Hydrogen Ion Titration Research Articles

Effect of a Good buffer on the fate of metastable protein-rich droplets near physiological composition

Metastable protein-rich microdroplets are produced from liquid-liquid phase separation (LLPS) of protein aqueous solutions. These globules can be intermediates for the formation of other protein-rich phases. Lysozyme aqueous solutions undergo LLPS around 0 °C in the presence of NaCl near physiological conditions. Here, it is shown that insertion of small amounts of 4-(2-hydroxyethyl)-1-piperazineethanesulfonate (HEPES, 0.1 M) as a second additive to lysozyme-NaCl-water solutions near physiological ionic strength (0.2 M) is an essential step for triggering conversion of protein-rich droplets into another phase. Specifically, LLPS induced by cooling reproducibly leads to a rapid and high-yield formation of compact tetragonal crystalline microparticles only in the presence of HEPES. These microcrystals exhibit small size (1-3 μm), narrow size distribution and guest-binding properties. The temperature-concentration phase diagram shows a characteristic topology with LLPS boundary metastable with respect to tetragonal microcrystals, which in turn become less stable than rod-shaped orthorhombic crystals above 40 °C. Interestingly, dynamic light scattering, hydrogen-ion titrations and isothermal titration calorimetry reveal that lysozyme-HEPES interactions were found to be weakly attractive and exothermic. Our findings indicate that additives of salting-in type can represent an important factor controlling the fate of metastable protein-rich microdroplets relevant to drug formulations, femtosecond crystallography, and potential implications in protein-driven cytoplasmic compartmentalization.

Amplification of Salt-Induced Protein Diffusiophoresis by Varying Salt from Potassium to Sodium to Magnesium Chloride in Water.

Salt-induced diffusiophoresis is the migration of a macromolecule or a colloidal particle induced by a concentration gradient of salt in water. Here, the effect of salt type on salt-induced diffusiophoresis of the protein lysozyme at pH 4.5 and 25 °C was examined as a function of salt concentration for three chloride salts: NaCl, KCl, and MgCl2. Diffusiophoresis coefficients were calculated from experimental ternary diffusion coefficients on lysozyme-salt-water mixtures. In all cases, diffusiophoresis of this positively charged protein occurs from high to low salt concentration. An appropriate mass transfer process was theoretically examined to show that concentration gradients of MgCl2 produce significant lysozyme diffusiophoresis. This is attributed to the relatively low mobility of Mg2+ ions compared to that of Cl- ions at low salt concentration and a strong thermodynamic nonideality of this salt at high salt concentration. These findings indicate that MgCl2 concentration gradients could be exploited for protein manipulation in solution (e.g., using microfluidic technologies) with applications to protein adsorption and purification. The dependence of lysozyme diffusiophoresis on salt type was theoretically examined and linked to protein charge. The effect of salts on hydrogen-ion titration curves was experimentally characterized to understand the role of salt type on protein charge. Our results indicate that binding of Mg2+ ions to lysozyme further enhances protein diffusiophoresis.

A Comprehensive Systematic Study on Thermoresponsive Gels: Beyond the Common Architectures of Linear Terpolymers.

In this study, seven thermoresponsive methacrylate terpolymers with the same molar mass (MM) and composition but various architectures were successfully synthesized using group transfer polymerization (GTP). These terpolymers were based on tri(ethylene glycol) methyl ether methacrylate (TEGMA, A unit), n-butyl methacrylate (BuMA, B unit), and 2-(dimethylamino)ethyl methacrylate (DMAEMA, C unit). Along with the more common ABC, ACB, BAC, and statistical architectures, three diblock terpolymers were also synthesized and investigated for the first time, namely (AB)C, A(BC), and B(AC); where the units in the brackets are randomly copolymerized. Two BC diblock copolymers were also synthesized for comparison. Their hydrodynamic diameters and their effective pKas were determined by dynamic light scattering (DLS) and hydrogen ion titrations, respectively. The self-assembly behavior of the copolymers was also visualized by transmission electron microscopy (TEM). Both dilute and concentrated aqueous copolymer solutions were extensively studied by visual tests and their cloud points (CP) and gel points were determined. It is proven that the aqueous solution properties of the copolymers, with specific interest in their thermoresponsive properties, are influenced by the architecture, with the ABC and A(BC) ones to show clear sol-gel transition.

Multicompartment thermoresponsive gels: does the length of the hydrophobic side group matter?

