Designed wrinkles for optical encryption and flexible integrated circuit carrier board.

Patterns on polymers usually have different mechanical properties as those of the substrates, causing deformation or distortion and even detachment of the patterns from the polymer substrates. Herein, we present a wrinkling strategy, which utilizes photolithography to define the area of stress distribution by light-induced physical crosslinking of polymers and controls diffusion of residual solvent to redistribute the stress and then offers the same material for patterns as substrate by thermal polymerization, providing uniform wrinkles without worrying about force relaxation. The strategy allows the recording and hiding of up to eight switchable images in one place that can be read by the naked eye without crosstalk, applying the wrinkled polymer for optical anti-counterfeiting. The wrinkled polyimide film was also utilized to act as a substrate for the creation of fine copper circuit by a full-additive process. It generates flexible integrated circuit (IC) carrier board with copper wire density of 400% higher than that of the state-of-the-art in industry while fulfilling the standards for industrialization.

Achieving Record External Quantum Efficiency of 11.5 % in Solution-Processable Deep-Blue Organic Light-Emitting Diodes Utilizing Hot Exciton Mechanism.

High performance solution-processable deep-blue emitters with a Commission International de l'Eclairage (CIE) coordinate of CIEy≤0.08 are highly desired in ultrahigh-definition display. Although, deep-blue materials with hybridized local and charge-transfer (HLCT) excited-state feature are promising candidates, their rigidity and planar molecular structures limit their application in solution-processing technique. Herein, four novel deep-blue solution-processable HLCT emitters were first proposed by attaching rigid imide aliphatic rings as functional units onto the HLCT emitting core. The functional units not only improve solubility, enhance thermal properties and morphological stability of the emitting core, but also promote photoluminescence efficiency, balance charge carrier transport, and inhibit aggregation-caused quenching effect due to the weak electron-withdrawing property as well as steric hindrance. The corresponding solution-processable organic light-emitting diodes (OLEDs) substantiate an unprecedented maximum external quantum efficiency (EQEmax) of 11.5 % with an emission peak at 456 nm and excellent colour purity (full width at half maximum=56 nm and CIEy=0.09). These efficiencies represent the state-of-the-art device performance among the solution-processable blue OLEDs based on the "hot exciton" mechanism. This simple strategy opens up a new avenue for designing highly efficient solution-processable deep-blue organic luminescent materials.

Ultralow Coefficient of Thermal Expansion and a High Colorless Transparent Polyimide Film Realized Through a Reinforced Hydrogen-Bond Network by In Situ Polymerization of Aromatic Polyamide in Colorless Polyimide.

Colorless polyimides (CPIs) are a key substrate material for flexible organic light-emitting diode (OLED) displays and have attracted worldwide attention. Here, in this paper, the dispersion and interfacial interaction of aromatic polyamide (PA) in CPI (synthesized from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2,2'-bis(trifluoromethyl)benzidine (TFMB)) were significantly improved by in situ polymerization, and colorless transparent macromolecular polyimide composites (CPI-PAx) were successfully prepared by PA and CPI. By adjusting the ratio of PA to CPI, a high-performance engineering plastic with excellent film-forming properties was obtained. Molecular simulations confirmed the uniform distribution of PA in CPI and its interaction in polymers. In CPI-PAx, the CPI was locked by the PA chain, and numerous molecular chains were mutually entangled to form a hydrogen-bond network structure. Due to the strong interaction between the chains imparted by the hydrogen bonds of the PA, they do not slide under external forces and heating. In addition, the additive PA has excellent dimensional stability, thermal, and mechanical properties, and CPI has outstanding optical properties, so the synthesized CPI-PAx combines the comprehensive properties of PA and CPI. The CPI-PAx has excellent thermal and mechanical properties, with a thermal decomposition temperature of 499 °C, a glass transition temperature of 385 °C, a coefficient of thermal expansion of 0.8 ppm K-1, a tensile strength of 50.9 MPa, and an elastic modulus of 3.9 GPa. Particularly, CPI-PAx has a 90% transmittance in the visible region. These data prove that the strategy of combining PA and CPI by in situ polymerization is an effective method to circumvent the bottleneck of CPI in the current flexible window application, and this design strategy is universal.

