Removal of hypertoxic Cr(VI) from water by polyaniline-coated ZIF-67-derived nitrogen-doped magnetic carbon.

Heavy metals are highly toxic and nonbiodegradable, posing a serious threat to the water environment and human beings. Therefore, it is crucial to develop a highly efficient adsorbent that is easy to recover and separate for the removal of heavy metals. In this paper, nitrogen-doped magnetic carbon (NC-67) was prepared by carbonization and hydrochloric acid treatment using cobalt-containing MOF (ZIF-67) as precursor. Then, polyaniline (PANI) was grown directly on NC-67 with high specific surface area by in situ polymerization to prepare polyaniline-coated nitrogen-doped magnetic carbon (NC-67@PANI), which was characterized by XRD, SEM, TEM and VSM, etc. and used for the removal of Cr(VI)from wastewater. The experimental results showed that the adsorption process of Cr(VI) by NC-67@PANI was spontaneous and endothermic, which conformed to the pseudo-second-order model and Freundlich adsorption isotherm model. Due to the synergistic effect of adsorption and reduction, the experimental adsorption capacity of NC-67@PANI for Cr(VI) was 410.2 mg/g. NC-67@PANI maintained a removal efficiency of 65.8% for Cr(VI) after five cycles. In addition, NC-67@PANI had good magnetism and was easy to separate under external magnetic field. The excellent adsorption capacity and easy separation characteristics of NC-67@PANI indicate that it is a promising adsorbent for Cr(VI) removal from wastewater.

Albumin-Based MUC13 Peptide Nanomedicine Suppresses Liver Cancer Stem Cells via JNK-ERK Signaling Pathway-Mediated Autophagy Inhibition.

Targeting liver cancer stem cells (LCSCs) is a promising strategy for hepatocellular carcinoma (HCC) therapy. Target selection and corresponding inhibitor screening are of vital importance for eliminating the stemness of LCSCs. Peptide-based agents are hopeful but have long been hindered for in vivo application. Herein, we selected a clinically significant target MUC13 and screened out a suitable peptide for preparation of an albumin-based MUC13 peptide nanomedicine, P3@HSA, which suppressed liver cancer stem cells via JNK-ERK signaling pathway-mediated autophagy inhibition. The selected target MUC13 was highly expressed in LCSCs and associated with the prognosis of liver cancer patients. Encouraged by this observation, we screened the corresponding peptide-based inhibitor P3 for further evaluation. P3 could interact with albumin through the intrinsic hydrophobic force and formed the nanomedicine P3@HSA. The prepared nanomedicine could inhibit LCSCs through JNK-ERK signaling pathway-mediated autophagy inhibition and exert potent antitumor effect both in vitro and in vivo. Together, this study provides a promising peptide-based nanomedicine for high-performance HCC treatment.

Unconventional Magnetic and Magneto-Transport Properties in Quasi-2D Ni0.28TaSeS Single Crystal.

Van der Waals (vdW) magnetic materials have broad application prospects in next-generation spintronics. Inserting magnetic elements into nonmagnetic vdW materials can introduce magnetism and enhance various transport properties. Herein, the unconventional magnetic and magneto-transport phenomena is reported in Ni0.28TaSeS crystal by intercalating Ni atoms into nonmagnetic 2H-TaSeS matrix. Magnetic characterization reveals a canted magnetic structure in Ni0.28TaSeS, which results in an antiferromagnetic (AFM) order along the c-axis and a ferromagnetic (FM) moment in the ab-plane. The presence of spin-flop (SF) behavior can also be attributed to the canted magnetic structure. Temperature-dependent resistivity exhibits a metallic behavior with an abrupt decrease corresponding to the magnetic transition. Magneto-transport measurements demonstrate a positive magnetoresistance (MR) with a plateau that is different from conventional magnetic materials. The field-dependent Hall signal exhibits nonlinear field dependence when the material is in magnetically ordered state. These unconventional magneto-transport behaviors are attributed to the field-induced formation of a complex spin texture in Ni0.28TaSeS. In addition, it further investigated the angle dependence of MR and observed an unusual fourfold anisotropic magnetoresistance (AMR) effect. This work inspires future research on spintronic devices utilizing magnetic atom-intercalated quasi-2D materials.

