Home About us Contact
|
Home About us Contact | ||
|
|
||
Monovalent Cations (monovalent + cation)
Kinds of Monovalent Cations Selected AbstractsMonovalent cations affect the free solution mobility of DNA by perturbing the hydrogen-bonded structure of water,BIOPOLYMERS, Issue 2 2005Earle Stellwagen Abstract The free solution mobilities of single- and double-stranded DNA molecules of various molecular weights have been measured by capillary electrophoresis in solutions of constant ionic strength containing a common anion and fifteen different monovalent cations. In solutions with the same ionic composition, the mobilities of different DNA molecules can vary by up to 20%, depending on molecular weight, the number of strands, and the presence or absence of A-tracts, runs of four or more contiguous adenine residues. Importantly, the mobilities observed for the same DNA sample can vary by up to 40% in solutions containing different cations. The mobility differences observed for the same DNA in solutions containing different cations cannot be rationalized by differences in the anhydrous radii or intrinsic conductivities of the various cations, or by the sequence-dependent binding of certain cations to A-tracts. Instead, the observed mobilities are linearly correlated with the average number of water,water hydrogen bonds that are present in solutions containing different cations. The mobilities are also correlated with the viscosity B coefficients of the various cations and with the rotational correlation times frictional coefficients observed for water molecules in solutions containing different cations. Hence, monovalent cations modify the free solution mobility of DNA primarily by perturbing the hydrogen-bonded structure of water, affecting the friction experienced by the migrating DNA molecules during electrophoresis. © 2005 Wiley Periodicals, Inc. Biopolymers 78: 62,68, 2005 [source] Synthesis and Luminescence Properties of BaMoO4:Sm3+ PhosphorsJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 5 2010Zhiguo Xia BaMoO4:Sm3+ phosphor system with a tetragonal structure was synthesized via a high-temperature solid-state method. The charge compensated behaviors, 2Ba2+,Sm3++M+, where M+ is a monovalent cation like Li+, Na+, and K+ acting as a charge compensator, were investigated in this paper. It has been found that BaMoO4:Sm3+ phosphor by doping with K+ ions show greatly enhanced reddish orange emission compared with pure BaMoO4:Sm3+ sample. Investigation on Sm3+ and K+ concentration-dependent emission spectra indicated that Ba0.84MoO4:0.08Sm3+,0.12K+ phosphor exhibited the strongest reddish orange emission with a CIE values of x=0.55 and y=0.43. After irradiation under the 402 nm ultraviolet (UV) excitation, three emission peaks centered at 561, 598, and 642 nm corresponding to the 4G5/2 to 6HJ (J=5/2, 7/2, 9/2) emission lines of Sm3+ were obviously observed, and the lifetimes of three emissions (4G5/2,6HJ=5/2, 7/2, 9/2) have been calculated based on the measured decay curves. [source] A solid-state 23Na NMR study of monovalent cation binding to double-stranded DNA at low relative humidityMAGNETIC RESONANCE IN CHEMISTRY, Issue 4 2008Alan Wong Abstract We report a solid-state 23Na NMR study of monovalent cation (Li+, Na+, K+, Rb+, Cs+ and NH4+) binding to double-stranded calf thymus DNA (CT DNA) at low relative humidity, ca 0,10%. Results from 23Na31P rotational echo double resonance (REDOR) NMR experiments firmly establish that, at low relative humidity, monovalent cations are directly bound to the phosphate group of CT DNA and are partially dehydrated. On the basis of solid-state 23Na NMR titration experiments, we obtain quantitative thermodynamic parameters concerning the cation-binding affinity for the phosphate group of CT DNA. The free energy difference (,G° ) between M+ and Na+ ions is as follows: Li+ (,1.0 kcal mol,1), K+ (7.2 kcal mol,1), NH4+ (1.0 kcal mol,1), Rb+ (4.5 kcal mol,1) and Cs+ (1.5 kcal mol,1). These results suggest that, at low relative humidity, the binding affinity of monovalent cations for the phosphate group of CT DNA follows the order: Li+ > Na+ > NH4+ > Cs+ > Rb+ > K+. This sequence is drastically different from that observed for CT DNA in solution. This discrepancy is attributed