啤酒酵母生理代谢过程中钠、钾、镁、钙离子含量变化的跟踪检测

采用空气-乙炔火焰原子吸收光谱法分别测定了啤酒酵母发酵液中的Na^ 、K^ 、Mg^2 、Ca^2 离子动态变化中的含量,用La^3 盐消除P对Ca^3 的干扰,以Sr^2 盐作为Na^ 、K^ 的消电离剂。本实验室采用配制培养基,通过对不同种类及不同发酵阶段培养的发酵液样品进行测定,以研究在啤酒酵母生长代谢过程中Na^ 、K^ 、Mg^2 、Ca^2 离子代谢动态变化。方法的Na^ 、K^ 、Mg^2 、Ca^2 相对标准偏差(RSD)分别为0．31％,0．73％。1．78％,0．28％;样品加标回收率为98％-107％;检出限：Na^ 为0．159mg／L,K^ 为0．789nag／L,Mg^2 为0．039mg／L,Ca^2 为0．029mg／L。该方法简便快速,具有很好的精密度。     

离子电极电位滴定法研究钙与钙调素结合平衡及其应用

利用钙离子与钙调素(CaM)有4个结合位点的特点,以钙离子选择电极络合电位滴定法测定了Ca2+与CaM络合反应的滴定终点,用滴定终点时Ca2+的准确浓度,结合cCa2＋＝4cCaM计算得到CaM浓度。此方法一般可估算低至5×10-6mol／L的钙调素浓度。所求钙调素浓度与凯氏定氮法测定的结果一致。采用此方法测量钙调素浓度具有用量少、方法简便、准确性高的优点。     

Comprehensive study on the solvation of mono- and divalent metal cations: Li+, Na+, K+, Be2+, Mg2+ and Ca2+

Hydration of mono- and divalent metal ions (Li(+), Na(+), K(+), Be(2+), Mg(2+) and Ca(2+)) has been studied using the DFT (B3LYP), second-order M?ller-Plesset (MP2) and CCSD(T) perturbation theory as well as the G3 quantum chemical methods. Double-zeta and triple-zeta basis sets containing both (multiple) polarization and diffuse functions were applied. Total and sequential binding energies are evaluated for all metal-water clusters containing 1-6 water molecules. Total binding energies predicted at lower levels of theory are compared with those from the high level G3 calculations, whereas the sequential binding energies are compared with available experimental values. An increase in the quality of the basis set from double-zeta to triple-zeta has a significant effect on the sequential binding energies, irrespective of the geometries used. Within the same group (I or II), the sequential binding energy predictions at the MP2 and B3LYP vary appreciably. We noticed that, for each addition of a water molecule, the change of the M-O distance in metal-water clusters is higher at the B3LYP than at the MP2 level. The charge of the metal ion decreases monotonically as the number of water molecules increase in the complex.     

Theoretical study of interaction of 2,6-dithiopurine with Li+, Na+, K+, Be2+, Mg2+, and Ca2+ metal cations

The geometries of the complexes of Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ metal cations with different possible 2,6-dithiopurine anions (DTP) were studied. The complexes were optimized at the B3LYP level and the 6-311++G(d, p) basis set. The interactions of the metal cations at different nucleophilic sites of various possible 2,6-dithiopurine anions were considered. It was revealed that metal cations would interact with 2,6-dithiopurine anions in a bicoordinate manner. In the gas phase, the most preferred position for the interaction of Li⁺, Na⁺, and K⁺ cations is between the N₃ and S₂ sites, while all divalent cations Be²⁺, Mg²⁺, and Ca²⁺ prefer binding between the N₇ and S₆ sites of the corresponding 2,6-dithiopurine. The influence of aqueous solvent on the relative stability of different complexes has been examined using the Tomasi’s polarized continuum model. The basis set superposition error (BSSE) corrected interaction energy was also computed for complexes. The AIM theory has been applied to analyze the properties of the bond critical points (electron densities and their Laplacians) involved in the coordination between 2,6-dithiopurine anions and the metal cations. It was revealed that aqueous solution would have significant effect on the relative stability of complexes obtained by the interaction of 2,6-dithiopurine anions with Mg²⁺ and Ca²⁺ cations. The effect of metal cations on different NH and CS stretching vibrational modes of 2,6-dithiopurine has also been discussed.     

