Micellar property

Micellization is a second-order or continuous type phase transition. Therefore, one observes continuous changes over the course of micelle fonnation. Many experimental teclmiques are particularly well suited for examining properties of micelles and micellar solutions. Important micellar properties include micelle size and aggregation number, self-diffusion coefficient, molecular packing of surfactant in the micelle, extent of surfactant ionization and counterion binding affinity, micelle collision rates, and many others. 

The effect of added inorganic salts on the micellar properties of the nonionic and cationic forms of dimethyl dodecyl amine oxide has been deterrnined (2). 

Micellar properties are affected by changes in the environment, eg, temperature, solvents, electrolytes, and solubilized components. These changes include compHcated phase changes, viscosity effects, gel formation, and Hquefication of Hquid crystals. Of the simpler changes, high concentrations of water-soluble alcohols in aqueous solution often dissolve micelles and in nonaqueous solvents addition of water frequendy causes a sharp increase in micellar size. 

Van Paassen [57] describes the CMC of some polyether carboxylates with different fatty chains and EO degrees (Fig. 2). In an extensive study, Binana-Limbele et al. [59] investigated the micellar properties of the alkylpolyether carboxylates of the general formula CnH + OCF CH OCI COONa with n = 8, x = 5, and n = 12 and x = 5,1, and 9, by means of electrical conductivity (CMC, apparent micellar ionization degree) and time-resolved fluorescence probing (micelle aggregation number A7) as a function of temperature and surfactant concentration (Table 1). 

The direct synthesis of poly(3-sulfopropyl methacrylate)-fr-PMMA, PSP-MA-fr-PMMA (Scheme 27) without the use of protecting chemistry, by sequential monomer addition and ATRP techniques was achieved [77]. A water/DMF 40/60 mixture was used to ensure the homogeneous polymerization of both monomers. CuCl/bipy was the catalytic system used, leading to quantitative conversion and narrow molecular weight distribution. In another approach the PSPMA macroinitiator was isolated by stopping the polymerization at a conversion of 83%. Then using a 40/60 water/DMF mixture MMA was polymerized to give the desired block copolymer. In this case no residual SPMA monomer was present before the polymerization of MMA. The micellar properties of these amphiphilic copolymers were examined. 

GTP was employed for the synthesis of block copolymers with the first block PDMAEMA and the second PDEAEMA, poly[2-(diisopropylamino)e-thyl methacrylate], PDIPAEMA or poly[2-(N-morpholino)ethyl methacrylate], PM EM A (Scheme 33) [87]. The reactions took place under an inert atmosphere in THF at room temperature with l-methoxy-l-trimethylsiloxy-2-methyl-1-propane, MTS, as the initiator and tetra-n-butyl ammonium bibenzoate, TBABB, as the catalyst. Little or no homopolymer contamination was evidenced by SEC analysis. Copolymers in high yields with controlled molecular weights and narrow molecular weight distributions were obtained in all cases. The micellar properties of these materials were studied in aqueous solutions. 

Although a considerable number of reports have been published on the surface and micellar properties of nonionics of this fundamental structure, there are only a few investigations using highly purified compounds in which chain length of either alkyl or POE group was varied systematically. 

During the past ten years, there have been numerous reports on the synthesis and the application of crown ethers of specific character to various fields. There have been also a few studies of the surface and micellar properties of crown ethers with hydrophobic groups (J - 17). The author has called them surface active crown ethers as a new class of surfactant possessing a promising function (11). 

Tori and Nakagawa (3-7), in a series of papers, described the micellar properties of Ca, Cio, and C12 C-alkylbetaines of the type (CH3)3 N-CH(R)C00-, and N-octylbetaine, CaHi7+N(CH3)2CH2C0Q-. From studies of the temperature dependence of the cmc, they were able to calculate Herrmann (8) studied Cio, C12, and Cia N-alkyl-... 

There has been a recent revival of interest in zwitterionic surfactants (L 4) because of certain useful properties shown by these molecules, including 1) mild behavior on the skin, 2) compatability with both anionics and cationics, 3) adsorption onto skin and hair, and 4) lime soap dispersing ability. Although this type of surfactant has been produced and used industrially for the last few decades, there have been few studies of the properties of well purified surfactants of this type (5-11) and almost all of these have been concerned with the micellar properties of these compounds rather than with their behavior at interfaces. 

Although the proposed theory has been used effectively in several practical applications, no experimental proof has been given that the oil solubilization rate is a function of surfactant aggregate size. In view of the importance of solubilization and the existence of practical methods of measuring and controlling surfactant aggregate size, we decided to correlate the solubilization rate with micellar properties for some anionic and nonionic surfactants. 

This paper presents a very basic principle in surfactant solubilization. More quantitative measurement in correlating solubilization rate with micellar properties and more applications of this principle to improve performance of various solubilization processes remain the subject of our investigation. 

Benson, H.L. Chiu, Y. C. "Relationship of Detergency to Micellar Properties for Narrow Range Alcohol Ethoxylates". Technical Bulletin, SC 443-80, Shell Chemical Co. Houston, Texas, U.S.A., 1980. 

The purpose of this article is to review studies carried out on hemes incorporated inside the micellar cavity, and examine the effect of micellar interaction on the electronic and structural properties of the heme. A comparison of these results with those on the metalloproteins is clearly in order to assess their suitability as models. The article begins with a general introduction to micellar properties, the incorporation of hemes in the micellar cavity, and then discusses results on hemes inside the micelles with different oxidation and spin states, and stereochemistry. The experimental techniques used in the studies on these aqueous detergent micelles are mostly NMR and optical spectroscopy. The present article has therefore a strong emphasis on NMR spectroscopy, since this technique has been used very extensively and purposefully for studies on hemes inside micellar cavities. 

Nagarajan R. Theory of micelle formation quantitative approach to predicting micellar properties from surfactant molecular structure. Surface Sci Ser 1997 70 1-81. 

Mixed surfactant systems are of importance from a fundamental and practical point of view. Therefore, many recent papers have reported on the micellar properties of mixed surfactant solutions. For example, Tokiwa et al. have measured the NMF spectra W Ingram has measured surface tension ( 5). Previously, we have reported the solution properties of anionic-nonlonlc surfactant mixed systems from the point of view of electrical (., 7) and surface tension measurements (8-10), and investigated the mixed micelle formation. 

In a previous publication ( ), results were presented on the micellar properties of binary mixtures of surfactant solutions consisting of alkyldimethylamine oxide (C12 to Cig alkyl chains) and sodium dodecyl sulfate. It was reported that upon mixing, striking alteration in physical properties was observed, most notably in the viscosity, surface tension, and bulk pH values. These changes were attributed to 1) formation of elongated structures, 2) protonation of amine oxide molecules, and 3) adsorption of hydronium ions on the mixed micelle surface. In addition, possible solubilisation of a less soluble 1 1 complex, form between the protonated amine oxide and the long chain sulfate was also considered. 

---