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1.
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.  相似文献   

2.
The cation exchange properties of alkali and alkaline earth metal cations at room temperature were investigated on an ultrafine, highly charged Na-4-mica (with the ideal mica composition Na4Mg6Al4Si4O20F4.xH2O). Ultrafine mica crystallites of 200 nm in size led to faster Sr2+ uptake kinetics in comparison to larger mica crystallites. The alkali metal ion (K+, Cs+, and Li+) exchange uptake was rapid, and complete exchange occurred within 30 min. For the alkaline earth metal ions Ba2+, Ca2+, and Mg2+, however, the exchange uptake required lengthy periods from 3 days to 4 weeks to be completed, similar to its Sr uptake, as previously reported. Kinetic models of the modified Freundlich and parabolic diffusion were examined for the experimental data on the Ba2+, Ca2+, and Mg2+ uptakes. The modified Freundlich model described well the Ba2+ ion uptake kinetics as well as that for the Sr2+ ion, while for the Ca2+ and Mg2+ ions the parabolic diffusion model showed better fitting. The alkali and alkaline earth ion exchange isotherms were also determined in comparison to the Sr2+ exchange isotherm. The thermodynamic equilibria for these cations were compared by using Kielland plots evaluated from the isotherms.  相似文献   

3.
The role of divalent cations in the mechanism of pyrophosphate-activated, template-directed oligoribonucleotide ligation has been investigated. The dependence of the reaction rate on Mg2+ concentration suggests a kinetic scheme in which a Mg2+ ion must bind before ligation can proceed. Mn2+, Ca2+, Sr2+, and Ba2+ can also catalyze the reaction. Although Pb2+ and Zn2+ do not catalyze the reaction in the absence of other divalent ions, they significantly modulate the reaction rate when added in the presence of Mg2+, with Pb2+ stimulating the reaction (up to 65-fold) and Zn2+ inhibiting the reaction. The logarithm of the ligation rate increases linearly, with slope of 0.95, as a function of pH, indicating that the reaction involves a single critical deprotonation step. The ligation rates observed with the different divalent metal ion catalysts (Mn2+ > Mg2+ > Ca2+ > Sr2+ = Ba2+) vary inversely with the pKa values of their bound water molecules. The pH profile and these relative ligation rates suggest a mechanism in which a metal-bound hydroxide ion located near the ligation junction promotes catalysis, most likely by deprotonation of the hydroxl nucleophile. The effects of changing either the leaving group or the attacking hydroxyl, together with the large delta S(++) value for oligonucleotide ligation (about -20 eu), are consistent with an associative transition state.  相似文献   

4.
We used both localized and periodic calculations on a series of monovalent (Li+, Na+, K+, Rb+, Cs+) and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations to monitor their effect on the swelling of clays. The activity order obtained for the exchangeable cations among all the monovalent and divalent series studied: Ca2+ > Sr2+ > Mg2+ > Rb+ > Ba2+ > Na+ > Li+ > Cs+ > K+. We have shown that, in case of dioctahedral smectite, the hydroxyl groups play a major role in their interaction with water and other polar molecules in the presence of an interlayer cation. We studied both type of clays, with a different surface structure and with/without water using a periodic calculation. Interlayer cations and charged 2:1 clay surfaces interact strongly with polar solvents; when it is in an aqueous medium, clay expands and the phenomenon is known as crystalline swelling. The extent of swelling is controlled by a balance between relatively strong swelling forces and electrostatic forces of attraction between the negatively charged phyllosilicate layer and the positively charged interlayer cation. We have calculated the solvation energy at the first hydration shell of an exchangeable cation, but the results do not correspond directly to the experimental d-spacing values. A novel quantitative scale is proposed with the numbers generated by the relative nucleophilicity of the active cation sites in their hydrated state through Fukui functions within the helm of the hard soft acid base principle. The solvation effect thus measured show a perfect match with experiment, which proposes that the reactivity index calculation with a first hydration shell could rationalize the swelling mechanism for exchangeable cations. The conformers after electron donation or acceptance propose the swelling mechanism for monovalent and divalent cations.  相似文献   

5.
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+.  相似文献   

6.
This study focused on further analysis of the aggregation behavior of pradimicin derivatives and their interaction with cations in aqueous solution. BMY was compared with two other pradimicin antibiotics (T2 and FB) with the same aglycone moiety but consisting of different substitute groups. The surface tension measurement showed a clear critical micelle concentration at 1-2 mM of the BMY aqueous solution. The role of Zn2+ in replacing the Ca2+ was examined using 1H nuclear magnetic resonance (NMR) method. From changes in the NMR spectrum and precipitability, it was concluded that zinc ion has lower affinity and higher precipitating ability to BMY than the divalent cations of alkaline earth metal. The aggregation behavior of T2 and FB in aqueous solution was also studied using NMR method. The results suggest that the supramolecular behavior of T2 is similar to BMY whether or not Ca2+ ions are present in solution and that there are two binding sites for calcium ions in a T2 molecule. Unlike BMY and T2, the NMR spectrum of FB does not show distinct change upon Ca2+ addition. The interaction of pradimicin antibiotics with divalent metal ions was thought to be related to ionic electronegativity and to the amphoteric property of the antibiotics.  相似文献   