ESR investigation on the phase transitions of DPPC vesicles in presence of high concentrations of Li+, Na+, K+ and Cs+

The partition of the spin label TEMPO in the hydrophobic region of di-palmitoyl-phosphatidylcholine unilamellar vesicles has been used to investigate the influence of high concentration (up 3M) of Li⁺, Na⁺, K⁺, and Cs⁺ on the phase transitions at 20–60°C. All of the above salts increase the permeation of TEMPO. The efficiency of monovalent cations in inducing the partition of the spin label in the hydrophobic environment of the bilayer increases in the order: Cs⁺+++. The disappearing of the pretransition and the downward shift of the main phase transition temperature from 37°C to 33.5°C is related to the increased permeation of TEMPO into the bilayer. The presence of salts in the bulk solution disturbs the hydration of the zwitterionic polar head of the DPPC molecules and changes the electrical interaction between the polar groups of the bilayer. This reduces the packing density of the lipid molecules and promotes the permeation of TEMPO.     

Redox Hyperactive MOF for Li+, Na+ and Mg2+ Storage

To create both greener and high-power metal-ion batteries, it is of prime importance to invent an unprecedented electrode material that will be able to store a colossal amount of charge carriers by a redox mechanism. Employing periodic DFT calculations, we modeled a new metal-organic framework, which displays energy density exceeding that of conventional inorganic and organic electrodes, such as Li- and Na-rich oxides and anthraquinones. The designed MOF has a rhombohedral unit cell in which an Ni(II) node is coordinated by 2,5-dicyano-p-benzoquinone linkers in such a way that all components participate in the redox reaction upon lithiation, sodiation and magnesiation. The spatial and electronic changes occurring in the MOF after the interaction with Li, Na and Mg are discussed on the basis of calculated electrode potentials versus Li⁰/Li⁺, Na⁰/Na⁺ and Mg⁰/Mg²⁺, respectively. In addition, the specific capacities and energy densities are calculated and used as a measure for the electrode applicability of the designed material. Although the highest capacity and energy density are predicted for Li storage, the greater structural robustness toward Na and Mg uptake suggests a higher cycling stability in addition to lower cost. The theoretical results indicate that the MOF is a promising choice for a green electrode material (with <10% heavy metal content) and is well worth experimental testing.     

Ionophoric properties of atropine: complexation and transport of Na+, K+, Mg2+ and Ca2+ ions across a liquid membrane

The activity of atropine on the complexation and transport of Na(+), K(+), Mg(2+) and Ca(2+) ions across a liquid membrane was investigated using a spectrophotometric method. Atropine is a natural drug that blocks muscarinic receptors. It is a competitive antagonist of the action of acetylcholine and other muscarinic agonists. Atropine is shown to extract Na(+), K(+), Mg(2+) and Ca(2+) ions from an aqueous phase into an organic one with a preference for Ca(2+) ions. According to a kinetic study, divalent cations (Mg(2+) and Ca(2+)) are more rapidly transported than monovalent ones (Na(+) and K(+)). In both complexation and transport, the flux of the ions increases with the increase of atropine concentration. Atropine might act on the membrane permeability; its complexation and ionophoric properties shed new lights on its therapeutic properties.     

Napthaquinone derived ionophores: interaction with biologically important metal ions (Li+, Na+, K+, Mg2+ and Ca2+)

The synthetic model systems based on the study of supramolecular compounds are proficient in mimicking the biological processes so as to get the insight of their processes. In this perspective, a series of naphthaquinone derived redox switchable ionophores namely D₁ (2,3,5,6,8,9,11,12-octahydronaphtho [2,3b] [1,4,7,10,13] pentaoxacyclo octadecine-14,19-dione) and D₂ (2,3,5,6,8,9-hexahydronaphtho[2,3-b] [1,4,7,10] tetraoxacyclododecine-11,16-dione) have been synthesized and interacted with Li⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺ cations. The isolated solid state soft materials obtained after interaction were characterized by melting point, TLC, ¹H NMR spectroscopy and CHN estimation. The extraction, transport potential and stability constant determination of these ionophores towards cations helped in investigating their binding strength in solution. The selective extraction of Na⁺ and Li⁺ by D₁ and D₂ correspondingly proves them an efficient compound for the manufacturing of chemosensor. Whereas efficient transport of Mg²⁺ by both the ionophores especially by D₁ may assist in developing biomodels for understanding its transport through membrane in living system. The selectivity of these ionophores towards metal ions can be modulated by molecular tailoring.     

