Constructing Donor–Acceptor‑Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li^(+)Migration in Quasi‑Solid‑State Battery

Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks(COFs)based on intramolecular charge transfer interactions.Unlike other reported COFbased solid-state electrolyte,the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li^(+)migration and inhibit Li dendrite,but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries.The introduced strong electronegativity F-based ligand in COF electrolyte results in highlyselective Li^(+)(transference number 0.83),high ionic conductivity(6.7×10^(-4)S cm^(−1)),excellent cyclic ability(1000 h)in Li metal symmetric cell and high-capacity retention in Li/LiFePO_(4)cell(90.8%for 300 cycles at 5C)than substituted C-and N-based ligands.This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms,which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li^(+)kinetics.Consequently,we anticipate that this work creates insight into the strategy for accelerating Li^(+)conduction in high-performance solid-state Li metal batteries through D–A system.

Hadoop-based secure storage solution for big data in cloud computing environment

In order to address the problems of the single encryption algorithm,such as low encryption efficiency and unreliable metadata for static data storage of big data platforms in the cloud computing environment,we propose a Hadoop based big data secure storage scheme.Firstly,in order to disperse the NameNode service from a single server to multiple servers,we combine HDFS federation and HDFS high-availability mechanisms,and use the Zookeeper distributed coordination mechanism to coordinate each node to achieve dual-channel storage.Then,we improve the ECC encryption algorithm for the encryption of ordinary data,and adopt a homomorphic encryption algorithm to encrypt data that needs to be calculated.To accelerate the encryption,we adopt the dualthread encryption mode.Finally,the HDFS control module is designed to combine the encryption algorithm with the storage model.Experimental results show that the proposed solution solves the problem of a single point of failure of metadata,performs well in terms of metadata reliability,and can realize the fault tolerance of the server.The improved encryption algorithm integrates the dual-channel storage mode,and the encryption storage efficiency improves by 27.6% on average.

COF-based single Li^(+)solid electrolyte accelerates the ion diffusionandrestrains dendritegrowthin quasi-solid-state organic batteries

A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Among the various SSEs,the single Li-ion conductor has advantages in terms of enhancing the ion conductivity,eliminating interfacial side reactions,and broadening the electrochemical window.Covalent organic frameworks(COFs)are optimal platforms for achieving single Li-ion conduction behavior because of wellordered one-dimensional channels and precise chemical modification features.Herein,we study in depth three types of Li-carboxylate COFs(denoted LiOOC-COFn,n=1,2,and 3)as single Li-ion conducting SSEs.Benefiting from well-ordered directional ion channels,the single Li-ion conductor LiOOC-COF3 shows an exceptional ion conductivity of 1.36×10^(-5) S cm^(-1) at room temperature and a high transference number of 0.91.Moreover,it shows excellent electrochemical performance with long-term cycling,high-capacity output,and no dendrites in the quasi-solid-state organic battery,with the organic small molecule cyclohexanehexone(C_(6)O_(6))as the cathode and the Li metal as the anode,and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.

An efficient strategy for generation of transgenic mice by lentiviral transduction of male germline stem cells in vivo