7.
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.  相似文献   

8.
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.  相似文献   

9.
Magnesium hydrogen phosphate, calcium hydroxyapatite, and strontium hydroxyapatite were successfully prepared from sol consisting of sodium alginate and Na4P2O7 with Mg2+, Ca2+, and Sr2+ in the corresponding nitrates, respectively. It is revealed that the order of the addition of those substrates and the role of sodium alginate are important factors for the preparation of desired phosphate compounds. According to the previous paper on the preparation of calcium hydroxyapatite, sodium alginate was mixed with aqueous Na4P2O7, followed by the addition of the aqueous divalent cations, resulting in the poor formation of the target phosphates. However, as a revised sol-gel technique, sodium alginate was added to the mixture of Na4P2O7 and aqueous Mg2+ and Sr2+, resulting in a rather favorable formation of MgHPO4 and strontium hydroxyapatite, respectively, while the sol thus obtained was stable within a few days. However for aqueous Ca2+, calcium hydroxyapatite could not be obtained through the revised sol-gel technique. In the preparation of magnesium hydrogen phosphate, sodium alginate contributes mainly to the sol formation of the precursor. The ion exchange between Na+ in sodium alginate and aqueous Ca2+ was important for the preparation of calcium hydroxyapatite. In contrast, the reaction of sodium alginate with the mixture of Na4P2O7 and aqueous Sr2+ afforded strontium hydroxyapatite at the specific ratio of those three substrates. The structure of calcium and strontium phosphates prepared from the revised sol-gel process evidently depended on the amount of sodium alginate introduced into the mixture of Na4P2O7 and the corresponding divalent cations.  相似文献   

10.
合成了一个新型香豆素/Betti碱主体化合物1,并对其进行了结构表征。在乙腈/水溶液中进行主体1和碱金属、碱土金属相关离子(Li+,Na+,K+,Rb+,Cs+,Be2+,Mg2+,Ca2+,Sr2+,Ba2+)的相互作用研究时,发现仅Rb+,Ba2+离子对主体1有敏感的紫外光谱及荧光光谱响应,而其它的碱金属、碱土金属离子无敏感性光响应。紫外光谱显示,Rb+,Ba2+离子使主体1产生明显的红移(ε=4.66×102L·(mol·cm)-1,Δ=91nm),肉眼可观察到明显的由浅黄向橙红色的颜色变化,并使主体1的荧光光谱发生一定程度的猝灭。  相似文献   

11.
Novel monoazacryptand-type fluorescent chemosensors, (derived from an 18-crown-6) and (derived from a 15-crown-5) both with a pyrene ring as their photoresponsive moiety, were synthesized. Their fluorescence properties for alkali metal and alkaline earth metal cations in water were then examined. The detection of metal cations was accomplished by a change in the fluorescence intensity of the host compounds, based on a photoinduced electron transfer (PET) mechanism. In aqueous solution, showed little fluorescence upon the addition of Ba2+ because of the very weak complexation with Ba2+, but the presence of micelles of polyoxyethylene(10) isooctylphenyl ether (Triton X-100) enabled to show highly sensitive and selective Ba2+ detection among alkali metal and alkaline earth metal cations. With respect to the selective fluorescent detection of important metal cations (Na+, K+, Mg2+, Ca2+) relevant to living organisms, was found to detect K+ with high selectivity in aqueous micellar solutions of polyoxyethylene(20) sorbitan monostearate (Tween-60). The selectivity for metal cations was mainly dependent on the goodness of fit of the host cavity and the metal cation size. In the presence of anionic surfactants, detected alkaline earth metal cations more effectively than alkali metal cations.  相似文献   

12.
The TLC behavior of all the rare earths except Pm has been surveyed on silica gel (pH 7.0) pretreated with 0.1 mol L(-1) tris(hydroxymethyl)aminomethane and 0.1 mol L(-1) HCl with aqueous nitrate solutions of alkaline earth metals as mobile phases. The RF values of the lanthanides varied in a regular and characteristic way accompanied by the tetrad effect with increasing atomic number, and when the mobile phases were changed the RF values of each metal decreased in the order Mg2+ > Ca2+ > Sr2+ > Ba2+, as the crystal ionic radii of the alkaline earth metals increased. This adsorption sequence was not observed with alkali metal nitrate and alkali metal chloride mobile phases. A brief discussion concerning the effect on RF values of the solvent cations and the adsorption mechanism is included; also presented are typical chromatograms for the separation of multi-component mixtures containing adjacent lanthanides.  相似文献   

