Added Salt Concentration Research Articles

On the Origins of the Salt-Concentration-Dependent Instability and Lateral Nanoscale Heterogeneities of Weak Polyelectrolyte Brushes: Gradient Brush Experiment and Flory-Type Theoretical Analysis

We investigated, by experiment and theory, the lateral structure of a weak polyelectrolyte brush at various added salt concentrations and chain grafting densities. Model poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes with grafting density gradients were developed for this study by using a novel "Langmuir-Blodgett-deposition-under-compression" (LB\C) method. Fluid AFM images of these brushes indicate that the lateral structure of the brush system is sensitive to both added salt concentration and grafting density. Under low salt conditions, 0-20 mM NaCl, the brush structure shows strong microscopic lateral heterogeneities at high grafting densities; both the width and height of the heterogeneities increase with increasing grafting density but are independent of the salt concentration. As the bulk salt concentration is increased to an intermediate regime, 60-100 mM NaCl, these heterogeneities become smaller in size and number, coexisting with smooth homogeneous regions. At high enough concentrations, 300-500 mM NaCl, the entire surface becomes homogeneous. A simple free energy-based Flory-type argument is presented which explains the essential features of the thermodynamic behavior of the brush system. In the zero-salt limit, relatively few monomers are charged, and the hydrophobicity of the backbone chain drives the collapse/aggregation of the chains. At high salt concentrations, the brush chains become sufficiently charged to overcome the hydrophobic nature of the monomers and stabilize the homogeneous state. However, at intermediate salt concentrations, it is found that the osmotic pressure of the counterions surrounding the charged polymer moieties can be decreased by collapsing the chain structure while simultaneously decreasing the number of charges along the backbone and releasing small ions into the bulk solution. This effect, which we term "osmotic instability", serves to destabilize the homogeneous brush configuration.

Theory of polyzwitterion conformations

Conformational characteristics of polyzwitterionic molecules in aqueous solutions are investigated using the variational method. Analytical relations are derived for the radius of gyration of a single polyzwitterionic chain as a function of the chain length, electrostatic interaction strength, added salt concentration, dipole moment, and degree of ionization of the zwitterionic monomers. In the absence of the small ions (counterions and coions) near the polyzwitterionic chain, attractive dipole-dipole interactions are shown to induce a collapse of the polyzwitterionic chain. However, in the presence of the small ions, the radius of gyration is shown to be an interplay of the screening of the electrostatic interactions and the counterion adsorption on the zwitterionic sites. In addition to the well-known Debye–Hückel screening of the charge-charge interactions, screening of the charge-dipole, and dipole-dipole interactions are found to play important roles in determining the size of the chain. Functional forms for the screened charge-dipole and dipole-dipole interaction potentials are presented. Furthermore, counterion adsorption on the zwitterionic monomers is predicted to be asymmetric depending on the nature of the added salt and the zwitterionic groups. Qualitative remarks regarding the solubility of these molecules in aqueous solutions along with the classical “antipolyelectrolyte” effect (increase in the solubility in water with the addition of salt) are presented.

DNA Duplex Length and Salt Concentration Dependence of Enthalpy−Entropy Compensation Parameters for DNA Melting

Systematical differential calorimetry experiments on DNA oligomers with different lengths and placed in water solutions with various added salt concentrations may, in principle, unravel important information about the structure and dynamics of the DNA and their water-counterion surrounding. With this in mind, to reinterpret the most recent results of calorimetric experiments on DNA oligomers of such a kind, the recent enthalpy-entropy compensation theory has been used. It is demonstrated that the application of the latter could enable direct estimation of thermodynamic parameters of the microphase transitions connected to the changes in DNA dynamical regimes versus the length of the biopolymers and the ionic strengths of their water solutions, and this calls for much more systematical experimental and theoretical studies in this field.

