Surfactants solubilisation

The primary aim of microemulsion research is to find the conditions under which the surfactant solubilises the maximum amounts of water and oil, i.e. the phase behaviour has to be studied. As the effect of pressure on the phase behaviour is (in general) rather weak [30 ], it is sufficient to consider the effect of the temperature. Furthermore, it hasbeen shown that simple ternary systems consisting of water, oil and non-ionic n-alkyl polyglycol ethers (QEj) exhibit all properties of complex and technically relevant systems [6]. Therefore, we will first describe the phase behaviour of ternary non-ionic microemulsions. 

The use of microemulsions in the dying process [186] is relatively new and little practiced. The major part of patents and other references are dedicated to the solubilisation of various dyes in surfactant micelles, and microemulsion compositions are given, which consist of a classical triad surfactant, co-surfactant, solubilisable substance (dye). In some cases, o/w emulsions were added, in which xylene or hexadecane were used as oil phase. Only few examples are... 

Solubility can be improved by chemical modifications (change of pH, use of buffer, derivatisation, complexation, salt formation) and other techniques (use of excipients such as surfactants, solubilisers, cyclodextrines and phospholipids). 

One of the most important characteristics of micelles is their ability to take up all kinds of substances. Binding of these compounds to micelles is generally driven by hydrophobic and electrostatic interactions. The dynamics of solubilisation into micelles are similar to those observed for entrance and exit of individual surfactant molecules. Their uptake into micelles is close to diffusion controlled, whereas the residence time depends on the sttucture of the molecule and the solubilisate, and is usually in the order of 10 to 10" seconds . Hence, these processes are fast on the NMR time scale. 

For ammonium surfactants there is evidence for the existence of an additional specific interaction between the headgroups of the surfactant and the aromatic solubilisate . This is in line with the observation that partition coefficients for benzene in CTAB solutions are much higher than those for... 

In retrospect, this study has demonstrated the limitations of two commonly accepted methods of analysing solubilisation and micellar catalysis, respectively. It has become clear that solubilisate ririg-current induced shifts need to be interpreted with due caution. These data indicate a proximity of solubilisate and parts of the surfactant and, strictly, do not specify the location within the micelle where the encounter takes place. Also the use of the pseudophase model for bimolecular reactions requires precaution. When distribution of the reactants over the micelle is not comparable, erroneous results are likely to be obtained... 

Surfactants in E/ectroc/eaners. Surfactants typically consist of a long-chain hydrocarbon molecule having a solubilising or water-loving group which can be anionic, cationic, or nonionic when solubilized. Thousands of surfactant products are marketed, usually under trade names (32). In commercially formulated electrocleaners, surfactants are usually anionic, and often mixtures of anionics and nonionics. 

For fluorescence PAH determination in tap water acid-induced cloud point extraction was used. This kind of extraction based on the phase separation into two isotropic liquid phases a concentrated phase containing most of the surfactant (surfactant-rich phase), where the solubilised solutes are exttacted, and an aqueous phase containing a surfactant concenttation closes to the critical micellar concentration. 

Below some critical surfactant concentration, the system is two-phase with excess oil or water depending on the oil/water concentration. On adding more surfactant, the system moves into a one-phase region with normal micelles forming in water-rich systems. The water constitutes the continuous phase, solvating the headgroups of the surfactant whose hydro-phobic tails solubilise oil in the core of the micelle. In oil rich systems, reverse-micelles form. With further increases in surfactant composition. 

A surfactant was defined in Chapter 8 as an agent, soluble or dispersible in a liquid, which reduces the surface tension of the liquid [1]. It is helpful to visualise surfactant molecules as being composed of opposing solubility tendencies. Thus, those effective in aqueous media typically contain an oil-soluble hydrocarbon-based chain (the hydrophobe) and a smaller water-solubilising moiety which may or may not confer ionic character (the hydrophile). The limitations of space do not permit a comprehensive detailed treatment of the chemistry of surfactants. The emphasis is therefore on a broad-brush discussion of the principal types of surfactant encountered in textile preparation and coloration processes. Comprehensive accounts of the chemistry and properties of surfactants are available [2-13]. A useful and lucid account of the chemistry and technology of surfactant manufacturing processes is given by Davidsohn and Milwidsky [ 14] ... 