13.
Tunell I  Lim C 《Inorganic chemistry》2006,45(12):4811-4819
Many of the group IA and IIA metal ions, such as Na+, K+, Mg2+, and Ca2+, play crucial roles in biological functions. Previous theoretical studies generally focus on the number of water molecules bound to a particular (as opposed to all) alkali or alkaline earth cations and could not establish a single preferred CN for the heavier alkali and alkaline earth ion-water complexes. Crystal structures of hydrated Na+, K+, and Rb+ also cannot establish the preferred number of inner-shell water molecules bound to these cations. Consequently, it is unclear if the gas-phase CNs of group IA metal hydrates increase with increasing ion size, as observed for the group IIA series from the Cambridge Structural Database, and if the same factors govern the gas-phase CNs of both group IA and IIA ion-water complexes. Thus, in this work, we determine the number of water molecules directly bound to the series of alkali (Li+, Na+, K+, and Rb+) and alkaline earth (Be2+, Mg2+, Ca2+, Sr2+, and Ba2+) metal ions in the gas phase by computing the free energy for forming an isolated metal-aqua complex as a function of the number of water molecules at 298 K. The preferred gas-phase CNs of group IA hydrates appear insensitive to the ion size; they are all 4, except for Rb+, where a CN of 6 seems as likely. In contrast, the preferred gas-phase CNs of the group IIA dications increase with increasing ion size; they are 4 for Be2+, 6 for Mg2+ and Ca2+, and 7 for Sr2+ and Ba2+. An entropic penalty disfavors a gas-phase CN greater than 4 for group IA hydrates, but it does not dictate the gas-phase CNs of group IIA hydrates. Instead, interactions between the metal ion and first-shell water molecules and between first-shell and second-shell water molecules govern the preferred gas-phase CNs of the group IIA metal hydrates.  相似文献   

14.
Electrospray ionization mass spectrometry (ESI-MS) was used to study the binding of selected group II and divalent transition-metal ions by cyclo(Pro-Gly)3 (CPG3), a model ion carrier peptide. Metal salts (CatXn) were combined with the peptide (M) at a molar ratio of 1:10 M/Cat in aqueous solvents containing 50% vol/vol acetonitrile or methanol and 1 or 10 mM ammonium acetate (NH4Ac). Species detected include [M+H]+, [M+Cat-H]+, [M2+Cat]2+, [M+Cat+Ac]+, and [M+Cat+X]+. The relative stabilities of complexes formed with different cations (Mg2+, Ca2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, and Zn2+) were determined from the abundance of 1:1 and 2:1 M/Cat species relative to that of the unbound peptide. The largest metal ions (Ca2+, Sr2+, and Mn2+) formed the most stable complexes. Reducing the buffer concentration increased the overall extent of metal binding. Results show that the binding specificity of CPG3 depends upon the size of the metal ion and its propensity for electrostatic interaction with oxygen atoms. Product ion tandem mass spectrometry of [M+H]+ and [M+Cu-H]+ confirmed the cyclic structure of the peptide, although the initial site(s) of metal attachment could not be determined.  相似文献   

15.
A series of molybdate, MoO4(2-), salts have been studied using solid-state 95Mo NMR spectroscopy at applied magnetic field strengths of 11.75, 17.63 and 21.14 T. In contrast to previous investigations, the principal components of the Mo shielding and EFG tensors have been obtained, as well as their relative orientations. At the fields employed, the anisotropic Mo shielding and quadrupolar interactions make significant contributions to the observed 95Mo central transition NMR lineshapes. Based on available structural data, the extent of distortion of the MoO4(2-) anion from T(d) symmetry is reflected in the observed 95Mo nuclear quadrupolar coupling constants for the molybdate salts with divalent cations (i.e., Ca2+, Sr2+, Cd2+, Ba2+, Pb2+), but no correlation is found for molybdate salts containing the monovalent alkali metal (Li+, K+, Rb+, Cs+) cations.  相似文献   

16.
The self-assembled guanosine (G 1)-based hexadecamers and isoguanosine (isoG 2)-based decamers are excellent 226Ra2+ selective ionophores even in the presence of excess alkali (Na+, K+, Rb+, and Cs+) and alkaline earth (Mg2+, Ca2+, Sr2+, and Ba2+) cations over the pH range 3-11. G 1 requires additional picrate anions to provide a neutral assembly, whereas the isoG 2 assembly extracts 226Ra2+ cations without any such additives. Both G 1-picrate and isoG 2 assemblies show 226Ra2+ extraction even at a 0.35 x 10(6) fold excess of Na+, K+, Rb+, Cs+, Mg2+, or Ca2+ (10(-2) M) to 226Ra2+ (2.9 x 10(-8) M) and at a 100-fold salt to ionophore excess. In the case of the G 1-picrate assembly, more competition was observed from Sr2+ and Ba2+, as extraction of 226Ra2+ ceased at an M2+/226Ra2+ ratio of 10(6) and 10(4), respectively. With the isoG 2 assembly, 226Ra2+ extraction also occurred at a Sr2+/226Ra2+ ratio of 10(6) but ceased at a 10(6) excess of Ba2+. The results clearly demonstrate the power of molecular self-assembly for the construction of highly selective ionophores.  相似文献   

