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.

Effects of heavy metal ions Cu^(2+)/Pb^(2+)/Zn^(2+)on kinetic rate constants of struvite crystallization

Struvite(MAP)crystallization technology is widely used to treat ammonia nitrogen in waste effluents of its simple operation and good removal efficiency.However,the presence of heavy metal ions in the waste effluents causes problems such as slow crystallization rate and small crystal size,limiting the recovery rate and economic value of the MAP.The present study was conducted to investigate the effects of concentrations of three heavy metal ions(Cu^(2+),Zn^(2+),and Pb^(2+))on the crystal morphology,crystal size,average growth rate,and crystallization kinetics of MAP.A relationship was established between the kinetic rate constant Ktcalculated by the chemical gradient model and the concentrations of heavy metal ions.The results showed that low concentrations of heavy metal ions in the solution created pits on the MAP surface,and high level of heavy metal ions generated flocs on the MAP surface,which were composed of metal hydroxides,thus inhibiting crystal growth.The crystal size,average growth rate,MAP crystallization rate,and kinetic rate constant Ktdecreased with the increase in heavy metal ion concentration.Moreover,the Ktdemonstrated a linear relationship with the heavy metal concentration ln(C/C~*),which provided a reference for the optimization of the MAP crystallization process in the presence of heavy metal ions.

Dual-functional pyrene implemented mesoporous silicon material used for the detection and adsorption of metal ions

A fluorescent active organic–inorganic hybrid material Py N-SBA-15 was synthesized by implementing pyrene derivatives into mesoporous SBA-15 silica.Py N-SBA-15 had detection and removal functionalities toward Al^(3+),Cu^(2+),and Hg^(2+).On the one hand,Py N-SBA-15 was used as a fluorescence sensor and displayed high sensitivity toward Al^(3+),Cu^(2+),and Hg^(2+)cations (limit of detection:8.0×10^(-7),1.1×10^(-7),and 2.9×10^(-6)mol·L^(–1),respectively) among various analytes with“turn-off”response.On the other hand,the adsorption studies for these toxic analytes (Cu^(2+),Hg^(2+),and Al^(3+)) showed that the ion removal capacity could reach up to 45,581,and 85 mg·g^(-1),respectively.Moreover,the Langmuir isotherm models were better fitted with the adsorption data,indicating that the adsorption was mono-layer adsorption.Kinetic analysis revealed that the adsorption process was well described by the pseudo-second-order kinetic model for Cu^(2+)and Hg^(2+)and pseudo-first-order kinetic model for Al^(3+).The prepared silica material could be reused in four recycles without significantly decreasing its adsorption capacity.Therefore,the Py N-SBA-15 material can serve as a promising candidate for the simultaneous rapid detection and efficient adsorption of metal ions.

Effect of mono-/divalent metal ions on the conductivity characteristics of DNA solutions transferring through a microfluidic channel

Interactions between deoxyribonucleic acid(DNA) and metal ions are vital for maintaining life functions, however,there are still unsolved questions about its mechanisms. It is of great practical significance to study these issues for medical chip design, drug development, health care, etc. In this investigation, the conductivity properties of λ-DNA solutions with mono-/divalent metal ions(Na+, K^(+), Mg^(2+), and Ca^(2+)) are experimentally studied as they are electrically driven through a 5 μm microfluidic channel. Experimental data indicate that the conductivities of λ-DNA solutions with metal ions(M+/M2+) basically tend to reduce firstly and then increase as the voltage increases, of which the turning points varied with the metal ions. When the voltage surpasses turning points, the conductivity of λ-DNA-M+solutions increases with the concentration of metal ions, while that of λ-DNA-M^(2+)solutions decrease. Moreover, the conductivity of λ-DNA-M^(2+)solutions is always smaller than that of λ-DNA-M+solutions, and with high-concentration M^(2+), it is even smaller than that of the λ-DNA solution. The main reasons for the above findings could be attributed to the polarization of electrodes and different mechanisms of interactions between metal ions and λ-DNA molecules. This investigation is helpful for the precise manipulation of single DNA molecules in micro-/nanofluidic space and the design of new biomedical micro-/nanofluidic sensors.