Background： Male germline stem cells（MGSCs） are a subpopulation of germ cells in the testis tissue. MGSCs are capable of differentiation into spermatozoa and thus are perfect targets for genomic manipulation to generate transgenic animals.Method： The present study was to optimize a protocol of production of transgenic mice through transduction of MGSCs in vivo using lentiviral-based vectors. The recombinant lentiviral vectors with either EF-1 or CMV promoter to drive the expression of enhanced green fluorescent protein（e GFP） transgene were injected into seminiferous tubules or inter-tubular space of 7-day-old and 28-day-old mouse testes. At 5 or 6 wk post-surgery, these pre-founders were mated with wild-type C57BL/6J female mice（1.5 to 2.0-month-old）.Results： Sixty-seven percent of F1 generation and 55.56 % of F2 offspring were positive for eG FP transgene under the control of EF-1 promoter via PCR analysis. The transgenic pups were generated in an injection site-and age-independent manner. The expression of transgene was displayed in the progeny derived from lentiviral vector containing CMV promoter to drive transgene, but it was silenced or undetectable in the offspring derived from lentiviral vector with transgene under EF-1 promoter. The methylation level of g DNA in the promoter region of transgene was much higher in the samples derived lentiviral vectors with EF-1 promoter than that with CMV promoter,suggesting e GFP transgene was suppressed by DNA methylation in vivo.Conclusion： This research reported here an effective strategy for generation of transgenic mice through transduction of MGSCs in vivo using lentivirus vectors with specific promoters, and the transgenic offspring were obtained in an injection site-and age-independent manner. This protocol could be applied to other animal species, leading to advancement of animal transgenesis in agricultural and biomedical fields.

Understanding the Mechanism for the In-Plane Yielding Anisotropy of a Hot-Rolled Zirconium Plate

Previously,the in-plane mechanical anisotropy of Zr hot-rolled plates is ascribed mainly to the different activities of the deformation modes activated when loading along different directions.In this work,a quantitative study on the deformation behavior of a pure Zr hot-rolled plate under tension along the rolling direction(RD)and transverse direction(TD)reveals that both the activities of deformation modes and the anisotropy of grain boundary strengthening account for a tensile yield strength anisotropy along the TD and RD.Crystal plasticity simulations using viso-plastic self-consistent model show that prismatic slip is the predominant deformation mode for tension along the RD(RD-tension),while prismatic slip and basal slip are co-dominant deformation modes under tension along the TD(TD-tension).A low fraction of■under TD-tension,while hardly activated under RD-tension.The activation of basal slip with a much higher critical resolve shear stress under TD-tension contributes to a higher yield strength along the TD than along the RD.The grain boundary strengthening effect under tension along the TD and RD were compared by calculating the activation stress difference(△Stress)and the geometric compatibility factor(m′)between neighboring grains.The results indicate a higher grain boundary strengthening for TD-tension than that for RD-tension,which will lead to a higher yield strength along the TD.That is,the anisotropy of grain boundary strengthening between TD-tension and RD-tension also plays an important role in the in-plane anisotropy along the RD and TD.Afterward,the reasons for why there is a grain-boundary-strengthening anisotropy along the TD and RD were discussed.

喷丸表面粗糙度对纯Ti焊接接头在HCl溶液中应力腐蚀开裂行为的影响

采用慢应变速率拉伸(SSRT)实验研究了TA2纯Ti焊接接头原始试样、超声喷丸(USSP)处理试样和USSP+表面打磨处理试样在10%HCl溶液中的应力腐蚀行为,通过OM、TEM、SEM分别对焊接接头各区域组织及腐蚀断口形貌进行了观测,对不同工艺处理试样的表面粗糙度、残余应力进行了测定,并对其腐蚀机理进行了分析。结果表明,纯Ti焊接接头在该体系中应力腐蚀与氢脆同时存在,焊缝区为焊接接头的薄弱环节,最先发生失效。原始试样在该体系中应力腐蚀开裂敏感性指数(ISCC)为25.61%,具有应力腐蚀倾向;USSP处理试样的ISCC为18.24%,USSP+1500#表面打磨处理试样的ISCC为11.96%,均无明显应力腐蚀倾向。USSP处理试样表面粗糙度较大,易引起应力集中形成裂纹源,与腐蚀坑作用相似;USSP+表面打磨处理减小了试样表面粗糙度,应力分配更加均匀,试样延伸率增加,塑性提升,进一步改善了材料的抗应力腐蚀开裂性能。

Interfacial engineering of perfluoroalkyl functionalized covalent organic framework achieved ultra-long cycled and dendrite-free lithium anodes