17.
二价金属离子对鲑鱼精DNA热稳定性的影响   总被引:2,自引:0,他引:2  
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 +…  相似文献   

18.
Room-temperature rate coefficients and product distributions are reported for the reactions of ozone with the cations and dications of the alkaline-earth metals Ca, Sr, and Ba. The measurements were performed with a selected-ion flow tube (SIFT) tandem mass spectrometer in conjunction with either an electrospray (ESI) or an inductively coupled plasma (ICP) ionization source. All the singly charged species react with ozone by O-atom transfer and form monoxide cations rapidly, k = 4.8, 6.7, and 8.7 x 10(-10) cm3 molecule(-1) s(-1) for the reactions of Ca+, Sr+, and Ba+, respectively. Further sequential O-atom transfer occurs to form dioxide and trioxide cations. The efficiencies for all O-atom transfer reactions are greater than 10%. The data also signify the catalytic conversion of ozone to oxygen with the alkaline-earth metal and metal oxide cations serving as catalysts. Ca2+ reacts rapidly with O3 by charge separation to form CaO+ and O2+ with a rate coefficient of k = 1.5 x 10(-9) cm3 molecule(-1) s(-1). In contrast, the reactions of Sr2+ and Ba2+ are found to be slow and add O3, (k >/= 1.1 x 10-11 cm3 molecule-1 s-1). The initial additions are followed by the rapid sequential addition of up to five O3 molecules with values of k between 1 and 5 x 10(-10) cm3 molecule(-1) s(-1). Metal/ozone cluster ions as large as Sr2+(O3)5 and Ba2+(O3)4 were observed for the first time.  相似文献   

19.
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.  相似文献   

20.
The paper presents results of investigation of exchange of the clinoptilolite tuff cations with hydrogen ions from HCl solution of concentration 0.1 mmol cm(-3) and ammonium ions solutions of concentrations 0.0071 to 2.6 mmol cm(-3). Molal concentrations, x (mmol g(-1)) of cations exchanged in acid solution and in ammonium ions solutions were compared with molal concentrations of cations obtained by determination of the cation-exchange capacity of clinoptilolite tuff. The obtained results show that at ammonium ion concentrations lower than 0.1 mmol cm(-3), with regard to exchange capacity for particular ions, best exchanged are Na+ ions, followed by Mg2+ and Ca2+ ions, while exchange of K+ ions is the poorest (Na+ > Mg2+ > Ca2+ > K+). At ammonium concentrations from 0.2 to 1 mmol cm(-3) the order is Na+ > Ca2+ > Mg2+ > K+. At concentrations higher than 1 mmol cm(-3) the order is Na+ > Ca2+ > K+ > Mg2+. The results are a consequence of the uptake of hydrogen ions by zeolite samples in ammonium ions solutions at concentrations lower than 1 mmol cm(-3) and indicate the importance of Mg2+ (besides Na+ ions) for the exchange between clinoptilolite cations and H+ ions, in contrast to K+ ions, whose participation in the reaction with H+ ions is the lowest. During decationization of the clinoptilolite in acid solution, best exchanged are Na+, Mg2+, and Ca2+ ions, while exchange of K+ ions is the poorest. Due to poor exchange of K+ and H+ ions and good exchange of Na+, Mg2+, and Ca2+ ions, it is to be assumed that preservation of stability of the clinoptilolite structure is caused by K+ ions present in the channel C. Clinoptilolite is dissolved in the clinoptilolite A and B channels where Na+, Mg2+, and Ca2+ ions are present. On the acid-modified clinoptilolite samples, exchange of ammonium ions is poorer than on natural zeolite. The longer the contact time of the zeolite and acid solution, the worse ammonium ions exchange. It can be assumed that H+ ions exchanged with zeolite cations are consumed for solution of aluminum in the clinoptilolite structure; therefore the concentration of H+ ions as exchangeable cations decreases. In the ammonium ion solution at a concentration of 0.0065 mmol cm(-3), from the acid-modified zeolite samples, Al3+ ions are exchanged best, followed by Na+, Mg2+, Ca2+, and K+ ions. Further to the results, it is to be assumed that exchangeable Al3+ ions available from clinoptilolite dissolution are best exchanged with H+ ions in acid solution.  相似文献   

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