Multifunctional Interface Layer Constructed by Trace Zwitterions for Highly Reversible Zinc Anodes.

The inhomogeneous plating/stripping of Zn anode, attributed to dendrite growth and parasitic reactions at the electrode/electrolyte interface, severely restricts its cycling life-span. Here, trace zwitterions (trifluoroacetate pyridine, TFAPD) are introduced into the aqueous electrolyte to construct a multifunctional interface that enhances the reversibility of Zn anode. The TFA- anions with strong specific adsorption adhere onto the Zn surface to reconstruct the inner Helmholtz plane (IHP), preventing the hydrogen evolution and corrosion side reactions caused by free H2O. The Py+ cations accumulate on the outer Helmholtz plane (OHP) of Zn anode with the force of electric field during Zn2+ plating, forming a shielding layer to uniformize the deposition of Zn2+. Besides, the adsorbed TFA- and Py+ promote the desolvation process of Zn2+ resulting in fast reaction kinetics. Thus, the Zn||Zn cells present an outstanding cycling performance of more than 10000 hours. And even at 85% utilization rate of Zn, it can stably cycle for over 200 hours at 10 mA cm-2 and 10 mAh cm-2. The Zn||I2 full cell exhibits a capacity retention of over 95% even after 30000 cycles. Remarkably, the Zn||I2 pouch cells (95 mAh) deliver a high-capacity retention of 99% after 750 cycles.

Activatable Lanthanide Nanoprobes with Dye-Sensitized Second Near-Infrared Luminescence for in Vivo Inflammation Imaging.

Lanthanide nanoparticles exhibit unique photophysical properties and thus emerge as promising second near-infrared (NIR-II) optical agents. However, the limited luminescence brightness hampers their construction of activatable NIR-II probes. Herein, we report the synthesis of dye-sensitized lanthanide nanoprobes (NaGdF4:Nd/ICG; indocyanine green (ICG)) and their further development for in vivo activatable imaging of hypochlorite (ClO-). Dye sensitization using ICG not only shifts the optimal doping concentration of Nd3+ from 5 to 20 mol % but also leads to a 5-fold NIR-II enhancement relative to the ICG-free counterpart. Mechanistic studies reveal that such a luminescence enhancement of NaGdF4:Nd at high Nd3+ concentration is ascribed to an alleviated cross-relaxation effect due to the broad absorption of ICG and faster energy transfer process. Taking advantage of dye oxidation, the nanoprobes enable activatable NIR-II imaging of hypochlorous acid (ClO-) in a drug-induced lymphatic inflammation mouse model. This work thus provides a simple, yet effective luminescence enhancement strategy for constructing lanthanide nanoprobes at higher activator doping concentration toward activatable NIR-II molecular imaging.

Artificial Atomic Vacancies Tailor Near-Infrared II Excited Multiplexing Upconversion in Core-Shell Lanthanide Nanoparticles.

Epitaxial growth of an inert shell around the optical active lanthanide upconversion nanoparticles (UCNPs) is a general strategy to enhance their brightness. Yet, its potential as a tool in multiplexing emission tailoring has rarely been reported. Here, by developing the atomic vacancies into color selectivity actuators, we present an efficient strategy to achieve inert-shell-modulated multiplexing upconversion in 1540 nm activated UCNPs. Artificially generated fluoride atomic vacancies, owing to the decreased NaOH/NH4F dosage during shell growth, reduce the coordination number of Y-F and lattice densities in the inert shell, leading to the core-engineered shell nanoparticles with distinctive emission profiles. The multicolor tailoring is independent of shell thickness and can be readily applied to Lu3+/Gd3+-based shells. The upconversion emission can be exploited to visualize in security decoding and in vivo multiplexing bioimaging. This method of regulating atomic vacancies based on the inert-shell engineering opens new insights of upconversion modulation in core-shell lanthanide nanostructures.

Enhanced Efficiency of Dye-Sensitized Solar Cells Benefited from Graphene Modified by Ag Nanoparticles.

