介体溶剂在碱金属PVC膜离子电极中选样性的研究

考察了不同介溶剂(苯基膦酸二正辛酯, 磷酸三丁酯, 硝基苯, 邻硝基苯正辛醚, 邻苯二甲酸二辛酯癸二酸二丁酯)的四苯硼酸盐PVC膜对碱金属离子的选择性, 探讨了不同介体溶剂的膜对选择性的影响. 所得结论与实验结果一致. 也就是硝基芳香族化合物介体溶剂适用于大半径碱金属离子, 而膦酸酯类介体溶剂适用于具有小离子半径的碱金属离子.     

Triton X-100推动碱金属离子在液/液界面上转移的机制和伏安行为

本文用四电极循环伏安法研究了非离子型表面活性剂Triton X-100推动碱金属离子K^+, Na^+等在水/硝基苯, 水/1,2-二氯乙烷界面上的转移过程, 根据实验结果提出Triton X-100推动金属离子转移的一种机制, 推导了转移半波电位方程式, 并用实验进行了验证。     

Liquid-liquid extraction of some lanthanide metal ions by polyoxyalkylene systems

Polyoxyalkylene systems, namely, polypropylene glycol (PPG-1025), polyethylene glycol (PEG-600) and polybutadieneoxide (PBDO-700) dissolved in either nitrobenzene or 1,2-dichloroethane have been tested as prospective extractants for some lanthanide metal ions (Eu(3+), Pr(3+) and Er(3+)) from their aqueous solutions in the presence of picrate anions. The metal ions were quantified before and after extraction using the inductively coupled plasma emission spectrophotometry technique. The percent extraction and the distribution coefficients have indicated that pH of the aqueous phase, picrate concentration and the organic solvent are the major parameters that affect the extraction efficiency of the metal ions. The optimum pH range was found to be 3.5-5.5 and the picrate concentration should be as high as possible; however, a picrate concentration of about 0.05 M proved to be adequate for a near quantitative extraction. In all cases, nitrobenzene enhanced a higher percent extraction compared to 1,2-dichloroethane. The efficiency of the polyoxyalkylene systems to extract certain lanthanide metal ions was in the order PBDO-700>PPG-1025>PEG-600 when nitrobenzene was the organic solvent and in the order PPG-1025>PBDO-700 approximately PEG-600 when 1,2-dichloroethane used as the solvent in the organic phase. The extractability of PPG-1025 towards the lanthanide metal ions was in the order Pr(3+)>Eu(3+)>Er(3+) irrespective of the organic solvent used. The stoichiometry of the extracted polyoxyalkylene ion-pairs with the lanthanide metal ions has been estimated. Each mole of metal ions is associated with three moles of picrate anions and 13 to 14 moles of propyleneoxide units in the case of PPG-1025, and about 9 to 10 moles of ethyleneoxide units in the case of PEG-600 and 10 moles of butadieneoxide units in the case of PBDO-700.     

Liquid-liquid extraction of iron(III) and gallium(III) with macrocyclic Schiff bases containing bisphenol A subunits

The quantitative extraction of iron(III) and gallium(III) was investigated with the recently synthesized macrocyclic Schiff base containing bisphenol A subunits. The phenol groups in the Schiff base moiety led to a large increase in the percent extraction of trivalent metal ions. The substitution of methoxy groups for phenolic OH ligands resulted in a marked decrease in the extractability of metal ions, and no iron(III) was extracted. The corresponding acyclic Schiff base was found to have a reasonable reactivity toward metal ions and a better solubility in organic solvents. The iron(III) and gallium(III) complexes with macrocyclic and acyclic Schiff bases were quantitatively extracted into nitrobenzene without the presence of bulky counter anions. A single extraction gave a good separation of iron(III) from iron(II) in the mole ratios 4:1 to 1:3. The red iron(III) complexes can be used for the extraction-spectrophotometric determination of iron(III). The apparent molar absorptivity at 518 nm is 5.43 × 10³lmol⁻¹ cm⁻¹.     

