Chemodynamic therapy (CDT) utilizes iron‐initiated Fenton chemistry to destroy tumor cells by converting endogenous H2O2 into the highly toxic hydroxyl radical (.OH). There is a paucity of ...Fenton‐like metal‐based CDT agents. Intracellular glutathione (GSH) with .OH scavenging ability greatly reduces CDT efficacy. A self‐reinforcing CDT nanoagent based on MnO2 is reported that has both Fenton‐like Mn2+ delivery and GSH depletion properties. In the presence of HCO3−, which is abundant in the physiological medium, Mn2+ exerts Fenton‐like activity to generate .OH from H2O2. Upon uptake of MnO2‐coated mesoporous silica nanoparticles (MS@MnO2 NPs) by cancer cells, the MnO2 shell undergoes a redox reaction with GSH to form glutathione disulfide and Mn2+, resulting in GSH depletion‐enhanced CDT. This, together with the GSH‐activated MRI contrast effect and dissociation of MnO2, allows MS@MnO2 NPs to achieve MRI‐monitored chemo–chemodynamic combination therapy.
Self‐reinforcing weapon: The Fenton‐like Mn2+ delivery and glutathione (GSH) depletion abilities of MnO2 allow it to exert enhanced chemodynamic efficacy in cancer treatment. An activatable theranostic platform based on multifunctional MnO2‐coated mesoporous silica nanoparticles (MS@MnO2 NPs) has been developed for MRI‐monitored combination chemotherapy and chemodynamic therapy (CDT). ADS=antioxidant defense system.
Background and Aims
There is growing evidence that single‐stranded, circular RNA (circRNA) plays a key role in the development of certain cancers, including hepatocellular carcinoma (HCC). It is less ...clear, however, what role circRNA plays in HCC metastasis.
Approach and Results
In this study, through circRNA sequencing, we identified a circRNA: circASAP1 (a circRNA derived from exons 2 and 3 of the ASAP1 gene, hsa_circ_0085616), which is associated with pulmonary metastasis after curative resection in patients with HCC. CircASAP1 was overexpressed in HCC cell lines with high metastatic potential and in metastatic HCCs. In vitro, circASAP1 promoted cell proliferation, colony formation, migration, and invasion, and in vivo, it enhanced tumor growth and pulmonary metastasis. Mechanism studies showed that circASAP1 acts as a competing endogenous RNA for microRNA 326 (miR‐326) and microRNA 532‐5p (miR‐532‐5p), both of which are tumor suppressors in HCC. We found that mitogen‐activated protein kinase (MAPK) 1 and colony stimulating factor (CSF)‐1 were direct common targets for microRNA 326 (miR‐326) and microRNA 532‐5p (miR‐532‐5p), which were regulated by circASAP1. CircASAP1 promotes HCC cell proliferation and invasion by regulating miR‐326/miR‐532‐5p‐MAPK1 signaling and, furthermore, mediates tumor‐associated macrophage infiltration by regulating the miR‐326/miR‐532‐5p‐CSF‐1 pathway. Clinical HCC samples exhibited a positive correlation between circASAP1 expression and levels of CSF‐1, MAPK1, and CD68+ tumor‐associated macrophages, all of which were predictive of patient outcomes.
Conclusion
We identified circASAP1 as a key regulator of HCC metastasis that acts on miR‐326/miR‐532‐5p‐MAPK1/CSF‐1 signaling and serves as a prognostic predictor in patients with HCC.
Backscattering suppression in silicon-on-insulator (SOI) is one of the central issues to reduce energy loss and signal distortion, enabling for capability improvement of modern information processing ...systems. Valley physics provides an intriguing way for robust information transfer and unidirectional coupling in topological nanophotonics. Here we realize topological transport in a SOI valley photonic crystal slab. Localized Berry curvature near zone corners guarantees the existence of valley-dependent edge states below light cone, maintaining in-plane robustness and light confinement simultaneously. Topologically robust transport at telecommunication is observed along two sharp-bend interfaces in subwavelength scale, showing flat-top high transmission of ~10% bandwidth. Topological photonic routing is achieved in a bearded-stack interface, due to unidirectional excitation of valley-chirality-locked edge state from the phase vortex of a nanoscale microdisk. These findings show the prototype of robustly integrated devices, and open a new door towards the observation of non-trivial states even in non-Hermitian systems.
