Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries

Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonetheless,the intricate energy storage mechanisms in aqueous electrolytes place stringent require-ments on the host materials.Prussian blue analogs(PBAs),with their open three-dimensional framework and facile synthesis,stand out as leading candidates for aqueous energy storage.However,PBAs possess a swift capacity fade and limited cycle longevity,for their structural integrity is compromised by the pronounced dis-solution of transition metal(TM)ions in the aqueous milieu.This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs.The dissolution mechanisms of TM ions in PBAs,informed by their structural attributes and redox processes,are thoroughly examined.Moreover,this study delves into innovative design tactics to alleviate the dissolution issue of TM ions.In conclusion,the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.

Asymmetric Electrolytes Design for Aqueous Multivalent Metal Ion Batteries

With the rapid development of portable electronics and electric road vehicles,high-energy-density batteries have been becoming front-burner issues.Traditionally,homogeneous electrolyte cannot simultaneously meet diametrically opposed demands of high-potential cathode and low-potential anode,which are essential for high-voltage batteries.Meanwhile,homogeneous electrolyte is difficult to achieve bi-or multi-functions to meet different requirements of electrodes.In comparison,the asymmetric electrolyte with bi-or multi-layer disparate components can satisfy distinct requirements by playing different roles of each electrolyte layer and meanwhile compensates weakness of individual electrolyte.Consequently,the asymmetric electrolyte can not only suppress by-product sedimentation and continuous electrolyte decomposition at the anode while preserving active substances at the cathode for high-voltage batteries with long cyclic lifespan.In this review,we comprehensively divide asymmetric electrolytes into three categories:decoupled liquid-state electrolytes,bi-phase solid/liquid electrolytes and decoupled asymmetric solid-state electrolytes.The design principles,reaction mechanism and mutual compatibility are also studied,respectively.Finally,we provide a comprehensive vision for the simplification of structure to reduce costs and increase device energy density,and the optimization of solvation structure at anolyte/catholyte interface to realize fast ion transport kinetics.

Effect of metallic ions on dispersibility of fine diaspore

Dispersion experiments were conducted to study the influence of metallic cations on the dispersibility of diaspore. The reaction mechanisms were investigated based on the analysis of zeta （ξ） potential and calculations of solution chemistry and DLVO theory. The results show that the valence of cations, instead of the cation type, plays an important role in the dispersibility of diaspore The impact of multivalent metallic cations is greater than that of monovalent cations. In the presence of Ca^2＋ and Mg^2＋, the dispersion of diaspore doesn＇t change in the range of pH value below 10. However, Ca^2＋ and Mg^2＋ may induce strong coagulation of particles when pH value is higher than 10. The adsorption of species of calcium and magnesium ions on diaspore can cause the compression of electric double layer, the decrease of the absolute value of zeta potential and the repulsion force between diaspore particles. The new IEP （isoelectric point） appeared at pH value of 11 may attribute to the adsorption of Mg（OH）2（s）.

Cloning and Expression Patterns of a Metallothionein-like GenehtMT2 of Helianthus tuberosus

A novel cDNA sequencehtMT2, which encodes a type 2 metallothionein_like protein, was isolated from Helianthus tuberosus L. tuber cDNA library. The whole sequence is 509 bp, including an open reading frame (ORF) of 240 bp, a 5′ UTR of 62 bp and a 3′ UTR of 207 bp. Two genomic sequences covering the coding region ofhtMT2were cloned by PCR reaction. Sequence analysis revealed that the genomic sequences htMTG_1 of 986 bp and htMTG_2 of 982 bp were both composed of three exons and two introns. The deduced protein consisted of 79 amino acid residues with a predicted molecular weight of 7.8 ku (kD). Amino_terminal and carboxy_terminal domains contained 8 and 7 cysteine residues respectively, separated by a central cysteine free spacer. Sequence alignment revealed that the predicted protein ofhtMT2 was homologous to type 2 metallothioneins (MTs) of plants. Southern blotting analysis indicated that htMT2was encoded by a small multi_gene family in H. tuberosus genome. Northern blotting analysis showed that htMT2 transcripts were detected in stems, leaves and leafstalks, but no transcripts were detected in roots. The expression level in stems was the highest among the above tissues. Transcripts in stems were significantly reduced by Cu 2+ treatment. Judging from the homologies between the deduced HtMT2 and other type 2 plant metallothioneins as well as responses to metal ions, we believe thatwere cloned by PCR reaction. Sequence analysis revealed that the genomic sequences htMTG_1 of 986 bp and htMTG_2 of 982 bp were both composed of three exons and two introns. The deduced protein consisted of 79 amino acid residues with a predicted molecular weight of 7.8 ku (kD). Amino_terminal and carboxy_terminal domains contained 8 and 7 cysteine residues respectively, separated by a central cysteine free spacer. Sequence alignment revealed that the predicted protein ofhtMT2 was homologous to type 2 metallothioneins (MTs) of plants. Southern blotting analysis indicated that htMT2was encoded by a small multi_gene family in H. tuberosus genome. Northern blotting analysis showed that htMT2 transcripts were detected in stems, leaves and leafstalks, but no transcripts were detected in roots. The expression level in stems was the highest among the above tissues. Transcripts in stems were significantly reduced by Cu 2+ treatment. Judging from the homologies between the deduced HtMT2 and other type 2 plant metallothioneins as well as responses to metal ions, we believe that[ShtMT2 encodes a new type 2 metallothionein.