Nanostructure of a Poly(acrylic acid) Brush and Its Transition in the Amphiphilic Diblock Copolymer Monolayer on the Water Surface

The nanostructure and its transition of in a poly(acrylic acid) (PAA) brush in the water surface monolayers of poly(hydrogenated isoprene)-b-poly(acrylic acid) with different block lengths and block ratios were investigated by X-ray reflectivity as a function of surface pressure (brush density) and salt concentration in the subphase. The PAA brush showed the same behavior after salt addition as did the poly(methacrylic acid) (PMAA) brush, which was investigated previously. The brush chains expanded and then shrunk after passing the maximum with increasing added salt concentration. This behavior could be explained by the change in electric charges on the PAA brush chains as was observed on the PMAA brush. The PAA brush chains showed a critical brush density, where there was a transition between the carpet layer only and carpet + brush layer structures, as did the PMAA and poly(styrene sulfonic acid) (PSS) brushes. The critical brush density was about 0.4 chains nm(-2), which was higher than that of the PSS brush, a strong acid brush, and was close to that of the PMAA brush, a weak acid brush. However, the critical brush density of the PAA brush was independent of the hydrophilic chain length whereas that of the PMAA brush decreased with increasing PMAA chain length. In addition, the PAA brush had a thicker carpet layer than the PSS and PMAA brushes. Hence, the mechanism of PAA brush formation was predicted to be different from that of not only the PSS brush (strong acid brush) but also the PMAA brush.

Effect of the counterion behavior on the frictional–compressive properties of chondroitin sulfate solutions

Chondroitin sulfate is a major constituent of articular cartilage, which is known to affect in a decisive way the mobility and flexibility of our joints. A deviation from the physiological conditions, like e.g. a deficiency of water and salt content, in the cartilage tissue has long been suspected to be a possible trigger for rheumatoid diseases. Progresses in understanding the frictional–compressive behavior on the molecular level have been hindered due to the lack of reliable experimental data and the multitude of controlling parameters, influencing the structure and properties of cartilage tissue in its natural environment. In this paper we study the thermodynamic response of aqueous chondroitin sulfate solutions to changes in the monomer and added salt concentrations, using a recently developed field-theoretic approach beyond the mean field (MF) level of approximation. Our approach relies on the method of Gaussian equivalent representation, which has recently been shown to provide reliable thermodynamic information for polyelectrolyte solutions without and with added salt over the whole range of monomer concentrations. We compare our calculation results to experimental as well as molecular modeling data, and demonstrate that it provides useful estimates for important thermodynamic properties. Moreover, we obtain conclusive insights about the hydration effects and counterion behavior under various conditions, which show that, at the physiological salt concentration, CS solutions have optimal compressive and tribological properties. Finally, our work provides support for the possibility that a long-term deviation from the physiological conditions may trigger rheumatoid diseases.

Improving rheological sludge characterization with electrical measurements

The present work is an attempt to obtain information on the rheological behaviour of sewage sludge by performing electrical resistivity measurements. The underlying hypothesis is that, in such gel-like complex fluids, the electrical conductivity is determined not only by the free ions charge and mobility in the interstitial solution, like in simple electrolyte solutions, but also by the structure and the dynamics of the macromolecular and colloidal network. In addition, electrical measurements offer the advantage of being a non-destructive technique suitable for implementation in the field. The viscosity and resistivity of sludges containing between 4 and 15% dry matter were measured as a function of three parameters: (i) temperature, from 278 to 323 K, (ii) added salt concentration, between 0 and 22.3% KCl with respect to dry mass and (iii) ageing, from 0 to 25 days. Both viscosity and resistivity were found to follow the same non-Arrhenius temperature dependence, typical of cooperative molecular motions in glass-forming liquids, with the same thermodynamic parameters. In spite of this complex behaviour, a linear relationship between viscosity and resistivity was obtained. This linear relationship was destroyed by the addition of salt and by ageing, but an empirical parameter combining resistivity and viscosity could still be linearly related to resistivity, allowing for the indirect determination of the sludge viscosity from electrical measurements.

