Acid–base Properties of Ion-exchange Resins. Dissociation and Swelling of Resin Copolymers of Methacrylic Acid,Methyl Methacrylate,Divinylbenzene, and Ethylvinylbenzene

The dissociation, capacity, swelling, and water content of crosslinked methacrylic acid—methyl methacrylate resins have been measured. Resins were prepared with different degrees of crosslinking for the same carboxylate content, and vice versa. The ionic strength of the external solution was also varied, and the behavior of commercial resins compared with that of the laboratory resins. Potentiometric titration curves were obtained, and curves were also obtained by back-titration of the salt form of the resins with acid. The capacities showed that almost all carboxyl groups are accessible in resins containing 2.5% or 4.0% divinylbenzene, but not in those containing 8% or 12%. For these highly crosslinked resins the back-titration curves differed from the forward curves. Apparent dissociation constants pK′_a = pH + n log [(1 ? α)/α] decreased with increased ionic strength, increased with increased crosslinking, and showed no trend with carboxylate content. Swelling is decreased by increased salt concentration, particularly for lightly crosslinked resins. Maximum swelling is achieved at about 80% dissociation. The reciprocal of the swollen volume is proportional to the per cent of divinylbenzene. Commercial resins showed much lower swelling than laboratory prepared resins ostensibly having the same composition. The Gibbs-Donnan theory of resin dissociation was applied to calculate the intrinsic dissociation constant (pK′₀). Assuming a model of randomly kinked chains dissolved in the sorbed solution, good agreement with the expected value of 4.85 was found (calcd. pK′₀ = 4.81 = 0.14), except for the most highly crosslinked resins. For polyampholyte resins, agreement was found by using a model having a uniform potential distribution throughout the resin (pK′₀ = 4.9).     

Acid-base properties of solid polyelectrolytes: Dissociation of cellulosic polyanions

The potentiometric titration behavior of nitrogen dioxide and periodate-chlorite oxycellulose has been studied both in the presence and absence of sodium chloride. The apparent pK values in general increase with increasing degree of dissociation, but the reverse is true for periodate-chlorite oxycellulose in the absence of added salt. This behavior is interpreted in terms of electrostatic and hydrogen bonding interaction of carboxyl groups. The Gibbs–Donnan theory of polyaid dissociation was applied to calculate the intrinsic dissociation constant pK′₀. Assuming a model having a uniform potential distributin throughout the fiber, good agreement with the expected value of 3.24 was found (compared to pK′₀ = 3.25 calculated for periodate-chlorite oxycellulose).     

Partitioning of hexavalent chromium in temperature-sensitive,polyelectrolyte hydrogels

Partitioning data for hexavalent chromium (Cr(VI)) are presented for systems where thermally sensitive poly-N-isopropylacrylamide (NIPA)-based hydrogels are in contact with aqueous solutions of potassium dichromate (K₂Cr₂O₇). The poly-NIPA hydrogels contain 0–3% quatemized amine comonomer. Experimental results are given for the effect of gel charge, ionic strength and temperature on the partitioning of Cr(VI) into these NIPA-copolymer gels. At low ionic strength, the partition coefficient increases with the content of quatemized amine. The effect of rising temperature is to increase the partition coefficient. Swelling equilibria in aqueous K₂Cr₂O₇ solutions decrease with ionic strength and, at ionic strengths <0.1 M, are lower compared to swelling in aqueous sodium chloride solutions. Experimental partitioning data as a function of ionic strength and gel charge are compared with predictions based on two theoretical models for mixed electrolyte solutions. Predictions based on the cell model for polyelectrolyte solutions agree best with experimental results. Calculated results are in semi-quantitative agreement with experimental data for the effects of solution ionic strength and gel charge on Cr(VI) partitioning and in qualitative agreement for the effect of temperature.     