Effects of Metal Ions and Organic Solvents on Alkaline Phosphatase from Rice-field Eel

[Objective]The mechanism of alkaline phosphatase（ALP） was studied to promote rice-field eel aquaculture industry. [ Method] The effects of effectors such as multiple metal ions and organic solvents on ALP in viscera of rice-field eel. [ Result] Na^＋ and K ^＋ didn＇t generate big influences on enzyme activity;Mg^2＋ and Ca^2＋ could promote ALP while Li^＋,Cu^2＋ and Zn^2＋ could restrain ALP enzyme activity. Both HPO4^2- and WO4^2- generated by en- zyme catalyzing disodium phenyl phosphate possessed strong inhibitory effects on emzymc, and 9.5 mmol/L HPO4^2 - would make enzyme activity decline by 13% while 9.5 mmol/L WO4^3- would make enzyme decline by 34%. The inhibition types of them were both competitive inhibition on enzyme activity. The organic solvents such as methanol, ethanol,ethylene glycol,isopropannl all generated influences on ALP and the order according to their inhibitory effects was isopropanol 〉 ethanol 〉 methanol 〉 ethylene glycol. [ Conclusion] The inflncnces of various effeetors on ALP aetivity of rice-field eel were studied from dynamics perspective to provide theoretical basis for further clarifying ALP mechanism.

Effects of Exogenous Amylases and Metal Ions on the Amylase Specific Activities and Starch Degradation of the Upper Leaves of ‘KRK_(26)' during Flue-curing

Objective] The aim of this study was to investigate the effects of exoge-nous amylases and Ca2＋, Mn2＋ and K＋ on the amylase specific activities and starch degradation of the upper leaves of ＇KRK26＇ planted in Yunnan Province during flue-curing. [Method] The amylase specific activities and starch degradation of the leaves were determined by using spectrophotometry. [Result] The 8 U/g exogenous α-amy-lase could improve the specific activity of the leaf α-amylase at yel owing and color-fixing stages, but could not at stem-drying stage, and similarly, the 80 U/g exoge-nous β-amylase could improved the specific activity of the leaf β-amylase at the yel owing stage and the early period of color-fixing stage. The leaf starch could be enhanced to degrade by the exogenous α- or β-amylases and the enhancing effect of the former was stronger than that of the later. 1.50 mg/ml Ca2＋ improved the specific activity of the leaf （α＋β）-amylase mainly due to its enhancing effect on the leaf α-amylase, and increased the starch degradation. 4 mmol/L Mn2＋ inhibited the leaf α-amylase from yel owing to the early period of color-fixing and the β- and （α＋β）-amylases from the yel owing to the later period of color-fixing, but enhanced the leafα-amylase from the later period of color-fixing to the later period of stem-drying and the β- and （α＋β）-amylases at the later period of stem-drying. Meanwhile, Mn2＋ ham-pered the starch degradation during yel owing, but promoted it from the early period of color-fixing to stem-drying. 1 mg/ml K＋ enhanced the leaf α-, β- and （α＋β）-amy-lases during the yel owing stage, but lowered them from the early period of color-fix-ing to the later period of stem-drying, and always inhibited the leaf starch degrada-tion. [Conclusion] The exogenous α-, β- amylases and Ca2＋ of suitable concentra-tions could be used to treat the tobacco leaves before flue-curing to improve the leaf starch degradation during the curing.