Multicompartment thermoresponsive gels are novel materials with fascinating self-assembly and interesting applications. The aim of this study was to investigate for the first time the effect of the length of the alkyl side group of a hydrophobic monomer on the thermoresponsive and self-assembly behaviour of terpolymers. Specifically twelve well-defined terpolymers based on the hydrophilic monomers 2-(dimethylamino)ethyl methacrylate (DMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA), and on the hydrophobic monomer ethyl-, n-butyl or n-hexyl methacrylate (EtMA, BuMA or HMA) of varying architectures (ABC, ACB, BAC and statistical) were synthesised using Group Transfer Polymerisation. The A, B and C blocks were based on PEGMA, the alkyl containing methacrylate monomer, and DMAEMA, respectively. The molecular weights (MWs) and compositions of the polymers were kept the same. The polymers and their precursors were characterised in terms of their MWs, MW distributions and compositions. Aqueous solutions of the polymers were studied by turbidimetry, hydrogen ion titration, light scattering and rheology to determine their cloud points, pKas, hydrodynamic diameters and thermoresponsive behaviour and investigate the effect of the architecture and the hydrophobic alkyl side group of the terpolymers. It was found that the pKas and the Tgs were mostly affected by the hydrophobicity of the side groups and not by the architecture, while the cloud points and the sol–gel transition of the polymers were affected by both the length of the alkyl side group and the polymer architecture. Interestingly the sharpest sol–gel transitions and stable multicompartment hydrogels were observed for the ABC triblock copolymers with the short alkyl-side groups even though the sol–gel transition occurred at higher temperatures.

Thermoresponsive triblock copolymers based on methacrylate monomers: effect of molecular weight and composition

A series of amphiphilic thermoresponsive ABC triblock copolymers was synthesised by Group Transfer Polymerisation (GTP). In total nine polymers were prepared based on the non-ionic hydrophobic n-butyl methacrylate (BuMA), the ionisable hydrophilic and thermoresponsive 2-(dimethylamino)ethyl methacrylate (DMAEMA) and the non-ionic hydrophilic methoxy poly(ethylene glycol) methacrylate (PEGMA). The architecture of the copolymers was kept constant with the hydrophobic block in the middle and the two hydrophilic blocks at the two ends, while the composition and the molecular weight of the polymers were varied. Specifically the molecular weight of the polymers was varied while the composition and the architecture were kept constant. The precursors to the polymers and the polymers were characterised in terms of their molecular weight and composition using gel permeation chromatography and proton nuclear magnetic resonance spectroscopy, respectively. Aqueous solutions of the polymers were studied by turbidimetry, hydrogen ion titration and light scattering to determine their cloud points, pKas, and hydrodynamic diameters and investigate the effect of the composition and the molecular weight of the copolymers. Finally, the thermoresponsive behaviour of the copolymers was also studied and it was found that the cloud point and gel point of the polymers were strongly affected by both the composition and molecular weight of the triblock copolymers.

The Characteristics of Surface Functional Groups and Interlayer Space in lon-Exchanged Magadiites (II) Hydrogen ion titration and surface ionized groups

The Characteristics of Surface Functional Groups and Interlayer Space in lon-Exchanged Magadiites (II) Hydrogen ion titration and surface ionized groups

Thermoresponsive terpolymers based on methacrylate monomers: Effect of architecture and composition

AbstractA series of amphiphilic thermoresponsive copolymers was synthesized by group transfer polymerization. Seven copolymers were prepared based on the nonionic hydrophobic n‐butyl methacrylate (BuMA), the ionizable hydrophilic and thermoresponsive 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and the nonionic hydrophilic poly(ethylene glycol)methyl methacrylate (PEGMA). In particular, one diblock copolymer and six tricomponent copolymers of different architectures and compositions, one random and five triblock copolymers, were synthesized. The polymers and their precursors were characterized in terms of their molecular weight and composition using gel permeation chromatography and proton nuclear magnetic resonance spectroscopy, respectively. Aqueous solutions of the polymers were studied by turbidimetry, hydrogen ion titration, and light scattering to determine their cloud points, pKas, and hydrodynamic diameters and investigate the effect of the polymers' composition and architecture. The thermoresponsive behavior of the copolymers was also studied. By increasing the temperature, all polymer solutions became more viscous, but only one polymer, the one with the highest content of the hydrophobic BuMA, formed a stable physical gel. Interestingly, the thermoresponsive behavior of these triblock copolymers was affected not only by the terpolymers' composition but also by the terpolymers' architecture. These findings can facilitate the design and engineering of injectable copolymers for tissue engineering that could enable the in situ formation of physical gels at body temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 775–783, 2010

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.

