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At least 19 recordsLinked to original sources
PubMed2001

Evaluation of column temperature as a means to alter selectivity in the cation exchange separation of alkali metals, alkaline earth metals and amines.

The merits of varying column temperature in a cation exchange separation of alkali metals, alkaline earth metals and amines are considered. Increasing the column temperature (up to 60 degrees C) reduced the retention of all cations, but by varying extents. Consequently, selectivity changes were seen, with reversals in elution order in some cases. To ascertain when temperature is most useful as a separation aid, analytes were classed into three groups according to their temperature behaviour: alkali metals; alkaline earth metals; and amines. Adjusting the column temperature caused selectivity changes between analytes in different groups, but no selectivity changes occurred between analytes in the same group. Further, temperature was compared to the addition of modest amounts of acetonitrile as another means to alter selectivity. The benefits of elevated temperature were not just limited to selectivity changes. Improvements in the efficiencies of all analytes were noted at 60 degrees C. This was especially true for the amines which are severely tailed at ambient temperatures.

Journal Article↗
PubMed2002

Solid-phase extraction for the decontamination of alkali metal, alkaline Earth metal, and ammonium salts from heavy metal ions.

Salicylaldoxime-immobilized silica gel was characterized and used as a potential sorbent for heavy metal ions, viz. Cu(II), Ni(II), Co(II), and Zn(II). The experimental conditions were optimized both in batch and column processes to achieve the maximum efficiency. Kinetic and thermodynamic parameters as well as isotherm constants were evaluated to test the feasibility of the process. The role of various metal ions and different anions were tested in order to monitor the process in case of real samples. The alkali metal, alkaline earth metal, and ammonium salts do not have any effect on the said process. This differential behavior can be effectively used for the decontamination of alkali metal, alkaline earth metal, and ammonium salts from Cu(II), Ni(II), Co(II), and Zn(II) ions via solid phase extraction following AAS measurement. The purification of the salts was confirmed by voltammetric experiment.

Journal Article↗
PubMed2005

Fluorometric sensing of alkali metal and alkaline earth metal cations by novel photosensitive monoazacryptand derivatives in aqueous micellar solutions.

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.

Journal Article↗
PubMed2004

Synthesis of double-armed lariat ethers with pyrene moieties at each end of two sidearms and their fluorescence properties in the presence of alkali metal and alkaline earth metal cations.

Two types of double-armed lariat ether derivatives having pyrene moieties at each end of two sidearms, (3x + 1)-crown-x derivatives 1 (x = 5), 2 (x = 6), and 3 (x = 4) (type A) and 3y-crown-y derivatives, 6 (y = 5) and 7 (y = 6) (type B), were synthesized, and their complexation behavior toward alkali metal and alkaline earth metal cations was examined by fluorescence spectroscopy. Pyrene excimer emission decreased accompanied by an increase in monomer emission upon metal ion complexation. This finding is ascribed to the change of the spatial distance of two pyrene rings by movement suppression of both the crown ring and one of the two sidearms based on complexation with the metal cation. The selectivity for alkaline earth metal cations was highly dependent on the fitness of the host cavity and the guest size. Although most of the fluorophores did not respond to alkali metal cations, only trans-7a containing an 18-crown-6 ring showed K(+) selectivity.

Journal Article↗
PubMed2006

Electron capture dissociation of peptides metalated with alkaline-earth metal ions.

The possible use of divalent alkaline-earth metal ions, including Mg2+, Ca2+, Sr2+, and Ba2+, as charge carrier for electron capture dissociation of peptides was investigated. Model peptides of RGGGVGGGR and NGGGWGGGN were used to simplify the interpretation of spectral information. It was demonstrated that useful electron capture dissociation (ECD) tandem mass spectra of these metalated peptides could be generated. Interestingly, peptides metalated with different alkaline-earth metal ions generated very similar ECD tandem mass spectra. Metalated c-ions and z-ions were the predominant fragment ions. Only Mg2+-metalated peptides gave somewhat different results. Some nonmetalated c-ions were observed from ECD of [RGGGVGGGR + Mg]2+ but not from [NGGGWGGGN + Mg]2+. Together with some ab initio calculations, it was established that the bound metal ions might activate the acidity of the amide hydrogen. With the presence of high proton affinity moiety, such as N-terminal amino group and/or side chain of the arginine residues, the metalated peptide ions could exist predominantly in their zwitterion forms, in which one or two backbone amide group(s) was deprotonated and the high proton affinity functional group(s) was protonated. It was believed that electron capture leads primarily to the reduction of the mobile proton rather than the metal ions. With this zwitterion model, the formation of nonmetalated c-fragments and the generation of similar ECD spectra for peptides metalated with various alkaline-earth metal ions could readily to be explained. Another interesting observation in the ECD mass spectra of metalated peptides is related to the enhanced formation of the minor ECD products, i.e., (c - 1)(+*) and (z + 1)+ ions. Together with ab initio calculations using a truncated peptide model, various possible reaction mechanisms for the formation of these minor ECD products were evaluated. It was concluded that hydrogen transfer between the initiated formed c and z(.) species plays an important role in the formation (c - 1)(+*) and (z + 1)+ ions. Although peptides metalated with these metal ions do not have better ECD efficiency compared to the multiply-protonated peptides, it provides practical accessibility of ECD methods to analyze small peptides with no basic amino acid residues.

