Exciting lattice oxygen of nickel–iron bi-metal alkoxide for efficient electrochemical oxygen evolution reaction

High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.

Injectable Nanorobot-Hydrogel Superstructure for Hemostasis and Anticancer Therapy of Spinal Metastasis

Surgery remains the standard treatment for spinal metastasis.However,uncontrolled intraoperative bleeding poses a significant challenge for adequate surgical resection and compromises surgical outcomes.In this study,we develop a thrombin(Thr)-loaded nanorobothydrogel hybrid superstructure by incorporating nanorobots into regenerated silk fibroin nanofibril hydrogels.This superstructure with superior thixotropic properties is injected percutaneously and dispersed into the spinal metastasis of hepatocellular carcinoma(HCC)with easy bleeding characteristics,before spinal surgery in a mouse model.Under near-infrared irradiation,the self-motile nanorobots penetrate into the deep spinal tumor,releasing Thr in a controlled manner.Thr-induced thrombosis effectively blocks the tumor vasculature and reduces bleeding,inhibiting tumor growth and postoperative recurrence with Au nanorod-mediated photothermal therapy.Our minimally invasive treatment platform provides a novel preoperative therapeutic strategy for HCC spinal metastasis effectively controlling intraoperative bleeding and tumor growth,with potentially reduced surgical complications and enhanced operative outcomes.

“Three‐in‐one”strategy:Heat regulation and conversion enhancement of a multifunctional separator for safer lithium-sulfur batteries

The safety problems encountered with lithium–sulfur batteries(LSBs)hinder their development for practical applications.Herein,a highly thermally conductive separator was constructed by cross‐weaving super‐aligned carbon nanotubes(SA‐C)on super‐aligned boron nitride@carbon nanotubes(SA‐BC)to create a composite film(SA‐BC/SA‐C).This separator was used to fabricate safe LSBs with improved electrochemical performance.The highly aligned separator structure created a uniform thermal field that could rapidly dissipate heat accumulated during continuous operation due to internal resistance,which prevented the development of extremely high temperatures.The array of boron nitride nanosheets endowed the composite separator with a large number of adsorption sites,while the highly graphitized carbon nanotube skeleton accelerated the catalytic conversion of high‐valence polysulfides into low‐valence polysulfides.The arrayed molecular brush design enabled the regulation of local current density and ion flux,and considerably alleviated the growth of lithium dendrites,thus promoting the smooth deposition of Li metal.Consequently,a battery constructed with the SA‐BC/SA‐C separator showed a good discharge capacity of 685.2 mAh g−1 over 300 cycles(a capacity decay of 0.026%per cycle)at 2 C and 60°C.This“three‐in‐one”multifunctional separator design strategy constitutes a new path forward for overcoming the safety problems of LSBs.

Conversion electrochemistry of copper selenides for robust and energetic aqueous batteries

The development of highly safe and low-cost aqueous batteries is of great significance in the background of carbon neutrality.However,the practical deployment of aqueous batteries has been plagued due to their relatively low capacity and poor cycling stability.Herein,we propose unique conversion electrochemistry of copper selenides for robust and energetic aqueous charge storage.In situ X-ray diffraction and operando Raman techniques reveal a reversible transformation from CuSe to Cu_(2)Se through the intermediates of Cu_(3)Se_(2) and Cu_(1.8)Se.Such a conversion process activates the redox carrier of Cu^(2+)ion and delivers a remarkable rate capability of 285 mAh g^(-1) at 20 A g^(-1) and electrochemical durability up to 30,000 cycles.Furthermore,Cu^(2+)and H+coinsertion chemistry is proposed to facilitate the conversion process.As a proof-of-concept,a hybrid aqueous pouch cell coupling CuSe//Zn is capable of affording maximum energy and power densities of 190 Wh kg^(-1) and 1366W kg^(-1),respectively.

Tuning desolvation kinetics of in-situ weakly solvating polyacetal electrolytes for dendrite-free lithium metal batteries

The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.

Ultrasensitive detection of methamphetamine by antibody-modified transistor assay

Effective detection of methamphetamine(Met)requires a fast,sensitive,and cheap testing assay.However,commercially available methods require expensive instruments and highly trained operators,which are time-consuming and labor-intensive.Herein,an antibody-modified graphene transistor assay is developed for sensitive and minute-level detection of Met in complex environments.The anti-Met probe captured charged targets within 120 s,leading to a p-doping effect near the graphene channel.The limit of detection reaches 50 aM(5.0×10^(-17)M)Met in solution.The graphene transistor would be a valuable tool for Met detection effective prevention of drug abuse.