The finite lithium-ion utilization,short cycling life,and lower capacity retention caused by irreversible dendrite growth become the maximum dilemma in lithium metal batteries’(LMBs’)commercialization.Herein,a perfluoroalkyl-functionalized covalent organic framework(COF-F6)equipped with high stability and supernal proton conduction is introduced as an artificial solid electrolyte interface to stable the lithium metal anode.Benefiting from the strong electron-withdrawing effect of perfluoroalkyl,Li^(+)will be freed more by the competition of electronegative fluorine(F)and bis(trifluoromethanesulphonyl)imide anion(TFSI^(-)).The dissociation of LiTFSI and process of Li^(+)desolvation are easier to achieve.In addition,high electronegative fluorine can also regulate local electron-cloud density to induce the fast immigration of Li^(+).All the above roles contribute to improving the Li^(+)transfer number(0.7)and achieving the goal of inhibiting Li dendrite.As a result,the perfluoroalkyl COF-F6 modified LMB presents outstanding cycling stability.The symmetric batteries accomplish an overlong life-span of more than 5000 h with a lower hysteresis voltage(11 mV)at 5 mA·cm^(-2).Also,no dendrites are observed when using an in-situ optical microscope to learn the process of Li deposition.Therefore,this dendrite-free protection tactic holds broad prospects for the practical application of Li metal anodes.

The novel ER stress inducer Sec C triggers apoptosis by sulfating ER cysteine residues and degrading YAP via ER stress in pancreatic cancer cells

Pancreatic adenocarcinoma(PAAD) is one of the most lethal malignancies. Although gemcitabine(GEM) is a standard treatment for PAAD, resistance limits its application and therapy. Secoemestrin C(Sec C) is a natural compound from the endophytic fungus Emericella, and its anticancer activity has not been investigated since it was isolated. Our research is the first to indicate that Sec C is a broad-spectrum anticancer agent and could exhibit potently similar anticancer activity both in GEM-resistant and GEM-sensitive PAAD cells. Interestingly, Sec C exerted a rapid growth-inhibiting effect(80% death at 6 h), which might be beneficial for patients who need rapid tumor shrinkage before surgery. Liquid chromatography/mass spectrometry and N-acetyl-L-cysteine(NAC) reverse assays show that Sec C sulfates cysteines to disrupt disulfide-bonds formation in endoplasmic reticulum(ER) proteins to cause protein misfolding, leading to ER stress and disorder of lipid biosynthesis. Microarray data and subsequent assays show that ER stress-mediated ER-associated degradation(ERAD) ubiquitinates anddownregulates YAP to enhance ER stress via destruction complex(YAP-Axin-GSK-βTr CP), which also elucidates a unique degrading style for YAP. Potent anticancer activity in GEM-resistant cells and low toxicity make Sec C a promising anti-PAAD candidate.

二维sp^(2)碳连接共价有机框架作为无枝晶锂金属电池的人工SEI膜

锂金属负极(LMA)具有前所未有的理论比容量和超低的氧化还原电位,因此锂金属电池(LMBs)得到了广泛的研究.然而,不可控的锂枝晶生长和易碎的固体电解质界面相(SEI)严重阻碍了LMBs的实际商业应用.本文制备了二维sp^(2)碳连接的共价有机框架sp^(2)c-COF,并在LMA表面构建了人工SEI膜,以抑制锂枝晶的形成,并调节界面稳定性.sp^(2)c-COF被设计成沿x和y方向全π共轭的高导电性的结构,从而起到降低界面阻抗、促进Li^(+)通量均匀分布的作用.因此,sp^(2)c-COF改性的对称电池Li^(+)迁移数高达0.85,并且在5mA cm^(-2)电流密度下具有较长的循环寿命(4000 h)和极低的过电位(10 mV).此外还利用原位光学显微镜研究了锂沉积行为,结果表明sp^(2)c-COF能显著提高LMA的界面稳定性.该策略对抑制锂枝晶的形成具有重要的应用价值,可促进COF人工SEI膜的发展.