Determination of thallium(I) in solutions containing cations interfering in potentiometric ion-pair formation-based titrations

The possibility of the use of simple potentiometric coated-wire sensors in the analysis of mixtures of ions, the determination of which is based on the ion-pairing principle, was studied. Attention was especially paid on the determination of thallium(I) in the presence of alkali metal ions, mercury(II), copper(II) and silver(I). It was found that thallium(I) can selectively be titrated with sodium tetraphenylborate in diluted solutions. Interferences of ions of the alkali metals are practically negligible if their concentrations are lower than 10(-3) mol dm(-3). Interference of Cu(II) is minimized using EDTA as a masking agent, Hg(II) and Ag(I) ions are sufficiently screened by additions of sodium cyanide. In mixtures containing higher concentrations of alkali metals, thallium(I) can be oxidized to thallium(III) and selectively titrated as TlCl(-)(4) with a cationic titrant.     

Substoichiometric separation in activation analysis: extraction of co-ordinatively-unsolvated salts

The necessary conditions have been examined for the use of extraction of coordinatively-unsolvated salts for substoichiometric separations in activation analysis, especially the influence of interfering ions and of the concentration of the carrier. A study has been made of the substoichiometric extraction of halide ions, oxyanions and anionic metal complexes by means of the tetraphenylarsonium ion into chloroform and dichloroethane, and of the extraction of alkali metal ions into nitrobenzene with tetraphenylborate. Substoichiometric extraction can be combined with neutron-activation analysis for the determination of traces of iodine, caesium, rubidium, manganese, rhenium, chromium, thallium, gold, gallium and tantalum.     

Effects of different alkali metal ions on the cationization of poly(ethylene glycol)s in matrix-assisted laser desorption/ionization mass spectrometry: a new selectivity parameter

The cationization of poly(ethylene glycol)s, PEG 4000 and PEG 6000, under matrix-assisted laser desorption/ionization conditions was studied by using different concentration ratios of the sodium ion, as the reference ion, and another alkali metal ion (Li(+), K(+), Rb(+), Cs(+)). A linear correlation was found between the intensity ratio of the sodiated PEGs and PEGs cationized with alkali metal ions versus the initial concentration ratio of sodium and alkali metal ions. The slopes of these straight lines are proposed as a novel selectivity ratio for the ionization process. The intensity distribution of the cationized PEGs was also investigated. It was found that the cationized oligomers follow Poisson statistics. The M(n) and M(w) values were also evaluated. An explanation for the observed effects is given.     

PPb Level Monitoring of Dy(III) Ions by a Highly Sensitive and Selective Dy(III) Sensor Based on a New Asymmetrical Schiff's Base

Abstract

A Dy(III) ion‐selective membrane sensor has been fabricated from polyvinyl chloride (PVC) matrix membrane containing a new asymmetrical Schiff's base [(E)‐N‐(2‐hydroxybenzylidene)benzohydraide] or BBH as a neutral carrier, sodium tetraphenyl borate (NaTPB) as an anionic excluder and nitrobenzene (NB) as a plasticizing solvent mediator. The membrane sensor displays linear potential response in the concentration range of 1.0×10^?2–1.0×10^?6 M of Dy(III). The electrode exhibits a nice Nernstian slope of 20.1±0.8 mV/decade in the pH range of 3.0–8.0. The sensor has a relatively short response time in whole concentration ranges (<20 s). The detection limit of the proposed sensor is 8.0×10^?7 M (～128 ng/mL), and it can be used over a period of six weeks. The selectivity of the proposed sensor with respect to other cations, (alkali, alkaline earth, transition and heavy metal ions) and especially lanthanid ions, is excellent. The practical utility of the sensor has been demonstrated by using it as an indicator electrode in the potentiometric titration of Dy(III) with EDTA.     