Effect of Metal Ions on Protease Activities in the Intestines and Hepatopancreas of Red-white Ornamental Carp (Cyprinus carpio L)

[Objective] The aim of this study was to study effects of metal ions on the protease activities in digestive tissues and gland of red-white ornamental carp（Cyprinus carpio L）.[Method] Effects of four kinds of metal ions （K＋,Na＋,Mg2＋ and Ca2＋） on protease activities in hepatopancreas,foregut,midgut,hindgut of red-white ornamental carp were studied by enzyme analysis method.[Result] Effects of four kinds of metal ions on protease activities of red-white ornamental carp were different in the range of experimental concentration from 25 mmol/L to 150 mmol/L.K＋ could promote protease activities in hepatopancreas and hindgut at different levels.Especially,K＋ had the promoting effect at low-concentration level,but the inhibitory effect at high-concentration level in midgut and the inhibitory effect in foregut.Na＋ had the promoting effect on protease activities in hepatopancreas,foregut and hindgut at different levels,but the inhibitory effect in midgut.Mg2＋ and Ca2＋ had the inhibitory effect on protease activities in intestinal and hepatopancreas at different levels.[Conclusion] This study provides basic data and theoretical foundation for researches on the digestive physiology of red-white ornamental carp or the development and optimization of compound feed.

Identification of DNA Damage Caused by Heavy Metal Ions with Small Molecular DNA

[Objective] The aim was to establish a convenient and effective method to evaluate the toxicity of heavy metal ions by using small molecular DNA. [Method] pUC18 DNA which had exposed to the four heavy metal ions of Hg2＋, Cr6＋, Pb2＋, Cd2＋ was used to study the bioactivity of DNA; simultaneously, gel electrophoresis and hyperchromic effect were employed to detect the mechanism of DNA damage. [Result] The bioactivity of the exposed DNA was decreased and the influence degree was Hg2＋Cr6＋Pb2＋Cd2＋; the gel electrophoresis and hyperchromic effect proved that the main reason leading to reduce the bioactivity was DNA cross link, in the order pf Hg2＋Cr6＋Pb2＋Cd2＋. [Conclusion] The study indicated that pUC18 DNA could be used to assay the damage of DNA causing by heavy mental ions, which may be a potential, simple and effective tool to evaluate toxicity of heavy metal ions to DNA.

Control Effects of Several Metal Ions in Micronutrient Fertilizer on the Bulb Rot of Iphigenia indica Kunth.

[Objective] The control methods of the bulb rot of Iphigenia indica Kunth.caused by Fusarium orthoceras App.et Wr.var.longius （Sherb.） were explored.[Method] The effect of eight different kinds of metal ions on the pathogen was studied;the contents of seven different kinds of metal ions in rhizosphere soil and bulb were also determined.[Result] The results showed that when the concentration of Cu2＋ or Mg2＋ was greater than 1.0mg/L or the concentration of Zn2＋ or Ca2＋ was lower than 0.5mg/L,the growth of pathogen could be inhibited.The results also showed that the bulb could enrich K highly,enrich Zn and Mg,limit the absorption of Ca and Fe,and inhibit the absorption of Cu and Mn during the growth process of bulb in I.indica Kunth.[Conclusion] Micronutrient fertilizer containing Mg could be used to prevent and cure the bulb rot of I.indica Kunth.

Inhibition of cysteine protease papain by metal ions and polysulfide complexes,especially mercuric ion

Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.

Fluorescence Enhancement of Polyamine Derivatives of 1,8-Naphthalimide with Transition Metal Ions

A series of fluorescent chemosensors 1-3 were synthesized to detect transition metal ions. At the room temperature, fluorescence intensities of these chemosensors in acetonitrile without transition metal ions were found to be very weak, due to the process of the efficient intramolecular photoinduced electron transfer （PET）. However, after addition of the transition metal ions, the chemoscnsor 1-3 exhibits obvious fluorescence enhancement. Moreover, the intensity of the fluorescence emission of chemosensors increases significantly in the presence of Zn^2＋ and Cd^2＋. The fluorescent chemosensors with different polyamine as receptors show diverse affinity abilities to the transition metal ions and signal the receptor-metal ion interaction by the intensity change of fluorescence emission.