to the different modes of cation binding in dry and wet states of DNA. In the wet state of DNA, cations are fully hydrated. Our results suggest that the free energy balance between direct cation,phosphate contact and dehydration interactions is important. The reported experimental results on relative ion-binding affinity for the DNA backbone may be used for testing theoretical treatment of cation-phosphate interactions in DNA. Copyright © 2008 John Wiley & Sons, Ltd. [source] Zinc Oxide/Zinc Hexacyanoferrate Hybrid Film-Modified Electrodes for Guanine DetectionELECTROANALYSIS, Issue 18 2007Hung-Wei Chu Abstract An electroactive polynuclear hybrid films of zinc oxide and zinc hexacyanoferrate (ZnO/ZnHCF) have been deposited on electrode surfaces from H2SO4 solution containing Zn(NO3)2 and K3[Fe(CN)6] by repetitive potential cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements demonstrate the steady growth of hybrid film. There are two redox couples present in the voltammograms of hybrid film and it is obvious in the case of pH,2. Surface morphology of hybrid film was investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Energy dispersive spectrometer (EDS) data confirm existence of zinc oxide in the hybrid film. The effect of type of monovalent cations on the redox behavior of resulting film was investigated. In pure supporting electrolyte, electrochemical responses of modified electrode resemble with that of a surface immobilized redox couple. The electrocatalytic activity of ZnO/ZnHCF hybrid film was investigated towards guanine using cyclic voltammetry and rotating disc electrode (RDE) techniques. Finally, feasibility of using ZnO/ZnHCF hybrid film-coated electrodes for guanine estimation in flow injection analysis (FIA) was also investigated. [source] Effect of monovalent cations and G-quadruplex structures on the outcome of intramolecular homologous recombinationFEBS JOURNAL, Issue 11 2009Paula Barros Homologous recombination is a very important cellular process, as it provides a major pathway for the repair of DNA double-strand breaks. This complex process is affected by many factors within cells. Here, we have studied the effect of monovalent cations (K+, Na+, and NH4+) on the outcome of recombination events, as their presence affects the biochemical activities of the proteins involved in recombination as well as the structure of DNA. For this purpose, we used an in vitro recombination system that includes a protein nuclear extract, as a source of recombination machinery, and two plasmids as substrates for intramolecular homologous recombination, each with two copies of different alleles of the human minisatellite MsH43. We found that the presence of monovalent cations induced a decrease in the recombination frequency, accompanied by an increase in the fidelity of the recombination. Moreover, there is an emerging consensus that secondary structures of DNA have the potential to induce genomic instability. Therefore, we analyzed the effect of the sequences capable of forming G-quadruplex on the production of recombinant molecules, taking advantage of the capacity of some MsH43 alleles to generate these kinds of structure in the presence of K+. We observed that the MsH43 recombinants containing duplications, generated in the presence of K+, did not include the repeats located towards the 5,-side of the G-quadruplex motif, suggesting that this structure may be involved in the recombination events leading to duplications. Our results provide new insights into the molecular mechanisms underlying the recombination of repetitive sequences. [source] Characterization of Arginine Transport in Helicobacter pyloriHELICOBACTER, Issue 4 2003George L. Mendz ABSTRACT Background. The amino acid L-arginine is an essential requirement for growth of Helicobacter pylori. Several physiological roles of this amino acid have been identified in the bacterium, but very little is known about the transport of L-arginine and of other amino acids into H. pylori. Methods. Radioactive tracer techniques using L-(U- 14C) arginine and the centrifugation through oil method were employed to measure the kinetic parameters, temperature dependence, substrate specificity, and effects of analogues and inhibitors on L-arginine