The Association of Tetraalkylammonium Ions with Poly(vinyl methyl ether) in Water and its Effect on Phase‐Separation Behavior as Studied by Micro‐Raman Spectroscopy

Summary: The thermosensitive phase‐separation of poly(vinyl methyl ether) in water has been investigated by micro‐Raman spectroscopy in the presence of tetraalkylammonium bromides. The equilibrium distribution of both polymer and salts to the polymer‐rich and solvent‐rich phases was determined as a function of temperature. Tetraalkylammonium ions with longer alkyl chains associate more strongly with PVME and raise the phase‐transition temperature due to an increase in hydrophilicity.

     

Salt effect on polymer solutions

The salt effect was investigated by measurements of viscosity, cloud point, and solubility of aqueous solutions of poly(vinyl alcohol—acetate) copolymers, as these copolymers in water are sensitive in various ways to addition of various electrolytes. The major role in the salt effect is played by the anions, and water-structure breaking anions produce salting-in of the copolymers. Tetraalkylammonium halides (bromides and iodides) cause salting-in of the copolymers more effectively with increase of size of the hydrophobic cations. The Setschenow equation does not hold for the polymers except for very dilute polymer concentration. In salts of monoalkyl-substituted anions (R? COONa and R? SO₄Na) and cations (R? NH₃Cl and Br), so long as the alkyl chain is short, the salt effect is also dominated by the anions. With increase of the alkyl chain length, sodium salts of the monoalkyl-substituted anions exert a stronger salting-in effect upon the polymers than chlorides of similar long-chain cations. The significance of the counteranions is suggested for the interaction of nonionic polymers and the long-chain cations. The action of the salts on the copolymers is discussed in terms of medium effects (change of the water structure) and of the binding effect of the single ions to the polymers.     

The conformational stability of tactic poly(2-hydroxyethyl methacrylate) in aqueous salt solutions

The conformational stability of tactic poly(2-hydroxyethyl methacrylate) (PHEMA) in aqueous salt solutions was investigated by measurements of swelling, surface-free energy, and differential scanning calorimetry, as this polymer in water is sensitive in various electrolytes. In the case of inorganic salts, the major role for the salt effect is played by the anions, and the exposure of hydrophobic components at the PHEMA surface can be correlated with the increase of the degree of swelling. The influence of cations is considerably weaker. In the case of organic salts, tetraalkylammonium halides cause the chain extension more effectively with the increase of alkyl chain length in the cations. This result indicates that the breakdown of the hydrophobic parts in PHEMA provides an important clue on conformational stability. The amount of water molecules bound with the hydrophilic sites of tactic-PHEMA mainly depends on the chain extension and the hydration of cations. Since the sites in tactic-PHEMA influenced by the cation and the anion are different, their effects cause the conformational transition at a specific range of salt concentration. © 1993 John Wiley & Sons, Inc.     

测定溶解度组装阴离子手性离子液体的研究

本文利用无机盐和有机盐在有机溶剂中的溶解度的差异,设计组装手性羧酸阴离子离子液体.测定氯化钠、氯化钾、溴化钠和溴化钾和手性有机羧酸盐((R)-2-羟基-4-苯丁酸钠或钾)在甲醇、乙醇或丙酮中的溶解度,一定温度下计算溶解度比值,理论推测该条件下阴离子交换比例.研究发现,当无机盐与有机盐的溶解度比值小于0.05时,阴离子交...     

Phase-transfer-mediated electrochemical reaction: anodic disulfide bond formation under biphasic condition

The use of bromide ion as a redox mediator promotes electrochemical reactions in the non-conductive cyclohexane phase. Anodically oxidized species of bromide ion in the conductive methanol phase can bring oxidizing power across phases to induce oxidative disulfide bond formation of a hydrophobically-tagged tripeptide, which is located predominantly in the cyclohexane phase. In addition to commonly used tetraalkylammonium salts, inorganic sodium salt can also be effective alternatives for the bromide source.     

Crystallization of carboxylic acid salts in poly(ethylene oxide) oligomers at higher temperatures

Many alkali metal carboxylates when dissolved in poly(ethylene oxide) (PEO) oligomers, are phaseseparated by heating. These were revealed to be the crystals of the initially dissolved corresponding salts from the X-ray diffraction patterns. Some acetate salts achieve the lower limit of the lattice energy for phase separation of ordinary inorganic salts by heating in PEO oligomers. These carboxylate salts were therefore expected to show crystallization behavior in PEO oligomers by heating. The effects of cation size, alkyl chain length and molecular weight of PEO on the solubility are summarized. Negative temperature dependence of solubility of these acetate salts is seen in the PEO oligomers only when the salts have long alkyl chains. The salts containing larger cations needed a longer chain length of PEOs for crystallization by heating. These salts with longer alkyl chains showed positive temperautred dependence in lower molecular weight polyethers, but negative temperature dependence in solubility in PEO with molecular weights higher than 400. In PEO₄₀₀, all the carboxylates with longer alkyl chains were phase separated by heating.     

