Targeting HSP47 for cancer treatment.

Heat shock protein 47 (HSP47) serves as an endoplasmic reticulum residing collagen-specific chaperone and plays an important role in collagen biosynthesis and structural assembly. HSP47 is encoded by the SERPINH1 gene, which is located on chromosome 11q13.5, one of the most frequently amplified regions in human cancers. The expression of HSP47 is regulated by multiple cellular factors, including cytokines, transcription factors, microRNAs, and circular RNAs. HSP47 is frequently upregulated in a variety of cancers and plays an important role in tumor progression. HSP47 promotes tumor stemness, angiogenesis, growth, epithelial-mesenchymal transition, and metastatic capacity. HSP47 also regulates the efficacy of tumor therapies, such as chemotherapy, radiotherapy, and immunotherapy. Inhibition of HSP47 expression has antitumor effects, suggesting that targeting HSP47 is a feasible strategy for cancer treatment. In this review, we highlight the function and expression of regulatory mechanisms of HSP47 in cancer progression and point out the potential development of therapeutic strategies in targeting HSP47 in the future.

Magnetic FNS/MILs nanofibers for highly efficient removal of norfloxacin via adsorption and Fenton-like reaction.

Iron-containing MOFs have attracted extensive interest as promising Fenton-like catalysts. In this work, magnetic Fe3O4 nanofiber (FNS)/MOFs composites with stable structure, included FNS/MIL-88B, FNS/MIL-88A and FNS/MIL-100, were prepared via the in-situ solvothermal method. The surface of the obtained fibers was covered by a dense and continuous MOFs layer, which could effectively solve the agglomeration problem of MOFs powder and improved the catalytic performance. The adsorption and catalytic properties of FNS/MOFs composites were evaluated by removal of norfloxacin. FNS/MIL-88B showed the best performance with a maximum adsorption capacity up to 214.09 mg/g, and could degrade 99% of NRF in 60 min. Meanwhile, FNS/MIL-88B had a saturation magnetization of 20 emu/g, and could be rapidly separated by an applied magnetic field. The self-supported nanofibers allowed the adequate contact between MOFs and pollutants, and promoted the catalytic activity and high stability. We believe that this work provided a new idea for the design and preparation of Fenton-like catalysts especially MOFs composites.

Advances in Small Molecular Agents against Oral Cancer.

Oral cancer is a common malignancy with a high mortality rate. Although surgery is the best treatment option for patients with cancer, this approach is ineffective for advanced metastases. Molecular agents are irreplaceable in preventing and treating distant metastases. This review aims to summarise the molecular agents used for the treatment of oral cancer in the last decade and describe their sources and curative effects. These agents are classified into phenols, isothiocyanates, anthraquinones, statins, flavonoids, terpenoids, and steroids. The mechanisms of action of these agents include regulating the expression of cell signalling pathways and related proteases to affect the proliferation, autophagy, migration, apoptosis, and other biological aspects of oral cancer cells. This paper may serve as a reference for subsequent studies on the treatment of oral cancer.

Non-Noble Metal High-Entropy Alloy-Based Catalytic Electrode for Long-Life Hydrogen Gas Batteries.

The development of efficient, stable, and low-cost bifunctional catalysts for the hydrogen evolution/oxidation reaction (HER/HOR) is critical to promote the application of hydrogen gas batteries in large scale energy storage systems. Here we demonstrate a non-noble metal high-entropy alloy grown on Cu foam (NNM-HEA@CF) as a self-supported catalytic electrode for nickel-hydrogen gas (Ni-H2) batteries. Experimental and theoretical calculation results reveal that the NNM-HEA catalyst greatly facilitates the HER/HOR catalytic process through the optimized electronic structures of the active sites. The assembled Ni-H2 battery with NNM-HEA@CF as the anode shows excellent rate capability and exceptional cycling performance of over 1800 h without capacity decay at an areal capacity of 15 mAh cm-2. Furthermore, a scaled-up Ni-H2 battery fabricated with an extended capacity of 0.45 Ah exhibits a high cell-level energy density of ∼109.3 Wh kg-1. Moreover, its estimated cost reaches as low as ∼107.8 $ kWh-1 based on all key components of electrodes, separator and electrolyte, which is reduced by more than 6 times compared to that of the commercial Pt/C-based Ni-H2 battery. This work provides an approach to develop high-efficiency non-noble metal-based bifunctional catalysts for hydrogen batteries in large-scale energy storage applications.

An All-Climate Nonaqueous Hydrogen Gas-Proton Battery.