Corrosion Engineering of Part-Per-Million Single Atom Pt1/Ni(OH)2 Electrocatalyst for PET Upcycling at Ampere-Level Current Density.

The plastic waste issue has posed a series of formidable challenges for the ecological environment and human health. While conventional recycling strategies often lead to plastic down-cycling, the electrochemical strategy of recovering valuable monomers enables an ideal, circular plastic economy. Here a corrosion synthesized single atom Pt1/Ni(OH)2 electrocatalyst with part-per-million noble Pt loading for highly efficient and selective upcycling of polyethylene terephthalate (PET) into valuable chemicals (potassium diformate and terephthalic acid) and green hydrogen is reported. Electro-oxidation of PET hydrolysate, ethylene glycol (EG), to formate is processed with high Faraday efficiency (FE) and selectivity (>90%) at the current density close to 1000 mA cm-2 (1.444 V vs RHE). The in situ spectroscopy and density functional theory calculations provide insights into the mechanism and the understanding of the high efficiency. Remarkably, the electro-oxidation of EG at the ampere-level current density is also successfully illustrated by using a membrane-electrode assembly with high FEs to formate integrated with hydrogen production for 500 h of continuous operation. This process allows valuable chemical production at high space-time yield and is highly profitable (588-700 $ ton-1 PET), showing an industrial perspective on single-atom catalysis of electrochemical plastic upcycling.

Spatial Confinement of Pt Nanoparticles in Carbon Nanotubes for Efficient and Selective H2 Evolution from Methanol.

H2 generation from methanol-water mixtures often requires high pressure and high temperature (200-300 °C). However, CO can be easily generated and poison the catalytic system under such high temperature. Therefore, it is highly desirable to develop the efficient catalytic systems for H2 production from methanol at room temperature, even at sub-zero temperatures. Herein, carbon nanotube-supported Pt nanocomposites are designed and synthesized as high-performance nano-catalysts, via stabilization of Pt nanoparticles onto carbon nanotube (CNT), for H2 production upon methanol dehydrogenation at sub-zero temperatures. Therein, the optimal Pt/CNT nanocomposite presents the superior catalytic performance in H2 production upon methanol dehydrogenation at the expense of B2(OH)4, with the TOF of 299.51 min-130 oC. Compared with other common carriers, Pt/CNT exhibited the highest catalytic performance in H2 production, emphasizing the critical role of CNT in methanol dehydrogenation. The confinement of Pt nanoparticles by CNTs is conducive to inhibiting the aggregation of Pt nanoparticles, thereby significantly increasing its catalytic performance and stability. The kinetic study, detailed mechanistic insights, and density functional theory (DFT) calculation confirm that the breaking of O─H bond of CH3OH is the rate-controlling step for methanol dehydrogenation, and both H atoms of H2 are supplied by methanol. Interestingly, H2 is also successfully produced from methanol dehydrogenation at -10 °C, which absolutely solves the freezing problem in the H2 evolution upon water-splitting reaction.

High-Surface Area Mesoporous Sc2O3 with Abundant Oxygen Vacancies as New and Advanced Electrocatalyst for Electrochemical Biomass Valorization.

Scandium oxide (Sc2O3) is considered as omnipotent "Industrial Ajinomoto" and holds promise in catalytic applications. However, rarely little attention is paid to its electrochemistry. Here, the first nanocasting design of high-surface area Sc2O3 with abundant oxygen vacancies (mesoporous VO-Sc2O3) for efficient electrochemical biomass valorization is reported. In the case of the electro-oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), quantitative HMF conversion, high yield, and high faradic efficiency of FDCA via the hydroxymethylfurancarboxylic acid pathway are achieved by this advanced electrocatalyst. The beneficial effect of the VO on the electrocatalytic performance of the mesoporous VO-Sc2O3 is revealed by the enhanced adsorption of reactants and the reduced energy barrier in the electrochemical process. The concerted design, in situ and ex situ experimental studies and theoretical calculations shown in this work should shed light on the rational elaboration of advanced electrocatalysts, and contribute to the establishment of a circular carbon economy since the bio-plastic monomer and green hydrogen are efficiently synthesized.

Biomass substrate-derived graphene-like N-doped porous carbon nanosheet-supported PtCo nanocatalyst for efficient and selective hydrogenation of unsaturated furanic aldehydes.