STUDIES ON RELATION BETWEEN INTRINSIC VISCOSITY OF POLYELECTROLYTES IN SOLUTIONS USED FOR LAYER-BY-LAYER SELF-ASSEMBLY AND THEIR CORRESPONDING ADSORPTION AMOUNTS IN THE RESULTANT MULTILAYER MEMBRANES

The adsorption amount of poly(styrene sulfonate) and poly(dimethyldiallyl ammonium chloride) (PSS/PDDA) self-assembled multilayer membranes in designed dipping solvents were measured by UV-Vis-spectroscopy and quartz crystal microbalance (QCM). Intrinsic viscosities of PSS and PDDA in corresponding dipping solvents were determined by an Ubbelohde viscometer. It is found that the adsorption amount of PSS/PDDA self-assembled multilayer membranes built up in different dipping solutions, added salt concentration, pH of solution and solvent quality, respectively changed oppositely with the corresponding intrinsic viscosity of PSS and PDDA in dipping solvents. A negative relation between the adsorption amount and intrinsic viscosity was revealed, and explained in term of the concept of excluded volume of polymer molecule in dilute solutions.

Protonation Behavior and Stability of Micelles of N-Lauroylaminoalkyl-Dimethylamine Oxides-Effects of Added Salt Concentration and Spacer Length

The protonation behavior and the stability of micelles of N-lauroylaminopropyl-N',N'- dimethylamine oxide (C12AmCn; n=3) were studied by the hydrogen ion titration and the equilibrium surface tension measurement. The surface potential of C12AmC3 micelles estimated from the results of hydrogen ion titration was lower than that of dodecyldimethylamine oxide micelles at added NaCl concentration, C(S), of 0.1M. The critical micelle concentration (cmc) estimated from surface tension measurements revealed that a reversal of the stability of the cationic and the nonionic micelles of C12AmC3 takes place in the range of C(S) higher than about 0.2M, that is, the cationic micelles become more stable than the nonionic ones in the range C(S) >or= 0.2M. In addition, the surface tension measurements were carried out for C12AmCn with different spacer length, n, ranging from 2 to 6 methylene units at C(S) = 0.1M. The cmc values of nonionic species were kept at almost constant for n <or= 4, while they decreased with n for n >or= 4. The cmc values of cationic species also tended to decrease with n for n >or= 4. These results were compared with those obtained for alkyldimethylamine oxides, and the effect of amide group and spacer groups introduced into amine oxide surfactants was discussed.

Centrifugal Length Separation of Carbon Nanotubes

Separation of single-wall carbon nanotubes (SWCNTs) by length via centrifugation in a high density medium, and the characterization of both the separated fractions and the centrifugation process are presented. Significant quantities of the separated SWCNTs ranging in average length from <50 nm to approximately 2 microm were produced, with the distribution width being coupled to the rate of the separation. Less rapid separation is shown to produce narrower distributions; these length fractions, produced using sodium deoxycholate dispersed SWCNTs, were characterized by UV-visible-near-infrared absorption and fluorescence spectroscopy, dynamic light scattering, Raman scattering, and atomic force microscopy. Several parameters of the separation were additionally explored: SWCNT concentration, added salt concentration, liquid density, rotor speed, surfactant concentration, and the processing temperature. The centrifugation technique is shown to support 10 mg per day scale processing and is applicable to all of the major SWCNT production methods. The cost per unit of the centrifugation-based separation is also demonstrated to be significantly less than size exclusion chromatography-based separations.

DNA binding during expanded bed adsorption and factors affecting adsorbent aggregation

DNA-induced aggregation and contraction of expanded bed adsorption chromatography beds have been examined using strong anion exchanger Q HyperZ and calf thymus DNA in buffers containing added NaCl. Two batches of adsorbent with different ionic capacities were used allowing the effects of different ligand densities to be examined. Very high dynamic binding capacities at 10% breakthrough were found in the absence of added salt. However, the highest binding capacities (∼10 and ∼19 mg DNA ml −1 gel) were found in buffers containing added salt at concentrations of either 0.25 or 0.35 M, for the low and high ligand density adsorbents, respectively. Bed contraction was observed, but did not correlate with dynamic binding capacity or with the amount of DNA loaded. No differences in bed contraction were seen by varying the concentration of DNA loaded in the range of 20–80 μg ml −1 even though the dynamic binding capacity was reduced as DNA concentration was increased. The extent of bed contraction during DNA loading was found to be a function of added salt concentration and ligand density of the adsorbent. The results imply that ligand density significantly affects the salt tolerance of anion exchangers when binding DNA. However, more importantly, with the adsorbents examined here, attempts to reduce bed aggregation by feedstock conditioning with added salt may increase DNA binding leading to a reduction in expanded bed adsorption performance compromising protein capture in real feedstocks.

