Self-Assembled and Polymerized Hierarchical Nanostructure Films of Cyanostilbene-Based Reactive AIEgens for Smart Chemosensors.

For the development of acid-responsive advanced fluorescent films with a 2D nanostructure, a pyridyl cyanostilbene-based AIEgen (PCRM) is newly synthesized. The synthesized PCRM exhibits aggregation-induced emission (AIE) and responds reversibly to acid and base stimuli. To fabricate the nanoporous polymer-stabilized film, PCRM and 4-(octyloxy)benzoic acid (8OB) are complexed in a 1:1 ratio through hydrogen bonding. The PCRM-8OB complex with a smectic mesophase is uniaxially oriented at first and photopolymerized with a crosslinker. By subsequently removing 8OB in an alkaline solution, nanopores are generated in the self-assembled and polymerized hierarchical 2D nanostructure film. The prepared nanoporous fluorescent films exhibit not only the reversible response to acid and base stimuli but also mechanical and chemical robustness. Since the nanoporous fluorescent films have different sensitivities to trifluoroacetic acid (TFA) depending on the molecular orientation in the film, advanced acid vapor sensors that can display the risk level according to the concentration of TFA are demonstrated. Reactive AIEgens-based hierarchical nanostructure films with nanopores fabricated by a subsequent process of self-assembly, polymerization, and etching can open a new door for the development of advanced chemosensors.

Coatable Negative Dispersion Retarder: Kinetically Controlled Self-Assembly Pathway of Butterfly-Shaped Molecular Building Blocks for the Construction of Nanocolumns.

Disc-shaped building blocks with columnar phases have attracted attention for their potential in optical applications, including a retarder. However, to achieve coatable high-performance optical films, it is essential to understand a subtle interaction balance between building blocks and relevant self-assembled behaviors during material processing. Herein, we studied a self-assembled nanocolumn evaluation of linear butterfly-shaped dendrons (T-A3D) consisting of thiophene-based conjugated core and flexible alkyl dendron. X-ray diffraction provided insight into the unique hexagonal columnar liquid crystal phase of T-A3D, driven by intermolecular hydrogen bonding and coplanarity of the thiophene-based conjugated core. The formation of a self-assembled nanocolumn with high mobility enabled the uniaxial orientation of butterfly-shaped T-A3D on the aligned rod-shaped nematic reactive mesogens, resulting in a transparent and colorless two-layered negative retarder. The self-assembled nanocolumn consisting of butterfly-shaped molecule would break a new ground for developing advanced optical thin films.

Encryptable Electrochromic Smart Windows: Uniaxially Oriented and Polymerized Hierarchical Nanostructures Constructed by Self-Assembly of Tetrathiafulvalene-Based Reactive Mesogens.

Tetrathiafulvalene (TTF)-based reactive mesogens (TTF-E and TTF-T) are synthesized, self-assembled, uniaxially oriented, and polymerized for the development of encryptable electrochromic smart windows. Electrochemical and spectroscopic experiments prove that the self-assembled TTF mixture (TTFM, TTF-E:TTF-T = 1:1) can reversibly switch the absorption wavelength of the TTF chromophore according to the redox reactions. Based on the identification of the phase transition and crystallographic structure, uniaxially oriented hierarchical nanostructures are easily constructed on the macroscopic area by simple coating and a self-assembly process. Subsequent polymerization of hierarchical nanostructures of TTFM significantly enhances thermal and mechanical stabilities and makes it possible for them to be fabricated as an electrochromic device. The angularly dependent correlation between the anisotropy of mesogens and the linearly polarized light allow us to demonstrate TTFM as smart windows capable of various optical security applications, including privacy protection and information encryption.

The transfer and amplification of cyanostilbene molecular function to advanced flexible optical paints through self-crosslinkable side-chain liquid crystal polysiloxanes.