Strain transfer behavior and crystallographic mechanism of crack initiation during cyclic deformation in zirconium

Fully-reversed cyclic deformation of a pure Zr(a thickness of 17 mm)was conducted at two different strain amplitudes(0.4%and 0.8%)to investigate the deformation and crack initiation behaviors based on slip trace analysis.It was found that prismaticaslip with a higher Schmid Factor(m>0.4)was the dominant deformation mode.The grains containing persistent slip bands(PSBs)tended to go towards[1210]pole and the Schmid Factor had a critical value of 0.4 above which prismatic and pyramidal slip were dominant.Fatigue cracks were mainly initiated at PSBs and grain boundaries(GBs).It showed that 61.1%of the cracks were PSB cracks under a strain amplitude of 0.4%,while it decreased to 53.5%at a strain amplitude of 0.8%.PSB cracks were mainly parallel to prismaticaslip with higher Schmid Factor while some cracks tended to be initiated at GBs with higher misorientation angles.The interaction of PSBs with GBs would result in strain transferring to the neighboring grain.Strain transfer was more likely to occur at the condition of the higher geometrical compatibility factor m,and lower residual Burgers vectorb,which could reduce strain localization.

Fatigue life improvement and grain growth of gradient nanostructured industrial zirconium during high cycle fatigue

The effect of surface gradient nanostructure on the fatigue life of commercial pure(CP)Zr was investigated.Four point bending fatigue tests indicated that the fatigue limit of CP Zr with surface gradient nanostructure was increased by about 28.3%compared with the original sample(annealed state).The microstructure evolution at different fatigue loading stages was characterized.The high strength of surface gradient nanostructure could increase the crack initiation resistance.Furthermore,electron back scattered diffraction(EBSD)analysis demonstrated that the surface nanocrystals grew and rotated gradually during the fatigue loading,which was beneficial to reducing stress concentration,inhibit fatigue crack initiation,and prolong crack initiation life.The stored distortion energy of CP Zr calculated before and after fatigue indicated that the stored distortion energy decreased dramatically during cyclic loading,which provided the driving force for grain growth.Besides,the growth of nanocrystals consumed the mechanical energy produced by the applied load to a certain extent,thus,slowing down the accumulation of fatigue damage.The coarse grains at the interior could deform plastically and reduce the crack growth rate.In addition,the compressive residual stress caused by USSP treatment reduced the local effective stress and the driving force of crack growth.

Understanding a Single-Li-Ion COF Conductor for Being Dendrite Free in a Li-Organic Battery

In addition to improving ion conductivity and the transference number,single-Li-ion conductors(SLCs)also enable the elimination of interfacial side reactions and concentration difference polarization.Therefore,the SLCs can achieve high performance in solid-state batteries with Li metal as anode and organic molecule as cathode.Covalent organic frameworks(COFs)are leading candidates for constructing SLCs because of the excellent 1D channels and accurate chemical-modification skeleton.Herein,various contents of lithium-sulfonated covalently anchored COFs(denoted as LiO,S-COF1 and LiO,S-COF2)are controllably synthesized as SLCs.Due to the directional ion channels,high Li contents,and single-ion frameworks,LiO,SCOF2 shows exceptional Li-ion conductivity of 5.47×10^(-5)S.cm^(-1),high transference number of 0.93,and low activation energy of 0.15eV at room temperature.Such preeminent Li-ion-transported properties of LiO_(3)S-F2 permit stable Li+plating/stripping in a symmetric lithium metal battery,effectively impeding the Li dendrite growth in a liquid cell.Moreover,the designed quasi-solid-state cell(organic anthraquinone(AQ)as cathode,Li metal as anode,and LiO_(3)S-COF2 as electrolyte)shows high-capacity retention and rate behavior.Consequently,LiO_(3)S-COF2 implies a potential value restraining the dissolution of small organic molecules and Li dendrite growth.