Osmotic deswelling of weakly charged poly(acrylic acid) solutions and gels

The osmotic pressure of weakly charged aqueous poly(acrylic acid) (PAA) solutions and the swelling pressure PAA gels were studied by osmotic deswelling at different degrees of ionization (α). In solution, the osmotic pressure was found to scale linearly with concentration, whereas the scaling power of the swelling pressure of gels was higher (1.66). The effect of the ionization degree on the osmotic coefficient in PAA solutions was in agreement with the theory of Borue and Erukhimovich [Macromolecules, 21 , 3240 (1988)]. Ionization increases the swelling capacity of the PAA gels until a plateau is reached at about 35% neutralization. The concentration at equilibrium swelling scales as C_e ～ α^?0.6. The contribution of the network to the gel swelling pressure is evaluated by subtracting the osmotic pressure of the polymer solution at the same concentration and degree of ionization. In swollen gels the extended network opposes swelling. As the gel is osmotically deswelled, a state of zero network pressure exists at a certain concentration, below which the network elasticity favors swelling. The crossover concentration shifts to lower values as the degrees of ionization increases. © 1995 John Wiley & Sons, Inc.     

Potentiometric titration of polyelectrolyte gels equilibrated with a solution of a strong polyelectrolyte: Influence of gel swelling

A weak acid gel (carboxylmethyldextran) was titrated with sodium hydroxide while equilibrated with a solution sodium poly(vinyl sulfate), a salt of a strong acid polyelectrolyte. It was found that the quantity in which V/V₀ is the volume of gel relative to its volume in acid form in pure water, is independent of the concentration C_p of the polyelectrolyte solution and of the relative volume of gel. The relation where α is the degree of ionization, pK′ is the apparent pK of the gel, γ is the activity coefficient of the counterion in the gel phase, and v is the number of ionizable groups, is found to be constant for all values of C_p and for 0.1 < α < 0.9. These results can be extended to highly crosslinked ionexchange resins.     

Determination of Dissociation Constants of Complicated Compounds by Capillary Zone Electrophoresis

In this work, the whole theoretical methods for the determination of pK_a1. and pK_a2. of complicated compounds are proposed by capillary zone electrophoresis. The pK_a values are achieved by non‐linear regression analysis by taking into consideration the effect of activity coefficient. This is the first report on determining the dissociation constants of gastrodin, magnolol, honokiol, quercetin, curcumin, diethylstilbestrol, 4‐acetamidophenol, eugenol and paeonol.     

Interaction of monovalent and divalent counterions with some carboxylic polysaccharides

Eleven samples of carboxylic polysaccharides were studied. The activity coefficients γ have been measured for monovalent (Na⁺) and divalent (Ca²⁺) counterions. There is no specific influence of the structure of the chain on γ values. Agreement with theoretical values confirms the rigidity of the chain; for low charge density, the theoretical treatment seems to be incorrect. Selectivity is discussed in term of selectivity coefficient K and free energy of exchange ΔG; ΔG is linearly related to the charge density but K which characterizes the competition of the two counterions is sensitive to the nature of the chain. The carboxymethylamyloses present a larger selectivity whose origin is not discussed here. The last point treated is the intrinsic constant of dissociation of polyacids. The pK₀ values are practically independent of the nature of the polyelectrolyte and of the charge density; the values are close to the pK₀ of monomeric unit and are not affected by the position of ? COOH in the anhydroglucose ring.     

High-molecular-weight hydrolyzed polyacrylamides. II. Potentiometric titrations

Potentiometric titrations in water of high-molecular-weight partly hydrolyzed polyacrylamides were analyzed by the Lifson—Katchalsky rodlike model. A fair concordance was found between theory and experimental curves with pK₀ of acid functions of about 4.75 when 0 < τ < 0.49. Two methods were derived to calculate the parameter n of the extended Henderson-Hasselbach equation by using a series expansion of pK_a vs. α, not yet reported in the literature. A new equation for n was established and comparison between two sets of values of n, obtained by using the theoretical ΔpK curves and series expansion is discussed.     