Metal ions as effectual tools for cancer with traditional Chinese medicine

Malignant tumor has become a major threat affecting human health,and is one of the main causes of human death.Recent studies have shown that many traditional Chinese medicines(TCM)have good anti-tumor activity,which may improve the therapeutic effect of routine treatment and quality of life with lower toxicity.However,the efficacy of TCM alone for the treatment of tumors is limited.Metal ions are essential substances for maintaining normal physiological activities.This article summarized the multiple mechanisms in which metal ions are involved in the prevention and treatment of tumors in TCM.

Revealing alkali metal ions transport mechanism in the atomic channels of Au@a-MnO_(2)

Understanding alkali metal ions’(e.g.,Li^(+)/Na^(+)/K^(+))transport mechanism is challenging but critical to improving the performance of alkali metal batteries.Herein using a-MnO_(2)nanowires as cathodes,the transport kinetics of Li^(+)/Na^(+)/K^(+)in the 2×2 channels of a-MnO_(2)with a growth direction of[001]is revealed.We show that ion radius plays a decisive role in determining the ion transport and electrochemistry.Regardless of the ion radii,Li^(+)/Na^(+)/K^(+)can all go through the 2×2 channels of a-MnO_(2),generating large stress and causing channel merging or opening.However,smaller ions such as Li^(+)and Na^(+)cannot only transport along the[001]direction but also migrate along the<110>direction to the nanowire surface;for large ion such as K^(+),diffusion along the<110>direction is prohibited.The different ion transport behavior has grand consequences in the electrochemistry of metal oxygen batteries(MOBs).For Li-O_(2)battery,Li^(+)transports uniformly to the nanowire surface,forming a uniform layer of oxide;Na^(+)also transports to the nanowire surface but may be clogged locally due to its larger radius,therefore sporadic pearl-like oxides form on the nanowire surface;K^(+)cannot transport to the nanowire surface due to its large radius,instead,it breaks the nanowire locally,causing local deposition of potassium oxides.The study provides atomic scale understanding of the alkali metal ion transport mechanism which may be harnessed to improve the performance of MOBs.

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.

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.

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.

Interactions of Heavy Metal Ions with Paddy Soils as Inferred from Wien Effect Measurements in Dilute Suspensions

Interactions of three heavy metal ions, Cu^2＋, Cd^2＋, and Pb^2＋, and, for comparison, Na^＋ with electrodialytic clay fractions （less than 2μm in diameter） of four paddy soils as well as a yellow-brown soil as a control soil were evaluated based on measurements of the Wien effect in dilute suspensions with a clay concentration of 10 g kg^-1 in four nitrate solutions of 2 × 10^-4/z mol L^-1, where z is the cation valence, and a nitric acid solution of 3 × 10^-5 mol L^-1, Field strengths ranging from 15 to 230 kV cm^-1 were applied for measuring the electrical conductivities （ECs） of the suspensions. The mean free binding energies between the various cations and all of the soils determined from exchange equilibrium increased in the order： Na^＋ 〈 Cd^2＋ 〈 Cu^2＋ 〈 Pb^2＋. In general, the ECs of the suspensions in the sodium nitrate solution were smaller than those of the suspensions in the heavy metal solutions because of the lower electrophoretic mobility of sodium compared to the divalent cations. In terms of relative electrical conductivity-field strength relationships, relative electrical conductivity （REC） of suspensions containing various cations at field strengths larger than about 50 kV cm^-1 were in the descending order： Na^＋ 〉 Cu^2＋ 〉 Cd^2＋ 〉 Pb^2＋ for all tested soils. A characteristic parameter of the REC-field strength curves, AREC200, REC at a field strength of 200 kV cm^-1 minus that at the local minimum of the concave segment of the REC-field strength curves, characterized the strength of adsorption of the cations stripped off by the applied strong electrical field, and for all soils the values of AREC200 were generally in the order： Na^＋ 〈 Cu^2＋ ≤ Cd^2＋ 〈 Pb^2＋.