Benzoxazole-Based Hybridized Local and Charge-Transfer Deep-Blue Emitters for Solution-Processable Organic Light-Emitting Diodes and the In fluences of Hexahydrophthalimido.

Hybridized local and charge-transfer (HLCT) emitters have attracted extensive attention, but the insolubility and severe self-aggregation tendency restrict their applications in solution-processable organic light-emitting diodes (OLEDs), particularly deep-blue OLEDs. Herein, two novel benzoxazole-based solution-processable HLCT emitters (BPCP and BPCPCHY) are designed and synthesized, in which benzoxazole acts as an acceptor, carbazole acts as a donor, and hexahydrophthalimido (HP, with a large intramolecular torsion angle and spatial distortion characteristics) acts as a bulky modified end-group with weak electron-withdrawing effects. Both BPCP and BPCPCHY exhibit HLCT characteristics and emit near ultraviolet in toluene at 404 and 399 nm. Compared to the BPCP, the BPCPCHY solid shows much better thermal stability (Tg, 187 vs 110 °C), higher oscillator strengths of the S1-to-S0 transition (0.5346 vs 0.4809), and faster kr (1.1 × 108 vs 7.5 × 107 s-1) and thus a much higher ΦPL in the neat film. The introduction of HP groups greatly suppresses the intra-/intermolecular charge-transfer effect and self-aggregation trends, and the BPCPCHY neat films placed in air for 3 months can still maintain an excellent amorphous morphology. The solution-processable deep-blue OLEDs utilizing BPCP and BPCPCHY achieved a CIEy of 0.06 with maximum external quantum efficiency (EQEmax) values of 7.19 and 8.53%, respectively, which are among the best results of the solution-processable deep-blue OLEDs based on the "hot exciton" mechanism. All of the above results indicate that benzoxazole is an excellent acceptor for constructing deep-blue HLCT materials, and the strategy of introducing HP as a modified end-group into an HLCT emitter provides a new perspective to develop solution-processable efficient deep-blue OLEDs with high morphological stability.

Rigid Polyimides with Thermally Activated Delayed Fluorescence for Polymer Light-Emitting Diodes with High External Quantum Efficiency up to 21 .

A series of rigid nonconjugated polyimide (PI)-based thermally activated delayed fluorescence (TADF) polymers were reported for the first time, based on a "TADF-Linker-Host" strategy. Among of which, the TADF unit contains a typical TADF luminous core structure, the "Host" unit exhibits effective conjugation length that endows polyimide with high triplet energy, and the "Linker" unit has an aliphatic ring structure to improve solubility and inhibits intramolecular charge transfer effect. All the TADF polymers exhibit high thermal stability (Tg >308.7 °C) and refractive index (1.76-1.79). Remarkably, highly-efficient polymer light-emitting diodes (PLEDs) based on the polymers are successfully realized, leading to a maximal external quantum efficiency of 21.0 % along with low efficiency roll-off. Such outstanding efficiency is amongst the state-of-the-art performance of nonconjugated PLEDs, confirming the effectiveness of structural design strategy, providing helpful and valuable guidance on the development of highly-efficient fluorescent polymer materials and PLEDs.

Preserving High-Efficiency Luminescence Characteristics of an Aggregation-Induced Emission-Active Fluorophore in Thermostable Amorphous Polymers.