Yolk–shell nanostructures (YSNs) composed of a core within a hollow cavity surrounded by a porous outer shell have received tremendous research interest owing to their unique structural features, ...fascinating physicochemical properties, and widespread potential applications. Here, a comprehensive overview of the design, synthesis, and biomedical applications of YSNs is presented. The synthetic strategies toward YSNs are divided into four categories, including hard‐templating, soft‐templating, self‐templating, and multimethod combination synthesis. For the hard‐ or soft‐templating strategies, different types of rigid or vesicle templates are used for making YSNs. For the self‐templating strategy, a number of unconventional synthetic methods without additional templates are introduced. For the multimethod combination strategy, various methods are applied together to produce YSNs that cannot be obtained directly by only a single method. The biomedical applications of YSNs including biosensing, bioimaging, drug/gene delivery, and cancer therapy are discussed in detail. Moreover, the potential superiority of YSNs for these applications is also highlighted. Finally, some perspectives on the future research and development of YSNs are provided.
Yolk–shell nanostructures (YSNs) attract increasing attention because of their unique structural features, fascinating physicochemical properties, and widespread potential applications. Various strategies for the fabrication of yolk–shell nanostructures, such as hard‐, soft‐, and self‐templating and multimethod combination synthesis, are discussed in detail. The biomedical applications of YSNs including biosensing, bioimaging, drug/gene delivery, and cancer therapy are also presented.
Abstract
Solar‐driven evaporation process brings exciting opportunities to recover clean water and resources in a sustainable way from diverse sources like seawater and wastewater. Separation ...membranes, as a vital material in many environmental and energy applications, can contribute significantly to this process owing to their structural features. However, the unique roles of membranes in solar evaporator construction and process design are seldom recognized and not summarized yet from scientific principles and application demands, which forms the motivation of this review. Herein, the roles of membranes in different processes based on solar‐driven evaporation are focused and the design principles of membrane materials and devices to meet the requirements of these applications are discussed. Fabrication strategies for photothermal membranes are introduced primarily, followed by a discussion on how to design membrane materials, devices, and processes to pursue optimal performance and realize advanced functions accompanied by evaporation. Furthermore, the future of this field is forecast with both challenges and opportunities.
Aqueous rechargeable Zn metal batteries have attracted widespread attention due to the intrinsic high volumetric capacity, low cost, and high safety. However, the low Coulombic efficiency and limited ...lifespan of Zn metal anodes resulting from uncontrollable growth of Zn dendrites impede their practical application. In this work, a 3D interconnected ZnF2 matrix is designed on the surface of Zn foil (Zn@ZnF2) through a simple and fast anodic growth method, serving as a multifunctional protective layer. The as‐fabricated Zn@ZnF2 electrode can not only redistribute the Zn2+ ion flux, but also reduce the desolvation active energy significantly, leading to stable and facile Zn deposition kinetics. The results reveal that the Zn@ZnF2 electrode can effectively inhibit dendrites growth, restrain the hydrogen evolution reactions, and endow excellent plating/stripping reversibility. Accordingly, the Zn@ZnF2 electrode exhibits a long cycle life of over 800 h at 1 mA cm−2 with a capacity of 1.0 mAh cm−2 in a symmetrical cell test, the feasibility of which is also convincing in Zn@ZnF2//MnO2 and Zn@ZnF2//V2O5 full batteries. Importantly, a hybrid zinc‐ion capacitor of the Zn@ZnF2//AC can work at an ultrahigh current density of ≈60 mA cm−2 for up to 5000 cycles with a high capacity retention of 92.8%.
A 3D interconnected ZnF2 matrix on the surface of Zn foil (Zn@ZnF2) is prepared through a simple and fast electrochemical anodic growth method. The as‐fabricated Zn@ZnF2 electrode can not only redistribute the Zn2+ ion flux, but also reduce the desolvation active energy significantly, leading to stable and facile Zn deposition kinetics.
