Selective Transport of Alkali-Metal Cations through Liquid Membranes by Non-Cyclic Carriers

The emission spectra of a series of naphthalene end-labeled oligo-oxyethylene(N-P_n-N) and their facilitated transport of cations across liquid membranes have beeninvestigated. Alkali-metal cations enhance or inhibit the intramolecular excimer formation ofN-P_n-N remarkably, suggesting that the polyether chain of N-P_n-N in solution complexes with thecations, and the orientation of the terminal chromophores depends on the cation size and the lengthof the polyether chain. These compounds are able to act as carriers to facilitate transport ofalkali-metal cations through organic liquid membranes. The transport efficiencies are comparablewith those of cyclic carriers such as crown ethers, and show remarkable selectivity.

Study of the Temperature-Programmed Desorption of Carbon Dioxide (CO2) on Zeolites X Modified with Bivalent Cations

Study of physisorbed and chemisorbed carbon dioxide (CO2) species was carried out on the NaX zeolite modified by cationic exchanges with bivalent cations (Ca2+ and Ba2+) by temperature-programmed desorption of CO2 (CO2-TPD). Others results were obtained by infrared to complete the study. The results of this research showed, in the physisorption region (213 - 473 K), that the cationic exchanges on NaX zeolite with bivalent cations increase slightly the interactions of CO2 molecule with adsorbents and/or cationic site. Indeed, the desorption energies of physisorbed CO2 obtained on the reference zeolite NaX (13.5 kJ·mol-1) are lower than that of exchanged zeolites E-CaX and E-BaX (15.77 and 15.17 kJ·mol-1 respectively). In the chemisorbed CO2 region (573 - 873 K), the desorption energies related to desorbed species (bidentate carbonates: CO32-) on the exchanged zeolites E-CaX and E-BaX are about 81 kJ·mol-1, higher than the desorbed species (bicarbonates: HCO32-) on the reference R-NaX (62 kJ·mol-1). In addition, the exchanged E-BaX zeolite develops the secondary adsorption sites corresponding to bicarbonates species with desorption energies of 35 kJ·mol-1 lower to desorption energies of bicarbonates noted on the reference zeolite NaX.

Waste acid recovery utilizing monovalent cation permselective membranes through selective electrodialysis

Selective electrodialysis(SED)has surfaced as a highly promising membrane separation technique in the realm of acid recovery owing to its ability to effectively separate monovalent ions through the utilization of a potential difference.However,the current SED process is limited by conventional commercial monovalent cation permselective membranes(MCPMs).This study systematically investigates the use of an independently developed MCPM in the SED process for acid recovery.Various factors such as current density,volume ratio,initial ion concentration,and waste acid systems are considered.The independently developed MCPM offers several advantages over the commercial monovalent selective cation-exchange membrane(CIMS),including higher recovered acid concentration,better ion flux ratio,improved acid recovery efficiency,increased recovered acid purity,and higher current efficiency.The SED process with the MCPM achieves a recovered acid of 95.9%and a concentration of 2.3 mol·L^(–1) in the HCl/FeCl_(2) system,when a current density of 20 mA·cm^(-2) and a volume ratio of 1:2 are applied.Similarly,in the H_(2)SO_(4)/FeSO_(4) system,a purity of over 99%and a concentration of 2.1 mol·L^(–1) can be achieved in the recovered acid.This study thoroughly examines the impact of operation conditions on acid recovery performance in the SED process.The independently developed MCPM demonstrates outstanding acid recovery performance,highlighting its potential for future commercial utilization.

Fabrication and Properties of a New Reactive Diluent for Cationic UV Curing

The reactive diluent prepared by siloxane modified Trimethylene oxide can improve the performance of the UV curing system.Therefore,1,7-bis[(3-ethyl-3-methoxyoxacylobutane)propyl]octadecylosiloxane(BEMOPOMTS)was synthesized from diethyl carbonate,trimethylopropanes,allyl bromide,and 1,1,3,3,5,5,7,7-octadecylosiloxane as the main raw materials.BEMOPOMTS can be used as reactive diluents in the field of cationic UV curing.It has good thermal stability,and the addition of BEMOPOMTS significantly improves the tensile strength and elongation at break of epoxy resin.Compared with the pure epoxy resin,adding 20%BEMOPOMTS increased the elastic modulus by 25%to 677 MPa.

