The self‐assembly of a rod–coil amphiphilic block copolymer (ABCP) led to Im3‾
m and Pn3‾
m polymer cubosomes and p6mm polymer hexasomes. This is the first time that these structures are observed in ...a rod–coil system. By varying the hydrophobic chain length, the initial concentration of the polymer solution, or the solubility parameter of the mixed solvent, head–tail asymmetry is adjusted to control the formation of polymer cubosomes or hexasomes. The formation mechanism of the polymer cubosomes was also studied. This research opens up a new way for further study of the bicontinuous and inverse phases in different ABCP systems.
Heads or tails? Im3‾
m and Pn3‾
m polymer cubosomes and p6mm polymer hexasomes are obtained through the self‐assembly of a rod–coil amphiphilic block copolymer in solution. Head–tail asymmetry was adjusted to control the formation of these structures, and the formation mechanism of polymer cubosomes was also studied. This research provides a new way for further study of the bicontinuous and inverse phases.
Construction of sub‐5 nm long‐range ordered structures through self‐assembly has received increasing attention. Herein, a series of ODMS‐based thermotropic liquid crystals (LCs) containing perylene ...diimide (PDI) were designed and synthesized. These LCs can form ordered nanostructures with periodic sizes around 5 nm including smectic J (SmJ), oblique columnar (Colob), and hexagonal columnar (Colh) phases with change in the volume fraction of ODMS, where the layer spacing of the SmJ phase is less than 5 nm. Thin films with parallel oriented nanolines with line width less than 5 nm can be obtained on PDMS‐modified silicon substrates by spin‐casting and simple thermal annealing processes. Moreover, owing to the strong π‐π interaction between PDI cores, these nanolines are long‐range ordered with uniaxial orientation in relatively large areas (1.5×1.5 μm2) with over 300 continuous microdomains without pre‐patterning. These nanostructures provide the possibility of preparing nanotemplates by oxygen plasma etching.
Perylene diimide‐based disc‐coil liquid crystals containing oligo(dimethylsiloxane) chains can form lamellar and columnar phases, and large‐area uniaxially orientated nanolines can be obtained through thin‐film self‐assembly.
The preparation of 3D functional isolated mesoscopic assemblies remains a challenge in the self‐assembly of polymers. Here, well‐defined 3D hexagonal and hexagram prisms with uniform dimensions are ...acquired by the crystallization of the inclusion complex composed of a crystalline molecule tris‐o‐phenylenedioxycyclotriphosphazene (TPP) and a block copolymer. The crystalline TPP plays an important role in the self‐assembling process. The faceted morphologies of the hexagonal and hexagram prisms are infrequent in the self‐assembly field of soft materials. The formation of the prisms experiences a 3D growth mechanism. The epitaxial growth, accompanied by the heterogeneous nucleation in the edges, yields the growth of inclusion crystals. This study provides a path to construct well‐defined polymeric soft materials with broad utility based on numerous supramolecular complexes.
Well‐defined and faceted hexagonal and hexagram prisms are prepared by the crystallization of a coil‐crystalline supramolecular block copolymer, which are infrequent in the self‐assembly field of soft materials. The epitaxial growth, accompanied by the heterogeneous nucleation on the edges, yields the growth of inclusion crystals. Based on numerous supramolecular complexes, polymeric soft materials with various applications can be constructed.
Doxorubicin (DOX) is one of the most frequently used anti-cancer drugs and the front line option for hepatocellular carcinoma (HCC) treatment. However, the clinical applications of DOX are restricted ...largely due to its toxicity and chemoresistance. Here, we report that miR-375 and DOX were co-delivered by liposomes (named L-miR-375/DOX-NPs) for combination therapy of HCC and drug resistance reversion of DOX. In vitro, L-miR-375/DOX-NPs could deliver DOX and miR-375 efficiently and simultaneously into HCC cells and ensure the successful release of mature miR-375 and DOX. Then, the released miR-375 suppressed the malignant hallmarks of HCC by significantly decreasing the expression of AEG-1, YAP1, and ATG7, while the released DOX evidently accelerated cell apoptosis and blocked cycle at a G2/M stage by activating the P53/Bax/Bcl-2, caspase-3, and P-JNK, P-P38 pathway. Furthermore, miR-375 dramatically inhibited drug resistance of DOX by reducing the expression of multidrug resistance gene 1 (MDR1). In vivo, L-miR-375/DOX-NPs exhibited enhanced anti-tumor efficiency in xenograft HCC mouse models with mild adverse effects compared with doxorubicin or miR-375 alone. In conclusion, our research demonstrated that L-miR-375/DOX-NPs had significant synergetic anti-tumor effects and added values in overcoming drug resistance, which may represent a promising approach for the therapy of HCC.