Low n‐doping efficiency and inferior stability restrict the thermoelectric performance of n‐type conjugated polymers, making their performance lag far behind of their p‐type counterparts. Reported ...here are two rigid coplanar poly(p‐phenylene vinylene) (PPV) derivatives, LPPV‐1 and LPPV‐2, which show nearly torsion‐free backbones. The fused electron‐deficient rigid structures endow the derivatives with less conformational disorder and low‐lying lowest unoccupied molecular orbital (LUMO) levels, down to −4.49 eV. After doping, two polymers exhibited high n‐doping efficiency and significantly improved air stability. LPPV‐1 exhibited a high conductivity of up to 1.1 S cm−1 and a power factor as high as 1.96 μW m−1 K−2. Importantly, the power factor of the doped LPPV‐1 thick film degraded only 2 % after 7 day exposure to air. This work demonstrates a new strategy for designing conjugated polymers, with planar backbones and low LUMO levels, towards high‐performance and potentially air‐stable n‐type polymer thermoelectrics.
Stability: A new rigid coplanar poly(p‐phenylene vinylene) (PPV) derivative, LPPV‐1, is synthesized with a rigid planar backbone and low‐lying LUMO, which lead to reduced conformational disorder and high n‐type doping efficiency. The conductivity of LPPV‐1 is up to 1.1 S cm−1, and the power factor is only 2 % after a 7 day exposure to air. This work represents an effective strategy towards high‐performance and potentially air‐stable n‐type polymer thermoelectrics.
Although photodynamic therapy (PDT) has served as an important strategy for treatment of various diseases, it still experiences many challenges, such as shallow penetration of light, high‐dose light ...irradiation, and low therapy efficiency in deep tissue. Here, a low‐dose X‐ray‐activated persistent luminescence nanoparticle (PLNP)‐mediated PDT nanoplatform for depth‐independent and repeatable cancer treatment has been reported. In order to improve therapeutic efficiency, this study first synthesizes W(VI)‐doped ZnGa2O4:Cr PLNPs with stronger persistent luminescence intensity and longer persistent luminescence time than traditional ZnGa2O4:Cr PLNPs. The proposed PLNPs can serve as a persistent excitation light source for PDT, even after X‐ray irradiation has been removed. Both in vitro and in vivo experiments demonstrate that low‐dose (0.18 Gy) X‐ray irradiation is sufficient to activate the PDT nanoplatform and causes significant inhibitory effect on tumor progression. Therefore, such PDT nanoplatform will provide a promising depth‐independent treatment mode for clinical cancer therapy in the future.
Low‐dose X‐ray activated persistent luminescence nanoparticle (PLNP)‐mediated photodynamic therapy (PDT) nanoplatform is fabricated based on W(VI)‐doped ZnGa2O4:Cr (ZGO:Cr/W) nanoparticles. Due to the superior persistent luminescence performance of ZGO:Cr/W PLNPs, this PDT nanoplatform significantly reduces the X‐ray dosage (0.18 Gy) both in vitro and in vivo, and also improves PDT efficiency in deep tissue.
Amino groups are common in both natural and synthetic compounds and offer a very attractive class of endogenous handles for bioconjugation. However, the ability to differentiate two types of amino ...groups and join them with high hetero‐selectivity and efficiency in a complex setting remains elusive. Herein, we report a new method for bioconjugation via one‐pot chemoselective clamping of two different amine nucleophiles using a simple ortho‐phthalaldehyde (OPA) reagent. Various α‐amino acids, aryl amines, and secondary amines can be crosslinked to the ϵ‐amino side chain of lysine on peptides or proteins with high efficiency and hetero‐selectivity. This method offers a simple and powerful means to crosslink small molecule drugs, imaging probes, peptides, proteins, carbohydrates, and even virus particles without any pre‐functionalization.
Simple ortho‐phthalaldehyde (OPA) reagent enables a facile and broadly applicable bioconjugation strategy via hetero‐selective clamping of two different endogenous amino handles such as ϵ‐NH2 of lysine and α‐NH2 of α‐amino acids without any pre‐functionalization.
Through oxygen profile engineering, we fabricated W/AlOx/Al2O3/Pt bilayer memristors with a 250-nm feature size. The AlOx fabricated by sputtering serves as an oxygen vacancy source, whereas the ...Al2O3 deposited by atomic layer deposition acts as a dominant resistive switching (RS) layer. Our devices show forming-free RS behaviors with high speed (28 ns), uniform resistance distribution, large on/off ratio (~103@100K, ~103@298K, and ~80@400K), and good retention. Besides, temperature stability with record high endurance from cryogenic to high-temperature (108@100K, 1010@298K, and 107@400K) is demonstrated, to the best of our knowledge.