Interaction Between an Anionic and an Amphoteric Surfactant. Part I: Monomer–Micelle Equilibrium

AbstractA mixture of anionic and amphoteric surfactants is composed of three components at intermediate pH levels: anionic, cationic (protonated amphoteric), and zwitterionic (unprotonated amphoteric). Knowledge of the composition of each surfactant in both monomer and micellar forms (monomer–micelle equilibrium) is important in applications using this mixture. Hydrogen ion titration of the mixed surfactant solution as a function of surfactant composition is combined with the pseudophase separation model and regular solution theory for the three‐surfactant mixture to calculate the concentration of each surfactant in monomer and in micelle forms at different pH levels. The specific systems studied here contain sodium dodecyl sulfate (SDS) and dimethyldodecylamine oxide (DDAO), which are used in a wide range of consumer products. The degree of protonation of monomeric DDAO is not affected by the presence of SDS, indicating an insignificant formation of ion pairs between these monomers. However, the presence of SDS in micelles shifts the micellar pKa of DDAO protonation significantly and the method used here allows the quantification of partial fugacities of each individual surfactant in micelle form. The composition in the monomer phase at each pH will aid in understanding and predicting solution compositions corresponding to anionic/amphoteric surfactant precipitation boundaries, which is the focus of the subsequent paper in this series.

Synthesis and characterization of amphiphilic star copolymers of 2-(dimethylamino)ethyl methacrylate and methyl methacrylate: Effects of architecture and composition

Six amphiphilic star copolymers comprising hydrophilic units of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and hydrophobic units of methyl methacrylate (MMA) were prepared by the sequential group transfer polymerization (GTP) of the two comonomers and ethylene glycol dimethacrylate (EGDMA) cross-linker. Four star-block copolymers of different compositions, one miktoarm star, and one statistical copolymer star were synthesized. The molecular weights (MWs) and MW distributions of all the star copolymers and their linear homopolymer and copolymer precursors were characterized by gel permeation chromatography (GPC), while the compositions of the stars were determined by proton nuclear magnetic resonance ( 1H NMR) spectroscopy. Tetrahydrofuran (THF) solutions of all the star copolymers were characterized by static light scattering to determine the absolute weight-average MW ( M ¯ w ) and the number of arms of the stars. The M ¯ w of the stars ranged between 359,000 and 565,000 g mol −1, while their number of arms ranged between 39 and 120. The star copolymers were soluble in acidic water at pH 4 giving transparent or slightly opaque solutions, with the exception of the very hydrophobic DMAEMA 10- b-MMA 30- star, which gave a very opaque solution. Only the random copolymer star was completely dispersed in neutral water, giving a very opaque solution. The effective p Ks of the copolymer stars were determined by hydrogen ion titration and were found to be in the range 6.5–7.6. The pHs of precipitation of the star copolymer solutions/dispersions were found to be between 8.8–10.1, except for the most hydrophobic DMAEMA 10-b-MMA 30- star, which gave a very opaque solution over the whole pH range.

Titration of Mixed Micelles Containing a pH-Sensitive Surfactant and Conventional (pH-Insensitive) Surfactants: A Regular Solution Theory Modeling Approach