Rechargeable hydrogen gas batteries, driven by hydrogen evolution and oxidation reactions (HER/HOR), are emerging grid-scale energy storage technologies owing to their low cost and superb cycle life. However, compared with aqueous electrolytes, the HER/HOR activities in nonaqueous electrolytes have rarely been studied. Here, for the first time, we develop a nonaqueous proton electrolyte (NAPE) for a high-performance hydrogen gas-proton battery for all-climate energy storage applications. The advanced nonaqueous hydrogen gas-proton battery (NAHPB) assembled with a representative V2(PO4)3 cathode and H2 anode in a NAPE exhibits a high discharge capacity of 165 mAh g-1 at 1 C at room temperature. It also efficiently operates under all-climate conditions (from -30 to +70 °C) with an excellent electrochemical performance. Our findings offer a new direction for designing nonaqueous proton batteries in a wide temperature range.

A dual-channel fluorescence probe for simultaneously visualizing cysteine and viscosity during drug-induced hepatotoxicity.

Cysteine (Cys), one of the important participants in protecting cells from oxidative stress, is closely associated with the occurrence and development of various diseases. Moreover, cell viscosity as a pivotal microenvironmental parameter has recently attracted increasing attention due to its dominant role in governing intracellular signal transduction and diffusion of reactive metabolites. Thus, simultaneous detection of Cys and viscosity is imperative for investigating their pathophysiological functions and cross-link. Herein we present a mitochondria-targetable dual-channel fluorescence probe ABDSP by grafting the acrylate modified pyridinium unit to dimethylaminobenzene. Whilst the probe is a seemingly simple, it could simultaneously discriminate Cys and viscosity in a fashion of distinguishable signals. Furthermore, the probe was successfully employed for visualizing mitochondrial Cys and viscosity, and probe into their cross-link during acetaminophen-induced hepatotoxicity.

Aqueous Organic Hydrogen Gas Proton Batteries with Ultrahigh-Rate and Ultralow-Temperature Performance.

Aqueous proton batteries (APBs) have emerged as one of the most promising batteries for large-scale energy storage technology. However, they usually show an undesirable electrochemical performance. Herein, we demonstrate a novel aqueous catalytic hydrogen gas powered organic proton (HOP) battery, which is driven by hydrogen evolution/oxidation redox reactions via commercial nanocatalysts on the anode and coordination/decoordination reactions of C═O with H+ on the cathode. The HOP battery shows an excellent rate capacity of 190.1 mAh g-1 at 1 A g-1 and 71.4 mAh g-1 at 100 A g-1. It also delivers a capacity of 96.6 mAh g-1 after 100000 cycles and operates at temperatures down to -70 °C. Moreover, the HOP battery is fabricated in a large-scale pouch cell with an extended capacity, exhibiting its potential for practical energy storage applications. This work provides new insights into the building of sustainable APBs, which will broaden the horizons of high-performance aqueous batteries.

Anions Regulation Engineering Enables a Highly Reversible and Dendrite-Free Nickel-Metal Anode with Ultrahigh Capacities.

The development of safe and high-energy metal anodes represents a crucial research direction. Here, the achievement of highly reversible, dendrite-free transition metal anodes with ultrahigh capacities by regulating aqueous electrolytes is reported. Using nickel (Ni) as a model, theoretical and experimental evidence demonstrating the beneficial role of chloride ions in inhibiting and disrupting the nickel hydroxide passivation layer on the Ni electrode is provided. As a result, Ni anodes with an ultrahigh areal capacity of 1000 mAh cm-2 (volumetric capacity of ≈6000 mAh cm-3 ), and a Coulombic efficiency of 99.4% on a carbon substrate, surpassing the state-of-the-art metal electrodes by approximately two orders of magnitude, are realized. Furthermore, as a proof-of-concept, a series of full cells based on the Ni anode is developed. The designed Ni-MnO2 full battery exhibits a long lifespan of 2000 cycles, while the Ni-PbO2 full battery achieves a high areal capacity of 200 mAh cm-2 . The findings of this study are important for enlightening a new arena toward the advancement of dendrite-free Ni-metal anodes with ultrahigh capacities and long cycle life for various energy-storage devices.

Ultrafast Electrical Pulse Synthesis of Highly Active Electrocatalysts for Beyond-Industrial-Level Hydrogen Gas Batteries.

