Gemini cationic surfactants are compounds which are composed of two hydrophilic head groups and two hydrophobic tails linked by a spacer at the head groups or closed to them. The spacer can be either hydrophobic or hydrophilic. It can be rigid or flexible. The neutral charge of the molecule is retained by the presence of organic or inorganic counterions. Critical micelle concentrations (CMCs), surface tension (γ) and minimal inhibitory concentration (MIC) are dozen times lower than corresponding parameters of monomeric surfactants. The unique properties of gemini surfactants with a wide range of hydrophiliclipophilic balance (HLB) make them a very useful, innovative material in detergents, cosmetics, personal care products, additives for paints and coatings, biocides, material science, organic synthesis, pharmacy, textiles, enhanced oil recovery, nanotechnology, petroleum and many other branches of life. A large number of papers concerning gemini surfactants have been published so far. This review presents a synthetic look at current work devoted to structure, synthesis and applications of gemini surfactants.
Aerobic biodegradability and aquatic toxicity of five types of quaternary ammonium-based gemini surfactants have been examined. The effect of the spacer structure and the head group polarity on the ecological properties of a series of dimeric dodecyl ammonium surfactants has been investigated. Standard tests for ready biodegradability assessment (OECD 310) were conducted for C12 alkyl chain gemini surfactants containing oxygen, nitrogen or a benzene ring in the spacer linkage and/or a hydroxyethyl group attached to the nitrogen atom of the head groups. According to the results obtained, the gemini surfactants examined cannot be considered as readily biodegradable compounds. The negligible biotransformation of the gemini surfactants under the standard biodegradation test conditions was found to be due to their toxic effects on the microbial population responsible for aerobic biodegradation. Aquatic toxicity of gemini surfactants was evaluated against Daphnia magna. The acute toxicity values to Daphnia magna, IC50 at 48 h exposure, ranged from 0.6 to 1 mg/L. On the basis of these values, the gemini surfactants tested should be classified as toxic or very toxic to the aquatic environment. However, the dimeric quaternary ammonium-based surfactants examined result to be less toxic than their corresponding monomeric analogs. Nevertheless the aquatic toxicity of these gemini surfactants can be reduced by increasing the molecule hydrophilicity by adding a heteroatom to the spacer or a hydroxyethyl group to the polar head groups.
Series of quaternary ammonium-based gemini surfactants with long alkyl chains (C12 and C18) containing different spacers and substituents attached to the polar head group have been synthesized and their aggregation properties in aqueous solution examined. The effect of the hydrophobic chain, the nature and structure of the spacer group and the polarity of the head group on the aggregation behavior of such dimeric surfactants has been investigated. The critical micelle concentration (cmc) values of gemini surfactants in aqueous solution were determined by conductivity, steady state fluorescence and potentiometric measurements. The size of aggregates formed by investigated amphiphiles above the cmc in aqueous solution was examined by dynamic light scattering. Gemini surfactants show cmc values significantly lower than those of comparable single chain surfactants. The tendency of trimeric surfactants with a rigid spacer to form aggregates is higher than that of the corresponding dimeric surfactants. As occurs for monomeric ionic surfactants, the cmc of gemini surfactants decreases with the elongation of the hydrophobic chain. However, the effect of lengthening the alkyl chain on the cmc depends on the structure of the spacer. C12 gemini surfactants with a rigid hydrophobic spacer exhibit cmc higher than those containing a flexible hydrophobic spacer. For gemini surfactants with C18 alkyl chains this effect is even more pronounced and leads to differences in cmc values greater than one order of magnitude. The structure of the spacer, flexible or rigid chain, has been found to be a critical parameter on the self-assembly of long chain gemini surfactants. Spherical micelles are spontaneously formed above the cmc for C12 gemini surfactants, whereas trimeric and C18 gemini surfactants seems to form vesicle-like aggregates when self-aggregation occurs.
Organic corrosion inhibitors are one of the five ways, besides material selection, design, cathodic protection and coatings, to protect materials against corrosion. Corrosion is an ubiquitous phenomena that deteriorates all materials, metals, plastics, glass and concrete. The costs of corrosion are tremendous and amounts to 4.0% of gross domestic product (GDP) in USA. The similar losses of GDP are noted in all countries around the world. At this point of time, there is no way to completely stop the corrosion processes. Some new solutions can only slow this process. Organic corrosion inhibitors are widely used in industry because of their effectiveness at wide range of temperatures, compatibility with protected materials, good solubility in water, low costs and relatively low toxicity. Organic corrosion inhibitors adsorb on the surface to form protective film which displace water and protect it against deteriorating. Effective organic corrosion inhibitors contain nitrogen, oxygen, sulfur and phosphorus with lone electron pairs as well can contain structural moieties with π-electrons that interact with metal favoring the adsorption process. This review presents mechanisms and monitoring of corrosion, laboratory methods for corrosion study, relationship between structure and efficacy of corrosion inhibitions, theoretical approach to design new inhibitors and some aspects of biocorrosion.
Micellization and some ecological properties of new cationic gemini surfactants with oxygensubstituted spacer and hydroxyethyl groups connected to the polar heads have been studied. The incorporation of a hydroxyethyl group in the polar head favors self-aggregation whereas the presence of the oxygen in the spacer increases critical micelle concentration. Surfactants investigated are not biodegradable due to their toxic effect on microorganisms responsible for biodegradation. Aquatic toxicity increases with the hydrophobic chain and decreases by increasing the hydrophilicity of spacer and polar heads. New gemini surfactants are less toxic to the aquatic environment than monomeric surfactants and non-oxygen-containing gemini surfactants.
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