Construction of 3D Shape-Changing Hydrogels via Light-Modulated Internal Stress Fields

The 3D shape-changing hydrogels are highly pursued for numerous applications.However,up to now,the construction of complex 3D shape-changing hydrogels remains a challenge.The reported design strategies are mainly applied to fabricate 2D ones by introducing anisotropic microstructures into hydrogel sheets/membranes.Herein,we present a convenient photolithography strategy for constructing complex 3D shape-changing hydrogels by simultaneously modulating anisotropic microstructures and internal stress fields of gel sheets.When the precursor solution containing ultraviolet(UV)absorber is irradiated by single-side UV light,the attenuated polymerization rate can cause the generation of asymmetric internal stress field in the resulting hydrogel sheet.In the meantime,the directional diffusion of unpolymerized monomers allows for the formation of vertical gradient structure within hydrogel.Therefore,by applying different photomasks to modulate the local gradient structures and internal stress fields of the gel sheets,they can spontaneously transform into various complex 3D shape-changing hydrogels in the air.Response to the external stimuli,these 3D shape-changing hydrogels(e.g.,fighter plane,birdie,and multi-storey origami lattices)can deform in a novel 3D_(1)-to-3D_(2)-to-3D_(3)mode.This new design strategy contributes to the development of complex biomedical implants and soft robotics.

Analysis of N6-methyladenosine-modified mRNAs in diabetic cataract

BACKGROUND Cataracts remain a prime reason for visual disturbance and blindness all over the world,despite the capacity for successful surgical replacement with artificial lenses.Diabetic cataract(DC),a metabolic complication,usually occurs at an earlier age and progresses faster than age-related cataracts.Evidence has linked N6-methyladenosine(m6A)to DC progression.However,there exists a lack of understanding regarding RNA m6A modifications and the role of m6A in DC pathogenesis.AIM To elucidate the role played by altered m6A and differentially expressed mRNAs(DEmRNAs)in DC.METHODS Anterior lens capsules were collected from the control subjects and patients with DC.M6A epitranscriptomic microarray was performed to investigate the altered m6A modifications and determine the DEmRNAs.Through Gene Ontology and pathway enrichment(Kyoto Encyclopedia of Genes and Genomes)analyses,the potential role played by dysregulated m6A modification was predicted.Real-time polymerase chain reaction was further carried out to identify the dysregulated expression of RNA methyltransferases,demethylases,and readers.RESULTS Increased m6A abundance levels were found in the total mRNA of DC samples.Bioinformatics analysis predicted that ferroptosis pathways could be associated with m6A-modified mRNAs.The levels of five methylation-related genes-RBM15,WTAP,ALKBH5,FTO,and YTHDF1-were upregulated in DC samples.Upregulation of RBM15 expression was verified in SRA01/04 cells with high-glucose medium and in samples from DC patients.CONCLUSION M6a mRNA modifications may be involved in DC progression via the ferroptosis pathway,rendering novel insights into therapeutic strategies for DC.

Thermo-and photo-driven soft actuators based on crosslinked liquid crystalline polymers

Crosslinked liquid crystalline polymers（CLCPs） are a type of promising material that possess both the order of liquid crystals and the properties of polymer networks.The anisotropic deformation of the CLCPs takes place when the mesogens experience order to disorder change in response to external stimuli; therefore,they can be utilized to fabricate smart actuators,which have potential applications in artificial muscles,micro-optomechanical systems,optics,and energyharvesting fields.In this review the recent development of thermo-and photo-driven soft actuators based on the CLCPs are summarized.