Luminophores usually suffer from luminescent quenching when introduced into a polymer backbone or side chain, which leads to the inefficient luminescence or even no luminescence of the polymer. In this work, alicyclic imide rings were found to be capable of balancing the donor-acceptor properties between the rigid spacer and the aggregation-induced emission-active fluorophore in light-emitting polymers. Along with the nonplanar and rigid emitter, the suppressed intramolecular charge-transfer effect and interchain disturbance can efficiently preserve the luminescence characteristics of the active center, resulting in high solid-state photoluminescence quantum yields of up to 89%. The amorphous polyimides exhibit excellent thermal properties, such as high glass transition temperature (Tg) values (398 °C) and high thermal decomposition temperature (Td) values (538 °C). As far as we know, these luminescent polymer materials are of excellent heat resistance with the highest luminescence efficiency reported. The results have significant impact for the precise prediction of the optical properties of light-emitting polymers by appropriate monomer design, providing controllable ways for synthesizing high thermal stability polymeric materials with efficient fluorescence properties.

Construction of coumarin-based cross-linked micelles with pH responsive hydrazone bond and tumor targeting moiety.

It is still a major challenge for targeted cancer chemotherapy to design a stable biocompatible micellar drug delivery system. To address this dilemma, novel responsive cross-linked micelles (x-micelles) based on polyurethane with photo-responsive coumarin derivatives and pH-responsive hydrazone groups were synthesized. The polymers could be self-assembled into micelles using a typical and facile way. The x-micelles were stable at physiological conditions after UV light induced cross-linking, and can be disassociated under acidic condition. The drug loading content (DLC) and the encapsulation efficiency (EE) of the obtained x-micelles (15.2% and 60.8% respectively) were higher than those of micelles (9.8% and 39.2% respectively), and the DOX release rate of x-micelles was also improved. For targeted therapy, folic acid (FA) was then conjugated to x-micelles, resulting in x-micelles-FA. Cellular viability experiments show that both x-micelles and micelles had a low cytotoxicity and good biocompatibility of up to 1000 µg mL-1, and DOX-loaded x-micelles-FA and x-micelles exhibited half-maximal inhibitory concentration (IC50) values of 1.17 and 2.40 µg mL-1, respectively, to HeLa cells, but have lower cytotoxicity to L929 cells. The pH-responsive x-micelles-FA exhibited superior extracellular stability but activated intracellular drug release. We have demonstrated that the polyurethane with UV- and pH-responsive properties as a novel platform for tumor-targeting drug delivery.

Layer-by-Layer (LBL) Self-Assembled Biohybrid Nanomaterials for Efficient Antibacterial Applications.

Although antibiotics have been widely used in clinical applications to treat pathogenic infections at present, the problem of drug-resistance associated with abuse of antibiotics is becoming a potential threat to human beings. We report a biohybrid nanomaterial consisting of antibiotics, enzyme, polymers, hyaluronic acid (HA), and mesoporous silica nanoparticles (MSNs), which exhibits efficient in vitro and in vivo antibacterial activity with good biocompatibility and negligible hemolytic side effect. Herein, biocompatible layer-by-layer (LBL) coated MSNs are designed and crafted to release encapsulated antibiotics, e.g., amoxicillin (AMO), upon triggering with hyaluronidase, produced by various pathogenic Staphylococcus aureus (S. aureus). The LBL coating process comprises lysozyme (Lys), HA, and 1,2-ethanediamine (EDA)-modified polyglycerol methacrylate (PGMA). The Lys and cationic polymers provided multivalent interactions between MSN-Lys-HA-PGMA and bacterial membrane and accordingly immobilized the nanoparticles to facilitate the synergistic effect of these antibacterial agents. Loading process was characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and X-ray diffraction spectroscopy (XRD). The minimal inhibition concentration (MIC) of MSN-Lys-HA-PGMA treated to antibiotic resistant bacteria is much lower than that of isodose Lys and AMO. Especially, MSN-Lys-HA-PGMA exhibited good inhibition for pathogens in bacteria-infected wounds in vivo. Therefore, this type of new biohybrid nanomaterials showed great potential as novel antibacterial agents.