Nearly all nonionic surfactants contain the same type of hydrophobes as do anionic and cationic surfactants, with solubilisation and surfactant properties arising from the addition of ethylene oxide to give a product having the general formula 9.40. Usually, depending on the... 

The physico-chemical theory of surface activity is a vast field and no more than broad principles can be touched on here major reference sources exist for those who require more detail of the relationship between chemical structure and the various surfactant properties such as wetting, detergency and emulsification-solubilisation [32-36]. 

S D Christian and J F Scamehorn, Solubilisation in surfactant aggregates (New York Marcel Dekker, 1995). 

Since cyclodextrins form complexes with various other substances, including many dyes and surfactants, it is clear that they could be useful in effluent treatment. They are potentially suitable for the reduction or removal of polluting substances either by immobilisation or by solubilisation and extraction and thus can accelerate detoxification [30]. 

Desizing by chemical decomposition is applicable to starch-based sizes. Since starch and its hydrophilic derivatives are soluble in water, it might be assumed that a simple alkaline rinse with surfactant would be sufficient to effect removal from the fibre. As is also the case with some other size polymers, however, once the starch solution has dried to a film on the fibre surface it is much more difficult to effect rehydration and dissolution. Thus controlled chemical degradation is required to disintegrate and solubilise the size film without damaging the cellulosic fibre. Enzymatic, oxidative and hydrolytic degradation methods can be used. 

Alvarez-Cohen et al. [91] explicitly showed that microbial transformation rates of trichloroethylene (TCE) were proportional to the aqueous TCE concentrations and independent from zeolite-sorbed TCE concentrations. Apparently in contrast to these findings, Crocker et al. [92] reported on the direct bioavailability of naphthalene sorbed to hexadecyltrimethylammonium (HDTMA)-modified smectite clay to Pseudomonas putida 17848, but not to Alcaligenes sp. strain NP-Alk. It should be noted that sorption to the hexadecyl chains of HDTMA resembles more the solubilisation by a surfactant than adsorption to a solid surface. Possibly, hydrophobic surface structures of strain 17848 allowed the close contact with HDTMA, thereby facilitating the uptake of naphthalene by a lipophilic pathway. 

At concentrations above their aqueous solubility, the so-called c.m.c., low-molar-mass biosurfactants form micelles in the aqueous phase. Micelles are spherical or lamellar aggregates with a hydrophobic core and a hydrophilic outer surface. They are capable of solubilising nonpolar chemicals in their hydrophobic interior, and can thereby mobilise separate phase (liquid, solid or sorbed) hydrophobic organic compounds. The characteristics for the efficiency of (bio)surfactants are the extent of the reduction of the surface or interfacial tension, the c.m.c. as a measure of the concentration needed to bring about this reduction, and the molar solubilisation ratio MSR, which is the number of moles of a chemical solubilised per mole of surfactant in the form of micelles [96]. 

Micelles forming above the c.m.c. incorporate hydrophobic molecules in addition to those dissolved in the aqueous phase, which results in apparently increased aqueous concentrations. It has to be noted, however, that a micelle-solubilised chemical is not truly water-dissolved, and, as a consequence, is differently bioavailable than a water-dissolved chemical. The bioavailability of hydrophobic organic compounds was, for instance, reduced by the addition of surfactant micelles when no excess separate phase compound was present and water-dissolved molecules became solubilised by the micelles [69], In these experiments, bacterial uptake rates were a function of the truly water-dissolved substrate concentration. It seems therefore that micellar solubilisation increases bioavailability only when it transfers additional separate phase substrate into the aqueous phase, e.g. by increasing the rates of desorption or dissolution, and when micelle-solubilised substrate is efficiently transferred to the microorganisms. Theoretically, this transfer can occur exclusively via the water phase, involving release of substrate molecules from micelles, molecular diffusion through the aqueous phase and microbial uptake of water-dissolved molecules. This was obviously the case, when bacterial uptake rates of naphthalene and phenanthrene responded directly to micelle-mediated lowered truly water-dissolved concentrations of these chemicals [69]. These authors concluded from their experiments that micellar naphthalene and phenanthrene had to leave the micellar phase and diffuse through the water phase to become... 

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