore diameter) did not affect the brightness of the rhodamine 6G-loaded PS.

An extraordinary cylinder-to-cylinder transition in the aqueous assemblies of fluorescently labeled rod-coil amphiphiles.

We report an unprecedented cylinder-to-cylinder transformation in the self-assemblies of pyrene-labeled rod-coil molecules in water. The extraordinary morphological transformation can be monitored by a fluorescence variation from exciplex to excimer emissions, suggesting the rod-packing transition from antiparallel to interdigitated arrangements as a function of PEO coil length.

Self-assembling behavior of amphiphilic dendron coils in the bulk crystalline and liquid crystalline states.

We prepared a series of amphiphilic dendron coils (1-3) containing aliphatic polyether dendrons with octadecyl peripheries and a poly(ethylene oxide) (PEO) coil (DP = 44). The molecular design in this study is focused on the variation of dendron generation (from first to third) with a fixed linear coil, upon which the thermal and self-assembling behavior of the dendron coils was investigated in the bulk. All the dendron coils exhibit two crystalline phases designated as k1 (both crystalline octadecyl chains and PEO) and k2 states (crystalline octadecyl chains and molten PEO). Crystallinities for both octadecyl peripheries and the PEO decrease as generation increases. In particular, the dendron coil (3) containing third generation shows a drastic reduction of the PEO crystallinity, which is attributed to the considerable chain folding and plasticization effects by the largest hydrophilic dendritic core segment. All the crystalline phases are bilayered lamellar morphologies. On going from k1 to k2, the periodic lamellar thickness decreases in the dendron coil (1) with first generation, but interestingly increases in 3. After melting of octadecyl peripheries, 1 shows no mesophase (i.e., liquid crystalline phase). Additionally, dendron coil 2 (3) displays a network cubic mesophase with Ia3d symmetry (micellar cubic with Pm3n) which is transformed into a lamellar (hexagonal columnar) mesophase upon heating. Remarkably, the temperature-dependent mesomorphic behavior in 2 and 3 is a completely reverse pattern in comparison with conventional linear-linear block copolymers. The unusual bulk morphological phenomena in the crystalline and liquid crystalline phases can be elucidated by the dendron coil architecture and the associated coil conformational energy.

Selectively chemodosimetric detection of Hg(II) in aqueous media.

A new series of benzoylthiourea derivatives of 1, 3, and 5 were prepared, and their chemodosimetric behaviors toward metal cations were investigated in aqueous media at room temperature. Among various metal cations tested, exclusively Hg2+ ion responses to irreversible color changes of receptors, along with distinctive blue shifts in UV/vis spectra. The receptors can be applicable for the monitoring of Hg2+ ion in aqueous solution with a pH span 4-9.