Microstructural Evolution of P(NDI2OD-T2) Films with Different Molecular Weight during Stretching Deformation.

Conjugated polymers exhibit excellent electrical and mechanical properties when their molecular weight (Mw) is above the critical molecular weight (Mc). The microstructural changes of polymers under strain are crucial to establish a structure-performance relationship. Herein, the tensile deformation of P(NDI2OD-T2) is visualized, and cracks are revealed either along the (100) crystal plane of side chain packing or along the main chain direction which depends on the Mw is below or above the Mc. When Mw < Mc, the film cracks along the (100) plane under small strains. When Mw > Mc, the polymer chains first undergo stretch-induced orientation and then fracture along the main chain direction at large strains. This is attributed to the fact that the low Mw film exhibits large crystalline domains and the absence of interdomain connectivity, which are vulnerable to mechanical stress. In contrast, the high Mw film displays a nearly amorphous morphology with adequate entanglements, the molecular chains can endure stresses in the stretching direction to release substantial strain energy under greater mechanical deformation. Therefore, the film with Mw > Mc exhibits the optimal electrical and mechanical performances simultaneously, i.e., the electron mobility is retained under 100% strain and after 100 stretching-releasing cycles.

Organic Transistors Based on Highly Crystalline Donor-Acceptor π-Conjugated Polymer of Pentathiophene and Diketopyrrolopyrrole.

Oligomers and polymers consisting of multiple thiophenes are widely used in organic electronics such as organic transistors and sensors because of their strong electron-donating ability. In this study, a solution to the problem of the poor solubility of polythiophene systems was developed. A novel π-conjugated polymer material, PDPP-5Th, was synthesized by adding the electron acceptor unit, DPP, to the polythiophene system with a long alkyl side chain, which facilitated the solution processing of the material for the preparation of devices. Meanwhile, the presence of the multicarbonyl groups within the DPP molecule facilitated donor-acceptor interactions in the internal chain, which further improved the hole-transport properties of the polythiophene-based material. The weak forces present within the molecules that promoted structural coplanarity were analyzed using theoretical simulations. Furthermore, the grazing incidence wide-angle X-ray scanning (GIWAXS) results indicated that PDPP-5Th features high crystallinity, which is favorable for efficient carrier migration within and between polymer chains. The material showed hole transport properties as high as 0.44 cm2 V-1 s-1 in conductivity testing. Our investigations demonstrate the great potential of this polymer material in the field of optoelectronics.

Incorporation of Diketopyrrolopyrrole into Polythiophene for the Preparation of Organic Polymer Transistors.

Polythiophene, as a class of potential electron donor units, is widely used in organic electronics such as transistors. In this work, a novel polymeric material, PDPPTT-FT, was prepared by incorporating the electron acceptor unit into the polythiophene system. The incorporation of the DPP molecule assists in improving the solubility of the material and provides a convenient method for the preparation of field effect transistors via subsequent solution processing. The introduction of fluorine atoms forms a good intramolecular conformational lock, and theoretical calculations show that the structure displays excellent co-planarity and regularity. Grazing incidence wide-angle X-ray (GIWAXS) results indicate that the PDPPTT-FT is highly crystalline, which facilitates carrier migration within and between polymer chains. The hole mobility of this π-conjugated material is as high as 0.30 cm2 V-1 s-1 in organic transistor measurements, demonstrating the great potential of this polymer material in the field of optoelectronics.

Hyperthermia promotes degradation of the acute promyelocytic leukemia driver oncoprotein ZBTB16/RARα.

The acute promyelocytic leukemia (APL) driver ZBTB16/RARα is generated by the t(11;17) (q23;q21) chromosomal translocation, which is resistant to combined treatment of all-trans retinoic acid (ATRA) and arsenic trioxide (ATO) or conventional chemotherapy, resulting in extremely low survival rates. In the current study, we investigated the effects of hyperthermia on the oncogenic fusion ZBTB16/RARα protein to explore a potential therapeutic approach for this variant APL. We showed that Z/R fusion protein expressed in HeLa cells was resistant to ATO, ATRA, and conventional chemotherapeutic agents. However, mild hyperthermia (42 °C) rapidly destabilized the ZBTB16/RARα fusion protein expressed in HeLa, 293T, and OCI-AML3 cells, followed by robust ubiquitination and proteasomal degradation. In contrast, hyperthermia did not affect the normal (i.e., unfused) ZBTB16 and RARα proteins, suggesting a specific thermal sensitivity of the ZBTB16/RARα fusion protein. Importantly, we found that the destabilization of ZBTB16/RARα was the initial step for oncogenic fusion protein degradation by hyperthermia, which could be blocked by deletion of nuclear receptor corepressor (NCoR) binding sites or knockdown of NCoRs. Furthermore, SIAH2 was identified as the E3 ligase participating in hyperthermia-induced ubiquitination of ZBTB16/RARα. In short, these results demonstrate that hyperthermia could effectively destabilize and subsequently degrade the ZBTB16/RARα fusion protein in an NCoR-dependent manner, suggesting a thermal-based therapeutic strategy that may improve the outcome in refractory ZBTB16/RARα-driven APL patients in the clinic.

Design of Novel Functional Conductive Structures and Preparation of High-Hole-Mobility Polymer Transistors by Green Synthesis Using Acceptor-Donor-Acceptor Strategies.

