Colloids and Surfaces A: Physicochemical and Engineering Aspects
Aggregation behaviour and solubilization capability of mixed micellar systems formed by a gemini lipoamino acid and a non-ionic surfactant
Graphical abstract
Introduction
Over the last years many efforts were made to design and develop new amphiphilic molecules or new systems of amphiphiles with adequate properties for application in different areas or technologies [1], [2], [3].
In this respect, gemini surfactants are an interesting type of surfactants consisting of two hydrophobic chains and two hydrophilic heads covalently attached through a spacer [4], [5]. These surfactants have attractive properties such as low critical micelle concentrations (CMC), higher surface activity, better solubilizing power and viscoelastic properties than those of monomeric ones [6], [7], [8]. However, the synthesis of these surfactants usually requires several steps and, in some cases, it is more expensive than certain commercial monomeric surfactants for application to large volumes. Some mixtures of surfactants show synergism, with better properties than those of the individual components [9], [10]. In the presence of synergic effect, the study of mixtures of surfactants could lead to the use of lower amounts of the more expensive or difficult to obtain surfactant, in combination with one more accessible, for different possible applications.
In our laboratory we synthesised, according to the literature [11], a gemini lipoamino acid surfactant named 3,3′-disulfanediyl bis 2-decamido propanoic acid (SDDC), Fig. 1, derived from the amino acid cystine and a fatty acid, decanoic acid. The use of surfactants from renewable sources is also particularly interesting due to the improved properties of these compounds, including enhanced biodegradability and biocompatibility, and a variety of chemical functionalities, with minimal environmental impact [12], [13].
Surfactants are important tools for solving many hazardous environmental problems caused by toxic water-insoluble organic compounds [14]. There are many examples in the literature of applications of surfactants to increase the solubilization of insoluble pollutants in water, by partition of the hydrophobic organic compounds in the micellar core [15], [16], [17]. Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants formed by incomplete combustion of organic matter due to natural and anthropogenic activities [18]. They display low water solubility and high adsorption capacity, thus their removal from soils depends largely on the desorption of the pollutant from the soil surface and its incorporation into the micelles. A variety of mixed surfactant systems was studied with the aim of obtaining better media to enhance the remediation of PAH contaminated soils, finding synergism in some mixtures [19], [20], [21]. A new and not so explored field is the application of gemini surfactants [22], [23] or binary systems formed by gemini-gemini [24] or gemini-conventional surfactants on the solubilization of PAHs [25], [26]. Synergism is also sometimes shown in these systems.
We had previously studied a mixture of a non-ionic surfactant (Tween 80) with an anionic one (sodium laurate), finding synergism for the solubilization of naphthalene in water [27] and for the desorption of naphthalene and phenanthrene from solid matrices [28]. The behaviour observed in that system was attributed to the formation of mixed micelles between both surfactants. In this work, we studied a new mixture of surfactants formed by the same non-ionic surfactant previously used (Tween 80) and the anionic gemini surfactant, SDDC, synthesized in our laboratory (Fig. 1). The aim of this work was twofold: first, to characterize the new mixed micellar system, where the previous anionic surfactant was changed for a compound with two hydrophobic chains and two anionic charges in the working conditions. The studies included surface tension, fluorometric determinations, and small-angle X-ray scattering measurements (SAXS). The changes in the structure of the anionic surfactant influenced considerably the characteristics of the mixed micellar system, providing it with different properties. Second, we proposed to analyse the application of these systems in the solubilization of naphthalene, phenanthrene, and pyrene (as representative PAHs) in water, seeking synergism in the mixture of surfactants.
Section snippets
Materials
Aqueous solutions were prepared from Milli Q water (Millipore purification equipment). Methanol (HPLC grade, J. T. Baker) was used as received.
PAHs were obtained from Sigma-Aldrich with purity higher than 98%.
The non-ionic surfactant, Tween 80, was obtained from Sigma-Aldrich and used without purification. SDDC was synthesised in the laboratory according to the literature by the reaction of cystine with decanoic chloride [11].
