NMR, UV-vis and CD study on the interaction of pradimicin BMY-28864 with divalent cations of alkaline earth metal

In order to clarify the mechanism of the calcium-activated anti-fungal action of pradimicin derivatives, we investigated the compatibility of four divalent metal cations, Ca2+, Mg2+, Sr2+ and Ba2+, when combined with pradimicin BMY-28864 in an aqueous solution. The 1H NMR studies suggest that all the tested cations can induce a chemical exchange between two types of aggregation of BMY-28864 in an aqueous solution. The exchange rate, however, varies according to the cation species. In descending order they are: Ba2+ > Sr2+ > Ca2+ > Mg2+. The differences in the binding ability of BMY-28864 to the cations and the solubility of the chloride salts are explained by the electronegativity of these cations. The UV-Vis and CD spectra of these solutions show isosbestic points that correspond to an exchange process in the cations' binding to BMY-28864. The results provide experimental support for the hypothesis that there is a common mechanism underlying their cations interactions with the antibiotic. The CD study also provided evidence about the stoichiometric relation of the divalent metal ions to the antibiotic, 1:2, which was obtained by NMR analyses.     

Enhanced aggregation of alginate-coated iron oxide (hematite) nanoparticles in the presence of calcium, strontium, and barium cations

Early-stage aggregation kinetics studies of alginate-coated hematite nanoparticles in solutions containing alkaline-earth metal cations revealed enhanced aggregation rates in the presence of Ca2+, Sr2+, and Ba2+, but not with Mg2+. Transmission electron microscopy (TEM) imaging of the aggregates provided evidence that alginate gel formation was essential for enhanced aggregation to occur. Dynamic light scattering (DLS) aggregation results clearly indicated that a much lower concentration of Ba2+ compared to Ca2+ and Sr2+ was required to achieve a similar degree of enhanced aggregation in each system. To elucidate the relationship between the alginate's affinities for divalent cations and the enhanced aggregation of the alginate-coated hematite nanoparticles, atomic force microscopy (AFM) was employed to probe the interaction forces between alginate-coated hematite surfaces under the solution chemistries used for the aggregation study. Maximum adhesion forces, maximum pull-off distances, and the work of adhesion were used as indicators to gauge the alginate's affinity for the divalent cations and the resulting attractive interactions between alginate-coated hematite nanoparticles. The results showed that alginate had higher affinity for Ba2+ than either Sr2+ or Ca2+. This same trend was consistent with the cation concentrations required for comparable enhanced aggregation kinetics, suggesting that the rate of alginate gel formation controls the enhanced aggregation kinetics. An aggregation mechanism incorporating the gelation of alginate is proposed to explain the accelerated aggregate growth in the presence of Ca2+, Sr2+, and Ba2+.     

二价金属离子对鲑鱼精DNA热稳定性的影响

二价金属离子与 DNA之间的作用在 DNA复制、转录以及新陈代谢过程中起到重要的作用 ,因此越来越受到关注 [1,2 ] .L uck等 [3 ]指出 ,碱土金属与 DNA分子的磷酸基团发生作用使 DNA的热稳定性升高 ,而二价过渡金属离子主要是与碱基作用而使 DNA热稳定性降低 . Eichhorn等 [4 ] 用变温紫外光谱法研究了在 DNA磷酸根离子的浓度较小 (0～ 4.0 )时 ,多种二价金属离子对小牛胸腺 DNA热稳定性的影响 ,发现 Mg2 + 及过渡金属离子 Mn2 + ,Co2 + 和 Ni2 + 都有利于 DNA的稳定 .最近 ,Duguid等 [5]用差示扫描量热法 (DSC)研究了在 c(M2 +…     

