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Alkali Metal Cations (alkali + metal_cation)
Selected AbstractsTowards Understanding of the Selective Precipitation of Alkali Metal Cations in Presence of Dipicrylamine AnionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2005Suresh Eringathodi Abstract Dipicrylamine anion (DPA,) precipitates out [K(DPA)] with high selectivity from salt bitterns containing Na+, K+, and Mg2+, whereas the same ligand shows poor selectivity towards K+ , and much higher selectivity towards Cs+ , in studies conducted with a mixture of K+, Rb+, and Cs+. Their single-crystal structures reveal that the K+ and Rb+ salts have similar layered structures, with 8 oxygen atoms from seven DPA, anions encapsulating the metal cation, whereas the Cs+ salt possesses a channel-like structure with the metal ion encapsulated by ten oxygen atoms from six DPA,. The conformation of DPA, in the [Cs(DPA)] single crystal matches closely that of DPA in crystalline state. M···O and intermolecular C,H···O interactions together stabilize the structures. The 133Cs NMR spectrum of the poorly soluble [Cs(DPA)] shows an upfield shift of the peak with respect to CsCl as a result of the interaction with the oxygen atoms of DPA,, whereas 23Na NMR spectrum of the highly soluble [Na(DPA)] shows no such upfield shift compared to NaCl. Powder XRD patterns of bulk [M(DPA)] (M = K+, Rb+, and Cs+) precipitates show that these are similar to the patterns obtained by simulation of the single-crystal X-ray data. The selectivity of precipitation correlates qualitatively with the size and hydration enthalpies of the ions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Effect of alkali metal hydroxides on the enantioseparation of amines using di- O -isopropylidene-keto- L -gulonic acid as the selector in NACEELECTROPHORESIS, Issue 22 2006Ylva Hedeland Dr. Abstract The present work demonstrates the importance of the ionic composition in the BGE for enantioseparation. (,)-2,3:4,6-di- O -Isopropylidene-2-keto- L -gulonic acid ((,)-DIKGA) has been used as the chiral selector in methanolic and ethanolic BGEs. The influence of added alkali metal hydroxides on the EOF and the chiral separation of amines (atenolol, isoprenaline, pindolol and propranolol) have been studied. The ion-pair formation constants in ethanol were determined by precision conductometry for the enantiomers of pindolol with (,)-DIKGA, for Li+, Na+ and Cs+ with (,)-DIKGA, and also for the corresponding alkali metal hydroxides. The effective mobilities and the enantiomeric mobility differences were affected by the type of alkali metal hydroxide (LiOH, NaOH, KOH, RbOH or CsOH) added to the BGE. The effective mobility and mobility difference were increased with decrease in solvated radius of the alkali metal cation. These differences could partly be correlated to the ion-pair formation constants of the alkali metal cations with the chiral selector, affecting the equilibrium concentration of the free selector. The electroosmosis was also affected by the alkali metal hydroxide added to the BGE. The cathodic electroosmosis decreased with decreasing solvated radius of the alkali metal cation added to the BGE. Interestingly, the cathodic EOF was even reversed, i.e. became anodic in the ethanolic BGEs containing KOH, RbOH or CsOH and the methanolic ones with RbOH and CsOH. [source] A strategy for quantitative bioanalysis of non-polar neutral compounds by liquid chromatography/electrospray ionization tandem mass spectrometry: determination of TS-962, a novel acyl-CoA:cholesterol acyltransferase inhibitor, in rabbit aorta and liver tissuesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 8 2001Jun-ichi Yamaguchi A strategy for the sensitive and reliable quantitative determination of non-polar neutral compounds in biological matrices by liquid chromatography/electrospray ionization tandem mass spectrometry is described in the context of assay development for TS-962, a novel acyl-CoA:cholesterol acyltransferase (ACAT) inhibitor, in rabbit aorta and liver tissues. The electrospray ionization (ESI) mass spectrum of this compound with a mobile phase of water/acetonitrile did not give abundant [M,+,H]+ ions, but did give alkali metal cation adducts such as [M,+,Na]+, [M,+,CH3CN,+,Na]+ and [M,+,K]+ ions. The cationized species are acknowledged as unsuitable precursor ions for selected reaction monitoring (SRM) for various reasons, such as difficulty in obtaining characteristic product ions in low-energy collision-induced