Anomalous small angle x-ray scattering determination of ion distribution around a polyelectrolyte biopolymer in salt solution

The distribution of counterions in solutions of high molecular mass hyaluronic acid, in near-physiological conditions where mono- and divalent ions are simultaneously present, is studied by small angle neutron scattering and anomalous small angle x-ray scattering. The solutions contain either sodium or rubidium chloride together with varying concentrations of calcium or strontium chloride. The effects of monovalent-divalent ion exchange dominate the amplitude and the form of the counterion cloud. In the absence of divalent ions, the shape of the anomalous scattering signal from the monovalent ions is consistent with the distribution calculated from the Poisson-Boltzmann equation, as found by other workers. In mixtures of monovalent and divalent ions, however, as the divalent ion concentration increases, both the diameter and the amplitude of the monovalent ion cloud decrease. The divalent counterions always occupy the immediate neighborhood of the charged polyanion. Above a given concentration their anomalous scattering signal saturates. Even in a large excess of divalent ions, ion exchange is incomplete.     

Influence of ion size on the stability of chloroplumbates containing PbCl<Stack><Subscript>5</Subscript><Superscript>−</Superscript></Stack> or PbCl<Stack><Subscript>6</Subscript><Superscript>2−</Superscript></Stack>

The enthalpies of formation of PbCl₄, PbCl₅⁻ and PbCl₆²⁻, originating from quantum mechanics, have enabled the thermodynamic behaviour of these ions with respect to Cl-detachment to be assessed. The stability of salts containing PbCl₅⁻ and PbCl₆²⁻ as a function of the dimensions of these anions and complementary cations was studied using an approach combining the Kapustinskii-Yatsimirskii equation with basic thermochemical relationships. It was found that hexachloroplumbates of monovalent metal cations will not dissociate into metal chlorides and PbCl₄, provided the complementary cations are suitably large in size. Hexachloroplumbates of divalent metal cations have not yet been synthesised since no known metal cations attain the requisite large size. Such salts will not dissociate if the divalent metal cations are able to complex suitably large electron-donating ligands. The pentachloroplumbates of both monovalent and divalent metal cations are unstable, since no known metal cations have appropriately large ionic radii. The approach adopted appears to be useful for the examination of the thermal behaviour, stability and reactivity of chloroplumbates.     

Effects of cations on the hydrogen bond network of liquid water: new results from X-ray absorption spectroscopy of liquid microjets

Oxygen K-edge X-ray absorption spectra (XAS) of aqueous chloride solutions have been measured for Li(+), Na(+), K(+), NH(4)(+), C(NH(2))(3)(+), Mg(2+), and Ca(2+) at 2 and 4 M cation concentrations. Marked changes in the liquid water XAS are observed upon addition of the various monovalent cation chlorides that are nearly independent of the identity of the cation. This indicates that interactions with the dissolved monovalent cations do not significantly perturb the unoccupied molecular orbitals of water molecules in the vicinity of the cations and that water-chloride interactions are primarily responsible for the observed spectral changes. In contrast, the addition of the divalent cations engenders changes unique from the case of the monovalent cations, as well as from each other. Density functional theory calculations suggest that the ion-specific spectral variations arise primarily from direct electronic perturbation of the unoccupied orbitals due to the presence of the ions, probably as a result of differences in charge transfer from the water molecules onto the divalent cations.     

Ion‐exchange induced change in the structure and osmotic properties of sodium polyacrylate hydrogels

The swelling and volume transition of fully neutralized sodium polyacrylate gels were investigated in salt solutions using osmotic and small angle neutron scattering measurements. The volume transition was induced by monovalent/divalent cation exchange. The overall salt concentration and the ratio of monovalent to divalent cations were varied in the biologically significant range. The neutron scattering response of fully neutralized polyacrylate gels in the presence of excess salt is described by the sum of a dynamic and a static component. The thermal correlation length determined from the intensity of the dynamic component displays a maximum at the transition.     

Influence of various monovalent cations and calcium ion on the colloidal fouling potential

The influence of various monovalent cations and of divalent calcium ions on colloidal fouling strength was investigated quantitatively on a bench-scale ultrafiltration device. A higher colloidal fouling potential (k) was consistently observed with lithium chloride compared to the same ionic strengths of chlorides of other monovalent cations (Na+, K+, and Cs+). This observation was attributed to the formation of an impervious layer around the colloidal particle by lithium ions that prevented the repulsive forces due to the interaction of the silica hairs formed on the particles in the presence of water. The impact of the divalent calcium ion on the fouling potential was more complex. The fouling potential first increased with calcium ion concentration and then decreased. The maximum value of fouling potential occurred at the ionic strength corresponding to the critical coagulation concentration, which decreased with increasing colloid concentration. The colloidal fouling potential was well correlated by a bilinear relationship with colloid concentration and ionic strength for all salts tested under the critical coagulation concentration.     