Exploring the Cation Regulation Mechanism for Interfacial Water Involved in the Hydrogen Evolution Reaction by In Situ Raman Spectroscopy

Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.

Cationic ordering transition in oxygen-redox layered oxide cathodes

Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.

Enabling an Inorganic-Rich Interface via Cationic Surfactant for High-Performance Lithium Metal Batteries

An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.

Risk Stratification and Prognosis of Pulmonary Arterial Hypertension Associated with Congenital Heart Disease

Background:Current guidelines for managing pulmonary arterial hypertension(PAH)recommend a risk strati-fication approach.However,the applicability and accuracy of these strategies for PAH associated with congenital heart disease(PAH-CHD)require further validation.This study aims to validate the reliability and predictive accuracy of a simplified stratification strategy for PAH-CHD patients over a three-year follow-up.Additionally,new prognostic variables are identified and novel risk stratification methods are developed for assessing and managing PAH-CHD patients.Methods:This retrospective study included 126 PAH-CHD patients.Clinical and biochemical variables across risk groups were assessed using Kruskal-Wallis and Fisher’s exact tests.Indepen-dent risk factors were identified using ordered logistic regression,while Kaplan-Meier and Cox proportional hazards regression analyses evaluated their impact on all-cause mortality.A new stratification model for the PAH-CHD population was constructed based on these analyses.Results:Significant survival differences across stratified risk groups were observed(p<0.001),validating the effectiveness of the simplified risk stratification method in PAH-CHD patients.Prothrombin activity was a strong independent predictor of adverse outcomes of PAH-CHD patients(Hazard ratio 0.95,p<0.001,C-index 0.70).A model combining N-terminal pro-brain natriuretic peptide,prothrombin activity,albumin,and right atrial area achieved an area under the curve of 0.89 and a C-index of 0.85.Conclusions:The simplified risk stratification method is applicable to PAH-CHD patients.Prothrombin activity is a strong independent predictor of adverse outcomes.A comprehensive risk stratification approach,incorporating both established and novel biomarkers,enhances accessibility and offers predictive efficacy during follow-up for PAH-CHD patients,comparable to established models.

Soil exchangeable base cations along a chronosequence of Caragana microphylla plantation in a semi-arid sandy land,China

As a pioneer leguminous shrub species for vegetation re-establishment, Caragana microphylla is widely distributed in the semi-fixed and fixed sandy lands of the Horqin region, North China. C. microphylla planta- tions modify organic carbon （SOC）, nitrogen （N） and phosphorus dynamics, bulk density and water-holding capacity and biological activities in soils, but little is known with regard to soil exchange properties. Variation in soil ex- changeable base cations was examined under C. microphylla plantations with an age sequence of 0, 5, 10, and 22 years in the Horqin Sandy Land, and at the depth of 0-10, 10-20, and 20-30 cm, respectively. C. microphylla has been planted on the non-vegetated sand dunes with similar physical-chemical soil properties. The results showed that exchangeable calcium （Ca）, magnesium （Mg）, and potassium （K）, and cation exchange capacity （CEC） were significantly increased, and Ca saturation tended to decrease, while Mg and K saturations were increased with the plantation years. No difference was observed for exchangeable sodium （Na） neither with plantation years nor at soil depths. Of all the base cations and soil layers, exchangeable K at the depth of 0-10 cm accumulated most quickly, and it increased by 1.76, 3.16, and 4.25 times, respectively after C. microphylla was planted for 5, 10, and 22 years. Exchangeable Ca, Mg, and K, and CEC were significantly （P〈0.001） and positively correlated with SOC, total N, pH and electrical conductivity （EC）. Soil pH and SOC are regarded as the main factors influencing the variation in ex- changeable cations, and the preferential absorption of cations by plants and different leaching rates of base cations that modify cation saturations under C. microphylla plantation. It is concluded that as a nitrogen-fixation species, C. microphylla plantation is beneficial to increasing exchangeable base cations and CEC in soils, and therefore can improve soil fertility and create favorable microenvironments for plants and creatures in the semi-arid sandy land ecosystems.