dissociation, and irreproducibility of the adduct-ion intensities. To overcome this problem, a solution of 3.4,mM trifluoroacetic acid in 2-propanol was added to the mobile phase as a postcolumn additive, resulting in a decrease of the undesirable adduct formation and significant enhancement of [M,+,H]+ ion intensity. An attempt was then made to prevent the matrix effect by employing a column-switching system, which allowed direct injection of a large volume of 2-propanolic tissue homogenate (950,µL) followed by sufficient clean-up, separation, and ESI-SRM on-line. This enabled development of a sensitive and reliable assay method for TS-962 in rabbit aorta and liver tissues in the concentration range of 5,500,ng/g wet tissue using a 25-mg aliquot of tissue sample. Application of this method to the determination of aortic TS-962 levels at 24,h after repeated oral administration of this compound (3,mg/kg) once a day for 12 weeks to 1% cholesterol-fed rabbits is also presented. Results showed that TS-962 is well distributed to both the thoracic and abdominal aorta tissues, at levels higher than the 50% inhibitory concentration value of this compound for microsomal ACAT activity from rabbit aorta. Copyright © 2001 John Wiley & Sons, Ltd. [source] Complexes between Lithium Cation and Diphenylalkanes in the Gas Phase: The Pincer EffectCHEMISTRY - A EUROPEAN JOURNAL, Issue 29 2006Jean-François Gal Prof. Abstract The gas-phase lithium cation basicities (LCB values, Gibbs free energies of binding) of ,,,-diphenylalkanes Ph-(CH2)n -Ph (n=2, 3, or 7) and 1,1-diphenylethane Ph-CH(Me)-Ph were investigated by means of Fourier-transform ion cyclotron resonance (FTICR) mass spectrometry. Their structures, and those of the corresponding Li+ complexes were optimized at the B3LYP/6-31G(d) level and their relative stabilities calculated at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) level. Whereas the most stable conformers of the free diphenylalkanes were found to adopt a completely stretched aliphatic chain connecting the two benzene rings, the most stable Li+ complexes correspond to conformers in which the alkali metal cation interacts simultaneously with both benzene rings through the folding of the aliphatic chain ("pincer effect"). This chelation brings about a significant enhancement of the Li+ binding enthalpies (LBE values), which were calculated to be approximately 75 kJ,mol,1 higher than those evaluated for conventional (singly coordinated) , complexes in which the metal cation interacts with only one of the benzene rings. The increase of the corresponding lithium cation basicities, however, (Gibbs free energies of Li+ binding, LCB values) was calculated to be smaller by approximately 15 kJ,mol,1 as the pincer effect is entropically disfavored. The good agreement between the calculated LCB values, assuming a statistical distribution of the different conformers present in the gas phase, and the experimental LCB values measured by means of FTICR mass spectrometry are considered indirect evidence of the existence of the pincer effect. [source] Supramolecular Derivatives of 9,10-Anthraquinone.ELECTROANALYSIS, Issue 5-6 2003Complexing Properties, Electrochemistry at Regular-, Low Ionic Strength Abstract Three newly synthesized polyanthraquinone derivatives: 7,13-bis(9,10-dioxo-1-anthryl)-1,4,10-trioxa-7,13-diazacyclopentadecane, (AQ)A215C5, 7,16-bis(9,10-dioxo-1-anthryl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, (AQ)A218C6, and tris[(9,10-diokso-1-antryl)-aminoethyl]amine, (AQNet)3N, were examined by cyclic and normal pulse voltammetry. All anthraquinone groups in these compounds were electroactive and formed the radicals and dianions similarly to simple anthraquinone. The differences between the voltammograms obtained in the absence and presence of supporting electrolyte are discussed, and the diffusion coefficients of the compounds and the rates of the chemical reactions following the first reduction step were evaluated. (AQNet)3N appears to be a good model compound for multi electron transfers in aprotic solvents. It offers two consecutive nearly reversible 3-electron redox systems: 0/,3 and ,3/,6. The interactions of the radicals and dianions of the above compounds with alkali metal cations were examined. [source] Effect of alkali metal hydroxides on the enantioseparation of amines using di- O -isopropylidene-keto- L -gulonic acid as the selector in NACEELECTROPHORESIS, Issue 22 2006Ylva Hedeland Dr. Abstract The present work demonstrates the