Abnormal Viscosity Increment Observed for an Ionic Liquid by Dissolving Lithium Chloride

The effect of adding an inorganic salt, lithium chloride, and water on the viscosity of an ionic liquid, 1-n-butyl-3-methylimidazolium chloride (BmimCl), was investigated by shear stress measurements with a rheometer. The shear rate dependence of the viscosity showed shear thinning behavior, which implies that some structure should exist in the liquid and the structure should change at high shear rates. Addition of LiCl enhances the viscosity of BmimCl. The logarithmic value of zero-shear viscosity, eta(0), of BmimCl increases linearly and largely with increasing added salt content. The increasing rate of the viscosity by addition of LiCl was about 10 times larger than that for an aqueous solution of LiCl. When water is added into BmimCl, viscosity decreased. The increasing rate of the viscosity by addition of LiCl for BmimCl with about 5 wt % of water was almost the same as that for BmimCl without addition of water.

DNA adsorption at functionalized Si/buffer interfaces studied by x-ray reflectivity

The adsorption of DNA on chemically homogeneous, functionalized, oxide-free single-crystal silicon surfaces is studied by x-ray reflectivity. The adsorption of monodisperse, 294 base-pair double-stranded DNA on a positively charged surface is detected through the deformation of the molecular monolayer of aminated alkyl-chain molecules covalently bonded to the surface. The adsorption of single-stranded DNA does not lead to the same deformation. A detailed quantitative characterization of the density profiles yield surface densities of the covalently grafted, molecular monolayers that are in excellent agreement with infrared spectroscopic measurements. The additional mass density that is measured following the adsorption of DNA corresponds either to the partial embedding of a densely-packed adsorbed layer or to a deeper penetration into the soft surface layer at a lower surface density of the adsorbed double-stranded DNA molecules. The adsorption is found to be irreversible under high added salt concentrations, suggesting a partial dehydration of the double-stranded DNA.

Density functional study on the structural and thermodynamic properties of aqueous DNA-electrolyte solution in the framework of cell model

A density functional theory (DFT) in the framework of cell model is proposed to calculate the structural and thermodynamic properties of aqueous DNA-electrolyte solution with finite DNA concentrations. The hard-sphere contribution to the excess Helmholtz energy functional is derived from the modified fundamental measure theory, and the electrostatic interaction is evaluated through a quadratic functional Taylor expansion around a uniform fluid. The electroneutrality in the cell leads to a variational equation with a constraint. Since the reference fluid is selected to be a bulk phase, the Lagrange multiplier proves to be the potential drop across the cell boundary (Donnan potential). The ion profiles and electrostatic potential profiles in the cell are calculated from the present DFT-cell model. Our DFT-cell model gives better prediction of ion profiles than the Poisson-Boltzmann (PB)- or modified PB-cell models when compared to the molecular simulation data. The effects of polyelectrolyte concentration, ion size, and added-salt concentration on the electrostatic potential difference between the DNA surface and the cell boundary are investigated. The expression of osmotic coefficient is derived from the general formula of grand potential. The osmotic coefficients predicted by the DFT are lower than the PB results and are closer to the simulation results and experimental data.

