Interactions of two homologues of cationic surface active ionic liquids with sodium carboxymethylcellulose in aqueous solution

In the preceding paper of this series, we studied the interactions of copolymers with the ionic liquids, 1-alkyl-3-methylimidazolium bromide (C _n mimBr, n?=?8, 10, 12, 14, 16) and N-alkyl-N-methylpyrrolidinium bromide (C _n MPB, n?=?12, 14, 16). An obvious difference was detected between the interaction mechanism and the alkyl chain length of the surfactant. In the present study, we performed a systematic study on the interaction of sodium carboxymethylcellulose (NaCMC) with ionic liquids in aqueous solution by isothermal titration microcalorimetry (ITC), conductivity, turbidity, and dynamic light scattering (DLS) measurements. The existence of electrostatic attraction between NaCMC and ILs could increase the complexity of these systems. The results show that the monomers of C₈mimBr can bind to the NaCMC chains and form free surfactant micelles in the solution, while no micelle-like C₈mimBr/NaCMC cluster is detected. For other surfactants, the formation of surfactant/NaCMC clusters in the solution is driven by electrostatic and hydrophobic interactions, which could be divided into two types. One type is the polymer-induced surfactant/NaCMC complexes that form in the solution for the surfactant of C _n mimBr (n?=?10, 12, 14) or C _n MPB (n?=?12, 14). The other type is that the surfactant-induced surfactant/NaCMC complexes come into being for the surfactant of C₁₆mimBr or C₁₆MPB. Finally, the different modes of complex formation proposed have a good interpretation of the experiment results, unraveling the details of the effect of surfactant alkyl chain length and headgroup on the surfactant–NaCMC interactions.     

Laser flash photolysis of carboxymethylcellulose in an aqueous solution

Laser flash photolysis with excitation at 248 nm was used to study photochemically derived changes of carboxymethylcellulose (CMC) in aqueous solutions. Transient absorption spectra of solutions after photolysis revealed a broad band with a maximum of approximately 720 nm, which could be ascribed to the signal of the hydrated electron. The interaction of the hydrated electron with CMC was slow (<10⁷ dm³ mol^?1 s^?1), but the OH radical, formed by the decomposition of H₂O₂, reacted with CMC at a high rate constant (9.5–11.0 × 10⁸ dm³ mol^?1 s^?1). The rate constant of the reactions of CMC with hydroxyl radicals depended on the conformation of the macromolecules, which was determined by the pH of the solution. Transient absorption was recorded at a wavelength shorter than 370 nm for CMC solutions photolyzed in the presence of H₂O₂. As a result of OH attack, long‐lived radicals were formed on CMC. The recombination of macroradicals led to the formation of crosslinking bonds between side‐chain groups, and as a result of it an insoluble gel arose in low‐pH solutions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 505–518, 2005     

Phase relationship and dynamics of anisotropic gelation of carboxymethylcellulose aqueous solution

Anisotropic gelation of carboxymethylcellulose (CMC) in aqueous NaOH sandwiched between two circular cover glasses by immersing it in aqueous CaCl₂ has been studied. In the course of dialysis, gelation and phase separation occurred simultaneously to make turbid stripes arranged radially. The time course of the gel layer width was well expressed in scaled linear plots predicted by a theory based on “moving boundary picture” at low CMC concentrations. On the other hand, at high CMC concentrations, the time course was expressed by a two-stage dynamics. The time course did not depend on the initial thickness of the CMC solution and the diameter of the cover glasses, whereas the rate of gelation decreased with increasing CMC concentration. It was attributed to the change in the calcium cation concentration required for forming the gel in the process. The universality and the individuality of the present system in the gelation dynamics are discussed.     

Molecular parameters of sodium amylose xanthate in dilute solution

Molecular parameters of sodium amylose xanthate in 1N NaOH solution have been determined by means of light scattering and viscometry. The expansion factor, α, has been determined from the expression due to Orofino and Flory. The value of a of the Mark-Houwink relation, [η] = KM^a, has been determined. The Stockmayer-Fixman relationship has been used to evaluate the unperturbed dimension of the chain. The effective bond length b, Kuhn-Kuhn equivalent chain segment length A_m and the steric factor σ, i.e., the ratio of the unperturbed dimension to the dimension assuming free rotation of the chain \documentclass{article}\pagestyle{empty}\begin{document}$(\bar R_o^2 )_z ^{1/2} /(\bar R_f^2 )^{1/2}$\end{document} have also been determined. From these data, it is concluded that sodium amylose xanthate in 1N NaOH solution behaves as a loosely coiled molecule.     