Unsaturated furanic aldehydes are derived from lignocellulosic biomass resources and subsequently used to produce valuable chemicals. However, the highly efficient, selective hydrogenation of the biomass-derived unsaturated furan CO bond remains challenging. Here we report that graphene-like nitrogen doped porous carbon (GNPC) nanosheets are synthesized from carbon-rich, sustainable, and renewable biomass precursors (glucose, fructose and 5-hydroxymethylfurfural, HMF) with high surface areas, large pore volumes and narrow mesopores. GNPC derived from HMF is an excellent catalyst support for PtCo nanoparticles with ultrafine nanoparticles size and homogeneous distributions. This catalyst is highly efficient for hydrogenation of biomass-derived furan-based unsaturated aldehydes, with high yields, to the corresponding unsaturated alcohols under mild conditions. This design strategy should further allow the development of selective, simple, green heterogeneous catalysts for challenging chemical transformations.

The Coexistence of Superconductivity and Topological Order in Van der Waals InNbS2.

The research on systems with coexistence of superconductivity and nontrivial band topology has attracted widespread attention. However, the limited availability of material platforms severely hinders the research progress. Here, it reports the first experimental synthesis and measurement of high-quality single crystal van der Waals transition-metal dichalcogenide InNbS2 , revealing it as a topological nodal line semimetal with coexisting superconductivity. The temperature-dependent measurements of magnetization susceptibility and electrical transport show that InNbS2 is a type-II superconductor with a transition temperature Tc of 6 K. First-principles calculations predict multiple topological nodal ring states close to the Fermi level in the presence of spin-orbit coupling. Similar features are also observed in the as-synthesized BiNbS2 and PbNbS2 samples. This work provides new material platforms ANbS2 (A = In, Bi, and Pb) and uncovers their intriguing potential for exploring the interplay between superconductivity and band topology.

Direct inhibition of microglial activation by a µ receptor selective agonist alleviates inflammatory-induced pain hypersensitivity.

Opioids are widely used in the treatment of moderate and severe pain. Nociceptive stimulation has been reported to potentially promote microglial activation and neuroinflammation, which also causes chronic pain sensitization. The aim of this study was to demonstrate whether the novel µ receptor agonist MEL-0614 could inhibit activated microglia directly and the associated signaling pathway. Mice were administered lipopolysaccharide and formalin to induce allodynia. Von Frey test was used to detect the anti-allodynia effect of MEL-0614 before and after LPS and formalin injection. In the spinal cord, the levels of proinflammatory cytokines and microglial activation were determined after MEL-0614 administration. BV2 and primary microglia were cultured to further explore the effect of MEL-0614 on LPS-induced microglial activation and key signaling pathways involved. MEL-0614 partially prevented and reversed allodynia induced by LPS and formalin in vivo, which was not inhibited by the µ receptor antagonist CTAP. Minocycline was effective in reversing the established allodynia. MEL-0614 also downregulated the activation of microglia and related proinflammatory cytokines in the spinal cord. Additionally, in BV2 and primary microglia, MEL-0614 inhibited the LPS-induced upregulation of proinflammatory factors, which was unaffected by CTAP. The NLR family pyrin domain containing 3 (NLRP3) related signaling pathway may be involved in the interaction between MEL-0614 and microglia. The opioid agonist MEL-0614 inhibited the activation of microglia and the subsequent upregulation of proinflammatory factors both in vivo and in vitro. Notably, this effect is partially mediated by the µ receptor.

Ferromagnetism above Room Temperature in Two Intrinsic van der Waals Magnets with Large Coercivity.

The emergence of two-dimensional (2D) van der Waals (vdW) magnets provides a broad platform for studying the magnetic properties of low-dimensional materials in condensed matter physics. However, the intrinsic ferromagnetism of 2D materials is mostly observed below room temperature, and most of them are soft ferromagnetic materials. Here, we report two intrinsic ferromagnetic vdW materials with Curie temperatures (TC) above room temperature, MnSiTe3 (TC ∼ 378 K) and MnGeTe3 (TC ∼ 349 K). Moreover, MnSiTe3 exhibits a large coercivity (HC) at room temperature with an unprecedented HC of 1450 Oe, which is an increase of nearly 500% compared to the reported room-temperature vdW ferromagnets. The discovery of these two materials fills the gap of vdW room-temperature hard ferromagnets, providing a broad platform and possibilities for future research on low-dimensional spin electronic device applications.