Metal ion binding to parvalbumin. A proton NMR study

The 1H NMR spectra of carp parvalbumin saturated with Ca2+, Cd2+, La3+ and Lu3+ were compared, using 2D 1H NMR techniques as well as conventional 1H NMR spectra. The Ca2+ and Cd2+ saturated parvalbumin (with both high affinity Ca2+-binding sites occupied) gave rise to very similar spectra. This shows that these two species have almost identical protein conformations. The 1H NMR spectrum from the Ln3+ saturated parvalbumins deviated from the other two and it was therefore concluded that Cd2+ is a better probe for Ca2+ than Ln3+ in parvalbumin and probably also for related calcium binding proteins. The addition of excess of divalent metal ions, such as Mg2+ or Ca2+, causes small changes in the chemical shift of some methyl resonances. This is presumably caused by binding of these metal ions to a third site close to the CD site which is made up of the carboxylic groups from Glu 60 and Asp 61.     

NMR study of pradimicin derivative BMY-28864 and its interaction with calcium ions in D2O

The dynamic structure of the antifungal antibiotic pradimicin BMY-28864 in D2O and its interaction with calcium ions were analyzed using one- and two-dimensional 1H nuclear magnetic resonance (NMR). Spectra indicate extensive self-association of molecules in the solution. Two-component spectra were observed simultaneously in a very dilute solution, suggesting equilibrium of two aggregative states. The addition of CaCl2 caused a number of changes in NMR spectra. Therefore we concluded that pradimicin BMY-28864 could form a complex with the Ca2+ ion, causing a movement of the equilibrium. The position of the bound calcium ion is determined indirectly by observing how the NMR shift affects protons that are close to the binding site. The stoichiometry of Ca2+ ion to the Pradimicin molecule for the Ca(2+)-saturated complex is verified to be 1:2. Signal broadening and changes in chemical shift in the 1H NMR spectroscopy of BMY-28864 are assumed to be related to changes in the molecular aggregate conformation.     

二元阴离子型丙烯酰胺共聚物在二价金属离子存在下相分离行为的研究

水溶性丙烯酰胺类共聚物 ,作为粘度改性剂 ,在工业上已得到广泛应用 .特别近年来 ,它们大量应用于石油工业强化采油技术 ,引起了人们很大的重视[1] .目前 ,这类用途的聚合物 ,主要在聚丙烯酰胺结构中 ,引入阴离子组分和不断增高产物分子量的方法 ,以提高聚合物溶液粘度和增粘效果 ,然而 ,在二价金属离子 (如Ｃａ2 + ,Ｍｇ2 + 等 )存在下 ,羧酸阴离子型丙烯酰胺类共聚物很容易络合发生沉淀 ,从而失去增粘作用[2 ] .同时这类聚合物中酰胺基不稳定 ,易发生水解反应转化为羧酸基 ,并随温度升高而加剧[3 ] ,因此在温度较高的应用条件下 ,二价金属…     

Effect of divalent cations on DMPC/DHPC bicelle formation and alignment

Many important classes of biomolecules require divalent cations for optimal activity, making these ions essential for biologically relevant structural studies. Bicelle mixtures composed of short-chain and long-chain lipids are often used in solution- and solid-state NMR structure determination; however, the phase diagrams of these useful orienting media and membrane mimetics are sensitive to other solution components. Therefore, we have investigated the effect of varying concentrations of four divalent cations, Ca(2+), Mg(2+), Zn(2+), and Cd(2+), on cholesterol sulfate-stabilized DMPC/DHPC bicelles. We found that low concentrations of all the divalent ions are tolerated with minimal perturbation. At higher concentrations Zn(2+) and Cd(2+) disrupt the magnetically aligned phase while Ca(2+) and Mg(2+) produce more strongly oriented phases. This result indicates that divalent cations are not only required to maintain the biological activity of proteins and nucleic acids; they may also be used to manipulate the behavior of the magnetically aligned phase.     