A self-crosslinkable side-chain liquid crystal polysiloxane containing cyanostilbene (Si-CSM) was newly synthesized for the development of a new generation of flexible optical paints. The photoisomerization of the cyanostilbene moiety at the molecular level was transferred and amplified to the phase transition of Si-CSM, resulting in changes in the macroscopic optical properties of the Si-CSM thin film. The self-crosslinking reaction between Si-H groups in the Si-CSM polymer backbone caused the self-crosslinked Si-CSM thin film to be very elastic and both thermally and chemically stable. Therefore, the self-crosslinked Si-CSM thin film endured stretching and bending deformations under relatively harsh conditions. In addition, the uniaxially oriented and self-crosslinked Si-CSM thin film generated linearly polarized light emission. Polarization-dependent and photopatternable secret coatings were fabricated via a spontaneous self-crosslinking reaction after coating the Si-CSM paint and irradiating ultraviolet (UV) light through a photomask. This newly developed flexible optical Si-CSM paint can be applied in next-generation optical coatings.

An Analysis of a Highly Sensitive and Selective Hydrogen Gas Sensor Based on a 3D Cu-Doped SnO2 Sensing Material by Efficient Electronic Sensor Interface.

In this research, a highly sensitive and selective hydrogen gas sensor was developed based on Cu-doped SnO2. Sensing characteristics were compared based on SnO2 doped with different concentrations of Cu, and the highest sensitivity and fastest response time were shown when 3% Cu was contained. A 3D structure was formed using a polystyrene to increase the surface-to-volume ratio, which allows more oxygen molecules to bond with the surface of the SnO2 sensing material. Extremely increased sensitivity was observed as compared to the planar structure. A temperature sensor and micro-heater were integrated into the sensor, and the surface temperature was maintained constant regardless of external influences. In addition, an electronic sensor interface was developed for the efficient analysis of real-time data. The developed sensor was wire-bonded to the flexible printed circuit board (FPCB) cable and connected with the sensor interface. Sensitivity and linearity measured based on the developed sensor and interface system were analyzed as 0.286%/ppm and 0.98, respectively, which were almost similar to the results observed by a digital multimeter (DMM). This indicates that our developed sensor system can be a very promising candidate for real-time measurement and can be applied in various fields. The enhanced sensitivity of 3% doped SnO2 toward hydrogen is attributed to the huge number of oxygen vacancies in the doped sample.

Development of Diketopyrrolopyrrole-Based Smart Inks by Substituting Ionic Pendants and Engineering Molecular Packing Structures.

A series of diketopyrrolopyrrole (DPP) luminogen amphiphiles were newly designed and synthesized by a single-step anionic exchange reaction for controlling the photoluminescence properties in both solution and solid states. Multicolor emission in response to thermal, mechanical, and chemical stimuli was successfully demonstrated by engineering well-defined supramolecular assemblies. Phase transformation from the metastable amorphous solid to the stable orthorhombic crystal of [DP-Im][Br] provided the reversibly patternable light emission. Self-organization into the smectic crystalline phase of [DP-Im][TFSI] allowed us to show the linearly polarized light emission. By simultaneously applying [DP-Im][Br] and [DP-Im][TFSI], we demonstrated the fabrication of smart sensors for packaging of food or vaccines that can detect thermal attacks.

Synthesis of poly(N-isopropylacrylamide) polymer crosslinked with an AIE-active azonaphthol for thermoreversible fluorescence.

A fluorescent polymer was synthesized using N-isopropylacrylamide (NIPAM) crosslinked with a divinylazonaphthol monomer via radical emulsion polymerization. Because the crosslinked polymer contained an aggregation-induced emissive (AIE) azonaphthol-based crosslinker, a thermoreversible sol-gel transformation and gelation-induced reversible fluorescence alteration were successfully attained in an aqueous medium. Like typical PNIPAM, the size and transmittance of the polymer dramatically decreased near the lower critical solution temperature (LCST, 36 °C). Such gelation facilitated aggregation of the polymer chains, resulting in the close contact between azonaphthol groups producing fluorescence. The crosslinked polymer exhibited changes in dual properties: one is related to PNIPAM structural alteration, which corresponds to conventional swelling/shrinkage behavior; and the other is involved in the reversible fluorescence change in response to the swelling/shrinkage. Because the major backbone of the polymer was composed of NIPAM with an LCST at 36 °C, the resultant polymer is expected to have potential applications in biologically related fields.