Regulation and application of supramolecular gel with circularly polarized luminescence

Supermolecular gel is a three-dimensional network structure assembled by small molecules or polymers in solvents through noncovalent interaction.The emergence of system complexity occurs spontaneously during the molecular self-assembly process.A multitude of chiral molecular self-assembly systems have been engineered,facilitating the achievement of circularly polarized luminescence(CPL)through the amalgamation of chiral entities with fluorophores.Hydrogen bonding,π-πstacking,and noncovalent forces,such as host-guest interactions and Van der Waals'forces,confer upon supramolecular gels the capacity to react to diverse stimuli.Due to the flexibility of supramolecular assembly,the CPL properties of supramolecular gels have rich controllability and can be used in various applications.In this review,we summarized the examples of CPL-active supramolecular gel assembly,and further summarized the assembly environment factors and external stimuli.Furthermore,the versatility of CPL applications in supramolecular gels is demonstrated,ranging from optical devices,information encryption,biosensing and chemical sensing,and other practical applications.In conclusion,the study provides insights into the multicultural factors influencing CPL in supramolecular gels,describes their applications in various domains,and presents future perspectives in the field.

Controlled Assembly of Luminescent Lanthanide‑Organic Frameworks via Post‑Treatment of 3D‑Printed Objects

Complex multiscale assemblies of metal-organic frameworks are essential in the construction of largescale optical platforms but often restricted by their bulk nature and conventional techniques.The integration of nanomaterials and 3D printing technologies allows the fabrication of multiscale functional architectures.Our study reports a unique method of controlled 3D assembly purely relying on the post-printing treatment of printed constructs.By immersing a 3D-printed patterned construct consisting of organic ligand in a solution of lanthanide ions,in situ growth of lanthanide metal-organic frameworks(LnMOFs)can rapidly occur,resulting in macroscopic assemblies and tunable fluorescence properties.This phenomenon,caused by coordination and chelation of lanthanide ions,also renders a sub-millimeter resolution and high shape fidelity.As a proof of concept,a type of 3D assembled LnMOFsbased optical sensing platform has demonstrated the feasibility in response to small molecules such as acetone.It is anticipated that the facile printing and design approach developed in this work can be applied to fabricate bespoke multiscale architectures of functional materials with controlled assembly,bringing a realistic and economic prospect.

Morphology and crystal-plane effects of Zr-doped CeO2 nanocrystals on the epoxidation of styrene with tert-butylhydroperoxide as the oxidant

The morphology effect of Zr-doped CeOwas studied in terms of their activities in the selective oxidation of styrene to styrene oxide using tert-butyl hydroperoxide as the oxidant. In the present work, Zrdoped CeOnanorods exhibited the highest catalytic performance（yield of styrene oxide and TOF value）followed by nanoparticles and nanocubes. For the Zr-doped CeOnanorods, the apparent activation energy is 56.3 k J/mol, which is much lower than the values of catalysts supported on nanoparticles and nanocubes（73.3 and 93.4 k J/mol）. The high resolution transmission electron microscopy results indicated that（100） and（110） crystal planes are predominantly exposed for Zr-doped CeOnanorods while（100）and（111） for nanocubes,（111） for nanoparticles. The remarkably increased catalytic activity of the Zrdoped CeOnanorods is mainly attributed to the higher percentage of Cespecies and more oxygen vacancies, which are associated with their exposed（100） and（110） crystal planes. Furthermore, recycling studies proved that the heterogeneous Zr-doped CeOnanorods did not lose its initial high catalytic activity after five successive recycles.

Fabrication of Melamine/Tb^3+-Intercalated Polydiacetylene Nanosheets and Their Thermochromic Reversibility

Polydiacetylene(PDA)is one kind of the conjugated polymer with layered structure,which can serve as a host to accommodate the guest components through intercalation.In these intercalated PDAs,some of them were reported to have a nearly perfect organized structure and perform completely reversible thermochromism.Till now,these reported intercalated PDAs were made by only introducing a single component for intercalation.Here,we chose 10,12-pentacosadiynoic acid(PCDA)as the monomer,of which the carboxyl-terminal groups can interact with either Tb^3+ ions or melamines(MAs).When the feeding molar ratio of PCDA,MA,and Tb^3+ ion was 3:267:1,only Tb^3+ ions were intercalated though excess MAs existed.Such Tb^3+- intercalated poly-PCDA exhibited completely reversible thermochromism,where almost all the carboxyl groups interacted with Tb^3+ ions to form the nearly perfect structure.When the feeding molar ratio of PCDA,MA,and Tb^3+ ion was 3:267:0.6,both Tb^3+ ions and MAs were intercalated.There existed some defects in the imperfect MA-intercalated domains and at the domain boundaries.The MA/Tb^3+- intercalated poly-PCDA exhibits partially reversible thermochromism,where the backbones near the defects are hard to return the initial conformation,while the rest,those at nearly perfect organized domains,are still able to restore the initial conformation.