transport. Results. The transport of arginine at millimolar concentrations was saturable with a Km of 2.4 ± 0.3 mM and Vmax of 1.3 ± 0.2 pmole min,1 (µl cell water),1 or 31 ± 3 nmole per minute (mg protein),1 at 20°C, depended on temperature between 4 and 40°C, and was susceptible to inhibitors. These characteristics suggested the presence of one or more arginine carriers. The substrate specificity of the transport system was studied by measuring the effects of L-arginine analogues and amino acids on the rates of transport of L-arginine. The absence of inhibition in competition experiments with L-lysine and L-ornithine indicated that the transport system was not of the Lysine-Arginine-Ornithine or Arginine-Ornithine types. The presence of different monovalent cations did not affect the transport rates. Several properties of L-arginine transport were elucidated by investigating the effects of potential inhibitors. Conclusions. The results provided evidence that the transport of L-arginine into H. pylori cells was carrier-mediated transport with the driving force supplied by the chemical gradient of the amino acid. [source] Geochemical weathering at the bed of Haut Glacier d'Arolla, Switzerland,a new modelHYDROLOGICAL PROCESSES, Issue 5 2002M. Tranter Waters were sampled from 17 boreholes at Haut Glacier d'Arolla during the 1993 and 1994 ablation seasons. Three types of concentrated subglacial water were identified, based on the relative proportions of Ca2+, HCO3, and SO42, to Si. Type A waters are the most solute rich and have the lowest relative proportion of Si. They are believed to form in hydrologically inefficient areas of a distributed drainage system. Most solute is obtained from coupled sulphide oxidation and carbonate dissolution (SO,CD). It is possible that there is a subglacial source of O2, perhaps from gas bubbles released during regelation, because the high SO42, levels found (up to 1200 µeq/L) are greater than could be achieved if sulphides are oxidized by oxygen in saturated water at 0 °C (c.414 µeq/L). A more likely alternative is that sulphide is oxidized by Fe3+ in anoxic environments. If this is the case, exchange reactions involving FeIII and FeII from silicates are possible. These have the potential to generate relatively high concentrations of HCO3, with respect to SO42,. Formation of secondary weathering products, such as clays, may explain the low Si concentrations of Type A waters. Type B waters were the most frequently sampled subglacial water. They are believed to be representative of waters flowing in more efficient parts of a distributed drainage system. Residence time and reaction kinetics help determine the solute composition of these waters. The initial water,rock reactions are carbonate and silicate hydrolysis, and there is exchange of divalent cations from solution for monovalent cations held on surface exchange sites. Hydrolysis is followed by SO,CD. The SO42, concentrations usually are <414 µeq/L, although some range up to 580 µeq/L, which suggests that elements of the distributed drainage system may become anoxic. Type C waters were the most dilute, yet they were very turbid. Their chemical composition is characterized by low SO42, : HCO3, ratios and high pH. Type C waters were usually artefacts of the borehole chemical weathering environment. True Type C waters are believed to flow through sulphide-poor basal debris, particularly in the channel marginal zone. The composition of bulk runoff was most similar to diluted Type B waters at high discharge, and was similar to a mixture of Type B and C waters at lower discharge. These observations suggest that some supraglacial meltwaters input to the bed are stored temporarily in the channel marginal zone during rising discharge and are released during declining flow. Little of the subglacial chemical weathering we infer is associated with the sequestration of atmospheric CO2. The progression of reactions is from carbonate and silicate hydrolysis, through sulphide oxidation by first oxygen and then FeIII, which drives further carbonate and silicate weathering. A crude estimate of the ratio of carbonate to silicate weathering following hydrolysis is 4 : 1. We speculate that microbial oxidation of organic carbon also may