The transfer of alkali metal ions across the water-nitrobenzene interface facilitated by neutral macrocyclic ionophores

The alkali metal ions transfer from water to the nitrobenzene phase containing macrocyclic neutral ionophores (crown polyethers, nonactin) has been investigated, applying the electrolysis at the interface of two immiscible electrolyte solutions (ITIES) in the single-sweep voltammetry mode. The stability constants of complexes formed in the non-aqueous phase have been determined from the peak voltammograms, as well as value of complex formation enthalpy. It has been concluded that the facilitated ion transfer in the temperature range 5–65°C is a diffusion-controlled process.     

Functions of Acyclic Poly(ethylene Oxide) Homologs: Acceleration of Nucleophilic Reactions and Selective Ion Transport through Membranes

The acceleration effect of poly(ethylene oxide) on nucleophilic reactions was investigated. The enhancement of the reaction rate was interpreted by the cooperative solvation of alkali metal ions with ethereal oxygens of PEO resulting in active nucleophilic anions. In relation to the complex formation of alkali metal ions with PEO, the oligo(ethylene oxide) derivatives were prepared as the synthetic ionophores, which were able to transport alkali metal ions selectively through a liquid membrane against the alkali metal ion concentration.     

Prussian Blue-coated interdigitated array electrodes for possible analytical application

Thin films of iron(III) hexacyanoferrate(II) (Prussian Blue) were electrochemically deposited on interdigitated array (IDA) electrodes, yielding systems which can be considered as chemiresistors in sensing alkali metal ion concentrations in an adjacent electrolyte. This is due to the fact that the conductivity of the film being measured by a steady-state current on application of a voltage to the two-fingered electrodes of the IDA depends on both the redox stare of the film and the cation concentration in the electrolyte. From the dependence of the steady-state current on the electrode (bias) potential at variable cation concentrations for different alkali metal ions and for mixtures of alkali metal ions, the possibilities of analytical application were elucidated. In addition, by using the methods of staircase coulometry and scanning conductivity, the electron diffusion coefficient D_e was determined as a function of the redox state of Prussian Blue. It is concluded that Prussian Blue-coated IDA electrodes are, in principle, suitable as chemiresistors for the determination of alkali metal ion concentrations with increasing selectivity in the series Li < Na < K < Rb < Cs.     

Chiroptical spectra of a series of tetrakis((+)-3-heptafluorobutylyrylcamphorato)lanthanide(III) with an encapsulated alkali metal ion: circularly polarized luminescence and absolute chiral structures for the Eu(III) and Sm(III) complexes

The luminescence and circularly polarized luminescence (CPL) spectra of M(I)[Eu((+)-hfbc)(4)] show a similar behavior to the exciton CD in the intraligand π-π* transitions when the alkali metal ions and solvents are manipulated. There is a difference in susceptibility in solvation toward the alkali metal ions but not toward the Eu(III) ion, as in the case of axially symmetric DOTA-type compounds. The remarkable CPL in the 4f-4f transitions provide much more information on the stereospecific formation of chiral Eu(III) complexes, since CPL spectroscopy is limited to luminescent species and reflects selectively toward helicity of the local structural environment around the lanthanide(III). While in comparison, exciton CD reveals the chiral structural information from the helical arrangement of the four bladed chelates. Of special importance, the observation of the highest CPL activities measured to date for lanthanide(III)-containing compounds (i.e., Eu and Sm) in solution supports the theory that the chirality of lanthanide(III) in the excited state corresponds to that in the ground state, which was derived from the exciton CD.     

Membrane transport of metal ions with lipophilic aminomethylphosphine oxides

The processes of membrane transport of ions of scandium(III), samarium(III), gadolinium(III), neodymium(III), aluminum(III), and a number of alkali and alkaline earth metals through liquid membrane impregnated with aminophosphoryl carriers of different structures were studied. Selectivity of bis (dialkylphosphinyl)amines towards scandium was found to be significantly higher than the selectivity of diphosphinylpiperazine and monophosphinylamine in particular. The dependence of transfer efficiency on the concentration of substrates and carriers was revealed. Optimal conditions for transporting rare and trace metal ions through the membrane were found, and the mechanism of transmembrane transport was discussed.     