Photoredox-Catalyzed Decarboxylative Bromination,Chlorination and Thiocyanation Using Inorganic Salts

Decarboxylative halogenation reactions of alkyl carboxylic acids are highly valuable reactions for the synthesis of structurally diverse alkyl halides. However, many reported protocols rely on stoichiometric strong oxidants or highly electrophilic halogenating agents. Herein, we describe visible-light photoredox-catalyzed decarboxylative halogenation reactions of N-hydroxyphthalimide-activated carboxylic acids that avoid stoichiometric oxidants and use inexpensive inorganic halide salts as the halogenating agents. Bromination with lithium bromide proceeds under simple, transition-metal-free conditions using an organic photoredox catalyst and no other additives, whereas dual photoredox-copper catalysis is required for chlorination with lithium chloride. The mild conditions display excellent functional-group tolerance, which is demonstrated through the transformation of a diverse range of structurally complex carboxylic acid containing natural products into the corresponding alkyl bromides and chlorides. In addition, we show the generality of the dual photoredox-copper-catalyzed decarboxylative functionalization with inorganic salts by extension to thiocyanation with potassium thiocyanide, which was applied to the synthesis of complex alkyl thiocyanates.     

The solubility of toluene in aqueous salt solutions

The solubility of toluene has been measured in distilled water, and in various inorganic salt solutions. Values of the Setschenow constant, K(S), which quantify toluene solubility versus salt concentration, have been determined for each salt. Values of K(S) are compared to the activity of water for the salt solutions. Data from this study, consistent with earlier data, suggests that the effects of salts upon toluene solubility are non-additive. This contrasts the additive behavior of inorganic salts upon the solubility of nonpolar organic compounds, such as benzene and naphthalene, reported in the literature. Specific interaction between slightly polar toluene and ions in solution is suggested as a possible explanation for the non-additive effect of salts on the solubility of toluene.     

Polymerization of surface-active monomers. I. Micellization and polymerization of higher alkyl salts of dimethylaminoethyl methacrylate

Micellization of cationic salts of dimethylaminoethyl methacrylate (DMAEMA) quaternized with n-alkyl bromides such as octyl, lauryl, myristyl, and stearyl bromide and their polymerizations were investigated. The critical micelle concentration (cmc) in water at 25°C was determined by electrical conductivity and dye(azobenzene) solubilization methods and the relation log(cmc) = 1.46–0.31N was obtained, where cmc is in mmol L^?1 and N corresponds to carbon number of alkyl bromides used for the monomer preparations. All of these monomeric salts exhibited a high radical polymerizability in water and benzene. The polymerizations in water appeared to proceed with a higher rate with increasing a chain length of the alkyl moiety of the monomers and those in benzene gave the polymers with a remarkably high viscosity. The rate of polymerization of lauryl bromide salt in anisotropic solutions (in water and benzene) was exceedingly fast as compared with that in isotropic solution(in acetonitrile). All of the polymers obtained here were insoluble in water. Solubility characteristics of these monomers and polymers in other solvents were also presented. The reduced viscosity, in dimethylformamide and methanol, of poly(lauryl bromide salt) prepared in water increased with dilution but that for the polymer obtained in benzene exhibited an inverse concentration dependence. Some discussions were made on the peculiarities of the polymerizations of these monomers and the resulting polymers.     

Chain-length and solvent dependent morphological changes in sodium soap fibers

Sodium soap fibers with varying alkyl chain lengths were studied by cryotransmission electron microscopy and differential scanning calorimetery in water and water-propylene glycol mixtures. The morphology of the lamellar fibers was found to be dependent on the chain length of the alkyl chain and the solvent polarity. Cryoelectron microscopy revealed that short-chain (C10-C14) sodium soaps have the bilayer plane perpendicular to the fiber width, which enables one to see the bilayer striations on the fibers, whereas long-chain (C16-C20) sodium soaps have bilayer planes parallel to the fiber width, and the bilayer striations are not visible. This change in morphology is accompanied by a change in dissolution enthalpy.     