Constructing a Pd-Co Interface to Tailor a d-Band Center for Highly Efficient Hydroconversion of Furfural over Cobalt Oxide-Supported Pd Catalysts.

Cobalt is an alternative catalyst for furfural hydrogenation but suffers from the strong binding of H and furan ring on the surface, resulting in low catalytic activity and chemoselectivity. Herein, by constructing a Pd-Co interface in cobalt oxide-supported Pd catalysts to tailor the d-band center of Co, the concerted effort of Pd and Co boosts the catalytic performance for the hydroconversion of furfural to cyclopentanone and cyclopentanol. The increased dispersion of Pd on acid etching Co3O4 promotes the reduction of Co3+ to Co0 by enhancing hydrogen spillover, favoring the creation of the Pd-Co interface. Both experimental and theoretical calculations demonstrate that the electron transfer from Pd to Co at the interface results in the downshift of the d-band center of Co atoms, accompanied by the destabilization of H and furan ring adsorption on the Co surface, respectively. The former improves the furfural hydrogenation with TOF on Co elevating from 0.20 to 0.62 s-1, and the latter facilitates the desorption of formed furfuryl alcohol from the Co surface for subsequently hydrogenative rearrangement of the furan ring to cyclopentanone on acid sites. The resultant Pd/Co3O4-6 catalyst delivers superior activity with a 99% furfural conversion and 85% overall selectivity toward cyclopentanone/cyclopentanol. We anticipate that such a concept of tailoring the d-band center of Co via interface engineering provides novel insight and feasible approach for the design of highly efficient catalysts for furfural hydroconversion and beyond.

High nitrogen content bimolecular co-functionalized graphene nanoflakes for hypertoxic Cr(VI) removal: Insights into adsorption behavior and mechanisms.

The proven high carcinogenicity to humans and high destructive force to the environment determine the extreme urgency of eliminating hypertoxic Cr(VI) in water bodies. Herein, a route of room temperature synthesis and secondary grafting was proposed to fabricate graphene oxide-based nanoadsorbent co-functionalized with polydopamine and branched polyethyleneimine (GOPP) to remove Cr(VI). The flexible decoration of polydopamine and polyethyleneimine on GO flakes could gradually enhance the amount of N-containing functional groups and realize selective removal of Cr(VI) with the maximum experimental adsorption capacity of 564.7 mg/g, displaying a significantly high separation factor against alkali metal, alkaline earth metal, and other transition metal ions. Various combination mechanisms, such as electrostatic attraction, reduction, complexation, and hydrogen bonding, were demonstrated to be involved in the adsorption process of Cr(VI) by XPS, ESP, and DFT calculations. And the interaction energies of the five protonated configurations of primary amine, tertiary amine, secondary amine, imine, and secondary amine on the ring with HCrO4- were: -22.66, -12.08, -24.92, -24.26, -27.64 kcal/mol. In the actual industrial wastewater study, a Cr(VI) removal rate of 85.8% was realized. This work provided a viable idea for the elimination of Cr(VI) and was expected to be applied in the field of wastewater treatment.

"On-Off" Control for On-Demand H2 Release upon Dimethylamineborane Hydrolysis over Ru0.8Ni0.2/MoS2 Nanohybrids.

In spite of the fact that remarkable developments are achieved in the design and development of novel nanocatalysts for H2 release upon dimethylamineborane hydrolysis, the development of an "on-off" switch for demand-based H2 evolution upon dimethylamineborane hydrolysis is still a matter of supreme importance, however. Herein, we synthesized a string of MoS2 nanosheet-supported RuNi bimetallic nanohybrids (RuxNi1-x/MoS2), by fixation of RuNi nanoparticles at the MoS2 surface, for the H2 evolution upon the hydrolysis of dimethylamineborane at 30 °C. For safely and effectively generating, transporting, and storing H2 gas, the selective "on-off" switch for on-demand H2 evolution upon dimethylamineborane hydrolysis over the Ru0.8Ni0.2/MoS2 nanohybrid has been successfully realized by the Zn2+/EDTA-2Na system. In particular, the H2 evolution is totally switched off by adding Zn(NO3)2. It seems that Zn2+ ions are attached and anchored at the Ru0.8Ni0.2/MoS2 surface, inhibiting their surface-active sites, leading to the termination of H2 evolution. Then, the H2 generation is subsequently reactivated by adding the EDTA-2Na solution because of its excellent coordination ability with Zn2+ ions. This study not only offers a new and efficient RuNi nanocatalyst for dimethylamineborane hydrolysis but also proposes a new method for the demand-based H2 production.