In situ AFM investigation of dual-mode self-assembling peptide

Nanostructures/patterns formed by biomolecules can produce different physicochemical properties in terms of hydrophobicity, zeta-potential, color, etc., which play paramount roles in life. Peptides, as the main bio-building blocks, can form nanostructures with different functions,either in solutions or on interfaces. Previously, we synthesized a short peptide with the inspiration of an Alzheimer’s disease-related peptide: amyloid β peptide(A-p),namely GAV-9, which can epitaxially self-assemble into regular nanofilaments on liquid-solid interfaces, and it was found that both the hydrophobicity and charge state of the interfaces can significantly influence its assembling behavior. It was also reported that another A-β-containing dipeptide, FF,can self-assemble into nanostructures in solutions. Owing to the close relationship between these two short peptides, it is interesting to conjugate them into a de novo peptide with two separated structural domains and study its self-assembling behavior. To this end, herein we have synthesized the GAV-FF peptide with a sequence of NH2-VGGAVVAGVFF-CONH2 and verified its selfassembling property using the in situ liquid-phase atomic force microscopy. The results show that the GAV-FF peptide can self-assemble into nanofilaments both in solutions and on aqueous-solid interfaces, but with different morphologies. The FF domain accelerates the template-assisted self-assembling(TASA) process of the GAV domain, which in return enhances the solubility of FF in aqueous solutions and further participates in the fibrillization of FF. The current results could help deepen the understanding of the aggregation mechanism of diseaserelated peptides and could also shed light on the strategies to create artificial bio-functional nanostructures/patterns,which hold a significant potential for biomedical applications.

Unraveling GLUT-mediated transcytosis pathway of glycosylated nanodisks

Glucose transporter(GLUT)-mediated transcytosis has been validated as an efficient method to cross the blood-brain barrier and enhance brain transport of nanomedicines.However,the transcytosis process remains elusive.Glycopeptide-modified nanodisks(Gly-A7R-NDs),which demonstrated high capacity of brain targeting via GLUT-mediated transcytosis in our previous reports,were utilized to better understand the whole transcytosis process.Gly-A7R-NDs internalized brain capillary endothelial cells mainly via GLUT-mediated/clathrin dependent endocytosis and macropinocytosis.The intracellular Gly-A7R-NDs remained intact,and the main excretion route of Gly-A7R-NDs was lysosomal exocytosis.Glycosylation of nanomedicine was crucial in GLUT-mediated transcytosis,while morphology did not affect the efficiency.This study highlights the pivotal roles of lysosomal exocytosis in the process of GLUT-mediated transcytosis,providing a new impetus to development of brain targeting drug delivery by accelerating lysosomal exocytosis.

SNORA23 inhibits HCC tumorigenesis by impairing the 2'-O-ribose methylation level of 28S rRNA

Objective:The dysregulation of ribosome biogenesis is associated with the progression of numerous tumors,including hepatocellular carcinoma(HCC).Small nucleolar RNAs(sno RNAs)regulate ribosome biogenesis by guiding the modification of ribosomal RNAs(r RNAs).However,the underlying mechanism of this process in HCC remains elusive.Methods:RNA immunoprecipitation and sequencing were used to analyze RNAs targeted by ribosome proteins.The biological functions of SNORA23 were examined in HCC cells and a xenograft mouse model.To elucidate the underlying mechanisms,the 2′-O-ribose methylation level of r RNAs was evaluated by q PCR,and the key proteins in the PI3 K/Akt/m TOR pathway were detected using Western blot.Results:Twelve sno RNAs were found to co-exist in 4 cancer cell lines using RPS6 pull-down assays.SNORA23 was downregulated in HCC and correlated with the poor prognoses of HCC patients.SNORA23 inhibited the proliferation,migration,and invasion of HCC cells both in vitro and in vivo.We also found that SNORA23 regulated ribosome biogenesis by impairing 2′-O-ribose methylation of cytidine4506 of 28 S r RNA.Furthermore,SNORA23,which is regulated by the PI3 K/Akt/m TOR signaling pathway,significantly inhibited the phosphorylation of 4 E binding protein 1.SNORA23 and rapamycin blocked the PI3 K/AKT/m TOR signaling pathway and impaired HCC growth in vivo.Conclusions:SNORA23 exhibited antitumor effects in HCC and together with rapamycin,provided a promising therapeutic strategy for HCC treatment.

