Liquid metal in prohibiting polysulfides shuttling in metal sulfides anode for sodium-ion batteries

Metal sulfides are a class of promising anode materials for sodium-ion batteries(SIBs)owing to their high theoretical specific capacity.Nevertheless,the reactant products(polysulfides)could dissolve into electrolyte,shuttle across separator,and react with sodium anode,leading to severe capacity loss and safety concerns.Herein,for the first time,gallium(Ga)-based liquid metal(LM)alloy is incorporated with MoS_(2)nanosheets to work as an anode in SIBs.The electron-rich,ultrahigh electrical conductivity,and self-healing properties of LM endow the heterostructured MoS_(2)-LM with highly improved conductivity and electrode integrity.Moreover,LM is demonstrated to have excellent capability for the adsorption of polysulfides(e.g.,Na_(2)S,Na_(2)S_(6),and S_(8))and subsequent catalytic conversion of Na_(2)S.Consequently,the MoS_(2)-LM electrode exhibits superior ion diffusion kinetics and long cycling performance in SIBs and even in lithium/potassium-ion battery(LIB/PIB)systems,far better than those electrodes with conventional binders(polyvinylidene difluoride(PVDF)and sodium carboxymethyl cellulose(CMC)).This work provides a unique material design concept based on Ga-based liquid metal alloy for metal sulfide anodes in rechargeable battery systems and beyond.

Nucleocytoplasmic shuttling of Smad proteins

Nuclear accumulation of active Smad complexes is crucial for transduction of transforming growth factor β （TGF-β）- superfamily signals from transmembrane receptors into the nucleus. It is now clear that the nucleocytoplasmic distributions of Smads, in both the absence and the presence of a TGF-β-superfamily signal, are not static, but instead the Smads are continuously shuttling between the nucleus and the cytoplasm in both conditions. This article presents the evidence for continuous nucleocytoplasmic shuttling of Smads. It then reviews different mechanisms that have been proposed to mediate Smad nuclear import and export, and discusses how the Smad steady-state distributions in the absence and the presence of a TGF-β-superfamily signal are established. Finally, the biological relevance of continuous nucleocytoplasmic shuttling for signaling by TGF-β superfamily members is discussed.

Atomic/nano-scale in-situ probing the shuttling effect of redox mediator in Na-O_(2) batteries

Sodium-oxygen batteries(Na-O_(2))have attracted extensive attention as promising energy storage systems due to their high energy density and low cost.Redox mediators are often employed to improve Na-O_(2) battery performance,however,their effect on the formation mechanism of the oxygen reduction product(NaO_(2))is still unclear.Here,we have investigated the formation mechanism of NaO_(2) during the discharge process in the presence of a redox mediator with the help of atomic/nano-scale in-situ characterization tools used in concert(e.g.atomic force microscope,electrochemical quartz crystal microbalance(EQCM)and laser nano-particle analyzer).As a result,real-time observations on different time scales show that by shuttling electrons to the electrolyte,the redox mediator enables formation of NaO_(2) in the solution-phase instead of within a finite region near the electrode surface.These findings provide new fundamental insights on the understanding of Na-O_(2) batteries and new consequently perspectives on designing high performance metal-O_(2) batteries and other related functions.

Targeting amyloid precursor protein shuttling and processing-long before amyloid beta formation

Targeting early steps in amyloid-beta production：Alzheimer’s disease（AD）has a long history as the＂amyloid deposit＂disorder.Many disorders are now known to be caused by proteinβ-sheet misfolding and aggregation（e.g.,Parkinson’s disease：α-synuclein;Huntington’s disease：Huntingtin;

P68 RNA helicase is a nucleocytoplasmic shuttling protein

P68 RNA helicase is a prototypical DEAD box RNA helicase. The protein plays a very important role in early organ development and maturation. Consistent with the function of the protein in transcriptional regulation and pre-mRNA splicing, p68 was found to predominately localize in the cell nucleus. However, recent experiments demon- strate a transient cytoplasmic localization of the protein. We report here that p68 shuttles between the nucleus and the cytoplasm. The nucleocytoplasmic shuttling of p68 is mediated by two nuclear localization signal and two nuclear exporting signal sequence elements. Our experiments reveal that p68 shuttles via a classical RanGTPase-dependent pathway.

