Ionic potency regulation of coagulation bath induced by saline solution to control over the pore structure of PBI membrane for highperformance lithium metal batteries

In this study,we have explored the use of water as a non-solvent for tuning the microstructure of poly-benzimidazole(PBI)membranes,which are potential separators for lithium metal batteries(LMBs).The traditional method for membrane synthesis called nonsolvent-induced phase separation(NIPS),usually relies on hazardous and costly organic non-solvents.By dissolving sodium chloride(Nacl)in water,we could adjust the water ionic potency and the exchange speed of the non-solvent with the DMAC solution to change the micropore structure of the PBI membrane.With increasing Nacl concentration,the micro-pores in the PBI membrane transitioned from finger-like to sponge-like morphology.Compared to com-mercial separators like the Celgard separator,the PBI membrane with sponge-like micropores exhibited better regulation of lithium deposition and improved Li^(+) transportation capability due to its good wetta-bility with the electrolyte.Consequently,the PBI membrane-based Li/Li symmetric cell and Li/LiFePO_(4) full cell demonstrated superior performance compared to the Celgard-based ones.This research proposes an eco-friendly and scalable synthetic approach for fabricating commercial separators for LMBs,addressing the issue of lithium dendrite growth and improving overall battery safety and performance.

响应面法优化蓝靛果花色苷提取工艺研究

以野生蓝靛鲜果为试材,以吸光度为评价指标,研究了乙醇浓度、料液比、提取时间、提取温度对蓝靛果花色苷提取量的影响;并通过响应面法优化,研究了蓝靛果花色苷提取的最佳工艺条件。结果表明:蓝靛果花色苷的最佳提取条件为料液比1∶12g/mL、乙醇体积分数66%、提取温度57℃、提取时间92min,在此条件下蓝靛果花色苷的提取量为328.55mg/100g。

浙江忍冬属植物新资料

报道了浙江忍冬科(Caprifoliaceae)忍冬属(Lonicera L.)植物分类研究的若干新发现:排除了L.macrantha在我国的分布和细毡毛忍冬(L.similis)在浙江的分布;恢复了L.guillonii的种级地位,并将异毛忍冬(L.macrantha var.heterotricha)作为其新异名,将灰毡毛忍冬(L.macranthoides)组合为其变种;描述了一新种——华大花忍冬(L.sinomacrantha)和一新变型——红花菰腺忍冬(L.hypoglauca f.pulchra),编制了浙江产大花忍冬复合群的分类检索表。

牛黄双口服液质量标准的研究

目的 :研究牛黄双口服液的质量标准。方法 :用薄层色谱法对牛黄双口服液中的黄芩 ,金银花进行鉴别 ,用紫外分光光度法测黄芩甙的含量。结果 :鉴别专属性强 ,回收率平均值为 99 74%,RSD为 1 41。结论 :此方法能控制牛黄双口服液的质量。

Encapsulation of ionic liquid, phosphotungstic acid inside the nanocages of MIL-101(Cr): Effective and reusable catalyst for efficient solvent-free oxidative desulfurization from fuel oil

Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.

Elucidating the diffusion pathway of lithium ions in superionic halide solid electrolytes Li_(2+x)Hf_(1-x)In_(x)Cl_(6) for all-solid-state lithium-metal based batteries

All-solid-state batteries(ASSBs) with inorganic solid-state-electrolytes(SSEs) have been regarded as the promising candidate for next-generation energy storage due to their high energy density and outstanding safety performance.However,the representative oxide and sulfide electrolytes suffer from low ionic conductivity and poor(electro)chemical stability,respectively.Herein,we report a series of new halide superionic conductors Li_(2+x)Hf_(1-x)In_(x)Cl_(6) with high ionic conductivity up to 1.05 mS cm^(-1) at 30 ℃ that are simultaneously stable to high voltage.By means of the characterization techniques and bond-valence site energy(BVSE) calculation,insights into the effect of the phase transformation and underlying ionic transport mechanism by In substitution for Hf in Li_(2)HfCl_(6) are provided.Importantly,with the increased amount of aliovalent substitution in Li_(2+x)Hf_(1-x)In_(x)Cl_(6) microcrystal framework,a gradual structure evolution from trigonal to monoclinic phase has been observed,which is accompanied by the redistribution of Li-ions to generate two dimensionally(2D) preferable diffusion pathways through octahedral-tetrahe dral-octahedral sites in In^(3+)-substituted Li_(2)HfCl_(6).Additionally,due to the oxidative stability of Insubstituted Li_(2)HfCl_(6),the bulk-type ASSBs with bare LiCoO_(2) deliver distinguished electrochemical performance.