Salt Effect on the Nanostructure of Strong Polyelectrolyte Brushes in Amphiphilic Diblock Copolymer Monolayers on the Water Surface

The nanostructure of a spread monolayer of diblock copolymers of poly(hydrogenated isoprene) and poly(styrenesulfonate) at the air/water interface were studied by in situ X-ray reflectivity as a function of the brush density and salt concentration. When the monolayer was compressed beyond the "critical brush density", its nanostructure changed from a flat, adsorbed "carpet" layer to a "carpet + brush" structure. The critical brush density was found to be about 0.12 nm-2, independent the brush length and salt concentration under a low-salt condition. The brush formation behavior was considered to be controlled by an electrostatic interaction between polyelectrolyte chains rather than by a steric hindrance. This might be because the distance between the chains at the critical point is rather long and also because of the effect of the salt on the critical brush density. The critical brush density increased at higher added salt concentration beyond 1 M. As a result, we found a new structure transition behavior of the polymer brushes between carpet-only and carpet + brush structures, which was induced by salt addition. Finally, we succeeded in the controlled release of salt ions from the salted brush layer by changing the brush density by compression of the monolayer.

Synthesis and rheological properties of an associative star polymer in aqueous solutions

Rheological properties of aqueous solutions and hydrogels formed by an amphiphilic star block copolymer, poly(acrylic acid)- block-polystyrene (PAA 54- b-PS 6) 4, were investigated as a function of the polymer concentration ( C p), temperature, and added salt concentration. The water-soluble polymer synthesised by atom transfer radical polymerization (ATRP) was found to form hydrogels at room temperature at polymer concentrations, C p, over 22 g/L due to the interpolymer hydrophobic association of the PS blocks. Increasing C p leads to stronger elastic networks at room temperature that show a gel-to-solution transition with increasing temperature. Increase of ionic strength decreases the moduli compared with the pure hydrogel but did not affect the gel–sol transition temperature significantly. Small-angle X-ray experiments showed two distinct scattering correlation peaks for samples above the gelling C p, which indicates the aggregates formed due to hydrophobic association. Upon heating the intensity of the scattering correlation peaks was found to decrease indicating the loss of the network structure due to thermal motion.

Location of Spectroscopic Probes in Self-Aggregating Assemblies. II. The Location of Pyrene and Other Probes in Sodium Dodecyl Sulfate Micelles

The location of pyrene in sodium dodecyl sulfate (SDS) micelles is determined as a function of the aggregation number, N, by exploiting the fact that spin probes 5- and 16-doxyl stearic acid methyl esters (5DSE and 16DSE, respectively) are effective quenchers of pyrene fluorescence. The locations of the two spin probes are known from Part 1 of this series (J. Phys. Chem. B 2006, 110, 9791) and the distance between the probes and pyrene is determined by using a hydrodynamic theory to predict the quenching rate constant. The hydrodynamic theory requires the microviscosity of the regions through which the probe and pyrene diffuse. The same spin probe that serves as quencher provides a measure of the microviscosity; thus, all the information needed to locate pyrene is available from each spin probe. Employing 5DSE, at N = 53, pyrene is found to diffuse through a zone 67% of which lies within the Stern layer and 33% in the core. As the micelle grows, due to increasing either the surfactant or added-salt concentration, this diffusion zone moves outward such that, at N = 130, near the sphere-rod transition, it lies approximately 75% within the Stern layer and 25% in the core. Employing 16DSE, the location of pyrene is within 0.4 A of that found from 5DSE at low values of N and within 0.8 A at high values. Full information required to locate pyrene by using the currently developed method is not yet available for other spin probes and other commonly employed quenchers; nevertheless, using a variety of strategies and reasonable assumptions leads to the same location of pyrene within the uncertainties of the method. All of the spectroscopic probes employed in this study are largely located within the polar shell of the micelles, the largest departure being about 4% of the diameter of the micelle.

Control of Gel Swelling and Phase Separation of Weakly Charged Thermoreversible Gels by Salt Addition

Doping of thermoreversible polymer gels with charged monomers provides a way to control phase separation and gelation conditions by coupling the properties of the gel with a tunable ionic environment. We analyze the dependence of the gelation and phase separation conditions on the amount of salt present using a mean field model of weakly charged associative polymers. The ions and co-ions present are explicitly considered at the mean field level, and we determine their concentrations in the different equilibrium phases when the system undergoes phase separation. For weak polymer charge, the entropic contributions of the ions to the free energy of the system play a central role in the determination of the location of phase equilibrium. In the simplest case, when the associative interaction responsible for gel formation is independent of the electrostatic interaction, the addition of salt changes the polymer equilibrium concentrations and indirectly changes the measurable swelling of the gel. We construct phase diagrams of these systems showing the location of the coexistence region, the gel-sol boundary and the location of the tie-lines. We determine the swelling of the gel within the co-existence region. Our main result is that the description of the effect of the salt on the properties of the weakly charged gel can be described through an extra contribution to the effective immiscibility parameter χ proportional to the square of the doping degree f(2) and to the inverse square of the added salt concentration s(-2).