Adsorption of Heavy Metal Ions by Adsorbent from Waste Mycelium Chitin

The adsorption properties of chitin adsorbent from mycelium of fermentation industries for the removal of heavy metal ions were studied. The result shows that the chitin adsorbent has high adsorption capacity for many heavy metal ions and Ni2+ in citric acid. The influence of pH was significant:When pH is higher than 4.0, the high adsorption capacity is obtained,otherwise H+ ion inhibits the adsorption of heavy metal ions. The comparison of the chitin adsorbent with some other commercial adsorbents was made, in which that the adsorption behaviorchitin adsorbent is close to that of commercial cation exchange adsorbents, and its cost is much lower than those commercial adsorbents.

Metal Ions Extraction with Glucose Derivatives as Chelating Reagents in Supercritical Carbon Dioxide

A series of glucose derivatives have been used as chelating reagents to extract metal ions in supercritical carbon dioxide. With perfluoro-l-octanesulfonic acid tetraethylammonium salt as additive, glucose derivatives were selective for Sr^2＋ and Pb^2＋ extraction in supercritical carbon dioxide.

Selective removal of heavy metal ions from aqueous solutions with surface functionalized silica nanoparticles by different functional groups

The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) triethoxysilane(MPTES) and(3-Amincpropyl) trithoxysilane(APTES). Some further modifications were studied by chloroaceetyl choride and 1,8-Diaminoaphalene for amino modified silica. The surface functionalized silica nanoparticles were characterized by Fourier transform infrared(FI-IR) and X-ray photoelectron spectroscopy(XPS). The prepared adsorbent of surface functionalized silica nanoparticles with differential function groups were investigated in the selective adsorption about Pb2+, Cu2+, Hg2+, Cd2+ and Zn2+ions in aqueous solutions. The results show that the(3-Mercaptopropyl) triethoxysilane functionalized silica nanoparticles(SiO2-MPTES) play an important role in the selective adsorption of Cu2+ and Hg2+, the(3-Amincpropyl) trithoxysilane(APTES) functionalized silica nanoparticles(SiO2-APTES) exhibited maximum removal efficiency towards Pb2+ and Hg2+, the 1,8-Diaminoaphalene functionalized silica nanoparticles was excellent for removal of Hg2+ at room temperature, respectively.

Hydroxylated graphene quantum dots as fluorescent probes for sensitive detection of metal ions

Highly sensitive methods are important for monitoring the concentration of metal ions in industrial wastewater.Here,we developed a new probe for the determination of metal ions by fluorescence quenching.The probe consists of hydroxylated graphene quantum dots(H-GQDs),prepared from GQDs by electrochemical method followed by surface hydroxylation.It is a non-reactive indicator with high sensitivity and detection limits of 0.01μM for Cu2+,0.005μM for Al3+,0.04μM for Fe3+,and 0.02μM for Cr3+.In addition,the low biotoxicity and excellent solubility of H-GQDs make them promising for application in wastewater metal ion detection.