Effects of alkaline cations (M^+= Li^+, Na^+, K^+, Cs^+) on the electrochemical synthesis of polyaniline in nitric acid electrolyte

The effects of alkaline cations （M^＋ = Li^＋, Na^＋, K^＋, Cs^＋）on the electrochemical synthesis of polyaniline were carfled out under cyclovoltammetric conditions using nitrates of Li^＋, Na^＋, K^＋, and Cs^＋ as the supporting electrolytes. The results show that the oxidation potentials of aniline in the electrolytes decrease as the protonation extent of aniline decreases from the fast scan, which is caused by the decrease of the ionic radius of alkaline metal ions at the same concentration of alkaline cations. With the scan number increasing, the deposit charge Q as the characteristic growth function also depends on the protonation of aniline, and it increases with the ionic radius of alkaline cations increasing. SEM images show the effect of alkaline cations on the morphology of polyaniline. It is clear that the ionic mobility of alkaline cations is further lower than that of W. Alkaline cations and counter-ions were the species responsible for the enhancement of Pani electrosynthesis. Therefore, this is exactly what SEM images show： a relatively rough fibrous structure in the case of Pani-H^＋ suggesting a sponge-like structure and a highly orderly fiber-like structure in the case of Pani-M^＋.

Influence of Types and Charges of Exchangeable Cations on Ciprofloxacin Sorption by Montmorillonite

As one of the most important soil components, montmorillonite plays a vital role in transport and retention of organic pollutants in soils. Ciprofloxacin （CIP）, an antibiotic of fluoroquiolones, has been frequently detected in water and soil environments due to its wide use in human and veterinary medicine. In this study, the adsorption of CIP onto different homoionic montmorillonite such as Na-, Ca- and Al-MMT was investigated, and the influence of types and charges of exchangeable cations in the interlayer of montmorillonite on CIP adsorption was evaluated. The results showed that different homoionic montmorillonite exhibited different sorption capacity of CIP. At pH 3, the sorption capacity of CIP decreased in the order Na-MMT Ca-MMT Al-MMT, following the lyotropic series. When solution pH increased to 11, the sorption capacity of CIP followed the order Ca-MMT Al-MMT Na-MMT. Accompanying CIP adsorption on Ca-MMT, a certain amount of Ca2＋ was released into solution. Compared to pH 3, the lower Ca concentration in solution at pH 11 indicated that the adsorption of CIP on Ca-MMT at strong alkaline pH was no longer via cation exchange, and surface complexation or cation bridging might contribute to CIP adsorption. The adsorption of CIP on Na- and Ca-MMT at pH 3 and 11 resulted in the expansion of d-spacing, indicative of intercalation of CIP into the interlayer space of the montmorillonite. However, a decrease of d-spacing was observed when CIP adsorbed on Al-MMT at pH 11, which might be attributed to the dissolution of Al-CIP complex formed between CIP and Al3＋ in the interlayer of montmorillonite. The results suggest that the types and charges of exchangeable cations in the interlayer of montmorillonite play an important role in CIP adsorption on montmorillonite.

Cations and Anions in Sewage Sludge from Gaza Waste Water Treatment Plant

This paper determined cations and anions concentrations, Total Kjeldahl Nitrogen (TKN), and heavy metals content in sewage sludge collected from the drying beds of wastewater treatment plant in Gaza. The aim was to test the possibility of using this sewage sludge as an alternative source of mineral fertilizers. Many instruments were used in this work: flame photometry (K, Na), EDTA titration (Ca, Mg), the turbidity method () , spectrophotometer (turbidity), ascorbic acid method (orthophosphate), titrimetric method (Cl﹣), inductive coupled plasma analyzer (ICP, heavy metals). All the processes of experiments and analyses were described clearly for reference. Results showed that concentrations of Na﹢, K﹢, Ca2﹢ and Mg2﹢ were 28.93, 2.53, 271 and 177 mg/kg respectively whereas? were 0.434, 18.59, 0.87 and 0.026 g/kg respectively. The concentrations of Fe, Cu, Pb, Zn and Mn were 125.12, 172.56, 76.88, 218.73 and 157.56 mg/kg respectively. These results indicate that sewage sludge from Gaza contained high fractions of most plant nutrients accordingly, and it may be advantageous to use the sludge as a natural source of plant fertilizers.