Amphiphilic cholesteryl-bearing carboxymethylcellulose derivatives: self-assembly and rheological behaviour in aqueous solution

The self-assembly of amphiphilic cholesteryl-bearing carboxymethylcellulose derivatives (CCMCs) from individual molecules to self-aggregates, in addition to their rheological behaviour in aqueous solution were investigated. The conformations of the individual CCMC individual molecules and self-aggregates, and the microstructures of CCMC self-aggregates were characterized using the static and dynamic light scattering analyses, and the steady fluorescence technology. The results showed that the individual CCMC chains became compact, and aqueous NaCl solution changed from an approximate θ solvent to a bad one when the number of hydrophobic cholesteryl groups increased. The CCMC self-aggregates exhibited as compact spheres. The microstructural characterization indicated that one CCMC self-aggregate consisted of multiple individual CCMC molecules and hydrophobic microdomains, and multiple cholesteryl groups self-associated into one hydrophobic microdomain. The atomic force microscopy images of CCMC self-aggregates in phase mode showed that the multiple interior hydrophobic phase separation regions were surrounded by hydrophilic polysaccharide chains, providing an evidence for multiple hydrophobic microdomains in one self-aggregate. The rheological analysis proved that the CCMC self-aggregates were a microgel, in which the associations of cholesteryl groups provided multiple cross-linking points in the polymer network. The microgel solutions displayed a unique thixotropy and a shear thinning behaviour.     

Physicochemical and macromolecular properties of sodium amylose xanthate in dilute solution

Sodium amylose xanthate has been studied in dilute solution. Potato starch was fractionated for this purpose into amylose and amylopectin fractions. Amylose was xanthated in solution under alkaline conditions and the Na amylose xanthate was then characterized by reaction with I₂ solution and ultraviolet spectra of the xanthate groups determined. Stability of the xanthate in alkaline condition under both oxygen and nitrogen atmospheres was also investigated. From light scattering measurements of dilute salt solutions of Na amylose xanthate, the weight-average molecular weight M _w as well as the molecular dimensions were determined. In 0.11M NaCl, which conforms to the θ solvent, Na amylose xanthate molecules appear to have a random-coil configuration. Two other configurational parameters, such as the effective bond length b, and the steric factor σ, i.e., (R₀²)^1/2/(R_f² )^1/2, where (R₀²)^1/2 is the Root-mean-square end-to-end distance in the unperturbed state and (R_f² )^1/2 is the unperturbed value calculated on the assumption of free rotation about each intermonomer C? O bond of the amylose chain were also calculated and found to be 6.24 and 1.020, respectively. It is thus concluded that the amylose chain in Na amylose xanthate behaves as a typical flexible coil in dilute salt solution.     

Adsorption of sodium phenylanthranylate on gold electrode from aqueous solution

Adsorption of sodium phenylanthranylate on a gold electrode from a borate buffer solution is studied using the methods of ellipsometry and piezo-quartz nanobalance. Statistical evaluation of adequacy between the obtained experimental isotherms and theoretical models is performed using the F-test. It is shown that they are adequately described using the Frumkin and Temkin equation.     

On the reduction of oxygen in aqueous solution by electrolytically precipitated cadmium

The reduction of oxygen in aqueous solution by electrolytically precipitated cadmium, used in a reductor column, has been studied in two ways. First, by analysis of the effluent for the hydrogen peroxide formed as a reaction intermediate, the conditions for quantitative reduction have been found. Attention is called to the fact that an effluent free from hydrogen peroxide also implies quantitative reduction of all dissolved oxygen. The practical consequences are pointed out. A comparison is also made with some other reductors. Secondly, the oxidation of electrolytically precipitated cadmium by hydrogen ion is strongly inhibited, so at pH 7 it is possible to determine oxygen as the equivalent amount of cadmium ion produced in the reductor column. The conditions of quantitative reduction of oxygen are determined and found to be in agreement with those obtained by the first method. From the results the solubility of oxygen in water in equilibrium with air is estimated and found to agree with a published result considered as reliable. An outline is given of a method for determination of oxygen in aqueous solution by measurement of the amount of cadmium ions produced.     

Influence of gas flow rate and sodium carboxymethylcellulose on foam properties of fatty alcohol sodium polyoxyethylene ether sulfate solution

Foamability, foam initial liquid volume, and bubble size of fatty alcohol sodium polyoxyethylene ether sulfate (AES) surfactant solution were studied with and without the addition of sodium carboxymethylcellulose (CMC) at different gas flow rates, using a sparging method. The generation time decreased with increasing gas flow rate. At low gas flow rates, the added CMC greatly enhanced the foamability by preventing bubble collapse. The initial liquid volume of the foam first increased rapidly, and then gradually decreased. Increasing the CMC concentration increased the initial liquid volume of the foam. The mean bubble diameter first clearly decreased, then increased slowly with increasing gas flow rate. CMC showed different effects on bubble size at high and low gas flow rates. Adsorption of CMC on AES molecules forms a network structure and improves bubble film stability, which can explain the above results. These findings provide guidelines for generating foam with excellent properties suitable for coal mine dust control by adjusting the gas flow rate and the concentration of the added water-soluble polymer.     