Determination of total acidity and of divalent cations by ion chromatography with n-hexadecylphosphocholine as the stationary phase

An ion chromatographic (IC) method is reported for simultaneous determination of total acidity (H+), Ba2+, Ca2+, and Mg2+ in aqueous samples. A standard ODS silica column modified by coating with n-hexadecylphosphocholine was used as the separation column. Water alone was used as the eluent, with conductivity detection of the sample ions. An excess of sodium iodide was added to each sample so that both H+ and divalent cations were always eluted with iodide as the counterion. The elution order was Ba2+, Mg2+, Ca2+, and H+ with H+ being eluted much later than the divalent cations. Acetic acid and several other weak acids could also be separated because all the protons were transposed from acetic acid (HAc) to HI by the sodium iodide. Detection limits for 100 microl injection, S/N=3 were in the low micromolar range for the divalent cations and approximately 0.3 mM for H+/I-. This method was used successfully for simultaneous determination of total acidity, magnesium and calcium in HCl-type of hot-spring water.     

Principal component analysis of the absorption and resonance Raman spectra of the metallochromic indicator antipyrylazo III

Metallochromic indicators, whose spectral properties are changed in the presence of metal cations, are used mainly in biological studies to monitor Ca2+ and Mg2+ ions. Antipyrylazo III is such indicator, employed for mid-range Ca2+ concentrations (10-1000 microM). The stoichiometry of the interactions of antipyrylazo III with Ca2+, Mg2+, Ba2+, Sr2+ and Zn2+ ions and the relevant binding constants were studied by principal component analysis (PCA) of the absorption spectral changes. The resonance Raman spectra of the above systems were measured as well, and the resolved Raman spectra of the various species were calculated and assigned. The vibrational spectra are more featured, more characteristic of the binding ions and exhibit stronger relative spectral changes upon binding the cations. The basis sets of Raman spectra could thus be used as an analytical tool for these divalent metallic cations.     

Ionization and collision-induced fragmentation of N-linked and related carbohydrates using divalent cations

Maltoheptaose and several N-linked glycans were ionized by electrospray as adducts with the divalent cations Mg2+, Ca2+, Mn2+, Co2+ and Cu2+. [M + metal]2+ ions were the major species in all cases with calcium giving the highest sensitivity. In addition, copper gave [M + Cu]+ ions. Other cations gave singly charged ions only by elimination of a protonated monosaccharide. Fragmentation of the [M + metal]2+ ions produced both singly and doubly charged ions with the relative abundance of doubly charged ions decreasing in the order Ca > Mg > Mn > Co > Cu. Singly charged ions were formed by elimination of a protonated monosaccharide residue followed, either by successive monosaccharide residue losses, or by a 2,4A cross-ring cleavage of the reducing-terminal monosaccharide. Formation of doubly charged fragments from [M + metal]2+ ions involved successive monosaccharide-residue losses either with or without O,2A or 2,4A cross-ring cleavages of the reducing-terminal monosaccharide. Abundant diagnostic doubly charged ions formed by loss of the 3-antenna from the O,2A cross-ring product were specific to [M + Ca]2+ ions. Fragmentation of [M + Cu]+ ions was similar to that of the corresponding [M + H]+ ions in that most cross-ring fragments were absent.     