In this paper, graphene modified by Ag nanoparticles was successfully applied into dye sensitized solar cells. The morphologies and compositions of graphene and graphene-Ag nanoparticles were characterized by scanning electron microscope and energy dispersive X-ray spectroscopy. The optical and electrical properties were evaluated by UV-vis-NIR absorption spectroscopy, electrochemical impedance spectroscopy and current-voltage curve. The results indicated that the incorporation of graphene or graphene-Ag nanoparticles can improve the light absorption and decrease the charge recombination. The solar cells with graphene-Ag nanoparticles exhibited short-circuit current density of 14.34 mA cm-2, open-circuit voltage of 709 mV and conversion efficiency of 6.01%, which were higher than those of DSSCs with graphene or pure TiO2.

Surface/Interfacial Structure and Chemistry of High-Energy Nickel-Rich Layered Oxide Cathodes: Advances and Perspectives.

The urgent prerequisites of high energy-density and superior electrochemical properties have been the main inspiration for the advancement of cathode materials in lithium-ion batteries (LIBs) in the last two decades. Nickel-rich layered transition-metal oxides with large reversible capacity as well as high operating voltage are considered as the most promising candidate for next-generation LIBs. Nonetheless, the poor long-term cycle-life and inferior thermal stability have limited their broadly practical applications. In the research of LIBs, it is observed that surface/interfacial structure and chemistry play significant roles in the performance of cathode cycling. This is due to the fact that they are basically responsible for the reversibility of Li+ intercalation/deintercalation chemistries while dictating the kinetics of the general cell reactions. In this Review, the surface/interfacial structure and chemistry of nickel-rich layered cathodes involving structural defects, redox mechanisms, structural evolutions, side-reactions among others are initially demonstrated. Recent advancements in stabilizing the surface/interfacial structure and chemistry of nickel-rich cathodes by surface modification, core-shell/concentration-gradient structure, foreign-ion substitution, hybrid surface, and electrolyte additive are presented. Then lastly, the remaining challenges such as the fundamental studies and commercialized applications, as well as the future research directions are discussed.

lincRNA-p21 inhibits invasion and metastasis of hepatocellular carcinoma through Notch signaling-induced epithelial-mesenchymal transition.

AIM: Emerging evidence has showed that long non-coding RNA (lncRNA) play an important role in the occurrence and development of various cancers. In the present study, the expression level of lincRNA-p21 was investigated in hepatocellular carcinoma (HCC), and its role in invasion of HCC was also explored. METHODS: The lincRNA-p21 levels in human HCC tumor tissue and cell lines HepG2 and SMMC-7721 were determined by real-time polymerase chain reaction. Transfected HCC cells with pcDNA-lincRNA-p21 or si-lincRNA-p21 for overexpression or downregulation of lincRNA-p21, the Notch signaling and epithelial-mesenchymal transition (EMT)-related proteins and cell invasion were measured by western blot and Transwell assay, respectively. A tumor xenotransplant mouse model was also established to investigate the role of lincRNA-p21 in tumor metastasis in vivo. RESULTS: The lincRNA-p21 expression was downregulated in HCC tissue and cells. Overexpression of lincRNA-p21 inhibited Notch singling and EMT, while its downregulation led to the reverse result. The invasion of HCC cell was also inhibited by pcDNA-lincRNA-p21, and activation of Notch signaling reversed this effect. In vivo, overexpression of lincRNA-p21 decreased the tumor metastasis, as well. CONCLUSION: lincRNA-p21 was downregulated in HCC and lincRNA-p21 overexpression contributed to the inhibition of tumor invasion through mediating Notch signaling induced EMT.

Enhanced Photocatalytic Performance Using One Dimensional Ordered TiO2 Nanorods Modified by Graphene Oxide.