The zinc-ion battery (ZIB) is a novel energy storage device, an attractive alternative to the lithium-ion battery. The frequently used aqueous electrolyte suffers from many problems such as zinc ...dendrites and leakage, which prompts hydrogel electrolytes and solid electrolytes as good replacements. However, hydrogel electrolytes are usually unstable, owing to water volatilization. Herein, a novel solid polymer electrolyte (SPE) utilizing coordination of zinc ions is designed and then introduced into an all-solid ZIB. Benefiting from the unique coordination structure between the polymer and zinc ions, the SPE shows outstanding flexibility, high ion conductivity, and self-healing properties. In addition, the imine bonds in the polymer allow the electrolyte to degrade in acid environments, endowing its recyclability. More importantly, solid-state ZIBs based on the polymer electrolytes exhibit an impressive cycling stability (125% capacity retention after 300 cycles) and a high coulombic efficiency (94% after 300 cycles). The results demonstrate the promising potentials of the developed SPEs that can be used in all-solid ZIBs.
The type of self-assembled structure has a significant impact on the ionic conductivity of block copolymer or liquid crystalline (LC) ion conductors. In this study, we focus on the effect of ...self-assembled structures on the ionic conductivity of a non-block copolymer, LC ion conductor, which is a mixture of an azobenzene monomer (NbAzo), pentaerythritol tetre(3-mercapropionate) (PETMP), and a lithium salt, lithium bis(trifluoromethane)sulfonimide (LiTFSI). The self-assembled structures and ionic conductivities of ion conductors having different doping ratios of lithium salt to monomer were examined. With the increase in the doping ratio, the self-assembled structure transforms from lamellae (LAM) to double gyroid (GYR). The effect of self-assembled structure on ionic conductivity was analyzed; it was found that the conductivity of the GYR structure was about 3.6 times that of the LAM one, indicating that obtaining the GYR structure is more effective in improving ionic conductivity.
The self-assembled structure plays an important role in the ionic conductivity of a non-block copolymer, LC ion conductor.
Background and Purpose
Osteoarthritis (OA) pain remains a major clinical problem. It is urgent to identify novel therapeutic approaches for OA pain states. Bromodomain and extra‐terminal (BET) ...protein inhibitors have robust anti‐inflammatory effects in several pain models. However, the underlying mechanisms of these inhibitors in OA pain have not been determined. We, therefore, investigated the effects and the underlying mechanism(s) of BET inhibition on pain‐related behaviours in a rat model of OA.
Experimental Approach
The OA model was established by intra‐articular injection of monosodium iodoacetate (MIA) in rat knees. Pain behaviours were assessed in rats by hindlimb weight‐bearing asymmetry, mechanical allodynia and thermal hyperalgesia. Possible mechanisms underlying BET inhibition were explored in the MIA‐induced OA pain model in the spinal cord and dorsal root ganglia (DRG).
Key Results
Inhibiting bromodomain‐containing protein 4 (Brd4) with either JQ1 or MS417, or using AAV2/9‐shRNA‐Brd4‐EGFP‐mediated knockdown of Brd4 genes, significantly attenuated MIA‐induced pain behaviours. Brd4 inhibition suppressed NF‐κB and NF‐κB‐mediated inflammatory cytokines in both the spinal cord and DRG in rats with MIA‐induced OA pain. Brd4 inhibition also attenuated the oxidative stress and promoted nuclear factor erythroid‐2‐related factor 2 (Nrf2)‐dependent antioxidant genes in both the spinal cord and DRG in our odel of MIA‐induced OA pain.