Transport of Ca2+, Sr2+, Ba2+, Na+, K+ and Cs+ through hollow fiber supported liquid membrane

The transport of metal ions (Ca²⁺, Sr²⁺, Ba²⁺, Na⁺, K⁺, Cs⁺) through hollow fiber supported dichlorobenzene liquid membrane has been studied. The transport of cations using 8-crown-6 ether as a carrier and picrate as co-counter ion as well as a pertraction device and capillary isotachophoresis (ITP) measurement of the cation concentration is described.     

金属离子(Na~+、K~+、Ca~(2+)、Mg~(2+)、Zn~(2+))与鸟嘌呤异构体配合物的稳定性

在B3LYP/6-311++G**水平上用极化连续介质模型(PCM)系统研究了金属离子(M+/2+=Na+,K+,Ca2+,Mg2+,Zn2+)和十三种鸟嘌呤异构体形成的配合物GnxM+/2+(n为鸟嘌呤异构体的编号,x表示M+/2+与鸟嘌呤异构体的结合位点)在气(g)液(a)两相中的稳定性顺序.着重探讨了液相中配合物的稳定性差异,并且从溶质-溶剂效应、结合能、形变能及异构体的相对能量等几个方面分析了造成稳定顺序发生变化的原因.报道了溶液中这五种金属离子与鸟嘌呤异构体结合形成的六种基态配合物:aG1N2,N3Na+,aG1N2,N3K+,aG1O6,N7Ca2+,aG1N2,N3Mg2+(aG1O6,N7Mg2+),aG2N3,N9Zn2+.可以看出,除了在Zn2+配合物中鸟嘌呤异构体为G2外,构成其余四种金属离子配合物的鸟嘌呤异构体都是G1,但结合位点不同.同时对气相中各类配合物稳定性也进行了系统的排序,并报道了几种较稳定的配合物,如:gG3N1,O6K+,gG5N1,O6K+,gG3N1,O6Ca2+/Mg2+,gG4O6,N7Ca2+/Mg2+.     

Neutral carrier-based Na+-selective electrode for application in blood serum

The ionophore N,N,N,N-tetracyclohexyl-1,2-phenylenedioxydiacetamide (4) shows higher lipophilicity and superior Na⁺/K⁺ selectivity than the previously described N,N-dibenzyl-N,N-diphenyl-1,2-phenylenedioxydiacetamide (2). It is a suitable component of Na⁺-selective liquid membrane electrodes for the assay of Na⁺ in clinical analysers.On leave from Hitachi Ltd., Central Research Laboratory, Kokubunji, Tokyo 185, Japan.     

电感耦合等离子体发射光谱（ICP-OES）法测定石灰性土壤中交换性盐基K+、Na+、Ca2+、Mg2+

石灰性土壤的交换性盐基常规检测方法过程手续繁琐、消耗乙醇量大、交换液过滤淋洗定容至250 mL容量瓶耗时过长。通过改变取样量和氯化铵-乙醇交换液的比例关系,选择合适的震荡时间,一次性交换完全,直接干过滤部分提取液到25 mL比色管中,再将滤液转移至聚四氟乙烯烧杯中,电热板加热挥发掉乙醇,用盐酸提取,使得乙醇体系转换为盐酸体系。该方法减少了乙醇的用量、缩短了前处理时间、解决了等离子体引入有机物熄火的问题,建立了电感耦合等离子体发射光谱（ICP-OES）法直接测定石灰性土壤盐基K+、Na+、Ca2+、Mg2+的方法。选用4个石灰性土壤有效态国家一级标准物质按照本方法进行处理,测定结果均在认定值的误差范围内;采用8个全国第三次土壤普查实际样品与标准方法进行比对实验,各组分检测结果无显著差异。各元素的光谱强度在0～100 μg/ mL浓度范围内呈良好的线性关系,相关系数（r）均在0.999 9以上,方法检出限值为0.004～0.015 cmol/kg,相对标准偏差RSD（n=12）为0.74 %～8.52 %。满足第三次全国土壤普查全程质量控制规范中对石灰性土壤基盐检测质量技术要求。     