Ionic liquids inhibit the dynamic transition fromα-helices toβ-sheets in peptides

Abnormalities in the transition betweenα-helices andβ-sheets(α-βtransition)may lead to devastating neurodegenerative diseases,such as Parkinson's syndrome and Alzheimer's disease.Ionic liquids(ILs)are potential drugs for targeted therapies against these diseases because of their excellent bioactivity and designability of ILs.However,the mechanism through which ILs regulate the aα-βtransition remains unclear.Herein,a combination of GPU-accelerated microsecond molecular dynamics simulations,correlation analysis,and machine learning was used to probe the dynamicalα-βtransition process induced by ILs of 1-alkyl-3-methylimidazolium chloride([C_(n)mim]cl)and its molecular mechanism.Interestingly,the cation of [C_(n)mim]+in ILs can spontaneously insert into the peptides as free ions(n≤10)and clusters(n≥11).Such insertion can significantly inhibit theα-β,transition and the inhibiting ability for the clusters is more significant than that of free ions,where[Ciomim]+and[C_(12)mim]+can reduce the maximumβ-sheet content of the peptide by 18.5% and 44.9%,respectively.Furthermore,the correlation analysis and machine learning method were used to develop a predictive model accounting for the influencing factors on theα-βtransition,which could accurately predict the effect of ILs on theα-βtransition.Overall,these quantitative results may not only deepen the understanding of the role of ILs in theα-βtransition but also guide the development of the IL-based treatments for related diseases.

Vinylogous Fluorine Stabilizing Effect Enables Rational Design of a Novel Donor-Acceptor Cyclopropane and Its Applications in[3+2]Cycloaddition Reaction and Ring-Opening Polymerization

Comprehensive Summary Discovery of unprecedented donor-acceptor patterns can essentially enrich the chemistry of donor-acceptor cyclopropanes.We herein introduce a concept of vinylogous fluorine stabilizing effect,which guides rational design of a novel donor-acceptor cyclopropane employing gem-difluorovinyl group as the electron donor,namely dFVCP.Application of such dFVCPs in a[3+2]cycloaddition with aldehydes and a controlled ring-opening polymerization by a Mg(OTf)2/DIPEA/C(sp3)-H initiator system have been demonstrated,providing direct access to fluorine-containing tetrahydrofurans and all-carbon main-chain polymers.

山东产忍冬藤中1个新有机酸化合物

目的对山东产忍冬藤Lonicerae Japonicae Caulis进行化学成分研究。方法通过反复硅胶、MCI-gel树脂、Sephadex LH-20等多种柱色谱技术进行化学成分分离纯化,依据化合物理化性质和波谱学数据鉴定其结构。结果从山东产忍冬藤中分离并鉴定了4个化合物,分别为11,14,15-三羟基-12-烯-十八碳酸甲酯(1)、金莲木黄酮(2)、β-胡萝卜苷(3)、马钱素(4)。结论化合物1为一个新化合物,命名为忍冬酸酯,化合物2为首次从忍冬藤中分离得到。

Preparation of hybrid perovskite-type Li_(0.33)La_(0.56)TiO_(3)by adding ionic liquids