Electrons↗
PubMed1999

[Simultaneous analysis of alkali metals and alkaline earth metals in Chinese herbal medicine by ion chromatography].

A simple and rapid method for the analysis of cations by using ion chromatography was developed. The results showed that the content ratio of Na+, NH4+, K+, Mg2+, Ca2+ in rhizoma chuanxiong and semen zizyphi spinosae are different. The detection limits of cations (S/N = 3) were 0.001-0.013 mg/L. The calibration curves of peak areas for all analytes were linear over two or three orders of magnitude with a regression coefficient (r2) of 0.9995-1.0000.

Chromatography↗
PubMed2006

Recent developments in the field of organic heterobimetallic compounds of the alkaline-earth metals.

Heterobimetallic compounds of the alkaline-earth metals show a wide structural variety with strongly differing reactivity patterns. The combination of magnesium and alkali metal amides yields cyclic molecules with an extreme high reactivity which often are considered as "inverse crowns" with the metal atoms as coordination sites for Lewis bases. In other metallates of the alkaline-earth metals an activation of alkyl groups succeeds. In alkaline-earth metal zincates an inverse coordination of the type M(2)[(mu-R)(2)ZnR](2) is observed and the alkyl groups are in bridging positions between zinc and the s-block metals thus forming a very reactive M-C-Zn three-center-two-electron bond. Furthermore, the metals of the carbon group form alkaline-earth metal-silicon, -germanium and -tin bonds or, in the presence of very strong Lewis bases, even solvent-separated ion pairs. For electronegative substituents at tin an inverse coordination mode such as M[(mu-R)(2)SnR](2) is observed.

Journal Article↗
PubMed1971

Studies on the interactions between purified bovine caseins and alkaline-earth-metal ions.

1. Alkaline-earth-metal cations at low concentrations form soluble complexes with bovine caseins. The relative order of binding capacities is: Mg(2+)>Ca(2+)>Ba(2+)>Sr(2+). 2. The cations interact with both free ionized carboxyl groups of aspartic acid and glutamic acid and with monoester phosphate groups covalently bound to serine and threonine; at low concentrations of the cations interactions are predominantly with the phosphate groups. 3. The order of binding capacities for purified components of the casein complex is: alpha(s1)-casein>beta-casein>kappa-casein.

Animals↗
PubMed2006

Accurate enthalpies of formation of alkali and alkaline earth metal oxides and hydroxides: assessment of the correlation consistent composite approach (ccCA).

Computing the enthalpies of formation for alkali metal and alkaline earth metal oxides (M(x)O) and hydroxides [M(OH)(n)] using the Gaussian-n (Gn) and Weismann-n (Wn) ab initio model chemistries is difficult due to an improper treatment of core-valence electron correlation effects. Using a new model chemistry called the correlation consistent Composite Approach (ccCA), enthalpies of formation were determined for eight different alkali/alkaline earth metal oxides and hydroxides. Unlike the Gn and Wn model chemistries, which must be modified to properly account for core-valence electron correlation, the standard implementations of the ccCA provide acceptable results, and all enthalpies of formation obtained with the ccCA are within the accepted range of recommended values.

Computer Simulation↗
PubMed2002

Alkali and alkaline-earth-metalated forms of calix[4]arenes: synthons in the synthesis of transition metal complexes.

This is the first coherent report on the metalation of calix[4]arene by alkali and alkaline-earth metals, thus providing a high-yield production of appropriate synthons for the synthesis of transition metal calix[4]arenes. In addition, various facets of the coordination chemistry by calix[4]arene anions of alkali and alkaline-earth metal ions have been singled out. Among them: 1) the exo and endo coordination of metal ions by the calix[4]arene skeleton; 2) the pi solvation of the ions by the phenyl rings; 3) the ion-carrier properties of metallacalix[4]arenes; 4) the simulation of the kinetically labile coordination sphere of alkali and alkaline-earth metal ions by a polyoxo rigid skeleton. The peculiarities of the complexation of alkali and alkaline-earth metal ions by calix[4]arenes outlined are deduced from the synthesis and the structural characterization both in solution ((1)H NMR) and in the solid state (X-ray structure analysis) of the following classes of compounds: 1) [p-tBu-calix[4](OMS(n))(4)](2) (M=Li, Na, K); 2) [p-tBu-calix[4](OR)(2)(O)(2)ML] (M=Mg, L=THF, R=C(5)H(9); M=Ca, L=TMEDA (tetramethylethylenediamine), R=C(5)H(9); M=Ca, L=DME (dimethoxyethane), R=C(5)H(9); M=Ba, L=TMEDA, R=C(5)H(9); M=Ba, L=none, R=C(5)H(9)); 3) [p-tBu-calix[4](OC(5)H(9))(2)(O)(2)Ca(2)I(2)(MeCN)(2)]; 4) [(p-tBu-calix[4](OR)(2)(O)(2))(2)BaNa(2)].