Estimation of the pK a of the amine groups of benzhydrylamine resin and its lysyl derivative by measurement of swelling

Summary For better evaluation of the potential of benzhydrylamine resin (BHAR), used as a solid support for peptide synthesis, as a novel anion-exchange resin, the pK _a of its amine group was estimated by microscopic measurement of the sizes of the dry and swollen beads. Using the volume of the bead occupied by the solvent (as a percentage) as the swelling parameter, a plot of the degree of swelling of BHAR loaded with 2.4 mmol g^–1 amine groups against the pH of the medium produced a decreasing sigmoidal-type curve with increasing pH. By considering the point of inflection of the curve, a pK _a value of approximately 7.5 was estimated for the amine group of the BHAR. The same approach was also applied to the lysyl derivative of the BHAR (Lys-BHAR) and pK _a values around 6.5 and 10.0 were obtained for the and amine groups, respectively.     

Effects of Nonionic, Cationic, and Mixed Nonionic-Cationic Surfactants on the Acid-Base Behavior of Phenyl Salicylate

The effects of Brij 35 micelles, CTABr micelles, and mixed Brij 35–CTABr micelles on the acid–base behavior of phenyl salicylate (PST) have been studied in aqueous solution containing 2% v/v acetonitrile. The apparent pK_b (pK^app_b) of PST is decreased by 1.5 pK units with the increase in [Brij 35] from 0 to 0.02 M which is attributed to micellar medium effect. The values of pK^app_b remain almost independent of [CTABr] within its range 0.01–0.03 M. The increase in [CTABr] from 0 to 0.03 M in aqueous solution containing 0.02 M Brij 35 has not resulted in a change in pK^app_b. This shows that the characeristic structural features of nonionic Brij 35 micelles remain essentially unchanged on addition of CTABr under the present experimental conditions.     

The role of swelling,amorphous vs. crystalline content,charge density,and applied stress on the transport properties of polymeric films

Previously reported results on the transport behavior of crosslinked collagen membranes are reviewed and discussed. Under isoelectric conditions, alteration of the degree of swelling and of the state of the membrane are induced by changing salt type and concentration. The filtration coefficient L_p increases when swelling is increased in the amorphous state, decreases when swelling is increased in the crystalline state, and increases during the crystal—amorphous transition. Under non-isoelectric conditions (low pH, low ionic strength), L_p and swelling have the same trend in the amorphous state while they have opposite trends in the crystalline state. The trend of the reflection coefficient σ as a function of pH (a maximum is exhibited at pH ～ 3) is quantitatively explained on the basis of the competition between swelling and fixed charge density (the former includes a contribution due to the charge-induced phase transition at pH ～ 2, in addition to the usual Donnan contribution). The permeability to THO, ω_T, increases with increasing strain on the amorphous membrane and then goes through a maximum and a minimum when a stress-induced phase transition occurs. The relationship between frictional coefficients derived from irreversible thermodynamics and polymer-salt-water interactions deduced from equilibrium thermodynamics is pointed out.     

Swelling equilibrium of poly(acrylamide) gels in aqueous salt and polymer solutions

The influence of some single salts (NaCl, KCl, Na₂HPO₄ and K₂HPO₄) and poly(ethylene glycol) (PEG) on the swelling of aqueous poly(arcylamide)-gels was studied at 25°C in more than 600 experiments. The chlorides and phosphates cause a different behavior at high salt concentrations: The polyacrylamide gels swell in aqueous solutions of sodium and potassium chloride whereas they shrink when chloride ions are substituted by hydrogen phosphate ions. These differences are due to differences in the interactions of chloride and hydrogen phosphate ions with the network groups. In aqueous solutions of poly(ethylene glycol) the gels shrink continuously with increasing polymer concentration. At constant PEG mass fraction in the liquid phase, the swelling of the gel decreases with increasing molecular weight of PEG. The experimental results (degree of swelling, partitioning of solutes to the coexisting phases) are correlated by combining a model for the Gibbs excess energy for aqueous systems of polymers and electrolytes with a modification of the phantom-network theory. The correlation gives a good agreement with the experimental data for the degree of swelling, whereas in most cases, there is only a qualitative agreement for the partitioning of the solutes.     