Simultaneous Determination of Na+, K+, Ca2+, Mg2+ and Cl− in Unstimulated and Stimulated Human Saliva Using All Solid State Multisensor Platform

Human saliva is one of the body fluids which collection method is relatively simple and non‐invasive. The article is dedicated to assess concentration (activity) of Na⁺, K⁺, Ca²⁺, Mg²⁺ and Cl⁻ in fresh, unstimulated or stimulated human saliva samples using single solid contact ion‐selective electrodes with conventional reference electrode and self‐made multisensor platform (MP) equipped with ion‐selective membranes for Na⁺, K⁺, Ca²⁺, Mg²⁺ and Cl⁻ and reference electrode made in solid state technology, based on dispersed KCl in the polymer. Both kind of electrodes, single ISE and miniaturized electrodes in multisensor platform (ISE‐MP) were made of glassy carbon. The electrode surfaces have been modified by conductive polymer (PEDOT) layer deposition; with the exception of Cl⁻ electrode, in which conducting polymer was not applied. Potentiometric measurements were used to compare the changes of the ionic composition in various samples of saliva.     

天然水中钙镁离子的测定

对Ｃａ２＋、Ｍｇ２＋在含２×１０３ｍｏｌ／ＬＥＤＴＡ和１５×１０２ｍｏｌ／Ｌ硼砂载体溶液中的毛细管电泳行为进行了讨论,并在２００ｎｍ、３５℃、２０ｋＶ的优化条件下,５ｍｉｎ内对天然水中的Ｃａ２＋、Ｍｇ２＋离子进行了同时定量,为分析水质硬度提供了一种高效、快速的测定方法。     

Computational study of the interaction of metal ions (Na+, K+, Mg2+, Ca2+, and Al3+) with Quercetin and its antioxidant properties

In recent years, the chelation between quercetin and transition metals has attracted much attention because the complexes formed have higher antioxidant and medicinal activities. However, the theoretical investigation of the mechanisms of flavonoid functioning along with the structures of quercetin–metal complexes is still not sufficiently studied. In this research work, quercetin–complexes with Na⁺, K⁺, Mg²⁺, Ca²⁺, and Al³⁺ are studied theoretically by using density functional theory (DFT) method in order to investigate the stability, reactivity, nature of interaction, and the application of the quercetin-metal complexes as potential antioxidants. From the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) results, the K-quercetin salt was observed to be more stable as compared to the other metals while Ca seemed to be the most reactive with the least values in the neutral form of the metal - quercetin interaction. The results of the antioxidant activity in the neutral state present Ca and Mg to have the higher values of ionization potential (IP) indicating that the antioxidant activity of Ca/Mg complexes with quercetin are less pronounced, while K-complex with the least value indicating the higher the electron donating reactivity. In comparison, it is worth to note that Mg-Q and Ca-Q in the deprotonated state of quercetin showcase lower IP, higher ability of H-atom transfer and electron transfer reactivity, therefore, better antioxidant candidates of the quercetin complexes than their other counterparts.     

Effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water coordination on the structure of glycine and zwitterionic glycine

Interactions between metal ions and amino acids are common both in solution and in the gas phase. Here, the effect of metal ions and water on the structure of glycine is examined. The effect of metal ions (Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) and water on structures of Gly.Mn+(H2O)m and GlyZwitt.Mn+(H2O)m (m = 0, 2, 5) complexes have been determined theoretically by employing the hybrid B3LYP exchange-correlation functional and using extended basis sets. Selected calculations were carried out also by means of CBS-QB3 model chemistry. The interaction enthalpies, entropies, and Gibbs energies of eight complexes Gly.Mn+ (Mn+ = Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) were determined at the B3LYP density functional level of theory. The computed Gibbs energies DeltaG degrees are negative and span a rather broad energy interval (from -90 to -1100 kJ mol(-1)), meaning that the ions studied form strong complexes. The largest interaction Gibbs energy (-1076 kJ mol(-1)) was computed for the NiGly2+ complex. Calculations of the molecular structure and relative stability of the Gly.Mn+(H2O)m and GlyZwitt.Mn+(H2O)m (Mn+ = Li+, Na+, K+, Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+; m = 0, 2, and 5) systems indicate that in the complexes with monovalent metal cations the most stable species are the NO coordinated metal cations in non-zwitterionic glycine. Divalent cations Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+ prefer coordination via the OO bifurcated bonds of the zwitterionic glycine. Stepwise addition of two and five water molecules leads to considerable changes in the relative stability of the hydrated species. Addition of two water molecules at the metal ion in both Gly.Mn+ and GlyZwitt.Mn+ complexes reduces the relative stability of metallic complexes of glycine. For Mn+ = Li+ or Na+, the addition of five water molecules does not change the relative order of stability. In the Gly.K+ complex, the solvation shell of water molecules around K+ ion has, because of the larger size of the potassium cation, a different structure with a reduced number of hydrogen-bonded contacts. This results in a net preference (by 10.3 kJ mol(-1)) of the GlyZwitt.K+H2O5 system. Addition of five water molecules to the glycine complexes containing divalent cations Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+ results in a net preference for non-zwitterionic glycine species. The computed relative Gibbs energies are quite high (-10 to -38 kJ mol(-1)), and the NO coordination is preferred in the Gly.Mn+(H2O)5 (Mn+ = Mg2+, Ca2+, Ni2+, Cu2+, and Zn2+) complexes over the OO coordination.     

Al3+, Ca2+, Mg2+, and Li+ in aqueous solution: calculated first-shell anharmonic OH vibrations at 300 K

The anharmonic OH stretching vibrational frequencies, ν(OH), for the first-shell water molecules around the Li(+), Ca(2+), Mg(2+), and Al(3+) ions in dilute aqueous solutions have been calculated based on classical molecular dynamics (MD) simulations and quantum-mechanical (QM) calculations. For Li(+)(aq), Ca(2+)(aq), Mg(2+)(aq), and Al(3+)(aq), our calculated IR frequency shifts, Δν(OH), with respect to the gas-phase water frequency, are about -300, -350, -450, and -750?cm(-1), compared to -290, -290, -420, and -830?cm(-1) from experimental infrared (IR) studies. The agreement is thus quite good, except for the order between Li(+) and Ca(2+). Given that the polarizing field from the Ca(2+) ion ought to be larger than that from Li(+)(aq), our calculated result seems reasonable. Also the absolute OH frequencies agree well with experiment. The method we used is a sequential four-step procedure: QM(electronic) to make a force field+MD simulation+QM(electronic) for point-charge-embedded M(n+) (H(2)O)(y) (second?shell) (H(2)O)(z) (third?shell) clusters+QM(vibrational) to yield the OH spectrum. The many-body Ca(2+)-water force-field presented in this paper is new. IR intensity-weighting of the density-of-states frequency distributions was carried out by means of the squared dipole moment derivatives.     

Correlated ab initio quantum chemical study of the interaction of the Na+, Mg2+, Ca2+, and Zn2+ ions with the tautomers of cytosine

The interaction of the metal ions Na(+), Mg(2+), Ca(2+), and Zn(2+) with cytosine have been reinvestigated at the density functional, M?ller-Plesset, and coupled cluster levels of theory, including hitherto unstudied tautomeric forms. It has been found that the interaction of the metal ion has a varying and often significant effect on the stabilities of the various tautomers, in some cases making most stable rare tautomeric forms. The results have been analyzed with respect to method and role of ion in binding, and confirm that, as has been found for the base cytosine tautomers, B3LYP does not give energetics consistent with highly accurate post-SCF methods for their interaction with these metal ions.