Chemodynamics of heavy metals in long-term contaminated soils:Metal speciation in soil solution

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. The soil solution was extracted at 70% maximum water holding capacity （MWHC） after equilibration for 24 h. The free metal concentrations （Cd^2＋, Cu^2＋, Pb^2＋, and Zn^2＋） in soil solution were determined using the Donnan membrane technique （DMT）. Initially the DMT was validated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predicted using MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2 and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used in the DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively. This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cation adsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd^2＋ （3%-52%） and Zn^2＋ （11%-72%） in soil solutions were generally higher than those of Cu^2＋ （0.2%-30%） and Pb^2＋ （0.6%-10%）. Among the key soil solution properties, dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showed only a weak relationship with free metal ion partitioning coefficients （Kp） and dissolved organic carbon did not show any significant influence on Kp.

Typical roles of metal ions in mineral flotation:A review

In flotation,metal ions possess significant roles that are usually fulfilled by either selectively activating or depressing the target minerals.Despite that tremendous efforts have been made to address the roles of metal ions in flotation,it still lacks a comprehensive review,especially to compare various ions instead of focusing on a specific one.This review begins by elaborately categorizing the factors involved in affecting the roles of metal ions in flotation.After that,well-accepted mechanisms are updated and discussed from the ore type.Furthermore,typical approaches to explore the underlying mechanisms are emphasized,including traditional techniques such as micro-flotation,contact angle measurement,zeta potential measurement,and other recent prevailing methodologies,like computational method,solution chemistry calculation,and cyclic voltammetry.This work will pave the way to promote flotations via activities like selectively adding/reducing metal ions,choosing reagents,and regulating the slurry chemistry.

Effects of Metallic Ions on the Flotation of Spodumene and Beryl

Effects of multivalent metallic cations, such as Ca2+ and Fe3+, on the flotation of spodumene and beryl were studied. The results show that Fe3+ and Ca2+ exhibit efficient activation on the flotation of spodumene and beryl. The ac- tivation of Fe3+ happens quite well within a pH range of 6-9 while the concentration of Fe3+ is 35 mg/L. Efficient acti- vation of Ca2+ takes place over at a pH over 11.6 at a concentration of 140 mg/L. The zeta potential of beryl and spo- dumene shifts slightly to positive values when activated by Ca2+, but markedly by Fe3+. New stretching frequencies of 1594.24 cm-1 and 1587.13 cm-1 have been found in the FTIR spectra of the two minerals after their interaction with Fe3+ and the collector. These new stretching frequencies are the asymmetric stretching frequencies of COO-(carboxyl anion), so thecollector may be chemically absorbed on the surface of Fe3+-activated beryl and spodumene.

Application of ionic liquids in hydrometallurgy of nonferrous metals

Ionic liquids as green solvents have shown important application in the extraction and separation of nonferrous metals.The new application perspective,the important fundamental and the applied studies of the extraction and separation of nonferrous metals in ionic liquids,including the dissolution and corrosion of metal and metal oxide,hydrometallurgy of chalcopyrite and metallic oxidized ore,and extraction and separation of metal ions,are introduced.

The research on the adsorption effect on metal ions by immobilized marine algae

The process of adsorption of Cu^2+ Cd^2+ by immobilized marine algae was investigated, it can be noted from the results that, the process for biosorption of heavy metals (copper, cadmium) by immobilized Laminaria japonica can be described by the Banerm model. According to the model, the adsorption rate constant calculated was 0.107 8 and 0.030 28 min^-1 for Cu^2+ and Cd^2+ respectively. The experimental biosorption equilibrium data for Cu^2+ and Cd^2+ were in good agreement with those calculated by the Langmuir model. The maximum uptake capacity calculated was 83.3 and 112.4 mg/g for Cu^2+ and Cd^2+ according to the Langmuir model, respectively. The appetency of Laminaria japonica to Cu^2+ was better than Cd^2+.