We present a thermodynamic theory to model the hydrogen-ion titration of mixed micelles containing a pH-sensitive surfactant and any number of conventional (pH-insensitive) surfactants. In particular, a simple expression is derived for the pKm, a parameter analogous to the pKa of simple acids, which describes the deprotonation equilibrium of the micellized pH-sensitive surfactant. The pseudophase approximation and regular solution theory (RST) are used to relate the pKm to (1) the pKa of the surfactant monomers, (2) the critical micelle concentrations (cmc's) of the protonated and deprotonated forms of the pH-sensitive surfactant, (3) the composition of the mixed micelle, and (4) parameters characterizing pairwise interactions between the surfactant molecules in the mixed micelle. Micellar titrations can be used to determine the magnitude of these interaction parameters. Conversely, knowledge of the cmc's and the interaction parameters allows the prediction of the pKm, which can then be used to calculate the micelle composition and surface charge as a function of solution pH. In addition, we have found that, in the context of RST, multicomponent surfactant mixtures are equivalent to a binary surfactant mixture of the pH-sensitive surfactant and a single effective surfactant whose interactions with the pH-sensitive surfactant are an average of those in the multicomponent surfactant mixture. We also discuss the experimental uncertainty in the pKm measurements. To account for the increased uncertainty in the pKm data at extreme micelle compositions, a weighted regression is proposed for the analysis of experimental titration data characterized by widely varying uncertainties. The theory presented here is validated using micellar titration data from the literature for several pH-sensitive surfactants in solutions containing 0.1 M salt. In most cases, the parameters extracted from an analysis of the titration data agree with the cmc and interaction parameters obtained by other means. One notable exception is the surfactant tetradecyldimethylamine oxide (C14DAO), which appears to have concentration-dependent interactions due to extensive growth of cylindrical micelles. Micellar titrations were also conducted on binary surfactant mixtures containing the pH-sensitive surfactant dodecyldimethylamine oxide (C12DAO) and either the cationic surfactant dodecyltrimethylammonium bromide (C12TAB) or the nonionic surfactant dodecyl octa(ethylene oxide) (C12E8). The theory provides a reasonable description of the experimental titration data at all surfactant mixing ratios, although a larger discrepancy is found in the C12DAO/C12E8 system, in which C12E8 interacts preferentially with the protonated, cationic form of C12DAO. Interestingly, C12TAB was also observed to interact preferentially with the protonated, cationic form of C12DAO, although the preference is much weaker than that in the C12DAO/C12E8 system.

Properties of Surface and Micelle in a pH‐Mediated Ternary Surfactant Mixture in Salt Solution

We have investigated the mixing behavoir of a pH‐mediated ternary surfactant mixture at constant ratio of dodecyldimethylamine oxide (DDAO) and Triton X‐100 (9:1). From the equilibrium surface tension measurements at different pHs, the critical micelle concentration (cmc) data were obtained as functions of the pH. Values of the cmc and composition of the micelles were predicted using the regular solution approximation. To some extent, the experimental cmc values agree with the predicted cmc. The average degree of ionization of dodecyldimethylamine oxide in the mixed surfactant systems was estimated using potentiometric titrations. The surface electric potential of the micelles (Ψo) was determined using two methods, one by hydrogen ion titration and the other by the dissociation constants of an acid‐base indicator. In a high degree of ionization of DDAO in the micelles phase (am), Ψo estimated from acid‐base indicator is much higher than that from hydrogen ion titration. In the protonated dodecyldimethylamine oxide/TX‐100 binary surfactant system, Ψo estimated from hydrogen ion titration was as high as 89 mV. The micellar aggregation numbers evaluated by the steady‐state fluorescence probe method increase with pH except at pH=5.03. At pH=5.03, the maximum micelle aggregation number was observed.

Effects of l-arginine on aggregates of fatty-acid/potassium soap in the aqueous media

In the present study, we investigated the effects of l-arginine on aggregates of fatty acid/fatty soap in the aqueous media as a function of pH, by means of hydrogen ion titration, viscoelastic measurement, cryo-transmission electron microscopy and phase contrast microscopy. We found out that l-arginine effectively inhibits the oil droplet growth of oleic acid or octanoic acid. The effect is explained in terms of the adsorption of arginine at the microscopic drop surface, or at the oil/water microinterface through the hydrophobic effect assisted by the hydrogen bonds between carboxyl group of fatty acid and carboxylate of arginine. As to the crystallization of lauric acid at temperatures below the melting point of the hydrocarbon chain, arginine is not effective. In addition, we also found out that the strong binding of arginine cation to anionic oleate micells induces the dominant micellar growth. l-arginine has been used in many refolding systems to suppress protein aggregation. These effects of l-arginine on the aggregates of fatty acid/fatty soap in the aqueous media observed in the present study is expected to form a basis to the specific function displayed in the protein refolding.