Effects of Anions and Cations on π-Complexation Between Olefin and Metal Halide

An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C_2H_4 on MX(M=Ag, Cu; X=F, Cl). The calculated results show the following order of adsorption strength: F ->Cl - for anions; Cu +>Ag + for cations. The results can be explained by the detailed analysis of atomic charge, orbital energy and orbital population by using the natural bond orbital(NBO) theory: (1) anions with stronger electronegativity can attract more electrons from the s orbital of M, while at the same time it does not obviously weaken the d orbital occupation of M, thus the nearly vacant s orbital and the sufficiently filled d orbitals of M help with forming σ-donation and d-π * backdonation with the π orbital and the π * orbital of olefin, respectively; (2) a smaller energy gap of symmetry-adapted orbitals between olefin and a cation can favor the electron transfer, that is why Cu + forms stronger adsorption with olefin than Ag + does.

Sheep manure application increases soil exchangeable base cations in a semi-arid steppe of Inner Mongolia

The long-term productivity of a soil is greatly influenced by cation exchange capacity（CEC）.Moreover,interactions between dominant base cations and other nutrients are important for the health and stability of grassland ecosystems.Soil exchangeable base cations and cation ratios were examined in a 11-year experiment with sheep manure application rates 0–1,500 g/（m2？a） in a semi-arid steppe in Inner Mongolia of China,aiming to clarify the relationships of base cations with soil p H,buffer capacity and fertility.Results showed that CEC and contents of exchangeable calcium（Ca2＋）,magnesium（Mg2＋）,potassium（K＋） and sodium（Na＋） were significantly increased,and Ca2＋ saturation tended to decrease,while K＋ saturation tended to increase with the increases of sheep manure application rates.The Ca2＋/Mg2＋ and Ca2＋/K＋ ratios decreased,while Mg2＋,K＋ and Na＋ saturations increased with increasing manure application rates.Both base cations and CEC were significantly and positively correlated with soil organic carbon（SOC） and soil p H.The increases of SOC and soil p H would be the dominant factors that contribute to the increase of cations in soil.On a comparison with the initial soil p H before the experiment,we deduced that sheep manure application could partly buffer soil p H decrease potentially induced by atmospheric deposition of nitrogen and sulfur.Our results indicate that sheep manure application is beneficial to the maintenance of base cations and the buffering of soil acidification,and therefore can improve soil fertility in the semi-arid steppes of northeastern China.

Electrochemical Behavior of Steel Bar in Electrolytes:Influence of pH Value and Cations

Steel bar corrosion on electrolytes and the influence of cation were investigated. Three electrolytes of Ca（OH）2, NaOH and KOH with pH levels of 12.5, 11.5, 10.5, 9.5, 8.5 were prepared, meanwhile, the methods of free corrosion potential and electrochemical impedance spectra （EIS） were used to evaluate the influence of cations on the depassivation of the steel bar in electrolytes. The experimental results indicate that the initial corrosion pH value of the steel bar is influenced by the cation in electrolyte and the influence of K＋ in electrolyte is the most remarkable, followed by Na＋ and Ca2＋. The initial corrosion pH values are 10.5 in KOH electrolyte, 9.5 in NaOH electrolyte and lower than 8.5 in Ca（OH）2 electrolyte.

Processes of DNA condensation induced by multivalent cations: Approximate annealing experiments and molecular dynamics simulations

The condensation of DNA induced by spermine is studied by atomic force microscopy （AFM） and molecular dynamics （MD） simulation in this paper. In our experiments, an equivalent amount of multivalent cations is added to the DNA solutions in different numbers of steps, and we find that the process of DNA condensation strongly depends on the speed of adding cations. That is, the slower the spermine cations are added, the slower the DNA aggregates. The MD and steered molecular dynamics （SMD） simulation results agree well with the experimental results, and the simulation data also show that the more steps of adding multivalent cations there are, the more compact the condensed DNA structure will be. This investigation can help us to control DNA condensation and understand the complicated structures of DNA--cation complexes.

MODIFICATION OF TRANSITION METAL CATIONS TO POLYMER-STABILIZED PLATINUM COLLOIDAL CLUSTERS IN ENANTIOSELECTIVE HYDROGENATION OF METHYL PYRUVATE

Modification of transition metal cations to polymer-stabilized Pt colloidal clusters modified with cinchonidine was studied in enantioselective hydrogenation of methyl pyruvate.Compared to the enantiomeric excess(e.e.)value(71.4%) obtained without the presence of metal cations,obvious e.e.enhancement(up to 82.5%)was resulted from the addition of Zn^(2+) but with a certain decrease in activity.The reaction parameters in the presence of Zn^(2+) were also studied.It was found that the Pt colloidal catalysts in the presence of metal cations performed very differently from that in the absence of metal cations.