Quenching of fluorophore-labeled DNA oligonucleotides by divalent metal ions: implications for selection, design, and applications of signaling aptamers and signaling deoxyribozymes

Recent years have seen a dramatic increase in the use of fluorescence-signaling DNA aptamers and deoxyribozymes as novel biosensing moieties. Many of these functional single-stranded DNA molecules are either engineered to function in the presence of divalent metal ion cofactors or designed as sensors for specific divalent metal ions. However, many divalent metal ions are potent fluorescence quenchers. In this study, we first set out to examine the factors that contribute to quenching of DNA-bound fluorophores by commonly used divalent metal ions, with the goal of establishing general principles that can guide future exploitation of fluorescence-signaling DNA aptamers and deoxyribozymes as biosensing probes. We then extended these studies to examine the effect of specific metals on the signaling performance of both a structure-switching signaling DNA aptamer and an RNA-cleaving and fluorescence-signaling deoxyribozyme. These studies showed extensive quenching was obtained when using divalent transition metal ions owing to direct DNA-metal ion interactions, leading to combined static and dynamic quenching. The extent of quenching was dependent on the type of metal ion and the concentration of supporting monovalent cations in the buffer, with quenching increasing with the number of unpaired electrons in the metal ion and decreasing with the concentration of monovalent ions. The extent of quenching was independent of the fluorophore, indicating that quenching cannot be alleviated simply by changing the nature of the fluorescent probe. Our results also show that the DNA sequence and the local secondary structure in the region of the fluorescent tag can dramatically influence the degree of quenching by divalent transition metal ions. In particular, the extent of quenching is predominantly determined by the fluorophore location with respect to guanine-rich and duplex regions within the strand sequence. Examination of the effect of both the type and concentration of metal ions on the performance of a fluorescence-signaling aptamer and a signaling deoxyribozyme confirms that judicious choice of divalent transition metal ions is important in maximizing signals obtained from such systems.     

聚马来酸包夹硅胶基质单柱弱阳离子色谱柱填料

用马来酸包夹硅胶基质制备出一种新型弱阳离子色谱柱填料，该填料具有良好的色谱性能，可以较好地分离碱金属离子、碱土金属离子及一价胺离子。另外该填料可同时分离一价、二价金属阳离子。本文还考察了流动相的ｐＨ值和浓度对溶质保留的影响。     

The chameleon-like nature of zwitterionic micelles: effect of cation binding

Addition of salts, especially perchlorates, to zwitterionic micelles of SB3-14, C(14)H(29)NMe(2)(+)(CH(2))(3)SO(3)(-), induces anionic character and uptake of H(3)O(+) by SB3-14 micelles. Thus, the addition of alkali metal perchlorates accelerates the acid hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane, HPD, in the presence of SB3-14 micelles, which depends on the local proton concentration at the micelle surface. The addition of metal chlorides to solutions of such perchlorate-modified SB3-14 micelles decreases both the negative zeta potential of the micelles and the observed rate constant for acid hydrolysis of HPD. The effect of the monovalent cations Li(+), Na(+), and K(+) is smaller than that of the divalent cations Be(2+), Mg(2+), and Ca(2+), and much smaller than that of the trivalent cations Al(3+), La(3+), and Er(3+). The major factor responsible for this cation valence dependence of these effects is shown to be electrostatic in nature, reflecting the strong dependence of the micellar surface potential on the cation valence. The fact that the salt effects are not identical after correction for the electrostatic effects indicates that additional secondary nonelectrostatic effects may contribute as well.     

Thermodynamic quantities of surface formation of aqueous electrolyte solutions X. Aqueous solution of 2:1 valence-type salts

The behaviors of a series of calcium halides and of alkali earth metal chlorides in the air/water surface region were studied in comparison with those of alkali metal halides by measuring the surface tension increments of solutions. The effect of salts with divalent cations on the surface tension increments is more pronounced than that of uni-univalent salts, but there are some similarities between these two types. It seems that the anions cause a marked effect on surface tension which is proportional to the magnitude of hydration in the bulk water. We also observed a decrease in the entropy change of surface formation with increasing concentration. The importance of an electrical double layer at the surface is discussed in relation to these surface tension increments.     