Effect of alkali metal ions on the intrazeolitic migration of Tb(III) ions in zeolite Y

The luminescence spectra of TbLi-Y, TbNa-Y and TbK-Y zeolites treated at different temperatures are reported. It is found that the intrazeolitic migration temperature of Tb(III) ions to hexagonal prisms is influenced by the type of the alkali metal ion present together with Tb(III) to neutralize the negative framework of zeolite Y.     

Alkali Metal Adducts of Aromatic Nitro Compounds—Reactions and Use in Polymerization of Vinyl Monomers

Abstract

The reaction of alkali metals with nitrobenzene and p-nitro-toluene in THF at various molar ratios was found to lead to the formation of radical ions, dianions, and alkali metal adducts of reduction derivatives of the nitro compounds such as azo- and azoxybenzene. The anionic polymerization of styrene, methyl methacrylate, methacrylonitrile, and acrylo-nitrile by these anions was investigated. All the initiators did not polymerize styrene while the least reactive radical-anion was found to polymerize acrylonitrile completely, methacrylonitrile to a small extent, but not methyl methacrylate.

The order of reactivity of those adducts toward organic halides was similar to that found in polymerization. Metalla-tion of polynitrostyrene by lithium biphenyl solution led only to partial conversion of the nitro groups to radical-anions which were not reactive.     

The Influence of Alkali Metal Ions on Homogeneous Nucleation of Al(OH)(3) Crystals from Supersaturated Caustic Aluminate Solutions

Homogeneous nucleation of Al(OH)(3) crystals from synthetic, optically clear, caustic aluminate solutions and the influence of alkali metal ion (Na(+) versus K(+)) have been investigated under isothermal, batch crystallization conditions. The nucleation kinetics showed a seventh-order dependence upon Al(III) relative supersaturation and a strong temperature effect. Activation energy of 160 kJ mol(-1) and interfacial energy of 33 mJ m(-2) were estimated and found to be independent of alkali ion, as was the Al(OH)(3) equilibrium solubility. The nucleation rate, however, was faster in aging sodium than in potassium aluminate solutions. It appears that Na(+) ions provide greater stability for the formation and densification of Al(III)-containing, supramolecular clusters which grow more rapidly into Al(OH)(3) crystallites than do K(+) ions. The development of the Al-OH octahedral structure of Al(OH)(3) nuclei is an alkali metal ion-mediated, chemical reaction-controlled condensation process, displaying specific gibbsite (gamma-Al(OH)(3))-bayerite (alpha-Al(OH)(3)) dimorphism. Furthermore, significant differences in the level of alkali ion incorporation, reflecting in the purity and morphology of the crystalline product, were observed. Copyright 2000 Academic Press.     

Alkali cation attachment to derivatized fullerenes studied by matrix-assisted laser desorption/ionization

The complexation of alkali metal ions with amphiphilic fullerene derivatives has been investigated by matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry. The formation of analyte ions occurs via two competing mechanisms including electron transfer from matrix-derived ions and metal ion attachment. The interplay of these processes has been examined by laser fluence dependent sample activation and by variation of the target composition. The attachment of metal ions has been established as the gentler and thus more efficient route towards the formation of intact analyte ions. Investigations into the metal ion complexation have been conducted to reveal the reactivity order of the alkali metals in these reactions and to elucidate the influence of structural differences of the analytes, as well as to unravel effects caused by the anionic counter ion of the metal. The experimental data have been derived by two complementary approaches. Competing reactants were either studied simultaneously, so that the product distribution would provide direct insight into the reactivity pattern, and/or product distributions were obtained in a large variety of separate experiments and normalized for reliable comparison. It has been found that the extent to which complexation is observed follows the charge density order of the alkali metal ions. The structural features of the fullerene-attached ligands were of profound influence on the attachment of the metal ion, inducing enhanced selectivity for the complexation with less reactive metals. The metal ion attachment is reduced with the use of smaller anionic counter ions. Rationalization of these findings is provided within the framework of the mechanisms of ion formation in MALDI.     