Long-range skin Josephson supercurrent across a van der Waals ferromagnet.

The emerging field of superconducting spintronics promises new quantum device architectures without energy dissipation. When entering a ferromagnet, a supercurrent commonly behaves as a spin singlet that decays rapidly; in contrast, a spin-triplet supercurrent can transport over much longer distances, and is therefore more desirable, but so far has been observed much less frequently. Here, by using the van der Waals ferromagnet Fe3GeTe2 (F) and spin-singlet superconductor NbSe2 (S), we construct lateral Josephson junctions of S/F/S with accurate interface control to realize long-range skin supercurrent. The observed supercurrent across the ferromagnet can extend over 300 nm, and exhibits distinct quantum interference patterns in an external magnetic field. Strikingly, the supercurrent displays pronounced skin characteristics, with its density peaked at the surfaces or edges of the ferromagnet. Our central findings shed new light on the convergence of superconductivity and spintronics based on two-dimensional materials.

A Novel Electrode for Value-Generating Anode Reactions in Water Electrolyzers at Industrial Current Densities.

Hydrogen generated in electrolyzers is discussed as a key element in future energy scenarios, but oxygen evolution as the standard anode reaction is a complex multi-step reaction requiring a high overpotential. At the same time,it does not add value-the oxygen is typically released into the atmosphere. Alternative anode reactions which can proceed at similar current densities as the hydrogen evolution are, therefore, of highest interest. We have discovered a high-performance electrode based on earth-abundant elements synthesized in the presence of H2 O2 , which is able to sustain current densities of close to 1 A cm-2 for the oxidation of many organic molecules, which are partly needed at high production volumes. Such anode reactions could generate additional revenue streams, which help to solve one of the most important problems in the transition to renewable energy systems, i.e. the cost of hydrogen electrolysis.

Exploration and functionalization of M1-macrophage extracellular vesicles for effective accumulation in glioblastoma and strong synergistic therapeutic effects.

Glioblastoma multiforme (GBM) is a highly aggressive brain tumor with an extremely low survival rate. New and effective approaches for treatment are therefore urgently needed. Here, we successfully developed M1-like macrophage-derived extracellular vesicles (M1EVs) that overcome multiple challenges via guidance from two macrophage-related observations in clinical specimens from GBM patients: enrichment of M2 macrophages in GBM; and origination of a majority of infiltrating macrophage from peripheral blood. To maximize the synergistic effect, we further functionalized the membranes of M1EVs with two hydrophobic agents (the chemical excitation source CPPO (C) and the photosensitizer Ce6 (C)) and loaded the hydrophilic hypoxia-activated prodrug AQ4N (A) into the inner core of the M1EVs. After intravenous injection, the inherent nature of M1-derived extracellular vesicles CCA-M1EVs allowed for blood-brain barrier penetration, and modulated the immunosuppressive tumor microenvironment via M2-to-M1 polarization, which increased hydrogen peroxide (H2O2) levels. Furthermore, the reaction between H2O2 and CPPO produced chemical energy, which could be used for Ce6 activation to generate large amounts of reactive oxygen species to achieve chemiexcited photodynamic therapy (CDT). As this reaction consumed oxygen, the aggravation of tumor hypoxia also led to the conversion of non-toxic AQ4N into toxic AQ4 for chemotherapy. Therefore, CCA-M1EVs achieved synergistic immunomodulation, CDT, and hypoxia-activated chemotherapy in GBM to exert a potent therapeutic effect. Finally, we demonstrated the excellent effect of CCA-M1EVs against GBM in cell-derived xenograft and patient-derived xenograft models, underscoring the strong potential of our highly flexible M1EVs system to support multi-modal therapies for difficult-to-treat GBM.