occur. Both sulphide oxidation and microbial oxidation of organic carbon are likely to drive the bed towards suboxic conditions. Hence, we believe that subglacial chemical weathering does not sequester significant quantities of atmospheric CO2 and that one of the key controls on the rate and magnitude of solute acquisition is microbial activity, which catalyses the reduction of FeIII and the oxidation of FeS2. Copyright © 2002 John Wiley & Sons, Ltd. [source] In depolarized and glucose-deprived neurons, Na+ influx reverses plasmalemmal K+ -dependent and K+ -independent Na+/Ca2+ exchangers and contributes to NMDA excitotoxicityJOURNAL OF NEUROCHEMISTRY, Issue 6 2002Aneta Czy Abstract Cerebellar granule cells (CGCs) express K+ -dependent (NCKX) and K+ -independent (NCX) plasmalemmal Na+/Ca2+ exchangers which, under plasma membrane-depolarizing conditions and high cytosolic [Na+], may reverse and mediate potentially toxic Ca2+ influx. To examine this possibility, we inhibited NCX or NCKX with KB-R7943 or K+ -free medium, respectively, and studied how gramicidin affects cytosolic [Ca2+] and 45Ca2+ accumulation. Gramicidin forms pores permeable to alkali cations but not Ca2+. Therefore, gramicidin-induced Ca2+ influx is indirect; it results from fluxes of monovalent cations. In the presence of Na+, but not Li+ or Cs+, gramicidin induced Ca2+ influx that was inhibited by simultaneous application of KB-R7943 and K+ -free medium. The data indicate that gramicidin-induced Na+ influx reverses NCX and NCKX. To test the role of NCX and/or NCKX in excitotoxicity, we studied how NMDA affects the viability of glucose-deprived and depolarized CGCs. To assure depolarization of the plasma membrane, we inhibited Na+,K+ -ATPase with ouabain. Although inhibition of NCX or NCKX reversal failed to significantly limit 45Ca2+ accumulation and excitotoxicity, simultaneously inhibiting NCX and NCKX reversal was neuroprotective and significantly decreased NMDA-induced 45Ca2+ accumulation. Our data suggest that NMDA-induced Na+ influx reverses NCX and NCKX and leads to the death of depolarized and glucose-deprived neurons. [source] Self-association of cromolyn sodium in aqueous solution characterized by nuclear magnetic resonance spectroscopyJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 5 2004Xuan Ding Abstract The major objective of this study was to investigate and characterize the solution properties of cromolyn sodium (in D2O or D2O/H2O phosphate buffer at pH 7.5) using nuclear magnetic resonance (NMR) spectroscopy. The self-association of cromolyn molecules was examined primarily via one-dimensional 1H and 13C, and two-dimensional homonuclear NOESY NMR. Significant spectral shifts were observed for a majority of cromolyn 1H and 13C resonances, and are attributed to inter-molecular ring-stacking association accompanied by intra-molecular conformational changes. The critical self-association concentration was determined to be 10 mg/mL at pH 7.5 and 25°C by measuring the chemical shift of a specific cromolyn 1H resonance. The observed magnitude and sign changes of NOESY correlations indicate the formation of cromolyn aggregates with restricted molecular mobility. Mesomorphic liquid crystal formation is suggested by uniformly pronounced line broadening in concentrated cromolyn solutions; the transition concentration was approximately 60 mg/mL at 25°C, which is consistent with literature findings based on other techniques. A stronger tendency toward association was observed at lower temperature but aggregation appeared to be independent of pH. Lastly, it was concluded that self-association of cromolyn is promoted by the presence of monovalent cations as a result of reduced electrostatic repulsive forces. © 2004 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 93:1351,1358, 2004 [source] Environmentally responsive micelles from polystyrene,poly[bis(potassium carboxylatophenoxy)phosphazene] block copolymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2005Youngkyu Chang Abstract Amphiphilic diblock copolymers that contained hydrophilic poly[bis(potassium carboxylatophenoxy)phosphazene] segments and hydrophobic polystyrene sections were synthesized via the controlled cationic polymerization of Cl3PNSiMe3 with a