The high reliability and proven ultra-longevity make aqueous hydrogen gas (H2 ) batteries ideal for large-scale energy storage. However, the low alkaline hydrogen evolution and oxidation reaction (HER/HOR) activities of expensive platinum catalysts severely hamper their widespread applications in H2 batteries. Here, cost-effective, highly active electrocatalysts, with a model of ruthenium-nickel alloy nanoparticles in ≈3 nm anchored on carbon black (RuNi/C) as an example, are developed by an ultrafast electrical pulse approach for nickel-hydrogen gas (NiH2 ) batteries. Having a competitive low cost of about one fifth of Pt/C benckmark, this ultrafine RuNi/C catalyst displays an ultrahigh HOR mass activity of 2.34 A mg-1 at 50 mV (vs RHE) and an ultralow HER overpotential of 19.5 mV at a current density of 10 mA cm-2 . As a result, the advanced NiH2 battery can efficiently operate under all-climate conditions (from -25 to +50 °C) with excellent durability. Notably, the NiH2 cell stack achieves an energy density up to 183 Wh kg-1 and an estimated cost of ≈49 $ kWh-1 under an ultrahigh cathode Ni(OH)2 loading of 280 mg cm-2 and a low anode Ru loading of ≈62.5 µg cm-2 . The advanced beyond-industrial-level hydrogen gas batteries provide great opportunities for practical grid-scale energy storage applications.

Solid-Liquid-Gas Management for Low-Cost Hydrogen Gas Batteries.

Aqueous nickel-hydrogen gas (Ni-H2) batteries with excellent durability (>10,000 cycles) are important candidates for grid-scale energy storage but are hampered by the high-cost Pt electrode with limited performance. Herein, we report a low-cost nickel-molybdenum (NiMo) alloy as an efficient bifunctional hydrogen evolution and oxidation reaction (HER/HOR) catalyst for Ni-H2 batteries in alkaline electrolytes. The NiMo alloy demonstrates a high HOR mass-specific kinetic current of 28.8 mA mg-1 at 50 mV as well as a low HER overpotential of 45 mV at a current density of 10 mA cm-2, which is better than most nonprecious metal catalysts. Furthermore, we apply a solid-liquid-gas management strategy to constitute a conductive, hydrophobic network of NiMo using multiwalled carbon nanotubes (NiMo-hydrophobic MWCNT) in the electrode to accelerate HER/HOR activities for much improved Ni-H2 battery performance. As a result, Ni-H2 cells based on the NiMo-hydrophobic MWCNT electrode show a high energy density of 118 Wh kg-1 and a low cost of only 67.5 $ kWh-1. With the low cost, high energy density, excellent durability, and improved energy efficiency, the Ni-H2 cells show great potential for practical grid-scale energy storage.

Aqueous Zinc-Chlorine Battery Modulated by a MnO2 Redox Adsorbent.

Aqueous zinc-chlorine battery with high discharge voltage and attractive theoretical energy density is expected to become an important technology for large-scale energy storage. However, the practical application of Zn-Cl2 batteries has been restricted due to the Cl2 cathode with sluggish kinetics and low Coulombic efficiency (CE). Here, an aqueous Zn-Cl2 battery using an inexpensive and effective MnO2 redox adsorbent (referred to Zn-Cl2 @MnO2 battery) to modulate the electrochemical performance of the Cl2 cathode is developed. Density functional theory calculations reveal that the existence of the intermediate state Clads free radical catalyzed by MnO2 on the Cl2 cathode contributes to the charge storage capacity, which is the key to modulate the electrode and improve the electrochemical performance. Further analysis of the Cl2 cathode kinetics discloses the adsorption and catalytic roles of the MnO2 redox adsorbent. The Zn-Cl2 @MnO2 battery displays an enhanced discharge voltage of 2.0 V at a current density of 2.5 mA cm-2 , and stable 1000 cycles with an average CE of 91.6%, much superior to the conventional Zn-Cl2 battery with an average CE of only 66.8%. The regulation strategy to the Cl2 cathode provides opportunities for the future development of aqueous Zn-Cl2 batteries.

Reversible, Dendrite-Free, High-Capacity Aluminum Metal Anode Enabled by Aluminophilic Interface Layer.

Aluminum (Al) metal is an attractive anode material for next-generation rechargeable batteries, because of its low cost and high capacities. However, it brings some fundamental issues such as dendrites, low Coulombic efficiency (CE), and low utilization. Here, we propose a strategy for constructing an ultrathin aluminophilic interface layer (AIL) to regulate the Al nucleation and growth behaviors, which enables highly reversible and dendrite-free Al plating/stripping under high areal capacity. Metallic Al can maintain stable plating/stripping on the Pt-AIL@Ti for over 2000 h at 10 mAh cm-2 with an average CE of 99.9%. The Pt-AIL also enables reversible Al plating/stripping at a record high areal capacity of 50 mAh cm-2, which is 1-2 orders of magnitude higher than the previous studies. This work provides a valuable direction for further construction of high-performance rechargeable Al metal batteries.