Designing metal sulfide-based cathodes and separators for suppressing polysulfide shuttling in lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries,known for their high energy density,are attracting extensive research interest as a promising next-generation energy storage technology.However,their widespread use has been hampered by certain issues,including the dissolution and migration of polysulfides,along with sluggish redox kinetics.Metal sulfides present a promising solution to these obstacles regarding their high electrical conductivity,strong chemical adsorption with polysulfides,and remarkable electrocatalytic capabilities for polysulfide conversion.In this review,the recent progress on the utilization of metal sulfide for suppressing polysulfide shuttling in Li-S batteries is systematically summarized,with a special focus on sulfur hosts and functional separators.The critical roles of metal sulfides in realizing high-performing Li-S batteries have been comprehensively discussed by correlating the materials’structure and electrochemical performances.Moreover,the remaining issues/challenges and future perspectives are highlighted.By offering a detailed understanding of the crucial roles of metal sulfides,this review dedicates to contributing valuable knowledge for the pursuit of high-efficiency Li-S batteries based on metal sulfides.

AgTFSI Pretreated Li Anode in LiI-Mediated Li-O_(2)Battery:Enabling Lithiophilic Solid Electrolyte Interphase Generation to Suppress the Redox Shuttling

Although lithium iodide(LiI)as a redox mediator(RM)can decrease the overpotential in Li-O_(2)batteries,the stability of the Li anode is still one critical issue due to the redox shuttling.Here,we firstly present a novel approach for generating Ag and LiTFSI enriched Li anode(designated as ALE@Li anode)via a spontaneous substitution between pure Li and bis(trifluoromethanesulfonyl)imide silver,in a LiI-participated Li-O_(2)cell.It can induce the generation of a lithiophilic solid electrolyte interphase(SEI)enriched with Ag,F,and N species(e.g.,Ag_(2)O,Li-Ag alloy,LiF,and Li_(3)N)during cell operation,which contributes to promoting the electrochemical performance through the shuttling inhibition.Compared to a cell with a bare Li anode,the one with as-prepared ALE@Li anode shows an enhanced cyclability,a considerable rate capability,and a good reversibility.In addition,a synchrotron X-ray computed tomography technique is employed to investigate the inhibition mechanism for shuttling effect by monitoring the morphological evolution on the cell interfaces.Therefore,this work highlights the deliberate design in the modified Li anode in an easy-to-operate and cost-effective way as well as providing guidance for the construction of artificial SEI layers to suppress the redox shuttling of RMs in Li-O_(2)batteries.

Nucieocytoplasmic Shuttling of Geminivirus C4 Protein Mediated by Phosphorylation and Myristoylation Is Critical for Viral Pathogenicity

Many geminivirus C4 proteins induce severe developmental abnormalities in plants.We previously demon- strated that Tomato leaf curl Yunnan virus (TLCYnV)C4 induces plant developmental abnormalities at least partically by decreasing the accumulation of NbSKη,an ortholog of Arabidopsis BIN2 kinase involved in the brassinosteroid signaling pathway,in the nucleus through directing it to the plasma membrane.However, the molecular mechanism by which the membrane-associated C4 modifies the localization of NbSKη in the host cell remains unclear.Here,we show that TLCYnV C4 is a nucleocytoplasmic shuttle protein,and that C4 shuttling is accompanied by nuclear export of NbSKTI.TLCYnV C4 is phosphorylated by NbSKη in the nucleus,which promotes myristoylation of the viral protein.Myristoylation of phosphorylated C4 favors its interaction with exportin-α(XPO I);which in turn facilitates nuclear export of the C4/NbSKTI complex. Supporting this model,chemical inhibition of N-myristoyltransferases or exportin-α enhanced nuclear retention of C4,and mutations of the putative phosphorylation or myristoylation sites in C4 resulted in increased nuclear retention ofrC4 and thus decreased severity of C4-induced developmental abnormalities. The impact of C4 on development is also lessened when a nuclear localization signal or a nuclear export signal is added to its C-terminus,restricting it to a specific cellular niche and therefore impairing nucleocytoplasmic shuttling.Taken together,our results suggest that nucleocytoplasmic shuttling of TLCYnV C4,enabled by phosphorylation by NbSKη,myristoylation,and interaction with exportin-α is critical for its function as a pathogenicity factor.