An experimental study of electroreduction of CO2 to HCOOH on SnO2/C in presence of alkali metal cations(Li^+,Na^+,K^+,Rb^+and Cs^+)and anions(HCO3^-,Cl^-,Br^-and I^-)

It is well-known that the electrolytes can influence the electrochemical reduction of carbon dioxide(ERCO2)in aqueous media.In this work,we explore the effects of alkali metal cations and anions(Li^+,Na^+,K^+,Rb^+,Cs^+,HCO3^-,Cl^-,Br^-,I^-)on the current density and product selectivity for the ERCO2 into formic acid(HCOOH)on the SnO2/carbon paper(Sn O2/C)electrode.Results of the ERCO2 experiments show that for the cations,the promotion effects on current density and faradaic efficiencies(FEs)are in the order of Li^+b Na^+b K^+b Cs^+b Rb^+.For the anions,the current density values are in the order of Na HCO3 b NaClb Na Br b Na I and KHCO3 b KCl≈KI b KBr,respectively,and that on the FEs for the formation of the HCOOH(FEHCOOH)is HCO3-b Cl-b Br-b I-.Based on this result,the effects of alkali metal cations and anions on ERCO2 are discussed.

A guide to use fluorinated aromatic bulky cations for stable and high-performance 2D/3D perovskite solar cells:The more fluorination the better?

While serious stability issues impede the commercialization of perovskite solar cells(PSCs),two-dime nsional(2D)perovskites based on fluorinated bulky cations have emerged as more intrinsically stable materials.However,the influence of fluorination degree of the bulky aromatic cation on the per-formance of resulting PSCs has not been scrutinized.Here,2D perovskites(FxPEA)_(2)PbI_(4)(x=1,2,3,5)are grown in situ on the surface of the three-dime nsion al(3D)perovskite and dem on strate effective passivation of the surface defects of 3D perovskite.The power conversion efficiency(PCE)of the optimized devices were boosted from 20.75%for the control device to 21.09%,22.06%,22.74%and 21.86%for 2D/3D devices treated with 4-fluorophenethylamine iodide,3,5-difluorophenylethylamine iodide,2,4,5-trifluoroethylphenylethylamine iodide,and 1,2,3,4,5-pentafluorophenylethylamine iodide,respectively.We firstly reported two unexplored RP-type layered perovskites with F_(2)PEAI and F_(3)PEAI as bulky cations.The combined experimental and theoretical analysis revealed the reasons behind the various morphology,device performances,dynamic behavior,and humidity stability.The best performing F_(5)PEAI-treated device retaining 95.0%of its initial PCE under ambient atmosphere(with RH of 60%±5%)without encapsulation for 300 h storage.This work provides useful guidance for selecting fluorinated bulky cations with different molecular electronic properties,which will play an essential role in further improving the performance/stability of PSCs for the sake of further commercialization.

A modified analytical model of the alkali-metal atomic magnetometer employing longitudinal carrier field

Alkali-metal atomic magnetometers employing longitudinal carrier magnetic field have ultrahigh sensitivity to measure transverse magnetic fields and have been applied in a variety of precise-measurement science and technologies.In practice,the magnetometer response is not rigorously proportional to the measured transverse magnetic fields and the existing fundamental analytical model of this magnetometer is effective only when the amplitudes of the measured fields are very small.In this paper,we present a modified analytical model to characterize the practical performance of the magnetometer more definitely.We find out how the longitudinal magnetization of the alkali metal atoms vary with larger transverse fields.The linear-response capacity of the magnetometer is determined by these factors:the amplitude and frequency of the longitudinal carrier field,longitudinal and transverse spin relaxation time of the alkali spins and rotation frequency of the transverse fields.We give a detailed and rigorous theoretical derivation by using the perturbation-iteration method and simulation experiments are conducted to verify the validity and correctness of the proposed modified model.This model can be helpful for measuring larger fields more accurately and configuring a desirable magnetometer with proper linear range.