Synthesis of N'-(1-pyridin-2-ylmethylene)-2-furohydrazide and its application in construction of a highly selective PVC-based membrane sensor for La(III) ions.

A highly La(III) ion-selective PVC membrane sensor based on N'-(1-pyridin-2-ylmethylene)-2-furohydrazide (NPYFH) as an excellent sensing material was successfully developed. The electrode shows a good selectivity for La(III) ion with respect to most common cations including alkali, alkaline earth, transition and heavy metal ions. The proposed sensor exhibits a wide linear response with slope of 19.2 +/- 0.6 mV per decade over the concentration range of 1.0 x 10(-6) - 1.0 x 10(-1) M, and a detection limit of 7.0 x 10(-7) M of La(III) ions. The sensor response is independent of pH in the range of 3.5-10.0. The proposed electrode was applied as an indicator electrode in potentiometric titration of La(III) ion with EDTA.     

阳离子交换色谱中色谱柱温度对碱金属与碱土金属离子保留的影响

研究了非抑制型阳离子交换色谱中色谱柱温度(25~50℃)对碱金属离子(Li+、Na+、K+、Rb+)和碱土金属离子(Mg2+、Ca2+、Sr2+)以及NH4+保留的影响。在Shim-pack IC-C1磺酸型阳离子交换柱上,以硝酸为流动相分离碱金属离子,以乙二胺或乙二胺-草酸(柠檬酸)为流动相分离碱土金属离子,随着色谱柱温度的升高,碱金属和碱土金属离子的保留时间均增长,其范特霍夫曲线具有良好的线性关系,斜率为负值,表明在此条件下碱金属和碱土金属离子的保留为吸热过程。在Shim-pack IC-SC1羧酸型阳离子交换柱上,以硫酸为流动相同时分离碱金属和碱土金属离子,随着色谱柱温度的升高,Mg2+、Ca2+的保留时间增长,而K+、Rb+的保留时间缩短,Li+、Na+、NH4+的保留时间基本不变。在此条件下,Mg2+、Ca2+、K+和Rb+的范特霍夫曲线具有良好的线性关系,其中Mg2+和Ca2+的曲线斜率为负值,K+和Rb+的曲线斜率为正值,表明Mg2+和Ca2+的保留表现为吸热过程,K+和Rb+的保留表现为放热过程。研究表明在不同固定相和流动相条件下,色谱柱温度对碱金属和碱土金属离子保留行为的影响不同。     

Charge inversion mass spectrometry: dissociation of resonantly neutralized molecules

Charge inversion mass spectrometry is an MS/MS method in which the electric charge of the precursor ions is opposite to that of the secondary product ions. Charge inversion mass spectrometry is classified into four types depending on the electric charge and time scale of collisions. Charge inversion mass spectrometry using collisions with gaseous targets in the keV energy collision range has provided insights into the structures and reactions of ions and neutral molecules. The characteristics of charge inversion experiments are presented in terms of the reaction endothermicities and the cross sections and their dependence on the target species. In the case of rare-gas or simple molecular targets, double-electron transfer in one collision is effective to form positive ions from negative ions, while, in the case of alkali metal targets, successive single-electron transfers in two collisions is effective to form negative ions from positive ions. On the basis of the observed target-density dependence of the product ion intensity and thermochemical considerations for internal energy distribution using thermometer molecules, the charge inversion processes using alkali metal targets have been confirmed to occur by electron transfers in successive collisions and the dissociation processes are found to occur in energy-selected neutral species formed from near-resonant neutralization with alkali metal targets. While collisionally activated dissociation (CAD) is due to dissociation of activated ions with broad internal energy distributions, the charge inversion process using alkali metal targets is due to dissociation of energy-selected neutral species with narrow internal energy distributions. The charge inversion/alkali metal spectra provide clear differentiation of the isomeric cations of C(2)H(2), C(3)H(4) and dichlorobenzenes. The CAD spectra of these isomeric cations are similar.