A new architecture of one dimensional ordered TiO2 nanorods modified by graphene oxide (GO) was assembled. The GO as the higher carrier mobility can reduce the recombination of carriers, which is more favourable for the methy orange (MO) degradation. Incorporating GO with the unblocked passageway for carrier transportation of the TiO2 nanorods can separate the transport pathway of electron and hole effectively. Furthermore, the large surface areas of TiO2 nanorods grown on the GO are beneficial to the enhancement of photocatalytic properties, and the reasonable band energy level can be obtained for the architecture, which is favorable for enhancing carrier separation and transportation. Finally, the higher transparency of the structure can enhance the light absorption. The photocatalyst grown on FTO substrates makes it easier to collect and recycle.

Template-assisted electrodeposition of iron nanostructures.

A facile approach to prepare iron nanostructures (nanowires, nanotubes, branched and multi-branched nanotubes) is reported by reduction of metal sulfide salts in the pores of an anodic aluminum membranes (AAMs) template with a back side Au sheet. The crystal structures and morphologies of Fe nanostructures are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM) and transmission electron microscope. The results indicate that the Fe nanostructures can replicate the inner architectures of the templates. The thickness of the Au film deposited on the back side of the AAMs and the inner structures of AAMs are the two key factors to determine the final morphologies of Fe nanostructures. This approach can be broadened to fabricate other metal nanostructures.

Incorporation of graphene oxide in quantum dot sensitized photocatalyst based on ZnO nanorods.

The novel efficient architecture of photocatalyst is fabricated by incorporating graphene oxide (GO) in quantum dots (QDs) sensitized ZnO nanorods and the photocatalytic properties for methyl orange (MO) degradation are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-vis-NIR absorption spectroscopy. The results indicate that the incorporating of grapheme oxide is more favourable for the degradation. The improved photocatalytic properties can take several advantages given that the higher carrier mobility of GO which can reduce the recombination of carriers, and assembled quantum dots which can facilitate the absorption of solar light. The paper provides the clue to design the effective and easy recyclable photocatalyst.

Synthesis and optical properties of Eu3+ doped ZnO nanoparticles used for white light emitting diodes.

ZnO nanoparticles doped with trivalent europium ions (Eu3+) were synthesized by the hydrothermal method. The structural properties of the samples were investigated by the X-ray diffraction (XRD). The results indicated that Eu3+ was incorporated into the lattice of ZnO. Photoluminescence (PL) measurements of ZnO:Eu3+ showed a strong red luminescence emission. Specially, the red emission can be obtained even under the nonresonant excitation of 320 nm, and it is explained by an energy transfer mechanism in which the energy is transferred from ZnO matrix to Eu3+. These results indicate that the ZnO:Eu3+ is the attractive candidate phosphor for the application in phosphor-converted light-emitting diodes (pc-LEDs) as red phosphor. The intensity of Eu3+ PL decreased with the increasing Eu3+ concentration and the concentration quenching mechanism was presented based on non-radiative recombination processes in ZnO and the energy back-transfer from the excited state of Eu3+ to the ZnO host. Moreover, the samples were synthesized under low temperature condition.

The influence of oxidation time on the morphologies of TiO2 nanostructures.

Highly-ordered TiO2 nanostructures have been successfully fabricated by anodic oxidation method on the surface of pure titanium and Ti film deposited on the Si substrates using 20 V of the DC voltage in 0.5% HF electrolyte. X-ray diffractometer (XRD), Raman spectroscopy and field emission scanning electron microscope (SEM) were used to characterize the transformations of morphologies and structures on the TiO2 nanostructures. The experimental results showed that the final morphologies of the nanostructures were time-dependent. The tube architectures were firstly fabricated, and with the increase of the oxidation time, the tube morphologies were ruined and the rod-like morphologies were formed. When the Ti films on the Si substrates were anodized, a new kind of porous nanostructures was formed on the surface of the Ti foils, which are different to the previous reports. The formation mechanisms of these nanostructures were also briefly discussed.

Crystalline/Amorphous Mo-Ni(OH)2/FexNiy(OH)3x+2y hierarchical nanotubes as efficient electrocatalyst for overall water splitting.