Journal Article↗
PubMed1985

Na+-dependent alkaline earth metal uptake in cardiac sarcolemmal vesicles.

The ability of alkaline earth metals (M2+) to substitute for Ca2+ in Na+-Ca2+ exchange was examined in sarcolemmal vesicles isolated from the canine heart. 85Sr2+ and 133Ba2+, in addition to 45Ca2+, were used to determine the characteristics of Na+-M2+ exchange. The Na+i-dependent M2+ uptake was measured as a function of time, with t ranging from 0.5 to 360 s, [Na+]i = 140 mM and [M2+]o = 40 microM. This function was linear for Ca2+ and Sr2+ uptake for approx. 6 s and for Ba2+ for about 60 s. Plateau levels were achieved within 120 s for Ca2+ and Sr2+ but Ba2+ took considerably longer. The Km values for Na+-M2+ exchange, derived from Eadie-Hofstee plots, were 30, 58, and 73 microM for Ca2+, Sr2+ and Ba2+, respectively. The Na+i-dependent uptake of all three ions was stimulated in the presence of 0.36 microM valinomycin. Na+-Ca2+ exchange was also measured in the presence of either 20 microM Sr2+ or 100 microM Ba2+. Both of these ions behaved (at these concentrations) as competitive inhibitors of Na+-Ca2+ exchange with the KI being 32 microM for Sr2+ and 92 microM for Ba2+. Passive efflux was determined by first allowing Na+-M2+ exchange to continue to plateau values and then diluting the loaded vesicles in the presence of EGTA. The rate constants for the passive efflux were 8.4, 6.3 and 4.4 min-1 for Ca2+, Sr2+ and Ba2+, respectively.

Animals↗
PubMed2005

Interaction between trehalose and alkaline-earth metal ions.

We investigated the interaction between trehalose and alkaline-earth metal ions. The nuclear relaxation times of carbon atoms of trehalose were shortened by addition of the alkaline-earth chloride salts, MgCl2, CaCl2, and SrCl2, indicating that trehalose formed metal-complexes with the alkaline-earth metal chlorides. From the data of the 1H-1H coupling constants of trehalose in the presence of the alkaline-earth chlorides, it appeared that trehalose formed complexes with MgCl2, and CaCl2 at the various complexing sites: Mg2+ was coordinated to O-4 and O-4' of trehalose, and Ca2+ to O-2 and O-3. We succeeded in the preparation of two types of crystals of the trehalose/CaCl2. One was a crystal consisting of trehalose, CaCl2, and water in a ratio of 1:1:1. The other was an anhydrous crystal containing trehalose and CaCl2 in a ratio of 1:2. Several applications of the complexing between trehalose and the metal ions for food processing are proposed.

Animals↗
PubMed2005

Towards accurate ab initio calculations on the vibrational modes of the alkaline earth metal hydrides.

The fundamental modes of the alkaline earth metal hydrides (BeH2, MgH2, CaH2) and their dimers, HX(H)2XH, have been studied by vibrational configuration-interaction calculations based on very accurate potential energy surfaces. Comparison with experimental data obtained from matrix isolation and gas phase measurements is provided and the agreement was found to be excellent for the monomers but poor for the dimers. In addition, many fundamental bands are predicted which have not yet been detected experimentally.

Journal Article↗
PubMed2004

Thin-layer chromatographic behavior and separation of alkaline earth metals on silica gel in aqueous sodium perchlorate solution.

The thin-layer chromatographic behavior of alkaline earth metal ions (Mg2+, Ca2+, Sr2+, and Ba2+) in aqueous sodium perchlorate solutions on silica gel thin-layers impregnated with sodium hydroxide has been surveyed as a function of salt concentration. At salt concentrations above 2 mol 1(-1), the selectivity of the metals increased with a decrease in the crystal ionic radii; with further increases in salt concentration, the selectivity differences among the metals expanded remarkably. In the present systems, it was supposed that the cation exchange, the surface complexation, and the salting-out effect participate simultaneously in the adsorption of the metals on silica gel. Typical chromatograms for the mutual separation of the alkaline earth metals are presented.

Adsorption↗