importance of the ionic composition in the BGE for enantioseparation. (,)-2,3:4,6-di- O -Isopropylidene-2-keto- L -gulonic acid ((,)-DIKGA) has been used as the chiral selector in methanolic and ethanolic BGEs. The influence of added alkali metal hydroxides on the EOF and the chiral separation of amines (atenolol, isoprenaline, pindolol and propranolol) have been studied. The ion-pair formation constants in ethanol were determined by precision conductometry for the enantiomers of pindolol with (,)-DIKGA, for Li+, Na+ and Cs+ with (,)-DIKGA, and also for the corresponding alkali metal hydroxides. The effective mobilities and the enantiomeric mobility differences were affected by the type of alkali metal hydroxide (LiOH, NaOH, KOH, RbOH or CsOH) added to the BGE. The effective mobility and mobility difference were increased with decrease in solvated radius of the alkali metal cation. These differences could partly be correlated to the ion-pair formation constants of the alkali metal cations with the chiral selector, affecting the equilibrium concentration of the free selector. The electroosmosis was also affected by the alkali metal hydroxide added to the BGE. The cathodic electroosmosis decreased with decreasing solvated radius of the alkali metal cation added to the BGE. Interestingly, the cathodic EOF was even reversed, i.e. became anodic in the ethanolic BGEs containing KOH, RbOH or CsOH and the methanolic ones with RbOH and CsOH. [source] A Cyclic Fc,Histidine Conjugate: Synthesis and Properties , Interactions with Alkali Metal IonsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2006Somenath Chowdhury Abstract The synthesis of the novel N,N, -(ferrocenophane-1,1,-diyldicarbonyl)-bridged histidine methyl ester 1 and of the acyclicbis(histidine methyl ester) derivative 3 are reported. The structure of 1 was studied in the solid state and in solution. The single-crystal structure of 1 shows that both proximal ferrocenyl (Fc) carbonyl groups are syn with respect to each other, which is a new structural motif for Fc,amino acid conjugates. This new syn conformation allows effective binding to alkali metal cations. Binding is evaluated by cyclic voltammetry monitoring the halfwave potential of the Fc group. Cation binding causes a shift to lower potential (Na+ > Li+ > K+, Cs+). Upon binding, compound 1 shows selectivity towards Na+ ions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Lack of main K+ uptake systems in Saccharomyces cerevisiae cells affects yeast performance in both potassium-sufficient and potassium-limiting conditionsFEMS YEAST RESEARCH, Issue 5 2010Clara Navarrete Abstract A new YNB medium containing very low concentrations of alkali metal cations has been developed to carry out experiments to study potassium homoeostasis. Physiological characterization of Saccharomyces cerevisiae BY4741 strain and the corresponding mutant lacking the main potassium uptake systems (trk1 trk2) under potassium nonlimiting and limiting concentrations was performed, and novel important differences between both strains were found. At nonlimiting concentrations of KCl, the two strains had a comparable cell size and potassium content. Nevertheless, mutants were hyperpolarized, had lower pH and extruded fewer protons compared with the BY4741 strain. Upon transfer to K+ -limiting conditions, cells of both strains became hyperpolarized and their cell volume and K+ content diminished; however, the decrease was more relevant in BY4741. In low potassium, trk1 trk2 cells were not able to accomplish the cell cycle to the same extent as in BY4741. Moreover, K+ limitation triggered a high-affinity K+/Rb+ uptake process only in BY4741, with the highest affinity being reached as soon as 30 min after transfer to potassium-limiting conditions. By establishing basic cellular parameters under standard growth conditions, this work aims to establish a basis for the investigation of potassium homoeostasis at the system level. [source] Aluminium-27 NMR investigation of the influence of cation type on aluminosilicate solutionsMAGNETIC RESONANCE IN CHEMISTRY, Issue 10 2002Naser Azizi Abstract The effects of tetraalkylammonium (TAA) and alkali metal cations on the equilibrium distribution of aluminosilicate oligomers in aqueous alkaline aluminosilicate solutions were investigated using 27Al NMR spectra and their evolution with time. The results indicate that there are no differences in the initial equilibria involving solutions containing both TAA and alkali metal cations on the one hand and those containing alkali metal cations only. However, re-equilibration of the aluminosilicate species for TAA/Na aluminosilicates is slow (usually not detectable on the time-scale of the experiments), whereas when purely alkali metal cations are used, the spectra alter over a period of ,1 h, such that resolution is degraded substantially. In the latter case, it is suggested that the anions aggregate into larger systems, although the solutions are still clear. 