Empirical correlations between Krafft temperature and tail length for amidosulfobetaine surfactants in the presence of inorganic salt

Long-chain amidosulfobetaine surfactants, 3-(N-fattyamidopropyl-N,N-dimethyl ammonium) propanesulfonates (n-DAS, n > 18), are insoluble in pure water due to their high Krafft temperature (T(K)), while they are soluble when inorganic salt is added to the surfactant solution as the T(K) of these zwitterionic surfactants is decreased. The influence of the salt content and ionic species of the added electrolytes on the T(K) of the series of amidosulfobetaine surfactants was examined by means of UV-vis spectrophometry and visual inspection. It was found that the T(K) of these surfactants depends strongly on not only the hydrophobic alkyl length (n), but also the salinity of the aqueous environment. When the salt concentration is increased from 0 to 100 mM, the T(K) shows a sharp decrease; when the salinity is fixed between 100 and 2000 mM, the T(K) varies linearly with n with a slope of ~7.7 irrespective of the salt species and the salt content. When the salt concentration is further increased above 2000 mM, a linear function is still observed, but the slope increases slightly.     

A Simple Preparation of Anhydrous Tetra Alkylammonium Salts

Tetraalkyl ammonium (TAA) salts are of great importance in many areas of chemistry (organic, physical etc.). Tetraalkylammonium (TAA) chlorides, bromides or iodides are usually prepared by direct quaternization of trial-kyl amines with the corresponding alkyl halides. However other tetraalkylammonium (TAA) salts - cyanides, rhoda-nides, azides etc. cannot be prepared in this direct way. A typical method of preparation of these salts consists in ion exchange between available TAA halides and various salts containing the required anions. In some instances simply treating the TAA halides with aqueous solution of silver salts can be applied. This procedure, however, besides being costly is limited to the cases when the required silver salts are soluble in water¹.     

Effect of electrolytes on the cloud point of chlorpromazine hydrochloride solutions

Cloud point (CP) phenomenon occurring in amphiphilic drug chlorpromazine hydrochloride (CPZ) solutions with and without salts is reported herein. The CP of a 50mM CPZ solution (prepared in 10mM sodium phosphate, SP, buffer) was found to decrease with increasing pH, both in the absence as well as presence (50mM) of added salts (NaCl, NaBr, LiBr, KBr, tetra-n-butylammonium bromide). Whereas, at a fixed concentration of NaCl, the CP increased with increasing CPZ concentration, addition of increasing amounts of salts (NaF, NaCl, NaBr, LiCl, KCl) to 50mM CPZ solution (at pH 6.7) caused continuous increase in CP. On the basis of these studies the binding-effect orders of counterions and co-ions have been deduced, respectively, as: Br(-)>Cl(-)>F(-) and Li(+)>Na(+)>K(+). The similar trend of increasing CP with addition of increasing amounts of quaternary bromides (tetramethylammonium bromide, TMeAB; tetraethylammonium bromide, TEtAB; tetra-n-propylammonium bromide, TPrAB; tetra-n-butylammonium bromide, TBuAB; tetra-n-pentylammonium bromide, TPeAB) to 50mM CPZ solutions (at pH 6.7) was found to be dependent upon the alkyl chain length of the particular salt. The overall behaviour has been discussed in terms of electrostatic interactions, micellar growth, and mixed micelle formation.     

Size-selective phase-transfer catalysis with interfacially cross-linked reverse micelles

Cross-linking of the reverse micelles (RMs) of a triallylammonium surfactant afforded organic nanoparticles with introverted cationic groups. The cross-linked reverse micelles catalyzed size-selective biphasic reaction between sodium azide and alkyl bromides. Size selectivity of up to 9:1 was obtained for alkyl bromides with similar structures. The selectivity was influenced strongly by the size of the water pool and proposed to happen as a result of the "sieving" effect of the alkyl corona.     

Melting of saturated fatty acid zinc soaps

The melting of alkyl chains in the saturated fatty acid zinc soaps of different chain lengths, Zn(C(n)H(2n+1)COO)(2); n = 11, 13, 15, and 17, have been investigated by powder X-ray diffraction, differential scanning calorimetry, and vibrational spectroscopy. These compounds have a layer structure with the alkyl chains arranged as tilted bilayers and with all methylene chains adopting a planar, all-trans conformation at room temperature. The saturated fatty acid zinc soaps exhibit a single reversible melting transition with the associated enthalpy change varying linearly with alkyl chain length, but surprisingly, the melting temperature remaining constant. Melting is associated with changes in the conformation of the alkyl chains and in the nature of coordination of the fatty acid to zinc. By monitoring features in the infrared spectra that are characteristic of the global conformation of the alkyl chains, a quantitative relation between conformational disorder and melting is established. It is found that, irrespective of the alkyl chain length, melting occurs when 30% of the chains in the soap are disordered. These results highlight the universal nature of the melting of saturated fatty acid zinc soaps and provide a simple explanation for the observed phenomena.     