polystyrenyl,phosphoranimine as a macromolecular terminator. These block copolymers self-associated in aqueous media to form micellar structures which were investigated by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The size and shape of the micelles were not affected by the introduction of different monovalent cations (Li+, K+, Na+, and Cs+) into the stable micellar solutions. However, exposure to divalent cations induced intermicellar crosslinking through carboxylate groups, which caused precipitation of the ionically crosslinked aggregates from solution. This micelle-coupling behavior was reversible: the subsequent addition of monovalent cations caused the redispersion of the polystyrene- block -poly[bis(potassium carboxylatophenoxy)phosphazene] (PS,KPCPP) block copolymers into a stable micellar solution. Aqueous micellar solutions of PS,KPCPP copolymers also showed pH-dependent behavior. These attributes make PS,KPCPP block copolymers suitable for studies of guest retention and release in response to ion charge and pH. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2912,2920, 2005 [source] A solid-state 23Na NMR study of monovalent cation binding to double-stranded DNA at low relative humidityMAGNETIC RESONANCE IN CHEMISTRY, Issue 4 2008Alan Wong Abstract We report a solid-state 23Na NMR study of monovalent cation (Li+, Na+, K+, Rb+, Cs+ and NH4+) binding to double-stranded calf thymus DNA (CT DNA) at low relative humidity, ca 0,10%. Results from 23Na31P rotational echo double resonance (REDOR) NMR experiments firmly establish that, at low relative humidity, monovalent cations are directly bound to the phosphate group of CT DNA and are partially dehydrated. On the basis of solid-state 23Na NMR titration experiments, we obtain quantitative thermodynamic parameters concerning the cation-binding affinity for the phosphate group of CT DNA. The free energy difference (,G° ) between M+ and Na+ ions is as follows: Li+ (,1.0 kcal mol,1), K+ (7.2 kcal mol,1), NH4+ (1.0 kcal mol,1), Rb+ (4.5 kcal mol,1) and Cs+ (1.5 kcal mol,1). These results suggest that, at low relative humidity, the binding affinity of monovalent cations for the phosphate group of CT DNA follows the order: Li+ > Na+ > NH4+ > Cs+ > Rb+ > K+. This sequence is drastically different from that observed for CT DNA in solution. This discrepancy is attributed to the different modes of cation binding in dry and wet states of DNA. In the wet state of DNA, cations are fully hydrated. Our results suggest that the free energy balance between direct cation,phosphate contact and dehydration interactions is important. The reported experimental results on relative ion-binding affinity for the DNA backbone may be used for testing theoretical treatment of cation-phosphate interactions in DNA. Copyright © 2008 John Wiley & Sons, Ltd. [source] Membrane depolarization induces K+ efflux from subapical maize root segmentsNEW PHYTOLOGIST, Issue 1 2002Fabio F. Nocito Summary ,,The role of potassium efflux from maize (Zea mays) root segments in maintaining transmembrane electric potential difference (Em) was studied in vivo, together with the involvement of outward rectifying K+ channels (ORCs). ,,Measurements were made of the efflux of potassium (K+) from roots when its uptake was competitively inhibited by rubidium (Rb+), of the Em of the root cells by microelectrodes and of the unidirectional fluxes of monovalent cations. ,,The influx of Rb+, caesium (Cs+) or ammonium (NH4+) into the segments induced an efflux of K+. Lithium (Li+) and sodium (Na+) were not taken up and did not induce K+ efflux. The permeating cations induced membrane depolarizations, which were closely related to the values of K+ efflux. Two K+ -channel blockers, tetraethylammonium-chloride and quinidine, inhibited K+ efflux. The inhibition was accompanied by a higher membrane depolarization induced by Rb+, whose influx was not affected. ,,The results suggest that a depolarizing event caused by cation uptake increased K+ efflux from the cells, probably through the activation of ORCs involved in restoration and stabilization of Em. [source] Properties of ion channels in the protoplasts of the Mediterranean seagrass Posidonia oceanicaPLANT CELL & ENVIRONMENT, Issue 3 2004A. CARPANETO ABSTRACT