29Si NMR evidence for slow equilibration of silicate and aluminosilicate solutions at higher concentrations is also discussed. Copyright © 2002 John Wiley & Sons, Ltd. [source] Energy-resolved in-source collisionally induced dissociation for the evaluation of the relative stability of noncovalent complexes in the gas phaseRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 23 2005Nataliya Lyapchenko Energy-resolved in-source collisionally induced dissociation (CID) studies on the complexation of alkali metal cations by some crown ethers, nucleic acid bases, and amino acids have been performed. It has been shown that the cone voltage corresponding to the maximum ion abundance (Vc,Imax) of the breakdown curve is characteristic of a given ion and not influenced by the cone desolvation process or the composition of the solution. Very good agreement of the Vc,Imax value with the bond strength of the ion has been observed. Determination of the Vc,Imax values for different ionic species is a useful, simple, and inexpensive way to obtain their relative stabilities in in-source CID conditions. Copyright © 2005 John Wiley & Sons, Ltd. [source] Synthetic, Structural, and Theoretical Investigations of Alkali Metal Germanium Hydrides,Contact Molecules and Separated IonsCHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2007Weijie Teng Dr. Abstract The preparation of a series of crown ether ligated alkali metal (M=K, Rb, Cs) germyl derivatives M(crown ether)nGeH3 through the hydrolysis of the respective tris(trimethylsilyl)germanides is reported. Depending on the alkali metal and the crown ether diameter, the hydrides display either contact molecules or separated ions in the solid state, providing a unique structural insight into the geometry of the obscure GeH3, ion. Germyl derivatives displaying MGe bonds in the solid state are of the general formula [M([18]crown-6)(thf)GeH3] with M=K (1) and M=Rb (4). The compounds display an unexpected geometry with two of the GeH3 hydrogen atoms closely approaching the metal center, resulting in a partially inverted structure. Interestingly, the lone pair at germanium is not pointed towards the alkali metal, rather two of the three hydrides are approaching the alkali metal center to display MH interactions. Separated ions display alkali metal cations bound to two crown ethers in a sandwich-type arrangement and non-coordinated GeH3, ions to afford complexes of the type [M(crown ether)2][GeH3] with M=K, crown ether=[15]crown-5 (2); M=K, crown ether=[12]crown-4 (3); and M=Cs, crown ether=[18]crown-6 (5). The highly reactive germyl derivatives were characterized by using X-ray crystallography, 1H and 13C,NMR, and IR spectroscopy. Density functional theory (DFT) and second-order Møller,Plesset perturbation theory (MP2) calculations were performed to analyze the geometry of the GeH3, ion in the contact molecules 1 and 4. [source] Cobalt(II) salen complex with two aza-crown pendants and its analogues as synthetic oxygen carriersCHINESE JOURNAL OF CHEMISTRY, Issue 6 2004Xing-Yue Wei Abstract Salen with two aza-crown ether pendants H2L1 and its analogues H2L2- H2L4 were successfully synthesized starting from benzo-10-aza-15crown-5 (BN15C5) or morpholine. Their structures were characterized by IR, MS, 1H NMR and elemental analysis, and were confirmed by X-ray diffraction analysis of H2L1. Moreover, the saturated oxygen uptake of their cobalt(II) complexes CoL1- CoL4 in diethyleneglycol dimethyl ether was determined at different temperature. The oxygenation contants (KO2 ) and thermodynamic parameters (,H° and ,S°) were calculated. The modulation of O2 -binding capabilities by pendant substituents were investigated as compared with the parent Schiff base complex CoL5 (CoSalen). The results indicate that the dioxygen affinities of CoL have been much more enhanced by aza-crown pendants than that by morpholino pendants, and the O2 -binding capabilities of CoL1 and CoL2 with aza-crown pendants would also be enhanced by adding alkali metal cations. [source] | |||||||||||||||||||||||||