Comparative evaluation of the structure and antitumor mechanism of mononuclear and trinucleated thiosemicarbazone Cu(II) complexes.

The ratio of ligand to Cu(II) ions has an essential effect on the geometrical configuration and anti-tumour activity of metal-based complexes. In this work, we synthesised two Cu(II) thiosemicarbazone complexes, namely, [Cu(L)(Cl)] (C1) and [Cu3(L)2(Cl)4] (C2), by controlling the ratio of Cu(II) ion to ligand, to evaluate their anti-tumour activity. The ability of C1 to catalyze hydrogen peroxide to produce reactive oxygen species (ROS) was significantly higher than that of Cu(II) ion. Moreover, the bridge of Cu(II) and two molecules generated a new complex (C2), which, in contrast to C1, enhanced the generation of Fenton-like-triggered ROS. Consequently, the produced ROS depleted reduced glutathione, caused oxidative cell stress and promoted apoptosis through mitochondrial apoptotic pathways. In addition, C2 exhibited better tumour suppression than C1 in a nude mouse tumour xenograft model.

Constructing robust heterostructured interface for anode-free zinc batteries with ultrahigh capacities.

The development of Zn-free anodes to inhibit Zn dendrite formation and modulate high-capacity Zn batteries is highly applauded yet very challenging. Here, we design a robust two-dimensional antimony/antimony-zinc alloy heterostructured interface to regulate Zn plating. Benefiting from the stronger adsorption and homogeneous electric field distribution of the Sb/Sb2Zn3-heterostructured interface in Zn plating, the Zn anode enables an ultrahigh areal capacity of 200 mAh cm-2 with an overpotential of 112 mV and a Coulombic efficiency of 98.5%. An anode-free Zn-Br2 battery using the Sb/Sb2Zn3-heterostructured interface@Cu anode shows an attractive energy density of 274 Wh kg-1 with a practical pouch cell energy density of 62 Wh kg-1. The scaled-up Zn-Br2 battery in a capacity of 500 mAh exhibits over 400 stable cycles. Further, the Zn-Br2 battery module in an energy of 9 Wh (6 V, 1.5 Ah) is integrated with a photovoltaic panel to demonstrate the practical renewable energy storage capabilities. Our superior anode-free Zn batteries enabled by the heterostructured interface enlighten an arena towards large-scale energy storage applications.

Ultralow-Temperature Aqueous Conductive Polymer-Hydrogen Gas Battery.

Hydrogen gas batteries are regarded as one of the most promising rechargeable battery systems for large-scale energy storage applications due to their advantages of high rates and long-term cycle lives. However, the development of cost-effective and low-temperature-tolerant hydrogen gas batteries is highly desirable yet very challenging. Herein, we report a novel conductive polymer-hydrogen gas battery that is suitable for ultralow-temperature energy storage applications and consists of a hydrogen gas anode, a conductive polymer cathode using polyaniline (PANI) or polypyrrole as examples, and protonic acidic electrolytes. The PANI-H2 battery using 1 M H2SO4 as the electrolyte exhibits a capacity of 67 mA h/g, a remarkable rate up to 15 A/g, a Coulombic efficiency around 100%, and an ultra-long life of 10,000 cycles. Using the anti-freezing 9 M H3PO4 electrolyte, the PANI-H2 battery can operate well at temperatures down to -70 °C, which maintains ∼70% of the capacity at room temperature and shows an excellent cycle stability under -60 °C. Benefiting from the fast redox kinetics of both electrodes, this work demonstrates excellent rate performance and low-temperature feasibility of conductive polymer-H2 batteries, providing a new avenue for further development of low-cost and reliable polymer-H2 batteries for large-scale energy storage.

High-Capacity Zinc Anode with 96 % Utilization Rate Enabled by Solvation Structure Design.

Aqueous zinc-ion batteries (AZBs) show promises for large-scale energy storage. However, the zinc utilization rate (ZUR) is generally low due to side reactions in the aqueous electrolyte caused by the active water molecules. Here, we design a novel solvation structure in the electrolyte by introduction of sulfolane (SL). Theoretical calculations, molecular dynamics simulations and experimental tests show that SL remodels the primary solvation shell of Zn2+ , which significantly reduces the side reactions of Zn anode and achieves high ZUR under large capacities. Specifically, the symmetric and asymmetric cells could achieve a maximum of ∼96 % ZUR at an areal capacity of 24 mAh cm-2 . In a ZUR of ∼67 %, the developed Zn-V2 O5 full cell can be stably cycled for 500 cycles with an energy density of 180 Wh kg-1 and Zn-AC capacitor is stable for 5000 cycles. This electrolyte structural engineering strategy provides new insight into achieving high ZUR of Zn anodes for high performance AZBs.