Posidonia oceanica (L) Delile, a seagrass endemic of the Mediterranean sea, provides food and shelter to marine organisms. As environment contamination and variation in physico-chemical parameters may compromise the survival of the few Posidonia genotypes living in the Mediterranean, comprehending the molecular mechanisms controlling Posidonia growth and development is increasingly important. In the present study the properties of ion channels in P. oceanica plasma membranes studied by the patch-clamp technique in protoplasts obtained from the young non-photosynthetic leaves were investigated. In protoplasts that were presumably originated from sheath cells surrounding the vascular bundles of the leaves, an outward-rectifying time-dependent channel with a single channel conductance of 58 ± 2 pS which did not inactivate, was selective for potassium and impermeable to monovalent cations such as Na+, Li+ and Cs+ was identified. In the same protoplasts, an inward-rectifying channel that has a time-dependent component with single channel conductance of the order of 10 pS, a marked selectivity for potassium and no permeation to sodium was also identified, as was a third type of channel that did not display any ionic selectivity and was reversibly inhibited by tetraethylammonium and lanthanum. A comparison of Posidonia channel characteristics with channels identified in terrestrial plants and other halophytic plants is included. [source] Spontaneously active and InsP3 -activated ion channels in cell nuclei from rat cerebellar Purkinje and granule neuronesTHE JOURNAL OF PHYSIOLOGY, Issue 3 2005Sergey M. Marchenko Increases in Ca2+ concentration in the nucleus of neurones modulate gene transcription and may be involved in activity-dependent long-term plasticity, apoptosis, and neurotoxicity. Little is currently known about the regulation of Ca2+ in the nuclei of neurones. Investigation of neuronal nuclei is hampered by the cellular heterogeneity of the brain where neurones comprise no more than 10% of the cells. The situation is further complicated by large differences in properties of different neurones. Here we report a method for isolating nuclei from identified central neurones. We employed this technique to study nuclei from rat cerebellar Purkinje and granule neurones. Patch-clamp recording from the nuclear membrane of Purkinje neurones revealed numerous large-conductance channels selective for monovalent cations. The nuclear membrane of Purkinje neurones also contained multiple InsP3 - activated ion channels localized exclusively in the inner nuclear membrane with their receptor loci facing the nucleoplasm. In contrast, the nuclear membrane of granule neurones contained only a small number of mainly anion channels. Nuclear InsP3 receptors (InsP3Rs) were activated by InsP3 with EC50= 0.67 ,m and a Hill coefficient of 2.5. Ca2+ exhibited a biphasic effect on the receptors elevating its activity at low concentrations and inhibiting it at micromolar concentrations. InsP3 in saturating concentrations did not prevent the inhibitory effect of Ca2+, but strongly increased InsP3R activity at resting Ca2+ concentrations. These data are the first evidence for the presence of intranuclear sources of Ca2+ in neurones. Ca2+ release from the nuclear envelope may amplify Ca2+ transients penetrating the nucleus from the cytoplasm or generate Ca2+ transients in the nucleus independently of the cytoplasm. [source] Multinuclear magnetic resonance, electrospray ionization,mass spectroscopy, and parametric method 5 studies of a new derivative of gossypol with 2-thiophenecarbohydrazide as well as its complexes with LI+, Na+, K+, RB+, and Cs+ cationsBIOPOLYMERS, Issue 3 2006Piotr Przybylski Abstract A new derivative of racemic gossypol with 2-thiophenecarbohydrazide (GHHT) and its complexes with monovalent cations have been synthesized and studied by electrospray ionization,mass spectroscopy (ESI-MS), multinuclear nuclear magnetic resonance (NMR), as well as by the Parametric Method 5 (PM5) methods. It is demonstrated that GHHT forms stable complexes of 1:1 stoichiometry with monovalent metal cations. The structures of the complexes are stabilized by three types of intramolecular hydrogen bonds. The spectroscopic methods have