Conclusions and Implications
In conclusion, Brd4 inhibition alleviated MIA‐induced OA pain in rats, via suppression of neuroinflammation and activation of Nrf2‐mediated antioxidant signalling. Although our model does not perfectly represent how OA develops in humans, inhibition of Brd4 may provide novel insights into possible treatments for OA pain.
Systemic diseases often have common characteristics. The aim of this study was to investigate the feasibility of targeting common pathological metabolism to inhibit the progression of malignant and ...proliferative diseases.
Gefitinib-resistant (G-R) nonsmall-cell lung cancer (NSCLC) and rheumatoid arthritis (RA) were studied as conditions representative of malignant and proliferative diseases, respectively. Strong lipogenic activity and high expression of sterol regulatory element-binding protein 1 (SREBP1) were found in both G-R NSCLC cells and synovial fibroblasts from RA patients (RASFs). Berberine (BBR), an effective suppressor of SREBP1 and lipogenesis regulated through reactive oxygen species (ROS)/AMPK pathway, selectively inhibited the growth of G-R NSCLC cells and RASFs but not that of normal cells. It effectively caused mitochondrial dysfunction, activated ROS/AMPK pathway, and finally suppressed cellular lipogenesis and cell proliferation. Addition of ROS blocker, AMPK inhibitor, and palmitic acid significantly reduced the effect of BBR. In an in vivo study, treatment of BBR led to significant inhibition of mouse tumor xenograft growth and remarkably slowed down the development of adjuvant-induced arthritis in rats. Innovation and Conclusion: Targeting ROS/AMPK/lipogenesis signaling pathway selectively inhibited the growth of G-R NSCLC cells and the progress of RASFs in vitro and in vivo, which provides a new avenue for treating malignancies and proliferative diseases. Antioxid. Redox Signal. 28, 339-357.
By combining reversible addition–fragmentation chain transfer (RAFT) with postfunctionalization and ion exchange, we synthesized a series of block copolymers (BCPs) containing an azobenzene-based ...liquid crystalline (LC) polymer (PAzo) and an imidazolium-containing poly(ionic liquid) (PIL, PVB(TFSI)) with the volume fraction of PIL (f PIL) values ranging from 15.9% to 69.9%. The samples obtained self-assemble into hexagonally packed cylinders (HEX), lamellae (LAM), and the mixed phase with coexisting HEX and LAM. The thin-film self-assembly of the samples PAzo101-b-PVB(TFSI)22 and PAzo101-b-PVB(TFSI)67 was studied systematically. We investigated the assembled structures of the thin films with various initial thicknesses after thermal annealing (145 °C for 12 h) or mixed solvent vapor annealing with tetrahydrofuran and n-hexane. Thin films with large-scale uniaxial PIL nanocylinders were obtained, which will greatly broaden the application of IL-based BCPs. Inverse phases were also observed for the thin films with thicknesses less than ∼120 nm. The different mechanisms of the formation of inverse nanostructures formed in the thinner films under the thermal annealing and mixed solvent vapor annealing conditions were also elucidated.
Liquid crystalline polymers (LCPs) have drawn much interest because of their superior properties and widespread applications in high-performance polymer fibers, optics, energy storage, shape memory, ...surface modification, data storage, actuator, etc. LCPs can self-assemble into various liquid crystalline (LC) phases, such as nematic, smectic, columnar, and cholesteric phases. The self-assembling structures of LCPs can be influenced by architectures and chemical structures of the polymer backbone, mesogenic unit, flexible spacer, surrounding alkyl tail, etc. In the last decades, the structure-property relationships of LCPs have been researched extensively. In this perspective, the history, self-assembly, and applications of main-chain, side-chain, mesogen-jacketed, dendronized, main-chain/side-chain, and crosslinked LCPs are briefly reviewed. Finally, the future direction of research on LCPs is also discussed.
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•The widespread use of liquid crystalline polymers has attracted much attention.•Main-chain liquid crystalline polymers possess excellent mechanical properties.•Side-chain liquid crystalline polymers are excellent functional and responsive materials.•Liquid crystalline elastomers have huge potentials in actuator applications.
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