Study of Ca-ATMP precipitation in the presence of magnesium ion

ATMP (aminotri(methylenephosphonic acid)), a phosphonate scale inhibitor used in the petroleum industry, was used as a model scale inhibitor in this study. One of the goals of this work was to determine the range of conditions under which Mg ions, which are formed in reservoir formations containing dolomite, modulate the formation of Ca-ATMP precipitate as a scale inhibitor. The results revealed that the amount of ATMP precipitated decreased with addition of Mg ions in solution at all values of the solution pH. Furthermore, an increase in both the solution pH and the concentration of the divalent cations in solution resulted in a change of the molar ratio of (Ca + Mg) to ATMP in the precipitates. At a low solution pH (pH 1.5), Mg ions had little effect on the composition of the Ca-ATMP precipitate. However, at higher values of the solution pH (pH 4 and 7), the Ca to ATMP molar ratio in the precipitates decreased with increasing concentration of the Mg. Here it was found that Mg ions replaced Ca ions on available reactive sites of ATMP molecules. These results determined the limits of the Mg ion concentration, which affects the precipitation of Ca-ATMP, Mg-ATMP, and (Ca + Mg)-ATMP. The dissolution of the scale inhibitors was studied using a rotating disk reactor. These experiments showed that the total divalent cation molar ratio (Ca + Mg) to ATMP in the precipitates is the primary factor that controls the rate of dissolution (release) of the phosphonate precipitates. The phosphonate precipitate dissolution rates decreased as the molar ratio of divalent cations to ATMP in the precipitates increased.     

Theoretical study of interaction of urate with li(+), na(+), k(+), be(2+), mg(2+), and ca(2+) metal cations

The geometries and energetics of complexes of Li(+), Na(+), K(+), Be(2+), Mg(2+), and Ca(2+)metal cations with different possible uric acid anions (urate) were studied. The complexes were optimized at the B3LYP level and the 6-311++G(d,p) basis set. Complexes of urate with Mg(2+), and Ca(2+)metal cations were also optimized at the MP2/6-31+G(d) level. Single point energy calculations were performed at the MP2/6-311++G(d,p) level. The interactions of the metal cations at different nucleophilic sites of various possible urate were considered. It was revealed that metal cations would interact with urate in a bi-coordinate manner. In the gas phase, the most preferred position for the interaction of Li(+), Na(+), and K(+) cations is between the N(3) and O(2) sites, while all divalent cations Be(2+), Mg(2+), and Ca(2+) prefer binding between the N(7) and O(6) sites of the corresponding urate. 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 urate and the metal cations. It was revealed that aqueous solvation would have significant effect on the relative stability of complexes obtained by the interaction of urate with Mg(2+) and Ca(2+)cations. Consequently, several complexes were found to exist in the water solution. The effect of metal cations on different NH and CO stretching vibrational modes of uric acid has also been discussed.     

Ion-specific swelling of poly(styrene sulfonic acid) hydrogel

Poly(styrene sulfonic acid) (PSSA) hydrogel was prepared by radiation crosslinking using methyl N,N-bis-acrylamide as crosslinker. Effects of ion species and concentration on the swelling behavior of PSSA hydrogel were investigated in aqueous solution of selected anions (F-, Cl-, Br-, SCN-), cations (Li+, Na+, K+, Ca2+), and hydrophobic ions (tetramethylammonium cation TMA+, tetrabutylammonium cation TBA+, and dodecyltrimethylammonium cation TAB+). The deswelling extent of PSSA hydrogel follows anion Hofmeister series, i.e., SCN- < Br- < Cl- < F-, in solutions containing selected anions and K+ as counterion up to a concentration of 2 mol.L(-1). On the contrary, the deswelling extent of PSSA hydrogel in solutions containing selected cations and Cl- follows the sequence of Li+ < Na+ < K+ < Ca2+, which is the reverse of the Hofmeister series except Ca2+. We have discussed the effects of ions on the hydrogen bonding through SO3- and phenyl ring in salt solutions at low and high concentrations. Other interactions, such as the cation-pi and hydrophobic interactions, also contributed to the ion-specific swelling of PSSA hydrogel. The proposed mechanism was further elucidated by FTIR and NMR analysis. A very specific deswelling-reswelling phenomenon of PSSA hydrogel in KF solution has been observed and ascribed to the F- binding to phenyl ring through a specific interaction.     