Chitosan Removes Toxic Heavy Metal Ions from Cigarette Mainstream Smoke

This study investigated the removal of heavy metal ions from cigarette mainstream smoke using chitosan. Chitosan of various deacetylation degrees and molecular weights were manually added to cigarette filters in different dosages. The mainstream smoke particulate matter was collected by a Cambridge filter pad, digested by a microwave digestor, and then analyzed for contents of heavy metal ions, including As（Ill/V）, Pb（II）, Cd（II）, Cr（III/VI） and Ni（II）, by graphite furnace atomic absorption spectrometry （GFAAS）. The results showed that chitosan had a removal effect on Pb（II）, Cd（II）, Cr（III/VI） and Ni（II）. Of these, the percent re- moval of Ni（II） was elevated with an increasing dosage of chitosan. Chitosan of a high deace tylation degree exhibited good binding performance toward Cd（II）, Cr（III/VI） and Ni（II）, though with poor efficiency for Pb（II）. Except As（III/V）, all the tested metal ions showed similar tendencies in the growing contents with an increasing chitosan molecular weight. Nonetheless, the percent removal of Cr（III/VI） peaked with a chitosan molecular weight of 200 kDa, followed by a dramatic decrease with an increasing chitosan mo- lecular weight. Generally, chitosan had different removal effects on four out of five tested metal ions, and the percent removal of Cd（II）, Pb（II）, Cr（III/VI） and Ni（II） was approximately 55%, 45%, 50%, and 16%, respectively. In a word, chitosan used in cigarette filter can remove toxic heavy metal ions in the mainstream smoke, improve cigarette safety, and reduce the harm to smokers.

Sensitive Determination of DNA by RLS Enhancement of Metal Ions

The interactions between metal ions and DNA have been studied by the resonance light scattering (RLS) spectra. In the acidic condition, the RLS signals of metal ions, especially the transition metal ions in group IB and IIB, were increased by DNA. And it is found that the enhancement of RLS signals is linear to the concentration of DNA, so the RLS method for DNA determination was proposed in the presence of Cu2+. On the optimum conditions, the linear range and the detect limit of ctDNA is 4×10?8–4×10?6 g· mL?1 and 1. 13×10?8 g·mL?1, respectively. The proposed method is successfully applied to determine the extracted plasmid DNA ofBacillus subtilis DB104. Key words resonance light scattering - DNA - metal ions CLC number O 657.3 Foundation item: Supported by National Natural Science Foundation of China (20275028) and the National Key Basic Research and Development Program (973 Program 2002CB211800).Biography: Huang Jian-ping(1964-), male, Associate professor, research direction: bioanalysis.

Effect of alkali metal ions on the formation mechanism of HCN during pyridine pyrolysis

The catalytic effects of alkali metal ions(Na^(+)and K^(+))on NO_(x)precursor formation during coal pyrolysis were investigated using the N-containing compound pyridine as a model compound.Density functional theory calculations at the B3LYP/6-31G(d,p)level of theory were conducted to elucidate the mechanism of pyridine pyrolysis and the pathways for HCN formation.The calculation results indicate that Na^(+)and K^(+)have distinct influences on different pyrolysis reactions;these alkali metal ions facilitate the initial hydrogen transfer from C_(1)to N and C_(2),whereas they hinder the other hydrogen migration reactions.Both Na^(+)and K^(+)significantly reduce the activation energies for C–C bond breakage and triple-bond formation,whereas they increase the activation energies for the isomerization reactions.The different effects essentially result from the distinct charge distributions induced by the two ions.Due to the distinct influences on the different reactions,the rate-determining steps are modulated,affecting the competitiveness of the different possible pathways of HCN formation.The formation of HCN from pyridine is promoted in the presence of Na^(+)and K^(+)because all the overall activation energies are decreased for different pathways.The calculation results agree well with previous experimental studies.Thus,the findings offer a new and promising approach to reveal the formation mechanism of NO_(x)and facilitate the control of NO_(x)for coal utilization.

Synthesis of a novel calix[4]arene-based fluorescent ionophore and its metal ions recognition properties

A novel fluorescent ionophore derived from calix[4]arene and pyrazoline was designed and synthesized.Its molecular structure was confirmed by ^1H NMR and element analysis.The resulting material shows specific fluorescent behavior toward the Zn^2＋ion among the other divalent metal ions,such as Co^2＋,Ni^2＋,Cu^2＋.The primary results indicate this ionophore material is a potential material for developing efficient fluorescent Zn^2＋ chemosensors.