Metallic LiMo3Se3 nanowire film sensors for electrical detection of metal ions in water

LiMo 3Se 3 nanowire film sensors were fabricated by drop-coating a 0.05% (mass) aqueous nanowire solution onto microfabricated indium tin oxide electrode pairs. According to scanning electron microscopy (SEM) and atomic force microscopy (AFM), the films are made of a dense network of 3-7 nm thick nanowire bundles. Immersion of the films in 1.0 M aqueous solutions of group 1 or 2 element halides or of Zn(II), Mn(II), Fe(II), or Co(II) chlorides results in an increase of the electrical resistance of the films. The resistance change is always positive and reaches up to 9% of the base resistance of the films. It occurs over the course of 30-240 s, and it is reversible for monovalent ions and partially reversible for divalent ions. The signal depends on the concentration of the electrolyte and on the size and charge of the metal cation. Anions do not play a significant role, presumably, because they are repelled by the negatively charged nanowire strands. The magnitude of the electrical response and its sign suggest that it is due to analyte-induced scattering of conduction electrons in the nanowires. An ion-induced field effect can be excluded based on gated conductance measurements of the nanowire films.     

Enzyme-polyelectrolyte complex: Salt effects on the reaction of urease with polyallylamine

The effects of inorganic mono- and divalent salts of different types on how the cation polyelectrolyte polyallylamine hydrochloride (PAA) binds with the oligomer enzyme urease were studied. It was shown that in solutions of the monovalent salts NaCl, KCl, and NH₄Cl, polyelectrolyte-protein complexes formed by electrostatic interactions, which decreased monotonically as the salt concentrations increased according to the classic law of statistical physics, correlating the Debye radius with the ionic strength of the solution. In solutions of the divalent salts Na₂SO₄ and (NH₄)2_SO₄, the efficiency of the formation of the polyelectrolyte-protein complexes changed abruptly (the enzyme was drastically activated) at low salt concentrations (∼0.6–0.8 mM), which was not consistent with the classic theory of charge interactions in solutions with different ionic strengths. Turbidimetric titration at different salt concentrations in the given range revealed a high aggregative ability for sulfates and low ability for chlorides. It was concluded that the anomalies in the concentration dependence of the enzyme activity and aggregative ability were related to the formation of stable bonds PAA to the divalent SO₄²⁻ anion, which increased drastically when the ratio of anion concentration to the number of positively charged PAA monomers in solution reached 1: 2.     

Comparative Study of Scattering and Osmotic Properties of Synthetic and Biopolymer Gels

Summary: The effect of monovalent/divalent cation exchange on the structure and osmotic properties of chemically cross-linked polyacrylate and DNA gels swollen in near physiological salt solutions has been investigated. Both systems exhibit a reversible volume phase transition in the presence of calcium ions. The small-angle neutron scattering spectra of these gels display qualitatively similar features. At low values of q surface scattering is observed, while in the intermediate q range the signal is characteristic of scattering from rod-like elements. At high values of q the scattering intensity is governed by the local (short-range) geometry of the polymer chains. The competition between monovalent and divalent cations has been studied by anomalous small-angle X-ray scattering (ASAXS). The ASAXS results reveal that the local concentration of the divalent counter-ions in the vicinity of the polymer chains significantly exceeds that of the monovalent counter-ions.     

Obtention and characterization of a ciclesonide: methyl-beta cyclodextrin complex

Conformationally mobile, di-ionizable 1,2-dimethoxy-p-tert-butylcalix[4]arene ligands are synthesized and compared with 1,3-dimethoxyl analogues to probe the influence of regiochemistry on metal ion extraction efficiency and selectivity. Extraction of hard alkali metal and alkaline earth metal cations, intermediate Pb²⁺, and soft Hg²⁺ from aqueous solutions into chloroform are utilized to evaluate the effect of this structural variation on the ability of the ligands to complex monovalent and divalent metal ion species.     

Rod-like polyelectrolyte adsorption onto charged surfaces in monovalent and divalent salt solutions

We analyze the adsorption of strongly charged polyelectrolytes onto weakly charged surfaces in divalent salt solutions. We include short-range attractions between the monomers and the surface and between condensed ions and monomers, as well correlations among the condensed ions. Our results are compared with the adsorption in monovalent salt solutions. Different surface charge densities (σ), and divalent (m) and monovalent (s) salt concentrations are considered. When the Wigner-Seitz cells diameter (2R) is larger than the length of the rod, the maximum amount of adsorption scales like n_max ∼ σ^4/3 in both monovalent and divalent solutions. For homogeneously charged surfaces, the maximum adsorption occurs at s* ∼ σ² when s* > ϕ, where ϕ is the monomer concentration, the counterpart for divalent salt solution, m* roughly scales as σ^2.2 when m* > ϕ. The effective surface charge density has a maximum absolute value at m′ < m*. A discrete surface charge distribution and short-range attractions between monomers and surface charge groups can greatly enhance surface charge inversion especially for high salt concentration. The critical salt concentration for adsorption in divalent salt solution roughly scales as m_c ∼ bσ^1.9, where b is the distance between two neighboring charged monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3642–3653, 2004     