Effects of Different Nitrogen Sources and Metal Ions on Biogas Generation by Corn Stalk Fermentation

[Objective] The present study was conducted to explore the effects of dif- ferent nitrogen sources and metal ions on the biogas production process and biogas yield by fermentation of corn stalk powder using self-designed anaerobic fermenta- tion system. [Method] The biogas produced during fermentation was collected by water displacement, and measured by ignition. [Result] Ammonium bicarbonate, urea and yeast extract powder all increased biogas yield. Among them, ammonium bi- carbonate was the best nitrogen source. Ammonium dihydrogen phosphate showed an inhibitory effect on biogas production. Biogas yield was significantly increased by adding NaCl, KCl, MgCl2 or CaCl2, among which, NaCl had the best effect. [Conclu- sion] It is not conducive to the growth and development of methanogenic flora in the production of biogas using corn stalks as the only material in fermentation. The biogas yield can be increased by adding exogenous nitrogen, which reduces the carbon to nitrogen （C：N） ratio of fermentation materials. The biogas yield can be significantly increased by adding appropriate types and amount of electrolytes, with appropriate C：N ratio. The methanogenic flora is more tolerant to NaCl and KCl than to MgCl2 and CaCl2. Moreover, NaCl can not only significantly increase the biogas production, but also shorten startup period of methanogenic flora, thereby shortening the gas producing cycle.

Air-Stable Ultrabright Inverted Organic Light-Emitting Devices with Metal Ion-Chelated Polymer Injection Layer

Here,this work presents an air-stable ultrabright inverted organic lightemitting device(OLED)by using zinc ionchelated polyethylenimine(PEI)as electron injection layer.The zinc chelation is demonstrated to increase the conductivity of the PEI by three orders of magnitude and passivate the polar amine groups.With these physicochemical properties,the inverted OLED shows a record-high external quantum efficiency of 10.0% at a high brightness of 45,610 cd m^(-2) and can deliver a maximum brightness of 121,865 cd m^(-2).Besides,the inverted OLED is also demonstrated to possess an excellent air stability(humidity,35%)with a half-brightness operating time of 541 h@1000 cd m^(-2) without any protection nor encapsulation.

Adsorption properties of a novel 3D graphene/MgO composite for heavy metal ions

A novel three-dimension(3D)graphene/MgO composite was synthesized through self-assembly and embedding MgO nanoparticle in reduced graphene in situ.Fourier transform infrared(FT-IR)spectroscopy,thermal gravimetric analysis(TGA),scanning electron microscopy(SEM),transmission electron microscope(TEM),powder X-raydiffraction(XRD)and X-rayphotoelectron spectroscopy(XPS)were employed to characterize the prepared 3D graphene/MgO composite.The adsorption performance of some metal ions on 3D graphene/MgO was investigated.The results showed that the adsorption capacity was greater than 3D graphene and the maximum adsorption capacity at 25℃was found to be 358.96 mg/g,388.4 mg/g and 169.8 mg/g for Pb^2+,Cd^2+and Cu^2+,respectively.The adsorption kinetic conformed to the pseudo-second-order kinetic model and the adsorption isotherm was well described by Langmuir model.The thermodynamic constants revealed that the sorption process was endothermic and spontaneous in nature.Based on the results of the removal of heavy metal ions from metal smelting wastewater,it can be concluded that the prepared 3D graphene/MgO composite is an effective and potential adsorbent.

Enhancement of removal efficiency of heavy metal ions by polyaniline deposition on electrospun polyacrylonitrile membranes

This paper describes the preparation of a membrane of polyacrylonitrile(PAN)and its corresponding membrane coated with polyaniline(PANI)for the adsorption of heavy metal ions.Scanning electron microscopy micrographs revealed that all the membranes exhibited nanofibrous morphology.The prepared membranes were characterized by Fourier transform infrared spectroscopy(FTIR).The prepared membranes were used as an adsorbent for hazardous heavy metal ions Pb^(2+) and Cr_(2)O^(2-)_(7).The adsorption capacity and the removal efficiency of the membranes were examined as function of the initial adsorbate concentration and pH of the medium.Coated membranes with PANI showed better adsorption performance and their direct current(DC)conductivities were correlated to heavy metal ion concentrations.Adsorption isotherms were also performed,and the adsorption process was tested according to the Langmuir and Freundlich models.The regeneration and reuse of the prepared membranes to re-adsorb heavy metal ions were also investigated.The enhancement in adsorption performance and reusability of PANI-coated membranes in comparison with non-coated ones is fully discussed.The results show that the maximum adsorption capacities of lead and chromate ions on the PANI-coated membranes are 290.12 and 1202.53 mg/g,respectively.