provided clear evidence that GHHT and its complexes exist in the DMSO-d6 solution in the N-imine,N-imine tautomeric forms. The structures of the GHHT and its complexes with Li+, Na+, K+, Rb+, and Cs+ cations are visualized and discussed in detail. © 2006 Wiley Periodicals, Inc. Biopolymers 83: 213,225, 2006 This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] Monovalent cations affect the free solution mobility of DNA by perturbing the hydrogen-bonded structure of water,BIOPOLYMERS, Issue 2 2005Earle Stellwagen Abstract The free solution mobilities of single- and double-stranded DNA molecules of various molecular weights have been measured by capillary electrophoresis in solutions of constant ionic strength containing a common anion and fifteen different monovalent cations. In solutions with the same ionic composition, the mobilities of different DNA molecules can vary by up to 20%, depending on molecular weight, the number of strands, and the presence or absence of A-tracts, runs of four or more contiguous adenine residues. Importantly, the mobilities observed for the same DNA sample can vary by up to 40% in solutions containing different cations. The mobility differences observed for the same DNA in solutions containing different cations cannot be rationalized by differences in the anhydrous radii or intrinsic conductivities of the various cations, or by the sequence-dependent binding of certain cations to A-tracts. Instead, the observed mobilities are linearly correlated with the average number of water,water hydrogen bonds that are present in solutions containing different cations. The mobilities are also correlated with the viscosity B coefficients of the various cations and with the rotational correlation times frictional coefficients observed for water molecules in solutions containing different cations. Hence, monovalent cations modify the free solution mobility of DNA primarily by perturbing the hydrogen-bonded structure of water, affecting the friction experienced by the migrating DNA molecules during electrophoresis. © 2005 Wiley Periodicals, Inc. Biopolymers 78: 62,68, 2005 [source] Self-Assembled Ionophores from Isoguanosine: Diffusion NMR Spectroscopy Clarifies Cation's and Anion's Influence on Supramolecular StructureCHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2007Tamar Evan-Salem Abstract Cation-templated self-assembly of the lipophilic isoguanosine (isoG,1) with different monovalent cations (M+=Li+, Na+, K+, NH4+, and Cs+) was studied in solvents of different polarity by using diffusion NMR spectroscopy. Previous studies that did not use diffusion NMR techniques concluded that isoG,1 forms both pentamers (isoG,1)5,M+ and decamers (isoG,1)10,M+ in the presence of alkali-metal cations. The present diffusion NMR studies demonstrate, however, that isoG,1 does not form (isoG,1)5,M+ pentamers. In fact, the diffusion NMR data indicates that both doubly charged decamers of formula (isoG,1)10,2,M+ and singly charged decamers, (isoG,1)10,M+, are formed with lithium, sodium, potassium, and ammonium tetraphenylborate salts (LiB(Ph)4, KB(Ph)4, NaB(Ph)4 and NH4B(Ph)4), depending on the isoG,1:salt stoichiometry of the solution. In the presence of CsB(Ph)4, isoG,1 affords only the singly charged decamers (isoG,1)10,Cs+. By monitoring the diffusion coefficient of the B(Ph)4, ion in the different mixtures of solvents, we also concluded that the anion is more strongly associated to the doubly charged decamers (isoG,1)10,2,M+ than to the singly charged decamers (isoG,1)10,M+. The (isoG,1)10,2,M+ species can, however, exist in solution without the mediation of the anion. This last conclusion was supported by the finding that the doubly charged decamers (isoG,1)10,2,M+ also prevail in 1:1 CD3CN:CDCl3, a solvent mixture in which the B(Ph)4, ion does not interact significantly with the self-assembled complex. These diffusion measurements, which have provided new and improved structural information about these decameric isoG,1 assemblies, demonstrate the utility of combining diffusion NMR techniques with conventional NMR methods in seeking to characterize labile, multicomponent, supramolecular systems in solution, especially those with high symmetry. [source] | |||||||||||||||||||||||||||||||