Flexible Conjugated Polyelectrolyte Solutions: A Small Angle Scattering Study

The aqueous solutions of a fully neutralized flexible conjugated polyacid, the poly(3-thiophene sodium acetate) (P3TNaA), are studied by small angle scattering techniques, as a function of polymer concentration, molecular weight and added salt concentration. The characteristic polyelectrolyte scattering peak obeys the predictions of the isotropic model, in good agreement with the behavior of saturated polyelectrolyte solutions. Despite the presence of irreversible aggregates formed during the synthesis, no further aggregation occurs in solution whatever the polymer or added salt concentration. Thus, these conjugated polyelectrolytes remain hydrosoluble and well-dispersed when the electrostatic repulsion is screened, probably due to their small bare persistence length that prevents large dispersion forces in the undoped state.

Collective diffusion in charge-stabilized suspensions: Concentration and salt effects

The authors present a joint experimental-theoretical study of collective diffusion properties in aqueous suspensions of charge-stabilized fluorinated latex spheres. Small-angle x-ray scattering and x-ray photon correlation spectroscopy have been used to explore the concentration and ionic-strength dependence of the static and short-time dynamic properties including the hydrodynamic function H(q), the wave-number-dependent collective diffusion coefficient D(q), and the intermediate scattering function over the entire accessible range. They show that all experimental data can be quantitatively described and explained by means of a recently developed accelerated Stokesian dynamics simulation method, in combination with a modified hydrodynamic many-body theory. In particular, the behavior of H(q) for de-ionized and dense suspensions can be attributed to the influence of many-body hydrodynamics, without any need for postulating hydrodynamic screening to be present, as it was done in earlier work. Upper and lower boundaries are provided for the peak height of the hydrodynamic function and for the short-time self-diffusion coefficient over the entire range of added salt concentrations.

Perfil sensorial e aceitação de presuntos crus produzidos por métodos tradicionais e acelerado

Existem muitos tipos de presuntos crus com perfis sensoriais particulares, em decorrência de diferentes matérias-primas e técnicas de processamento, que são apreciados por seus sabores e texturas característicos. Este trabalho objetivou caracterizar o perfil sensorial de presuntos crus através da Análise Descritiva Quantitativa e verificar a aceitação dos produtos pelo consumidor. Foram avaliados dois presuntos crus experimentais, produzidos por processo acelerado (denominados CTC 3,5 e 5,0% devido ao teor inicial de sal adicionado), e quatro produtos comercializados no Brasil, um Serrano espanhol, um Italiano e dois brasileiros (Tipo Serrano e Tipo Parma). Os produtos diferiram pelos seguintes atributos: CTC 3,5% - sabor mais ácido, menor intensidade de sabor de ranço e aroma de ranço, aparência: menor intensidade de cor vermelha e menor intensidade de suculência; CTC 5,0% - mais fibrosidade, menores intensidade e persistência de sabor e maciez; Serrano - maiores aroma de ranço, cor vermelha, intensidade e persistência de sabor e menor sabor salgado; Tipo Serrano - maior sabor de ranço e menor sabor doce; Italiano - maiores sabor salgado e maciez; Tipo Parma - sabor de carne, marmoreado e amarelo da gordura mais intensos. Todos os produtos obtiveram boa aceitação pelo consumidor. O presunto Tipo Serrano foi o mais aceito e o Serrano foi o menos aceito pelos consumidores brasileiros entrevistados. Os produtos CTC foram considerados de boa qualidade, apresentando características típicas de um presunto cru, apesar do curto período de maturação.