The development of efficient bifunctional catalysts for overall water splitting is highly desirable and essential for the advancement of hydrogen technology. In this work, Mo-Ni(OH)2/FexNiy(OH)3x+2y with hierarchical nanotube structure is constructed on flexible carbon cloth (CC) through simple electrochemical deposition and hydrothermal method. The hollow tube-structure is in favor of both exposing active sites and enhancing mass transfer capability. Moreover, the doping of Mo can enhance the electronic conductivity of heterostructures. The interfacial interaction between amorphous and crystal can enhance effectively the charge transfer kinetics across the interface. Therefore, Mo-Ni(OH)2/FexNiy(OH)3x+2y can achieve a low overpotential of 57 mV for hydrogen evolution reaction (HER) and 229 mV for oxygen evolution reaction (OER) at 10 mA·cm-2. In addition, Mo-Ni(OH)2/FexNiy(OH)3x+2y needs a potential of only 1.54 V at 10 mA·cm-2 for overall water splitting, and retains for a long period of time (60 h) reliable. The work will provide a valuable approach to the construction of highly efficient electrocatalysts for overall water splitting.

Cr doping and heterostructure-accelerated NiFe LDH reaction kinetics assist the MoS2 oxygen evolution reaction.

Although molybdenum disulfide (MoS2) has garnered significant interest as a potential catalyst for the oxygen evolution reaction (OER), its poor intrinsic activity and few marginal active spots restrict its electrocatalytic activity. Herein, we successfully constructed a catalyst via a simple hydrothermal method by forming a heterostructure of MoS2 with Cr-doped nickel-iron hydroxide (NiFe LDH) to synthesize a MoS2/NiFeCr LDH catalyst to significantly improve the OER catalytic performance. MoS2 plays a crucial function as an electron transport channel in the MoS2/NiFeCr LDH heterostructure, which increases the electron transport rate. Furthermore, a larger active surface area for NiFeCr LDH is provided by the ultrathin layered structure of MoS2, increasing the number of active sites and encouraging the OER. On the other hand, the introduction of Cr element increased the density of the catalytic center and provided additional Cr-OH active sites, which accelerated the oxygen decomposition reaction. These two factors act synergistically to improve the intrinsic structure of MoS2, increase the number of reactive sites, and dramatically enhance the OER catalytic performance. Excellent OER activity is demonstrated by the MoS2/NiFeCr LDH catalyst, which only needs an overpotential of 224 mV to obtain a current density of 10 mA cm-2 and a Tafel slope of 61 mV dec-1. The catalyst also demonstrated outstanding stability, with its activity practically holding steady after 48 h of testing. This work offers novel ideas for enhancing and designing MoS2-based OER catalysts, and it provides a crucial reference for research in the field of clean energy.

Botulinum toxin type A-targeted SPP1 contributes to neuropathic pain by the activation of microglia pyroptosis.

BACKGROUND: Neuropathic pain (NP) is the primary symptom of various neurological conditions. Patients with NP often experience mood disorders, particularly depression and anxiety, that can severely affect their normal lives. Microglial cells are associated with NP. Excessive inflammatory responses, especially the secretion of large amounts of pro-inflammatory cytokines, ultimately lead to neuroinflammation. Microglial pyroptosis is a newly discovered form of inflammatory cell death associated with immune responses and inflammation-related diseases of the central nervous system. AIM: To investigate the effects of botulinum toxin type A (BTX-A) on microglial pyroptosis in terms of NP and associated mechanisms. METHODS: Two models, an in vitro lipopolysaccharide (LPS)-stimulated microglial cell model and a selective nerve injury model using BTX-A and SPP1 knockdown treatments, were used. Key proteins in the pyroptosis signaling pathway, NLRP3-GSDMD, were assessed using western blotting, real-time quantitative polymerase chain reaction, and immunofluorescence. Inflammatory factors [interleukin (IL)-6, IL-1ß, and tumor necrosis factor (TNF)-α] were assessed using enzyme-linked immunosorbent assay. We also evaluated microglial cell proliferation and apoptosis. Furthermore, we measured pain sensation by assessing the delayed hind paw withdrawal latency using thermal stimulation. RESULTS: The expression levels of ACS and GSDMD-N and the mRNA expression of TNF-α, IL-6, and IL-1ß were enhanced in LPS-treated microglia. Furthermore, SPP1 expression was also induced in LPS-treated microglia. Notably, BTX-A inhibited SPP1 mRNA and protein expression in the LPS-treated microglia. Additionally, depletion of SPP1 or BTX-A inhibited cell viability and induced apoptosis in LPS-treated microglia, whereas co-treatment with BTX-A enhanced the effect of SPP1 short hairpin (sh)RNA in LPS-treated microglia. Finally, SPP1 depletion or BTX-A treatment reduced the levels of GSDMD-N, NLPRP3, and ASC and suppressed the production of inflammatory factors. CONCLUSION: Notably, BTX-A therapy and SPP1 shRNA enhance microglial proliferation and apoptosis and inhibit microglial death. It improves pain perception and inhibits microglial activation in rats with selective nerve pain.