Recent applications of dioxinone derivatives for macrocyclic natural product and terpenoid synthesis.

Dioxinone derivatives, a class of acetoacetate derivatives, have attracted widespread attention because of their multiple reactive sites, high reactivity, unique chemical properties, and potential synthetic applications. The dioxinone group is also stable under a wide range of reaction conditions, including strong acids, as well as a variety of transition-metal-catalysed processes, such as olefin metathesis and Pd-mediated cross-coupling. The inherent reactivity and diverse applications of dioxinones make them valuable reactive intermediates in organic synthesis. The conversion of dioxinones to acylketenes and their subsequent nucleophilic capture is also an excellent strategy for synthesising ß-keto acid derivatives, which can be applied even in complex molecular synthesis. This review focuses on the recent advances in the application of dioxinones in synthetic method research and the total synthesis of natural products, highlighting the exceptional utility of these synthetic methodologies in the construction of macrocyclic cores and terpenoid skeletons. In particular, successful transformations of dioxinone fragments are discussed.

Surface-Oxygen-Rich Bi@C Nanoparticles for High-Efficiency Electroreduction of CO2 to Formate.

The electrochemical CO2 reduction reaction (CO2RR) is a promising strategy to alleviate excessive CO2 levels in the atmosphere and produce value-added feedstocks and fuels. However, the synthesis of high-efficiency and robust electrocatalysts remains a great challenge. This work reports the green preparation of surface-oxygen-rich carbon-nanorod-supported bismuth nanoparticles (SOR Bi@C NPs) for an efficient CO2RR toward formate. The resultant SOR Bi@C NPs catalyst displays a Faradaic efficiency of more than 91% for formate generation over a wide potential range of 440 mV. Ex situ XPS and XANES and in situ Raman spectroscopy demonstrate that the Bi-O/Bi (110) structure in the pristine SOR Bi@C NPs can remain stable during the CO2RR process. DFT calculations reveal that the Bi-O/Bi (110) structure can facilitate the formation of the *OCHO intermediate. This work provides an approach to the development of high-efficiency Bi-based catalysts for the CO2RR and offers a unique insight into the exploration of advanced electrocatalysts.

Proton-Trapping Agent for Mitigating Hydrogen Evolution Corrosion of Zn for an Electrolytic MnO2/Zn Battery.

A rechargeable aqueous electrolytic MnO2/Zn battery (EMZB) based on a reversible Mn2+/MnO2 two-electron redox reaction in an acidic electrolyte is very attractive for large-scale energy storage due to its high output voltage, large gravimetric capacity, and low cost. However, severe hydrogen evolution corrosion (HEC) of the Zn anode in an acidic electrolyte limits its application. Here, a proton-trapping agent (PTA) is introduced in the electrolyte to improve the electrochemical performance of the EMZB. Experimental results and theoretical calculations demonstrate that HEC of the Zn electrode can be effectively mitigated through high binding energy between the protons and PTA. The optimized EMZB regulated by a PTA of acetate (EMZB-20% Ac) delivers a high discharge voltage of 1.91 V and over 400 stable cycles at 1 C, which is more than 5 times the cycle life of the battery without PTA. EMZB-20% Ac also shows a Coulombic efficiency of 90.7% at a high areal capacity of 8 mAh cm-2 and an energy retention of 83.6% after 1000 cycles at 5 C with an areal capacity of 1 mAh cm-2. This work provides a promising electrolyte regulation strategy for the design and application of a high-performance EMZB and other energy storage systems.

Brønsted Acid-Catalyzed Synthesis of 1,2,5-Trisubstituted Imidazoles via a Multicomponent Reaction of Vinyl Azides with Aromatic Aldehydes and Aromatic Amines.

A facile and efficient approach to the synthesis of 1,2,5-trisubstituted imidazoles is developed via a multicomponent reaction under metal-free catalysis. Under Brønsted acid catalysis, the desired products can be obtained from readily available vinyl azides, aromatic aldehydes, and aromatic amines without generating any toxic waste. The convenient operations and high functional group compatibility indicate that this approach offers an attractive alternative method for the synthesis of imidazole derivatives.