Dissipative crystallization of aqueous solution of sodium polymethacrylate

Drying dissipative structures of aqueous solution of sodium polymethacrylate (NaPMA) were studied on a cover glass, a watch glass, and a glass dish. Any convectional and sedimentation patterns did not appear during the course of dryness. Several important findings on the drying patterns are reported. Firstly, spherulite and hedrite dissipative crystals were observed when the polymer solutions were dried. The crystalline structures changed from hedrites to spherulites as polymer concentration increased. Secondary, the coupled structures of the spherulites and the broad rings were observed for NaPMA at the outside edge of the broad ring. However, the coupled crystalline structures of the lamellaes from the broad ring and the spherulites, which were observed for poly(ethylene glycol) (Okubo et al. 2009), were not observed clearly for NaPMA system. Thirdly, size of the broad ring at the outside edge of the dried film increased sharply as polymer concentration increased.     

Viscosity properties of sodium carboxymethylcellulose solutions

Through viscosity measurements, concentration and temperature dependences of viscosity of sodium carboxymethylcellulose (CMC) solution were recorded. Effects of glycerin, mechanical shearing and several electrolytes on the CMC solution were also determined. Results showed that the viscosity dependence on concentration obeyed the Huggins and Kramer equation, the dependence on temperature complied with the Arrhenius equation. CMC chain could synergize with glycerin, konjac glucomannan (KGM), and aluminum sulfate 18-hydrate. Sodium chloride, hydrochloric acid, and calcium dichloride reduced the viscosity of the CMC solution. By suggesting the ion-binding and hydrogen bond as the major form of the electrostatic interaction in the CMC solution, the synergistic and pseudoplastic phenomena as well as the maximum over stirring time were reasonably explained.     

The interaction between sodium carboxymethylcellulose and water

A differential scanning calorimeter has been used to study the nonfreezing of water in a series of solutions of sodium carboxymethylcellulose. In particular, the effects of molecular weight, degree of substitution, and particle size have been investigated. The results show that large amounts of water are associated with all the samples of sodium carboxymethylcellulose, suggesting a multilayer arrangement of water molecules about the solute. A change in degree of substitution has some effect on the hydration, but it appears less significant than a change in molecular weight.     

Hydrolysis of polyacrylonitrile in aqueous solution of sodium carbonate

The kinetics of homogeneous hydrolysis of polyacrylonitrile in an aqueous solution of sodium carbonate and the chemical structure of the resulting copolymer are studied by FTIR spectroscopy, ¹³C NMR analysis, and titration methods. It is found that hydrolysis in the presence of sodium carbonate does not include the stage of amidine formation and does not result in the complete exhaustion of nitrile groups in a polymer. The designed partial-hydrolysis method permits the use of polyacrylonitrile for the synthesis of the copolymer with a predominant unit alternation; this copolymer is identical in terms of chemical structure to the Rohacell copolymer obtained through block copolymerization of acrylonitrile and methacrylic acid.     

Nonequilibrium electrodialysis of aqueous solution of sodium dodecyl sulfate

Summary Special dialysis apparatus was constructed which enabled to trace a short time nonequilibrium dialysis by the continuous measurement of electric resistance of dialyzing solution. The apparatus is particularly suited for the study of the formation of micelles in surfactant solution. The dialysis curves were constructed by plotting the change of electric resistance against dialysis time. The diagrams consisted of a nearly straight line at low concentration and two nearly straight lines above a certain concentration, from which CMC was sharply determined and the constancy of a single ion concentration above CMC was also demonstrated.

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Zusammenfassung Es wurde ein neuartiger Dialyseapparat entwickelt, der es ermöglicht, die Nichtgleichgewichtsdialyse über kurze Zeiten auszuführen und den Lösungszustand der grenzflächenaktiven Substanzen, die die Mizellen enthalten, genauer zu bestimmen. Die gemessenen Dialysekurven, die die Abhängigkeit des elektrischen Widerstands von der Zeit geben, stellen unterhalb der CMC eine fast gerade Linie dar, während oberhalb der CMC jede Kurve aus zwei geraden Stücken mit einem Knick im Schnittpunkt besteht. Hieraus konnten wir die CMC genau bestimmen und die Konstanz der Zwischenmizellkonzentration feststellen.

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Authors wish to express their thanks to Assistant ProfessorS. Okazaki of Sophia University for her help in this research.