Qualitative and quantitative 1H NMR spectroscopy for determination of divalent metal cation concentration in model salt solutions,food supplements,and pharmaceutical products by using EDTA as chelating agent

This paper introduces an ¹H NMR method to identify individual divalent metal cations Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Sn²⁺, and Pb²⁺ in aqueous salt solutions through their unique signal shift and coupling after complexation with the salt of ethylenediaminetetraacetic acid (EDTA). Furthermore, quantitative determination applied for the divalent metal cations Ca²⁺, Mg²⁺, Hg²⁺, Sn²⁺, Pb²⁺, and Zn²⁺ (limit of quantification: 5–22 μg/ml) can be achieved using an excess of EDTA with aqueous model salt solutions. An internal standard is not required because a known excess of EDTA is added and the remaining free EDTA can be used to recalculate the quantity of chelated metal cations. The utility of the method is demonstrated for the analysis of divalent cations in some food supplements and in pharmaceutical products.     

Voltammetric study of the ion-exchange binding of non-electroactive metal cations to DNA-modified surfaces

We describe a simple electrochemical protocol for studying the ion-exchange binding of non-electroactive ions, specifically mono- and divalent metal cations of biological relevance (Mg(2+), Ca(2+), and K(+)), to DNA-modified surfaces. After incubation in a dilute solution of multiply charged transition metal complex (5.0 microM [Ru(NH(3))(6)]Cl(3)), gold electrodes modified with thiolate-DNA monolayers respond to the presence of these non-electroactive metal cations by producing significant changes in the cyclic voltammograms (i.e., decrease of the integrated charge and shift of formal potential) of the surface-bound redox complex ([Ru(NH(3))(6)](3+)). The divalent cations (particularly Mg(2+)) can be detected at very low concentrations (<10 microM), while the on-set value for K(+) is substantially higher (50 mM). The equilibrium binding constants for Mg(2+) and Ca(2+) to DNA-modified surfaces were calculated.     

Interaction of different metal ions with carboxylic acid group: a quantitative study

The binding strength of the carboxylic acid group (-COOH) with different divalent metal ions displays considerable variation in arachidic acid (AA) thin films. It is considered that in AA thin films the metal ions straddle the hydrophilic regions of the stacked bilayers of AA molecules via formation of carboxylates. In this study first the uptake of different divalent cations in films of AA is estimated by atomic absorption spectroscopy (AAS). Through the amount of cation uptake, it is found that the strength of binding of different cations varies as Ca2+>Co2+>Pb2+>Cd2+. Variation in the binding strength of different ions is also manifested in experiments where AA thin films are exposed to metal ion mixtures. The higher binding strength of AA with certain metal ions when exposed individually, as well as the preference over the other metal ions when exposed to mixtures, reveal some interesting deviation from the expected behavior based on considerations of ionic radii. For example, Pb2+ is always found to bind to AA much more strongly than Cd2+ even though the latter has smaller ionic radius, indicating that other factors also play an important role in governing the binding strength trends apart from the effects of ionic radii. Then, to get a more meaningful knowledge regarding the binding capability, first-principles calculations based on density functional theory have been applied to study the interaction of different cations with the simplest carboxylic acid, acetic acid, that can result in formation of metal diacetates. Their electronic and molecular structures, cohesive energies, and stiffness of the local potential energy well at the cation (M) site are determined and attempts are made to understand the diversity in geometry and the properties of binding of different metal ions with -COOH group. We find that the calculated M-O bond energies depend sensitively on the chemistry of M atom and follow the experimentally observed trends quite accurately. The trends in M-O bond energies and hence the total M-acetate binding energy trends can actually be related to their molecular structures that fall into different categories: Ca and Cd have tetrahedral coordination; Fe, Ni, and Co exhibit planar 4-fold coordination; and Pb is off-centered from the planar structure (forming pyramidal structure) due to its stereochemically active lone pair of electrons.     