Effect of nonelectrostatic interactions on the macromolecular behavior of polyelectrolyes. II. Influence of urea and dyes on the viscometric and optical behavior of PLL

The effect of urea and of dyes on the viscometric behavior of aqueous solutions of PLL has been investigated. The compact structure, which is characteristic of PLL in pure water, is found to disappear progressively as the amount of urea is increased. This is interpreted as due to the destruction in such media of nonelectrostatic interactions responsible for the stabilization of the compact structure of PLL in pure water. In 8M urea, the macromolecular behavior of PLL during the ionization is dependent only on the repulsive interactions between the charged groups. The extension of PLL is then practically independent of the nature of counterions, contrary to what was observed in pure water. In the presence of dye (acridine orange), the compact form of PLL is stabilized, and the dye is found to bind for the two structures of PLL. The analogy between the behavior of Bu₄N⁺ and that of dye is in agreement with the fact the Bu₄N⁺ leads to a stabilization of the compact structure by way of specific interactions between N-tetraalkylammonium counterions and the PLL chain through the structure of water. The hydrodynamic behavior of PLL is in good agreement with data obtained from potentiometric and optical activity measurements.     

Temperature-sensitive poly(vinyl methyl ether) hydrogel beads

Temperature-sensitive hydrogel beads were prepared by radiation crosslinking of poly(vinyl methyl ether) PVME spheres wrapped in Ca-alginate. The obtained gel beads have diameters in the sub-millimeter or millimeter range (depending on the PVME concentration). They were characterized by sol-gel analysis, swelling measurements, and differential scanning calorimetry. The gel content g increases with increasing radiation dose D. The swelling degree Q_v decreases with increasing PVME concentration c_p and increasing D. In comparison to PVME bulkgels the phase-transition temperature of the synthesized PVME gel beads is a little decreased.     

Effect of nonelectrostatic interactions on the macromolecular behavior of polyelectrolytes. I. Potentiometric titrations of PLL in water and aqueous–organic mixtures

The potentiometric and viscosity behavior of salt-free solutions of the polycondensate between L-lysine and 1,3-benzenedisulfonyl chloride (PLL) and related polyelectrolytes, have been investigated in water and in aqueous–organic mixtures (acetone–water). The effects of counterions and solvent on the pH-induced conformational transition is related to hydrophobic interactions. The transition from a compact state to a more extended one shifts towards high values of neutralization with increasing length of N-tetraalkylammonium counterions. Moreover, the above transition gradually disappears as the percentage of acetone in the mixture is increased, which is interpreted as reflecting the breakdown of the compact structure due to hydrophobic interactions stabilized by bulky counterions. A linear decrease in the free energy variation ΔG_t° is observed with increasing percentage of acetone up to about 40% of acetone, and a value of 1200 cal/unit is obtained for PLL in water, which is a reasonable value compared to other data for hydrophobic polyelectrolytes.     

Photoregulation of polymer conformation by photochromic moieties. I. Anionic ligand to an anionic polymer

Abstract— Photoregulated biological processes appear to make use of membrane-bound photochromic macromolecules. In order to elucidate various physicochemical pathways by which these processes can be triggered, model studies have been undertaken employing photochromic moieties bound to synthetic macromolecules with a labile fold structure. Inspired by Lovrien's 1967 work, attention was first focused on the anionic dis-azo stilbene dye chrysophenine (CHP) and poly(methacrylic acid) (PMA) in aqueous solution. This ligand is found to bind to and unfold PMA only if the degree of ionization of the polymer is below 0·75. Viscosity as well as equilibrium dialysis data indicate that maximally one CHP per ten monomer units PMA is bound. The apparent degree of ionization conferred to PMA by the ionic CHP ligand leading to polymer unfolding is the same as the known real degree of ionization leading to polymer unfolding in the absence of CHP. Upon trans→cis photoisomerization, the ligand either desorbs or creates a higher local dielectric constant because of the large cis-azo dipole moments. As a result some refolding to a more compact hydrodynamic volume occurs, as deduced from the viscosity measurements at a low degree of ionization. Simultaneously a lowering of the pK_app by 0·1 pK unit is observed at degrees of ionization below 0·075. Photoregulation of conformation as well as of pK_app indicates two possible pathways for the regulation of ionic fluxes such as have been postulated for photobiological transducers.     