SIRT1 activation synergizes with FXR agonism in hepatoprotection via governing nucleocytoplasmic shuttling and degradation of FXR

Farnesoid X receptor(FXR)is widely accepted as a promising target for various liver diseases;however,panels of ligands in drug development show limited clinical benefits,without a clear mechanism.Here,we reveal that acetylation initiates and orchestrates FXR nucleocytoplasmic shuttling and then enhances degradation by the cytosolic E3 ligase CHIP under conditions of liver injury,which represents the major culprit that limits the clinical benefits of FXR agonists against liver diseases.Upon inflammatory and apoptotic stimulation,enhanced FXR acetylation at K217,closed to the nuclear location signal,blocks its recognition by importin KPNA3,thereby preventing its nuclear import.Concomitantly,reduced phosphorylation at T442 within the nuclear export signals promotes its recognition by exportin CRM1,and thereby facilitating FXR export to the cytosol.Acetylation governs nucleocytoplasmic shuttling of FXR,resulting in enhanced cytosolic retention of FXR that is amenable to degradation by CHIP.SIRT1 activators reduce FXR acetylation and prevent its cytosolic degradation.More importantly,SIRT1 activators synergize with FXR agonists in combating acute and chronic liver injuries.In conclusion,these findings innovate a promising strategy to develop therapeutics against liver diseases by combining SIRT1 activators and FXR agonists.

Stereoblock Polypropylenes Prepared by Efficient Chain Shuttling Polymerization of Propylene with Binary Zirconium Catalysts and iBu3Al

Stereoblock polypropyienes bearing isotactic,atactic,and syndictactic polypropylene segments were successfully prepared by dry methylaluminoxane activated binary catalysts system,Ph2CFluCpZrCl2 and {Me2Si(2,5-Me2-3-(2-MePh)-cyclopento[2,3-b]thiophen-6-yl)2}ZCl2,in the presence of iBu3Al as a chain shutting agent.by studying the catalyst activity,chain transfer efficiency,and reversility of chain transfer reaction of each catalyst system,as well as the molecular weight and polydispersity of the resulting polymers,the allyl exchange reactions between the zirconium catalyst and different main-group metal alky were estimated,respectvely.Based on the optimized react condition,the chain shuttling polymerization was conducted by binary catalyst system in the presence of iBu3Al under both atmospheric and high pressure.Resultant polymers were identified as stereoblock polypropylenes according to microstructure and physical properties analyses by 13C{1H}-NMR,DsC,and GPC.

Optically probing molecular shuttling motion of[2]rotaxane by a conformation-adaptive fluorophore

A bistable[2]rotaxane with a conformation-adaptive macrocycle bearing a 9,14-diphenyl-9,14-dihydrodibenzo[a,c]phenazine(DPAC)unit was synthesized,which could be utilized to optical probe the molecular shuttling motion of the functionalized rotaxane system.The UV-vis,^(1) H NMR and PL spectroscopic data clearly demonstrated that the DPAC ring was interlocked onto the thread and the fluorescence intensity of the DPAC unit in the macrocycle was effectively regulated by the location change of the macrocycle along the thread under acid/base stimulation,which was attributed to the modulation of the intramolecular photo-induced electron transfer between the DPAC unit and the methyltriazole(MTA)unit.This bistable rotaxane system containing a conformation-adaptive fluorophore unit in the macrocycle moiety opens an alternative way to design functional bistable mechanically interlocked molecules.

Chloride ion battery:A new emerged electrochemical system for next-generation energy storage

In the scope of developing new electrochemical concepts to build batteries with high energy density,chloride ion batteries(CIBs)have emerged as a candidate for the next generation of novel electrochemical energy storage technologies,which show the potential in matching or even surpassing the current lithium metal batteries in terms of energy density,dendrite-free safety,and elimination of the dependence on the strained lithium and cobalt resources.However,the development of CIBs is still at the initial stage with unsatisfactory performance and several challenges have hindered them from reaching commercialization.In this review,we examine the current advances of CIBs by considering the electrode material design to the electrolyte,thus outlining the new opportunities of aqueous CIBs especially combined with desalination,chloride redox battery,etc.With respect to the developing road of lithium ion and fluoride ion batteries,the possibility of using solid-state chloride ion conductors to replace liquid electrolytes is tentatively discussed.Going beyond,perspectives and clear suggestions are concluded by highlighting the major obstacles and by prescribing specific research topics to inspire more efforts for CIBs in large-scale energy storage applications.