Enhanced photocatalytic activity of quantum-dot-sensitized one-dimensionally-ordered ZnO nanorod photocatalyst.

An efficient photocatalyst was fabricated by assembling quantum dots (QDs) onto one-dimensionally-ordered ZnO nanorods, and the photocatalytic properties for Methyl Orange degradation were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-Vis-NIR absorption spectroscopy and photoluminescence. The results indicate that the catalyst with assembled QDs is more favorable for the degradation than the pristine ZnO nanorods. The QDs with core-shell structure lower the photocatalytic ability due to the higher carrier transport barrier of the ZnS shell layer. Besides its degradation efficiency, the photocatalyst has several advantages given that the one-dimensionally-ordered ZnO nanorods have been grown directly on indium tin oxide substrates. The article provides a new method to design an effective and easily recyclable photocatalyst.

Sulfidation and NaOH etching in CoFeAl LDH evolved catalysts for an efficient overall water splitting in an alkaline solution.

In this study, a hierarchical interconnected porous metal sulfide heterostructure was synthesized from CoFeAl layered double hydroxides (LDHs) by a two-step hydrothermal process (sulfidation and a NaOH etching process). Among the as-made samples, the CoFeAl-T-NaOH electrode exhibited excellent oxygen and hydrogen evolution reaction catalytic activities with overpotentials of 344 mV and 197 mV at the current density of 100 mA cm-2, respectively. Meanwhile, small Tafel slopes of 57.7 mV dec-1 and 106.5 mV dec-1 for water oxidation and hydrogen evolution were observed for the CoFeAl-T-NaOH, respectively. Serving as both the cathode and anode for overall water splitting, the CoFeAl-T-NaOH electrode reached a current density of 10 mA cm-2 at a cell voltage of 1.65 V with excellent stability. The enhanced electrocatalytic activity could be attributed to: the hierarchical interconnected nanosheet structure facilitating mass transport; the porous structure promoting electrolyte infiltration and reactant transfer; the heterojunction accelerating charge transfer; and the synergistic effect between them. This study offered a new clue for in situ synthesizing porous transition-metal based heterojunction electrocatalysts with a careful tuning of the sequence of sulfuration and alkaline etching to enhance the electrocatalytic performance.

In-situ growth of 3D hierarchical γ-FeOOH/Ni3S2 heterostructure as high performance electrocatalyst for overall water splitting.

Obtaining efficient, stable, and low-cost electrocatalysts is the key to realizing large-scale water splitting. In this work, three-dimensional (3D) hierarchical γ-iron oxyhydroxide (γ-FeOOH)/Ni3S2 electrocatalyst on Ni foam is constructed for electrochemical overall water splitting. The 3D γ-FeOOH/Ni3S2 heterostructure can effectively enhance active sites and charge transfer capability, also the heterostructure can benefit electronic effect at the interfaces and synergistic effect of multiple components. Therefore, the γ-FeOOH/Ni3S2 exhibits excellent electrocatalytic activity with low overpotentials of 279 mV at 50 mA⋅cm-2 for oxygen evolution reaction and 92 mV at 10 mA⋅cm-2 for hydrogen evolution reaction, respectively. In addition, only a potential of 1.66 V is needed to attain 10 mA⋅cm-2 for the overall water splitting. In particular, the γ-FeOOH/Ni3S2 exhibits long-term stability for 120 h at 10 mA⋅cm-2 without significant degradation. This work provides a valuable idea for obtaining low-cost and high performance bifunctional electrocatalysts for water splitting.