Insights into the Metalation of Benzene and Toluene by Schlosser’s Base: A Superbasic Cluster Comprising PhK,PhLi, and tBuOLi

The metalation of benzene by Schlosser’s base (nBuLi/tBuOK) occurs smoothly in THF at low temperatures to afford a discrete mixed‐metal Li₂K₄ cluster that contains phenyl anions and tert‐butoxide. The aggregate itself exhibits superbasic behavior by metalating toluene. The delocalized benzyl anion obtained this way π bonds to potassium counterions, thereby creating a 2D coordination polymer.     

Walnut Oil Nanoemulsion: Optimization of the Emulsion Capacity,Cloudiness, Density,and Surface Tension

Response surface methodology (RSM) in conjunction with central composite rotatable design (CCRD) was employed to find out the influence of preparation properties of walnut oil/water nanoemulsion namely ultrasonic time (5–15 minutes), walnut oil content (4–10% w/w) and concentration ratio of Span 80 to Tween 80 (K ₀, 0.55–0.80) on response variables including emulsion capacity, cloudiness, density and surface tension. The calculated regression models with high value of coefficient of determination (0.910–0.973) and insignificant lack of fit test indicated satisfactory agreement of empirical models with experimental observations. The results revealed linear term of walnut oil concentration was the most significant (p < 0.05) parameter on the all responses. The overall optimum region to achieve the ideal characteristics was ultrasonic time of 11.74 minutes, walnut oil content of 4.00% (w/w) and K ₀ of 0.80.     

Detection of major xylanase-containing cellulose-binding domain from Penicillium verruculosum by combination of chromatofocusing and limited proteolysis

Adsorption on microcrystalline cell ulose of enzyme components of cellulase complex from Penicillium verruculosum was studied by chromatofocusing on a Mono P column. The most strongly adsorbed and major component was identified as xylanase (XYN) with MW 65 k Da and pl 4.5. The high adsorption degree of XYN on cellulose indicated the possible presence of a cellulose-binding domain in the molecular sturcture. Limited proteolysis of XYN with papain was carried out. Kinetics of proteolysis was monitored by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analysis and measuring activities toward insoluble xylan and 4-methylumbelliferyl-β-d-lactoside (MUF-LAC). During the proteolysis, formation of two polypeptides with MW 51 and 14k Da was observed. No loss of activity toward thesolu blesubstrate was observed, wherease the activity toward xylan decreased rapidly. Adsorption distribution coefficient (K _d) of the core protein separated by gel-filtration was found to be 15 times lower than the K _d for the initial nondigested XYN (0.02 and 0.29 L/g, respectively). The activity of core protein toward insoluble xylan was close to zero, whereas the activity toward MUF-LAC was close to that exhibited by the original enzyme. The results presented indicate a bifunctional organization of XYN, where one domain acts as a binding anchor for insoluble substrates and the other, localized in the core protein, contains the active site.     

Partition coefficients of ω-phenylalkanols between water and liposome membranes of phospholipids

For the liposome of two types of phospholipids (zwitterionic dipalmitoyl-phosphatidylcholine (DPPC) and anionic dimyristoylphosphatidic acid (DMPA)), the partition coefficient K _X for partition of homologous -phenylalkanols (C₆H₅(CH₂) _mp OH; m _p =0–8) between bulk water and the liposome membrane was determined on the basis of the gel to liquid crystalline phase transition temperature T _m of the liposome membrane. The plot of log K _X vs. m _p gave a break at m _p =7 for both phospholipids, and a second break at m _p =4 was observed for DPPC. The local polarity of the surface region and the orderliness of phospholipid molecules in the liposome membrane were estimated from ESR spectra of two spin probes solubilized in the membrane. The results suggest that the hydration of DPPC liposome membrane is relatively restricted to its surface region, but for DMPA the hydration spreads not only along the surface but also to the inside of the membrane. The main factor controlling the partitioning of the alkanols is the local polarity. The higher alkanols (m _p =7, 8) are solubilized not only in the liquid crystalline phase but also in the gel phase, although the other lower alkanols are solubilized in the liquid phase only.