Perovs kite-type Li_(0.33)La_(0.56)TiO_(3)(LLTO)shows greate r advantages than organic liquid electrolytes to be used in all-so lid-state lithium-ion batteries with high energy densities.Ionic liquid[BMIM][BF4]was used to improve the properties of Li_(0.33)La_(0.56)TiO_(3)by attrition milling in this study.The microstructure,crystallinity and lithium-ion conductivity of the samples were measured by scanning electron microscopy(SEM),X-ray diffraction(XRD),and impedance spectroscopy(IS).The total ionic conductivities of the samples LLTO+x wt%[BMIM][BF4]increase upon adding[BMIM][BF4]and the maximum conductivity reaches4.71×10^(-4)S/cm when x=12.5 wt%.The enhancement of the total conductivity is ascribed to the bridging role of the ionic liquid among grains,as evidenced by the low activation energy of 0.17-0.25 eV and the SEM observation.The Li+transference numbers of the hybrid samples are all lower than that of the pure LLTO,indicating the existence of electronic conductions.The hybrid mate rial with a mixed conductivity and good stability in the atmosphere can find uses in all-solid-state lithium-ion batteries to improve the interface contact between electrolytes and electrodes.

Stimuli-Responsive lonic Liquids and the Regulation of Aggrega-tion Structure and Phase Behavior

lonic liquids with stimuli-responsive characteristics are an essential branch in the comprehensive ionic liquids'family,which can meet the controllable and reversible needs in practical applications with different stimulation means.In this review,we summarize the recent research progress of these stimuli-responsive ionic liquids,mainly focusing on their chemical structures,properties,responsive mechanism,aggregation structures,and phase behaviors,which were driven by external stimuli,such as CO2,magnetism,light,temperature,redox,and pH.Then,the particular or potential applications of stimuli-responsive ionic liquids are expounded in various fields of science,including catalytic reaction,extraction,separation,nano-material preparation,and gas absorption.In the end,the challenges and strategies of the subject are briefly presented.It is expected that this review will contribute to the rational design and applications of stimu-liresponsive ionic liquids in the future.

Ionic Radius Dependent Kinetic Behavior for the Self-Assemblyand Chiral Amplification of Lanthanide Tetrahedral Cages

Comprehensive Summary Understanding the kinetic process during the self-assembly and chiral amplification of metal-organic polyhedra(MOPs)is critical for the rational preparation of chiral MOPs.Herein,we report the ionic radius dependent kinetic processes for the self-assembly and chiral amplification of Ln4L4-type(Ln,Lanthanides;L,ligand)lanthanide tetrahedral cages.The chiral Eu4(LR)4 tetrahedral cage is structurally characterized by nuclear magnetic resonance(NMR),electrospray ionization time-of-flight mass spectrometry(ESI-TOF-MS),and single crystal X-ray diffraction.Kinetic study on the stereo-controlled self-assembly of circularly polarized luminescence(CPL)-active Ln4(LR)4(Ln=LaIII,PrIII and EuIII)tetrahedra manifests that the larger ionic radius of Ln leads to faster assembly rates.Mixed-ligand cage assembly experiments with chiral LR/S,achiral Lac and Ln(1:3:4 molar ratio)reveal that the self-assembly and chiral amplification occur synchronously for the LaIII and PrIII cages,while two distinct steps,i.e.,first self-assembly and then chiral amplification,are observed for the EuIII cage.Such distinct kinetic behavior is attributed to different ligands exchange rates among the mixed-ligand Ln4L4 cages.This work provides fundamental guidance for fabrication and property-optimization of chiral lanthanide-based molecular materials.

A Conjugated Copolymer Bearing Imidazolium-based Ionic Liquid:Electrochemical Synthesis and Electrochromic Properties