Hydrogen ion titration of alkyldimethylamine oxides by 13C and 1H NMR and conventional methods

In the hydrogen ion titration of micelles, the degree of ionization of the micelle at a given pH has to be evaluated to obtain a p K a value of micelles ( K a being the proton dissociation constant) at the pH. We compared the degree of ionization obtained from 13C and 1H NMR spectra with that obtained from the stoichiometric method. We used dodecyldimethylamine oxide (C12DMAO) and hexyldimethylamine oxide (C6DMAO) to examine the titration behavior of micelles and monomers, respectively. We determined p K a values of amine oxides both in H 2O and D 2O. As to the monomer (C6DMAO), the degree of ionization from NMR, α NMR, coincided with that from the conventional stoichiometric method α. The difference of p K 1 of amine oxide monomer between D 2O and H 2O was about 0.5: p K 1(D) ≈ p K 1(H) + 0.5. The difference was about the same as that for carboxylic acids. As to the C12DMAO micelle, α NMR did not coincide with α over a considerable range of α. The NMR chemical shift might be influenced by micellar structure changes induced by the ionization, such as the sphere-to-rod transition. The intrinsic logarithmic dissociation constants of the micelle were 5.9 ± 0.1 for H 2O, and 6.5 ± 0.1 for D 2O.

Nanoscopic Cationic Methacrylate Star Homopolymers: Synthesis by Group Transfer Polymerization, Characterization and Evaluation as Transfection Reagents

Seven star polymers with degrees of polymerization (DPs) of the arms from 10 to 100 and dimensions in the nanometer range were prepared using sequential group transfer polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA, hydrophilic positively ionizable monomer) and ethylene glycol dimethacrylate (hydrophobic neutral cross-linker). The polymers were characterized in tetrahydrofuran by gel permeation chromatography and static light scattering to determine the molecular weights and the weight-average number of arms for each sample. The number of arms of the star polymers varied from 20 to 72. Aqueous solutions of the star polymers were studied by turbidimetry, hydrogen ion titration, and dynamic light scattering to determine their cloud points, pKs, and hydrodynamic diameters. The cloud points of the larger star polymers, with arm DP 30-100, were found to be 29-34 degrees C, almost independent of the DP of the arms. Similarly, the pKs of all star polymers were calculated to range between 6.7 and 7.0, again independent of the arm DP. In contrast, the hydrodynamic diameters of the star polymers strongly depended on the DP of the arms. In particular, by increasing the DP of the arms from 20 to 100, the hydrodynamic diameters in water increased from 7 to 31 nm. All star polymers were evaluated for their ability to transfect human cervical HeLa cancer cells with the modified plasmid pRLSV40 with the enhanced green fluorescent protein as the reporter gene. Our results showed that as the DP of the arms of the DMAEMA star homopolymers increased from 10 to 100, the overall transfection efficiency decreased, with the star polymer with DP of the arms of 10 emerging as the best transfection reagent. Systematic variation of the amounts of star polymer and plasmid DNA used in the transfections led to an optimization of the performance of this star polymer, yielding overall transfection efficiencies of 15%, comparable to the optimum overall transfection efficiency of the commercially available transfection reagent SuperFect of 13%.

Micelle–vesicle transition of oleyldimethylamine oxide in water

We studied the effects of the degree of ionization( α) and the surfactant concentration ( C d) on the micelle–vesicle transition in salt-free oleyldimethylamine oxide (OlDMAO) aqueous solutions by the dynamic light scattering (DLS), the hydrogen ion titration, the small angle neutron scattering (SANS), the electrophoretic light scattering (ELS) and viscoelastic measurements. From the study of ionization effects, the micelle–vesicle transition was recognized as a change of aggregate size by the DLS measurement; however, the micelle–vesicle transition was not detected both in the ELS measurement and the hydrogen ion titration, suggesting that the electric properties of the worm-like micelles and the vesicles are very similar despite a large difference of shapes between them. From the results of the SANS, the DLS and the viscosity measurements, it was suggested that a concentration-dependent micelle–vesicle transition took place around C p = 10 mmol kg −1 for the solutions at α = 0.5. In the concentration-range 10 mmol kg −1 < C d < 150 mmol kg −1, the micelles and the vesicles coexisted. In the concentration region ( C d = 10–50 mmol kg −1), the vesicle size increased with the surfactant concentration.