电位滴定判断二元金属氢氧化物的复合化

尖晶石型纳米复合金属氧化物目前主要的合成方法还是共沉淀法 [1,2 ] .但是此种方法常因不能准确掌握共沉淀的 p H范围 ,而出现组分金属离子偏析 ,难制得不含杂相的纯净复合金属氧化物纳米微粒[3] .混合金属离子能否形成复合氢氧化物 ,在什么条件下形成 ,这方面的研究还未见报道 .电位滴定法通常是研究单一金属离子的水解或氢氧化物生成的有效方法 [4 ,5] ,为此 ,我们以 Al3+、Fe3+分别与 Ni2 +、Zn2 +、Cu2 +等金属离子形成的二元金属混和溶液为对象 ,使用自动电位滴定仪测定这些混合体系的电位滴定曲线 ,并通过与相应的单一金属离子的…     

Dynamic dispersion stability of graphene oxide with metal ions

Graphene oxide(GO),an important chemical precursor of graphene,can stably disperse in aqueous surrounding and undergo aggregation as metal cations introduced.The usual instability of GO with ions is caused by the shielding effect of ions and crosslinking between GO and ions.However,the dynamic stability of GO under ions exchange still remains unclear.Here,we investigated the dynamic dispersion stability of GO with metal ions and observed a redispersion behavior in concentrated Fe~(3+) solution,other than permanent aggregation.The exchange with Fe~(3+) ions drives the reversion of zeta(ζ) potential and enables the redispersion to individual GO-Fe~(3+) complex sheets,following a dynamic electric double layer(EDL) mechanism.It is found that the specifically strong electrostatic shielding effect and coordination attraction between Fe~(3+) and functional oxygen groups allows the selective redispersion of GO in concentrated Fe~(3+) solution.The revealed dynamic dispersion stability complements our understanding on the dispersive stability of GO and can be utilized to fabricate graphene-metal hybrids for rich applications.     

改性生物凝胶对重金属离子的吸附性能研究

以桔子汁加工残渣为原料,制备钙型和氢型生物凝胶作为吸附剂,用于去除水溶液中的重金属离子.结果表明,上述凝胶在水溶液中稳定性较好,对重金属离子的吸附性能优良.钙型凝胶的吸附选择性顺序为:Fe3 ＞Pb2 ＞Cd2 ＞Zn2 ,饱和吸附容量分别为:Pb2 、Cd2 、Zn2 均为约1.1mmol/g、Fe3 为1.5mmol/g;氢型凝胶的吸附选择性顺序为:Pb2 ＞Zn2 ＞Cd2 .钙型凝胶对Fe3 的吸附行为明显不同于氢型凝胶,钙型凝胶以离子交换机理以及Fe3 与Ca2 之间的共沉淀作用为主;而氢型凝胶对Fe3 的吸附则以离子交换机理为主.     

荧光素衍生物水杨醛荧光素腙的合成及对铜(Ⅱ)离子的检测

以荧光素酰肼与5-溴水杨醛反应合成了一种新型荧光素衍生物5-溴水杨醛荧光素腙(BSFH),采用红外、核磁、质谱、元素分析等技术手段对其进行了表征。 通过吸收光谱考察了在水溶液中BSFH对常见金属离子的选择性响应,发现BSFH在可见光区几乎无吸收,当加入常见金属离子时,吸收光谱上除了Cu²⁺之外的其它金属离子在496 nm处出现非常弱的吸收,而当Cu²⁺存在时,可以裸眼看到溶液颜色迅速从无色变为黄色,吸收光谱上在496 nm处出现了相对很强的吸收峰,并且随着Cu²⁺浓度的增加溶液的吸收强度不断增强,说明在水溶液中BSFH对Cu²⁺有很好的选择性。 实验结果表明,该化合物与Cu²⁺的化学计量比为1:1,Cu²⁺浓度线性范围为0.30~10 μmol/L,许多常见的金属离子不干扰Cu²⁺的测定,检测限为0.30 μmol/L,说明在水溶液中BSFH对铜离子具有很高的灵敏度。 据此,BSFH可以简单、快速、灵敏地在水溶液中识别和检测低浓度的铜离子。