An imidazolium-based ionic liquid(IL)modified triphenylamine derivative,namely 1-(4-((4-(diphenylamino)benzoyl)oxy)butyl)-3-methyl imidazole tetrafluoroborate(TPAC_(6)IL-BF_(4)),was designed and synthesized,and further applied with 3,4-ethylene dioxythiophene(EDOT)to prepare conjugated copolymer P(EDOT:TPAC_(6)IL-BF_(4)) via electrochemical polymerization.The cyclic voltammetry curves show that the copolymer P(EDOT:TPAC_(6)IL-BF_(4))possesses two pairs of redox peaks,which should be ascribed to the redox behaviors of EDOT and triphenylamine.The ultraviolet-visible(UV-Vis)absorption spectrum of P(EDOT:TPAC_(6)IL-BF_(4))exhibits one maximum absorption peak at 580 nm and a small shoulder characteristic peak at 385 nm under neutral state which are assigned toπ-π^(*)conjugated structure of EDOT and triphenylamine.After being applied at the positive voltage,the copolymer color changes from dark blue to light blue,which is close to the color of poly(3,4-ethylenedioxythiophene)(PEDOT).Surprisingly,the copolymer P(EDOT:TPAC_(6)IL-BF_(4))shows shorter switching time of 0.37 s,0.30 s at 580 nm and 0.38 s,0.45 s at 1100 nm compared with PEDOT.It is more intriguing that the copolymer P(EDOT:TPAC_(6)IL-BF_(4))exhibits electrochromism even in free supporting electrolyte.The results confirm that the existence of imidazolium-based ionic liquid has an improvement on the ion diffusion properties and the switching time of conjugated polymer,which may provide a potential direction for the preparation of high-performance electrochromic materials.

Catalytic Cracking of Polylactic Acid to Acrylic Acid

Comprehensive Summary,As a typical type of sustainable plastic,polyesters can be recycled or upcycled into value-added chemicals in a variety of methods.However,excess reagents are required for most of the depolymerization and upcycling processes,causing the emission of environmental pollutants and the waste of chemical resources.Here we demonstrate a one-pot catalytic process to directly crack polylactic acid into acrylic acid by acid catalyst with the assistance of an ionic liquid,Bu4PBr.Polylactic acid is attacked by the Br–from Bu4PBr and the H+from acid to form oligomers containing Br or acryloyl group,and these oligomers serve as intermediates to produce acrylic acid during their mutual transformation.The acrylic acid is vaporized directly from the reactor and obtained in a collector with a selectivity around 90%when polylactic acid is fully converted.This green process shows great advantages in atom economy compared to the conventional recycling/upcycling methods for polyesters,in addition.

Tuning Polymer Molecular Weight Distribution in Cationic RAFT Polymerization by Mixing Chain Transfer Agents

Polymer dispersity (Đ) or molecular weight distribution (MWD) is a basic but vital parameter for the properties of polymeric materials. Developing new methodologies for controlling polymer MWD is emerging as a research hotspot. However, the methods to tune polymer MWD in cationic polymerization are still not well explored. Herein, we present a simple method to control the dispersity of poly(isobutyl vinyl ether) (PIBVE) by mixing two different chain transfer agents in batch visible light induced cationic RAFT polymerization. A broad dispersity range (Đ ≈ 1.16—1.80) was successfully achieved while maintaining monomodal MWD. Moreover, chain extension of PIBVE through both cationic polymerization and radical polymerization has been studied, which also provides a method to tune polymer MWD in mechanism transformation polymerization.

Recent Progresses in Liquid-Free Soft Ionic Conductive Elastomers

Comprehensive Summary With the rapid growth of soft electronic and ionotronic devices such as artificial tissues,soft luminescent devices,soft robotics,and human-machine interfaces,there is a demanding need to accelerate the development of soft ionic conductive materials.To date,the first-generation ionotronic devices are mainly based on hydrogels or ionogels.However,due to their intrinsic drawbacks,such as freezing or volatilization at extreme temperatures,and the leakage problem under external mechanical forces,the reliability of ionotronic devices under harsh conditions remains a great challenge.The advent of liquid-free ionic conductive elastomers(ICEs)has the potentials to solve the issues related to the gel-type soft conductive materials.The free ions shuttling within the ion-dissolvable polymer network enable liquid-free ICEs to exhibit unparalleled ionic conductivity and elasticity.Moreover,by tuning the composition and structure of the polymeric network,it is also feasible to integrate other desirable properties,such as self-healing ability,transparency,biocompatibility,and stimulus responsiveness,into liquid-free ICE materials.In this review,we summarize the design strategies of recently reported liquid-free ICEs,and further explore the methods to introduce multifunctionality,which originate from the rational molecular design and/or the synergy with other materials.Moreover,we highlight the representative applications of liquid-free ICEs in soft ionotronics.It is believed that liquid-free ICEs might provide a unique material platform for the next-generation ionotronics.