The design of novel acceptor molecular structures based on classical building blocks is regarded as one of the efficient ways to explore the application of organic conjugated materials in conductivity and electronics. Here, a novel acceptor moiety, thiophene-vinyl-diketopyrrolopyrrole (TVDPP), was envisioned and prepared with a longer conjugation length and a more rigid structure than thiophene-diketopyrrolopyrrole (TDPP). The brominated TVDPP can be sequentially bonded to trimethyltin-containing benzo[c][1,2,5]thiadiazole units via Suzuki polycondensation to efficiently prepare the polymer PTVDPP-BSz, which features high molecular weight and excellent thermal stability. The polymerization process takes only 24 h and eliminates the need for chlorinated organic solvents or toxic tin-based reagents. Density functional theory (DFT) simulations and film morphology analyses verify the planarity and high crystallinity of the material, respectively, which facilitates the achievement of high carrier mobility. Conductivity measurements of the polymeric material in the organic transistor device show a hole mobility of 0.34 cm2 V-1 s-1, which illustrates its potential for functionalized semiconductor applications.

Rational Design of Novel Conjugated Terpolymers Based on Diketopyrrolopyrrole and Their Applications to Organic Thin-Film Transistors.

Organic polymer semiconductor materials, due to their good chemical modifiability, can be easily tuned by rational molecular structure design to modulate their material properties, which, in turn, affects the device performance. Here, we designed and synthesized a series of materials based on terpolymer structures and applied them to organic thin-film transistor (OTFT) device applications. The four polymers, obtained by polymerization of three monomers relying on the Stille coupling reaction, shared comparable molecular weights, with the main structural difference being the ratio of the thiazole component to the fluorinated thiophene (Tz/FS). The conjugated polymers exhibited similar energy levels and thermal stability; however, their photochemical and crystalline properties were distinctly different, leading to significantly varied mobility behavior. Materials with a Tz/FS ratio of 50:50 showed the highest electron mobility, up to 0.69 cm2 V-1 s-1. Our investigation reveals the fundamental relationship between the structure and properties of materials and provides a basis for the design of semiconductor materials with higher carrier mobility.

Designing coexisting multi-phases in PZT multilayer thin films: an effective way to induce large electrocaloric effect.

Coexisting multi-phases in PbZr x Ti1-x O3 multilayer thin films were successfully fabricated using the sol-gel method. The microstructure and electrical of the multilayer films with different growth sequences, including the up multilayer films and down multilayer films, have been systematically investigated. The results indicate that a large electrocaloric effect (ECE) is obtained at the temperatures much below the Curie temperature. At room temperature (25 °C), the change in temperature (ΔT) values of the up multilayer and down multilayer thin films are 20.2 K with the applied electric field E = 826 kV cm-1 and 46.3 K with the E = 992 kV cm-1, respectively. In addition, both the films exhibit outstanding ECE of around 145 °C, and ΔT values of 28.9 K and 14.8 K have been obtained for the up multilayer and down multilayer thin films. The results indicate that the antiferroelectric/ferroelectric (AFE/FE), ferroelectric/ferroelectric (FE/FE) phase transition and the synergistic effect of the AFE/FE and FE/FE phase transition are as effective as the FE/PE phase transition. In particular, the multilayer thin films are endowed with refrigeration ability at multi-temperature zones due to the coexistence of multi-phases.

One-step hydrothermal synthesis of fluorescent nanocrystalline cellulose/carbon dot hydrogels.

Fluorescent nanocrystalline cellulose/carbon dots (NCC/CDs) hydrogels were successfully prepared by a facile one-step green hydrothermal carbonization process. The properties of NCC/CDs hydrogels prepared at different temperatures were investigated by fluorescence spectroscopy, transmission electron microscopy, nuclear magnetic resonance spectroscopy, X-ray diffraction, and thermogravimetric analysis. NCC/CDs hydrogels with high crystallinity, high thermal stability, and excellent fluorescence properties can be obtained by controlling the hydrothermal treatment temperature. Small rod-like NCC/CDs hydrogels with a diameter of 2-6nm, a length of 40-60nm, and the cellulose Ι structure were obtained when the hydrothermal carbonization temperature was 240°C. The NCC/CDs hydrogels exhibited an excellent broad spectral response and high fluorescence stability at various pH values. Considering of the wide natural abundance of NCC and the biocompatibility of the NCC/CDs hydrogels, Preparation in this simple, green approach is attractive for future bio-medical applications.

UV and dark-triggered repetitive release and encapsulation of benzophenone-3 from biocompatible ZnO nanoparticles potential for skin protection.

The present study reports a UV and dark-triggered highly intelligent drug delivery system for skin protection. ZnO nanoparticles (NPs), a UV filter, were synthesized and characterized to be the carrier for benzophenone-3 (Bp-3), a UV-absorption medicine, by varying the molar ratio of ZnO NPs to Bp-3 ranging from 300 : 1 to 20 : 1. The drug release under three cycles of UV and dark stimulation (each for two hours) and its cytotoxicity to human keratinocyte cells and skin fibroblasts were investigated. SEM studies showed the diameter of ZnO was around 30 to 40 nm, which assembled into loose and large NPs ranging from 500 to 1400 nm. Contact angle tests showed ZnO NPs switched to a more hydrophilic and back to a more hydrophobic state under two hours of UV and dark exposure. The optimized encapsulation efficiency and loading capacity of Bp-3 were 53.68 ± 0.13% and 133.61 ± 0.20% when the molar ratio of ZnO NPs to Bp-3 was 150 : 1 and 80 : 1. The Bp-3 was almost completely released from ZnO NPs under 2 hours of UV radiation and was mostly encapsulated in after 2 hours of dark stay in three cycles of UV and dark exposure. The Bp-3 loaded ZnO NPs showed low cytotoxicity to human keratinocyte cells and human skin fibroblasts. Overall, a UV and dark-triggered repetitively on-demand drug delivery system biocompatible to skin cells and potential for skin protection from UV radiation was developed.