Improved kinetics of OER on Ru-Pb binary electrocatalyst by decoupling proton-electron transfer

The acidic oxygen evolution reaction(OER)is central to water electrolysis using proton‐exchange membranes.However,even as benchmark catalysts in the acidic OER,Ru‐based catalysts still suffer from sluggish kinetics owing to the scaling relationship that arises from the traditional concerted proton‐electron transfer(CPET)process.Motivated by the knowledge that a charged surface may be favorable for accelerating the OER kinetics,we posited the incorporation of elements with pseudocapacitive properties into Ru‐based catalysts.Herein,we report a RuPbOx electrocatalyst for efficient and stable water oxidation in acid with a low overpotential of 191 mV to reach 10 mA cm^(−2) and a low Tafel slope of 39 mV dec^(−1).The combination of electrochemical analysis,X‐ray photoelectron spectroscopy,and in situ Raman spectroscopy demonstrated that the improved OER kinetics was associated with the formation of superoxide precursors on the strongly charged surface after Pb incorporation,indicating a non‐concerted proton‐electron transfer mechanism for the OER on RuPbOx.

Active straining engineering on self-assembled stacked Ni-based hybrid electrode for ultra-low overpotential

Generating sufficient strains on metal surfaces are highly challenging owing to that most metals can deform plastically to relax the strains on the surfaces.In this work,we developed a facile but highly efficient stacked deposition strategy to in situ activation and reconstruction of NiO/NiOOH on Ni matrix,following with the migration of Fe ions to NiOOH.The Fe sites on the Ni/NiO/NiOOH facilitate the formation of the stable*OH oxygenated intermediates,and the Ni matrix in the catalyst provides the catalyst excellent stability.The oxygen evolution reaction(OER)performance of the stacked NiFe-5 with compressive strain displays the strengthened binding to oxygenated intermediates and superior OER activity,the ultralow overpotentials of 162 versus reversible hydrogen electrode at 10 mA cm^(-2).On the other hand,the Ni-5 without the incorporation of Fe has shown an outstanding hydrogen evolution reaction(HER)activity,affording an overpotential of 47 mV at 10 mA cm^(-2).The NiFe-5‖Ni-5 enables the overall water splitting at a voltage of 1.508 V to achieve 20 mA cm^(-2) with remarkable durability.The stacked deposition strategy improves binding strength of Ni-based catalysts to oxygenated intermediates via generating compressive strain,causing high catalytic activities on OER and HER.

Mechanisms of inclusion-induced pitting of stainless steels:A review

Pitting is a common type of localized corrosion in passive alloys that can cause rapid failure of material or equipment.In the case of stainless steels,non-metallic inclusions have been identified as the most susceptible sites for pitting,and have therefore garnered significant attention.This review critically ex-amines the issue of how inclusions induce pitting,with a particular focus on three mechanisms:sponta-neous dissolution of inclusions,active dissolution of Cr-depleted regions,and propagation of microcracks at the inclusion-matrix interface.While researchers have made significant strides in understanding these mechanisms over the past few decades,many gaps and controversies remain.Details such as the ini-tial driving force of inclusion dissolution and factors affecting Cr-depleted regions require further study.Moreover,some old concepts and methods need to be revised to arrive at more credible conclusions.This review aims to delve deeply into these important issues and provide inspiration for future research.

Recent progress on rapid diagnosis of COVID-19 by point-of-care testing platforms

The outbreak of COVID-19 has drawn great attention around the world.SARS-CoV-2 is a highly infectious virus with occult transmission by many mutations and a long incubation period.In particular,the emergence of asymptomatic infections has made the epidemic even more severe.Therefore,early diagnosis and timely management of suspected cases are essential measures to control the spread of the virus.Developing simple,portable,and accurate diagnostic techniques for SARS-CoV-2 is the key to epidemic prevention.The advantages of point-of-care testing technology make it play an increasingly important role in viral detection and screening.This review summarizes the point-of-care testing platforms developed by nucleic acid detection,immunological detection,and nanomaterial-based biosensors detection.Furthermore,this paper provides a prospect for designing future highly accurate,cheap,and convenient SARS-CoV-2 diagnostic technology.