Interface strong-coupled 3D Mo-NiS@Ni-Fe LDH flower-cluster as exceptionally efficient electrocatalyst for water splitting in wide pH range.

It is crucial to create a bifunctional catalyst with high efficiency and low cost for electrochemical water splitting under alkaline and neutral pH conditions. This study investigated the in-situ creation of ultrafine Mo-NiS and NiFe LDH nanosheets as an effective and stable electrocatalyst with a three-dimensional (3D) flower-cluster hierarchical structure (Mo-NiS@NiFe LDH). The strong interfacial connection between Mo-NiS and NiFe LDH enhances the formation of metal higher chemical states in the material, optimizes the electronic structure, increases OH- adsorption capacity improves electron transfer/mass diffusion, and promotes O2/H2 gas release. As a result, at 10 mA cm-2, Mo-NiS@NiFe LDH/NF demonstrates the outstanding bifunctional electrocatalytic activity of just 107 mV (HER, hydrogen evolution reaction) and 184 mV (hydrogen evolution reaction) (OER, oxygen evolution reaction). The catalytic performance is remarkably stable after 72 h of continuous operation in 1 M KOH at high current densities (300 mA cm-2). More interestingly, in the overall water splitting system, the cell voltages for anode and cathode in both alkaline and neutral electrolytes for Mo-NiS@NiFe LDH/NF are only 1.54 V (alkaline) and 2.06 V (neutral) at 10 mA cm-2. These results demonstrated that the bifunctional electrocatalyst design concept is a viable solution for water splitting in both alkaline and neutral systems.

Near-Infrared Nano-Optogenetic Activation of Cancer Immunotherapy via Engineered Bacteria.

Certain anaerobic microbes with the capability to colonize the tumor microenvironment tend to express the heterologous gene in a sustainable manner, which will inevitably compromise the therapeutic efficacy and induce off-tumor toxicity in vivo. To improve the therapeutic precision and controllability of bacteria-based therapeutics, Escherichia coli Nissle 1917 (EcN), engineered to sense blue light and release the encoded flagellin B (flaB), is conjugated with lanthanide upconversion nanoparticles (UCNPs) for near-infrared (NIR) nano-optogenetic cancer immunotherapy. Upon 808 nm photoirradiation, UCNPs emit at the blue region to photoactivate the EcN for secretion of flaB, which subsequently binds to Toll-like receptor 5 expressed on the membrane of macrophages for activating immune response via MyD88-dependent signal pathway. Such synergism leads to significant tumor regression in different tumor models and metastatic tumors with negligible side effects. These studies based on the NIR nano-optogenetic platform highlight the rational of leveraging the optogenetic tools combined with natural propensity of certain bacteria for cancer immunotherapy.

Anodic formation of anatase TiO2 nanotubes with rod-formed walls for photocatalysis and field emitters.

Anatase TiO(2) nanotube arrays with rod-formed walls have been fabricated using a one-step anodic oxidation method for the first time. XRD, Raman spectroscopy, SEM, and HRTEM analysis were used for the structural characterization of the synthesized nanostructures. Their photocatalytic and field emission (FE) properties were also systematically investigated, and the experimental results indicated that the crystallization of the starting polycrystalline nanostructures turned into a better anatase phase after the annealed process. The photocatalytic properties showed that the nanostructures with optimized crystallization demonstrated faster degradation rate than the as-prepared polycrystalline counterparts, which would be caused by the improved crystallinity. Furthermore, the dependence of the FE properties on the distances between the anodes and the samples was investigated and the results revealed that the annealed samples have higher field enhancement factor ß compared to the as-prepared nanostructures. The formation mechanism of this novel rod-formed TiO(2) nanotubes is also briefly discussed.