稀土离子及其配合物对二棕榈酰磷脂酰乙醇胺相变性质的影响

用差示扫描量热研究了金属离子和稀土配合物对二棕榈酰磷脂酰乙醇胺(DPPE)脂双层由凝胶态向液晶态相转变的影响T~m的影响。发现加入金属离子提高了DPPE脂双层的相转变温度。其中, Na^+＜Ca^2^+＜Ln^3^+。Pr^3^+的影响较La^3^+强。在pH 7.4时, 柠檬酸镧对T~m影响很小, 相反在pH 2.0时, 则降低相变温度T~m。乳酸稀土在pH 2.0和pH 7.4时都显著提高T~m, 在中性条件下, 对T~m影响更大。同时, 乳酸稀土较相同浓度下的稀土离子影响大, 说明乳酸稀土中稀土离子和乳酸根配体存在协同作用。我们初步探讨了金属离子以及稀土配合物对DPPE脂双层相变温度影响的原因。     

Radiation of multicomponent aqueous salt solutions in the millimeter-wave spectral region

The low-intensity radiation and radiobrightness contrasts of multicomponent aqueous solutions of alkali metal chlorides have been studied at a frequency of 61.2 GHz. An additive character of changes in radiobrightness contrasts relative to initial binary systems (component ratio, 1: 1) is shown. The concentration dependence for solutions of potassium and lithium chlorides shows that initial different-sign radiation effects are eliminated. The radiation of mixed solutions proves to be close to the radiation of pure water (up to 4 m solutions).     

Effects of alkaline earth metal ion complexation on amino acid zwitterion stability: results from infrared action spectroscopy

The structures of isolated alkaline earth metal cationized amino acids are investigated using infrared multiple photon dissociation (IRMPD) spectroscopy and theory. These results indicate that arginine, glutamine, proline, serine, and valine all adopt zwitterionic structures when complexed with divalent barium. The IRMPD spectra for these ions exhibit bands assigned to carboxylate stretching modes, spectral signatures for zwitterionic amino acids, and lack bands attributable to the carbonyl stretch of a carboxylic acid functional group. Structural and spectral assignments are strengthened through comparisons with absorbance spectra calculated for low-energy structures and the IRMPD spectra of analogous ions containing monovalent alkali metals. Many bands are significantly red-shifted from the corresponding bands for amino acids complexed with monovalent metal ions, owing to increased charge transfer to divalent metal ions. The IRMPD spectra of arginine complexed with divalent strontium and barium are very similar and indicate that arginine adopts a zwitterionic form in both ions. Calculations indicate that nonzwitterionic forms of arginine are lowest in free energy in complexes with smaller alkaline earth metal cations and that zwitterionic forms are preferentially stabilized with increasing metal ion size. B3LYP and MP2 calculations indicate that zwitterionic forms of arginine are lowest in free energy for M = Ca, Sr, and Ba.     

Mixed brushes consisting of oppositely charged Y-shaped polymers in salt free,monovalent, and divalent salt solutions

The conformation and the internal stratification of mixed brushes formed from oppositely charged Y(−) and Y(+)-shaped chains in salt free, monovalent, and divalent salt solutions were studied by means of molecular dynamics simulations using the primitive model. Scaling relations of mixed brush height with respect to the grafting surface per chain, the ratio of the total positive to the total negative charge of polyelectrolyte chains, and salt concentrations were obtained. The simulations predicted that mixed brushes show a unique response to divalent salt (1:2) solutions. For symmetric brushes having the same spacer lengths, number of chains and charged units fractions the increase of the salt concentration leads to the enrichment of the outer brush surface with Y(+) units and the lamella microphase separation. For asymmetric brushes in high salt concentration cylindrical domain microphases are formed.     

Dissociation behavior of poly(α‐hydroxy acrylic acid)

Dissociation behavior of poly(α‐hydroxy acrylic acid) (PHA) was investigated by potentiometric titration in the presence of NaCl and/or divalent metal chlorides. It was found that pH values of PHA aqueous solutions increased with time when the degree of dissociation, α, is high (α ≧ 0.5 for NaCl system) and decreased in the lower α region (α < 0.5 for NaCl). The increase of pH was attributed to lactone ring formation that occurs between a carboxyl group and a neighbor hydroxyl group upon protonation to the former, and the decrease of pH to an induction effect by lactone ring to −COOH group. The pH‐increasing process was analyzed by assuming it being of a first order to obtain a time constant. On the basis of time constant thus estimated and pKa values for divalent counterion systems, a correlation between counterion binding and lactone ring formation was discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1523–1531, 1999     

Environmentally responsive micelles from polystyrene–poly[bis(potassium carboxylatophenoxy)phosphazene] block copolymers

Amphiphilic diblock copolymers that contained hydrophilic poly[bis(potassium carboxylatophenoxy)phosphazene] segments and hydrophobic polystyrene sections were synthesized via the controlled cationic polymerization of Cl₃P?NSiMe₃ 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