Lactate metabolism in neurodegenerative diseases

Lactate,a byproduct of glycolysis,was thought to be a metabolic waste until the discovery of the Warburg effect.Lactate not only functions as a metabolic substrate to provide energy but can also function as a signaling molecule to modulate cellular functions under pathophysiological conditions.The Astrocyte-Neuron Lactate Shuttle has cla rified that lactate plays a pivotal role in the central nervous system.Moreover,protein lactylation highlights the novel role of lactate in regulating transcription,cellular functions,and disease development.This review summarizes the recent advances in lactate metabolism and its role in neurodegenerative diseases,thus providing optimal pers pectives for future research.

Engineering Strategies for Suppressing the Shuttle Effect in Lithium–Sulfur Batteries

Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.

Stable immobilization of lithium polysulfides using three-dimensional ordered mesoporous Mn_(2)O_(3) as the host material in lithium-sulfur batteries

Lithium-sulfur batteries(LSBs)have drawn significant attention owing to their high theoretical discharge capacity and energy density.However,the dissolution of long-chain polysulfides into the electrolyte during the charge and discharge process(“shuttle effect”)results in fast capacity fading and inferior electrochemical performance.In this study,Mn_(2)O_(3)with an ordered mesoporous structure(OM-Mn_(2)O_(3))was designed as a cathode host for LSBs via KIT-6 hard templating,to effectively inhibit the polysulfide shuttle effect.OM-Mn_(2)O_(3)offers numerous pores to confine sulfur and tightly anchor the dissolved polysulfides through the combined effects of strong polar-polar interactions,polysulfides,and sulfur chain catenation.The OM-Mn_(2)O_(3)/S composite electrode delivered a discharge capacity of 561 mAh g^(-1) after 250 cycles at 0.5 C owing to the excellent performance of OM-Mn_(2)O_(3).Furthermore,it retained a discharge capacity of 628mA h g^(-1) even at a rate of 2 C,which was significantly higher than that of a pristine sulfur electrode(206mA h g^(-1)).These findings provide a prospective strategy for designing cathode materials for high-performance LSBs.

NbN quantum dots anchored hollow carbon nanorods as efficient polysulfide immobilizer and lithium stabilizer for Li-S full batteries

The shuttle effect of lithium polysulfides(LiPSs)and uncontrollable lithium dendrite growth seriously hinder the practical application of lithium-sulfur(Li-S)batteries.To simultaneously address such issues,monodispersed Nb N quantum dots anchored on nitrogen-doped hollow carbon nanorods(NbN@NHCR)are elaborately developed as efficient Li PSs immobilizer and Li stabilizer for high-performance Li-S full batteries.Density functional theory(DFT)calculations and experimental characterizations demonstrate that the sulfiphilic and lithiophilic NbN@NHCR hybrid can not only efficiently immobilize the soluble Li PSs and facilitate diffusion-conversion kinetics for alleviating the shuttling effect,but also homogenize the distribution of Li+ions and regulate uniform Li deposition for suppressing Li-dendrite growth.As a result,the assembled Li-S full batteries(NbN@NHCR-S||Nb N@NHCR-Li)deliver excellent long-term cycling stability with a low decay rate of 0.031%per cycle over 1000 cycles at high rate of 2 C.Even at a high S loading of 5.8 mg cm^(-2)and a low electrolyte/sulfur ratio of 5.2μL mg^(-1),a large areal capacity of 6.2 mA h cm^(-2)can be achieved in Li-S pouch cell at 0.1 C.This study provides a new perspective via designing a dual-functional sulfiphilic and lithiophilic hybrid to address serious issues of the shuttle effect of S cathode and dendrite growth of Li anode.

Fluorine-Modulated MXene-Derived Catalysts for Multiphase Sulfur Conversion in Lithium-Sulfur Battery