Enthalpies of Transfer of Tetraalkylammonium Bromides and CsBr from water to Aqueous DMF at 298.15 K

Enthalpies of transfer of tetraalkylammonium bromides and CsBr from water to aqueous DMF mixtures are reported and analyzed in terms of a new solvation theory. It was found that a previous equation could not reproduce these data over the whole range of solvent compositions. Using a new solvation theory to model the enthalpies of transfer shows excellent agreement between experimental and calculated values over the entire range of solvent compositions. The analyses show that tetrapropylammonium bromide, Pr₄NBr, and tetrapentylammonium bromide, Pen₄NBr, are preferentially solvated by water; in contrast tetrabutylammonium bromide, Bu₄NBr, is preferentially solvated by DMF. The solvation of tetramethylammonium bromide, Me₄NBr, and cesium bromide, CsBr, is random. The extent to which the tetraalkylammonium bromides disrupt solvent–solvent bonds increases systematically in going from Me₄NBr to Pen₄NBr.     

Thermodynamic properties of aqueous solutions of tetraalkylammonium salts: Dependence of the hydrophobic hydration effect on the cation size

The heats of solution of tetrahexylammonium and tetraheptylammonium bromides in water were measured at 318.15 and 328.15 K. The standard enthalpies and specific heats of solution and the temperature changes in the free energy and entropy of solution were calculated. A comparison of the thermodynamic properties of solutions for the homologous series of tetraalkylammonium salts demonstrated that the enthalpic, entropic, and specific heat characteristics of solution are positive and increase almost linearly up to tetrapentylammonium bromide. On passing to larger homologues, these parameters decrease, suggesting that the hydrophobic hydration effect is substantially weaker in solutions of tetraalkylammonium salts with larger cations. Original Russian Text ? A.V. Kustov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 2, pp. 368–373.     

Effect of Protonation on the Solution and Phase Behavior of Aqueous Sodium Myristate

Aqueous sodium myristate solutions have been shown to have unusually low dynamic tensions (1-10 mN/m) under pulsating area conditions. These solutions have no sharp solubility limit, evidently because they are protonated (or "hydrolyzed") to form the much less soluble myristic acid and acid soaps. With no added electrolytes, the protonation fraction is 1% or less. The apparent protonation equilibrium "constant" increases with increasing concentration, indicating strong solution nonidealities, in addition to micellization. This protonation seems to affect the solution and phase behavior of aqueous sodium myristate strongly, as evidenced by the effect of added NaOH. Ion-selective electrodes (for Na(+) and H(+)) and conductimetry indicate that at 25 degrees C dissolved surfactant concentrations keep increasing well after dispersed particles are observed (2 mM). A cmc of about 4.5 mM, micelles of aggregation number n=70 and counterion binding parameter beta=0.7 are inferred from these techniques. The cmc of sodium myristate increases slightly with temperature from 25 to 45 degrees C. FTIR analysis of the filtered particles indicates that the dispersed particles are mainly acid soaps for concentrations less than 6 mM. With 10 mM NaOH, the particles observed above 2 mM consist mostly of sodium myristate. From both conductivity and IR data, the solubility of sodium myristate in water at 25 degrees C is estimated to be about 6 mM, and as expected, it increases with increasing temperature and decreases with increasing sodium ion concentration. Copyright 2000 Academic Press.     

Interfacial and solution properties of tetraalkylammonium bromides and their sodium dodecyl sulfate interacted products: a detailed physicochemical study

The adsorption and solution behaviors of symmetrical tetramethyl-, tetraethyl-, tetrapropyl-, and tetrabutylammonium bromides (TMAB, TEAB, TPAB, and TBAB, respectively) were studied at the air/water interface and in the bulk aqueous environments. Their salts were prepared by reacting tetraalkylammonium bromide (TAAB) with sodium dodecyl sulfate (SDS) in a solution from which the products of the higher two homologues (tetrapropylammonium dodecyl sulfate (TPADS) and tetrabutylammonium dodecyl sulfate (TBADS)) could only be isolated as solids and for which detailed characterization has been performed. The interfacial behaviors of 1:1 molar mixtures of TAAB and SDS and the prepared TPADS and TBADS were examined. Micellization of the 1:1 mixtures along with the isolated species were studied in the presence and absence of NaBr salt. The energetics of the micellization process and the counterion binding of the micelles were evaluated. The interaction of the TAABs with SDS micelles was examined, and the results were evaluated in terms of single- and two-site binding interaction models. Of the formed tetraalkylammonium dodecyl sulfates (TAADSs), only TBADS evidenced clouding, which was investigated in detail along with 1:1 molar mixtures of TBAB and SDS in aqueous solution in the presence of additives such as NaBr, SDS, and TBAB. The solution behaviors of the TAADS and the clouding of TBADS have been rationalized in terms of a mixed micellar model.