Shielding Ferritin with a Biomineralized Shell Enables Efficient Modulation of Tumor Microenvironment and Targeted Delivery of Diverse Therapeutic Agents.

Ferritin (Fn) is considered a promising carrier for targeted delivery to tumors, but the successful application in vivo has not been fully achieved yet. Herein, strong evidence is provided that the Fn receptor is expressed in liver tissues, resulting in an intercept effect in regards to tumor delivery. Building on these observations, a biomineralization technology is rationally designed to shield Fn using a calcium phosphate (CaP) shell, which can improve the delivery performance by reducing Fn interception in the liver while re-exposing it in acidic tumors. Moreover, the selective dissolution of the CaP shell not only neutralizes the acidic microenvironment but also induces the intratumoral immunomodulation and calcification. Upon multiple cell line and patient-derived xenografts, it is demonstrated that the elaboration of the highly flexible Fn@CaP chassis by loading a chemotherapeutic drug into the Fn cavity confers potent antitumor effects, and additionally encapsulating a photosensitizer into the outer shell enables a combined chemo-photothermal therapy for complete suppression of advanced tumors. Altogether, these results support Fn@CaP as a new nanoplatform for efficient modulation of the tumor microenvironment and targeted delivery of diverse therapeutic agents.

Fusion of Infrared and Visible Images Based on Three-Scale Decomposition and ResNet Feature Transfer.

Image fusion technology can process multiple single image data into more reliable and comprehensive data, which play a key role in accurate target recognition and subsequent image processing. In view of the incomplete image decomposition, redundant extraction of infrared image energy information and incomplete feature extraction of visible images by existing algorithms, a fusion algorithm for infrared and visible image based on three-scale decomposition and ResNet feature transfer is proposed. Compared with the existing image decomposition methods, the three-scale decomposition method is used to finely layer the source image through two decompositions. Then, an optimized WLS method is designed to fuse the energy layer, which fully considers the infrared energy information and visible detail information. In addition, a ResNet-feature transfer method is designed for detail layer fusion, which can extract detailed information such as deeper contour structures. Finally, the structural layers are fused by weighted average strategy. Experimental results show that the proposed algorithm performs well in both visual effects and quantitative evaluation results compared with the five methods.

Ferritin-based targeted delivery of arsenic to diverse leukaemia types confers strong anti-leukaemia therapeutic effects.

Trivalent arsenic (AsIII) is an effective agent for treating patients with acute promyelocytic leukaemia, but its ionic nature leads to several major limitations like low effective concentrations in leukaemia cells and substantial off-target cytotoxicity, which limits its general application to other types of leukaemia. Here, building from our clinical discovery that cancerous cells from patients with different leukaemia forms featured stable and strong expression of CD71, we designed a ferritin-based As nanomedicine, As@Fn, that bound to leukaemia cells with very high affinity, and efficiently delivered cytotoxic AsIII into a large diversity of leukaemia cell lines and patient cells. Moreover, As@Fn exerted strong anti-leukaemia effects in diverse cell-line-derived xenograft models, as well as in a patient-derived xenograft model, in which it consistently outperformed the gold standard, showing its potential as a precision treatment for a variety of leukaemias.

Recent developments of nanocatalyzed liquid-phase hydrogen generation.

Hydrogen is the most effective and sustainable carrier of clean energy, and liquid-phase hydrogen storage materials with high hydrogen content, reversibility and good dehydrogenation kinetics are promising in view of "hydrogen economy". Efficient, low-cost, safe and selective hydrogen generation from chemical storage materials remains challenging, however. In this Review article, an overview of the recent achievements is provided, addressing the topic of nanocatalysis of hydrogen production from liquid-phase hydrogen storage materials including metal-boron hydrides, borane-nitrogen compounds, and liquid organic hydrides. The state-of-the-art catalysts range from high-performance nanocatalysts based on noble and non-noble metal nanoparticles (NPs) to emerging single-atom catalysts. Key aspects that are discussed include insights into the dehydrogenation mechanisms, regenerations from the spent liquid chemical hydrides, and tandem reactions using the in situ generated hydrogen. Finally, challenges, perspectives, and research directions for this area are envisaged.