Fluorine owing to its inherently high electronegativity exhibits charge delocalization and ion dissociation capabilities;as a result,there has been an influx of research studies focused on the utilization of fluorides to optimize solid electrolyte interfaces and provide dynamic protection of electrodes to regulate the reaction and function performance of batteries.Nonetheless,the shuttle effect and the sluggish redox reaction kinetics emphasize the potential bottlenecks of lithium-sulfur batteries.Whether fluorine modulation regulate the reaction process of Li-S chemistry?Here,the TiOF/Ti_(3)C_(2)MXene nanoribbons with a tailored F distribution were constructed via an NH4F fluorinated method.Relying on in situ characterizations and electrochemical analysis,the F activates the catalysis function of Ti metal atoms in the consecutive redox reaction.The positive charge of Ti metal sites is increased due to the formation of O-Ti-F bonds based on the Lewis acid-base mechanism,which contributes to the adsorption of polysulfides,provides more nucleation sites and promotes the cleavage of S-S bonds.This facilitates the deposition of Li_(2)S at lower overpotentials.Additionally,fluorine has the capacity to capture electrons originating from Li_(2)S dissolution due to charge compensation mechanisms.The fluorine modulation strategy holds the promise of guiding the construction of fluorine-based catalysts and facilitating the seamless integration of multiple consecutive heterogeneous catalytic processes.

Phosphorylated cellulose nanofibers establishing reliable ion-sieving barriers for durable lithium-sulfur batteries

The shuttle effect is among the most characteristic and formidable challenges in the pursuit of high-performance lithium-sulfur(Li-S)batteries.Herein,phosphorylated cellulose nanofibers(pCNF)are intentionally engineered to establish an ion-sieving barrier against polysulfide shuttling and thereby improve battery performance.The phosphorylation,involving the grafting of phosphate groups onto the cellulose backbone,imparts an exceptional electronegativity that repels the polysulfide anions from penetrating through the separator.Moreover,the electrolyte wettability and Li^(+)transfer can be significantly promoted by the polar nature of pCNF and the facile Li^(+)disassociation.As such,rational ion management is realized,contributing to enhanced reversibility in both sulfur and lithium electrochemistry.As a result,Li-S cells equipped with the self-standing pCNF separator demonstrate outstanding long-term cyclability with a minimum fading rate of 0.013%per cycle over 1000 cycles at 1 C,and a decent areal capacity of 5.37 mA h cm^(-2) even under elevated sulfur loading of 5.0 mg cm^(-2) and limited electrolyte of 6.0 mL g^(-1).This work provides a facile and effective pathway toward the well-tamed shuttle effect and highly durable Li-S batteries.

Tuning the solubility of polysulfides for constructing practical lithium-sulfur battery

Li-S batteries are regarded as one of the most promising candidates for next-generation battery systems with high energy density and low cost.However,the dissolution-precipitation reaction mechanism of the sulfur(S)cathode enhances the kinetics of the redox processes of the insulating sulfu r,which also arouses the notorious shuttle effect,leading to serious loss of S species and corrosion of Li anode.To get a balance between the shuttle restraining and the kinetic property,a combined strategy of electrolyte regulation and cathode modification is proposed via introducing 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoroprpyl ether(HFE)instead of 1,2-dimethoxyethane(DME),and SeS_(7)instead of S_8.The introduction of HFE tunes the solvation structure of the LiTFSI and the dissolution of intermediate polysulfides with Se doping(LiPSSes),and optimize the interface stability of the Li anode simultaneously.The minor Se substitution compensates the decrease in kinetic due to the decreased solubility of LiPSs.In this way,the Li-SeS_(7)batteries deliver a reversible capacity of 1062 and 1037 mAh g^(-1)with 2.0 and 5.5 mg SeS_(7)cm^(-2)loading condition,respectively.Besides,an electrolyte-electrode loading model is established to explain the relationship between the optimal electrolyte and cathode loading.It makes more sense to guide the electrolyte design for practical Li-S batteries.

Recent advances in producing hollow carbon spheres for use in sodium−sulfur and potassium−sulfur batteries

Sodium-sulfur(Na-S)and potassium-sulfur(K-S)batteries for use at room temperature have received widespread attention because of the abundance and low cost of their raw materials and their high energy density.However,their development is restricted by the shuttling of polysulfides,large volume expansion and poor conductivity.To overcome these obstacles,an effective approach is to use carbon-based materials with abundant space for the sulfur that has sulfiphilic sites to immobilize it,and a high electrical conductivity.Hollow carbon spheres(HCSs)with a controllable structure and composition are promising for this purpose.We consider recent progress in optimizing the electrochemical performance of Na-/K-S batteries by using these materials.First,the advantages of HCSs,their synthesis methods,and strategies for preparing HCSs/sulfur composite materials are reviewed.Second,the use of HCSs in Na-/K-S batteries,along with mechanisms underlying the resulting performance improvement,are discussed.Finally,prospects for the further development of HCSs for metal−S batteries are presented.