A thermodynamic analysis of the hydrogen ion titration of micelles

A thermodynamic analysis of hydrogen ion titration is presented for association colloids with particular emphasis on surfactant micelles. When a particular type of the micellar Gibbs–Duhem relation (MGD), α M dμ I +(1−α M ) dμ N =0 [ α M: the degree of ionization of micelles; μ I, μ N: chemical potentials of ionized and nonionized species], holds, the free energy change accompanying the ionization of the micelle G ex can be evaluated from the titration data in the same manner as for covalently bonded colloids such as linear polyions. In the case where the regular solution approximation is valid for mixed micelles, the titration curve should be a straight line with a slope yielding the interaction parameter, and G ex is given as a function of α M 2. For dodecyldimethylamine oxide micelles for which the MGD relation has been shown to hold, values of the calculated electrostatic free energy G el were close to but significantly greater than experimental G ex values when the former were calculated on the basis of the Poisson–Boltzmann equation for either a sphere or a plate with smeared charges in a salt solution of infinite volume. When the critical micelle concentration (cmc) data are combined with the hydrogen ion titration data, we obtain a criterion to judge whether the above MGD relation holds or not. When the MGD relation holds, the monomer concentration C 1 can be evaluated from the hydrogen ion titration. For most cases examined, the C 1/ C 1( α M=0) from the titration agrees well with cmc/cmc( α M=0), suggesting cmc= C 1 above the cmc. For tetradecyldimethylamine oxide, the MGD relation does not hold in the range of low ionic strength and even at 0.1 M NaCl it has been found that C 1/ C 1( α M=0)<cmc/cmc( α M=0), due probably to enormous micelle growth.

Hydrogen ion titration of oleic acid in aqueous media: further examinations on sodium and potassium oleate systems

Hydrogen ion titration profiles of the aqueous potassium oleate/oleic acid systems were examined as a function of the degree of neutralization, β, in corresponding metal chloride solutions. At temperatures higher than 5 °C, the titration curves were almost identical to those of sodium oleate systems at temperatures higher than 20 °C characterized by a single constant-pH region due to the multiple-phase equilibrium including metal oleate micelles. At a low temperature, 0 °C, on the other hand, different titration curves characterized by two constant-pH regions were observed. The ranges of β of the high constant-pH region were 0.6<β<0.95 in contrast to the sodium oleate system (0.5<β<0.95). These results suggested that the acid soap compositions, oleate acid/metal oleate ratios, were 2:3 for the potassium oleate and 1:1 for the sodium oleate systems. Differential scanning calorimetry analysis for the potassium oleate/oleic acid and the sodium oleate/oleic acid two-component systems detected the formation of an acid soap with equivalent compositions in aqueous media. To inspect further the changes in the temperature profiles of the titration curves, the temperature dependence of the solution properties of potassium and sodium oleates was examined.

Synthesis and aqueous solution characterization of novel diblock polyampholytes containing imidazole

A series of diblock copolymers of 2-(1-imidazolyl)ethyl methacrylate and tetrahydropyranyl methacrylate (THPMA) were synthesized by group transfer polymerization using propylene carbonate rather than tetrahydrofuran as the solvent to ensure homogeneous polymerizations. The resulting copolymers were characterized by gel permeation chromatography and proton nuclear magnetic resonance spectroscopy ( 1H NMR) to determine their molecular weights and compositions, respectively. The THPMA units of the copolymers were subsequently converted to methacrylic acid units by acid hydrolysis. The resulting polyampholytes were characterized in terms of their composition and solubility characteristics using 1H NMR and hydrogen ion titration. Moreover, dynamic light scattering in alkaline water (pH 9.3) indicated the presence of large non-micellar aggregates of the block polyampholytes.

Effects of Micellar Charge Density on the Coefficient of the Corrin–Harkins Relation

Effects of the micelle composition (ionic species fraction α M ) on the coefficient of the Corrin–Harkins relation ( k CH) of ionic/nonionic mixed micelles were examined in the case of dodecyldimethylamine oxide. Long alkyl chain amine oxides exist either in the nonionic or the cationic (protonated form) species depending on the pH of solutions and hence the control of the micelle composition near the critical micelle concentration (cmc) is possible by adjusting the pH of the solutions. On the basis of the cmc data from the surface tension measurements and the hydrogen ion titration curves, we evaluated the k CH values as a function of the micelle composition α M for the first time. The obtained k CH values were compared with the degree of the counterion binding, θ, in the solutions without added salt. The k CH values increased with α M, and were approximately identical with θ for α M>0.4. In the range α M<0.4, it is likely that θ is greater than k CH. An empirical relation proposed by D. G. Hall et al. (“Mixed Surfactant Systems,” Am. Chem. Soc., Washington, D.C. 1992) on the relation between θ and the micelle composition was also compared with these experimental results. Experimental values, k CH and θ, followed the empirical relation for α M>0.4; however, both k CH and θ increased steeply in the range α M 0.25–0.3.