The solutions were prepared in buffer of pH 9.16 (0.01 M Na2B4O7, 0.02
Micellar properties of mixed surfactant systems
The CMC of the pure surfactants and the Tween 80/SDDC mixtures were determined by surface tension measurements (Table 1). The break points in the plots of surface tension against the logarithm of the concentration of surfactants were taken as CMC values. Fig. 2 shows a representative plot. From Table 1 it can be seen that the experimental CMCs at different compositions of the mixture range between the CMC values of gemini surfactant and Tween 80, except the value for αTW80 = 0.8 that is even
Conclusions
We investigated the properties of mixed surfactant solutions formed by a commercial surfactant, Tween 80, and the lipoamino acid derivative SDDC. The mixed micelles had triaxial ellipsoid shape with properties in between both pure surfactants. The mixtures showed a non-ideal behaviour as indicated by a lower CMC than that of the individual surfactants, and negative interaction parameter, β, values.
The solubility of naphthalene, phenanthrene, and pyrene was measured in solutions of the
Acknowledgements
This research was supported in part by Agencia Nacional de Ciencia y Tecnología (FONCyT, PICT 2010–2001), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET, PIP 112-201101-00441), Ministerio de Ciencia y Tecnología de la Provincia deCórdoba (MINCyT, PID 2009–2011) and Universidad Nacional de Córdoba (UNC), Argentina (05/C579). We thank the Brazilian Synchrotron Light Laboratory (Beamline SAXS-1) for beamline under project 20150067. MAF and RGO hold researcher positions at
References (49)
- et al.
PEGylated and poloxamer-modified chitosan nanoparticles incorporating a lysine-based surfactant for pH-triggered doxorubicin release
Colloid Surf. B: Biointerfaces
(2016) - et al.
Structural diversity, physicochemical properties and application of imidazolium surfactants: recent advances
Adv. Colloid Interface Sci.
(2016) - et al.
Novel cationic surfactants for corrosion inhibition of carbon steel pipelines in oil and gas wells applications
J. Mol. Liq.
(2016) - et al.
Adsorption and micellization behavior of novel gluconamide-type gemini surfactants
J. Colloid Interface Sci.
(2008) - et al.
Mixed micellization of gemini and cationic surfactants: physicochemical properties and solubilization of polycyclic aromatic hydrocarbons
Colloids Surf. A: Physicochem. Eng. Aspects
(2014) - et al.
Studies of synergism/antagonism for lowering dynamic interfacial tensions in surfactant/alkali/acidic oil systems, part 2: synergism/antagonism in binary surfactant mixtures
J. Colloid Interface Sci.
(2002) - et al.
Synergistic interactions in mixed micelles of alkyltriphenylphosphonium bromides and triblock polymers
Colloids Surf. A: Physicochem. Eng. Aspects
(2005) - et al.
Active control of surface properties and aggregation behavior in amino acid-based gemini surfactant systems
J. Colloid Interface Sci
(2008) - et al.
Gemini surfactants from natural amino acids
Adv. Colloid Interface Sci.
(2014) - et al.
Physical chemical characteristics of dicarboxylic amino acid-based surfactants
Colloids Surf. A: Physicochem. Eng. Aspects
(2011)
Reductive degradation of chlorinated organic pollutants-contaminated water by bimetallic Pd/Al nanoparticles: effect of acidic condition and surfactants
Chem. Eng. J.
Investigation on the solubilization of polycyclic aromatic hydrocarbons in the presence of single and mixed gemini surfactants
J. Hazard. Mater.
Solubilization and adsorption behaviors of 2,4,6-trichlorophenol in the presence of surfactants
Chem. Eng. J.
Effect of nonionic surfactants on the solubilization of alachlor
J. Hazard. Mater. B
VOCs and PAHs emissions from creosote-treated wood in a field storage area
Sci. Total Environ.
Enhanced desorption of phenanthrene from contaminated soil using anionic/nonionic mixed surfactant
Environm. Pollut.
Synergistic solubilization of polycyclic aromatic hydrocarbons by mixed micelles composed of a photoresponsive surfactant and a conventional non-ionic surfactant
Sep. Purif. Technol.
Effect of structure of polycyclic aromatic substrates on solubilization capacity and size of cationic monomeric and gemini 14-s-14surfactant aggregates
Colloid Surf. A: Physicochem. Eng. Aspects
Enhanced aqueous solubility of polycyclic aromatic hydrocarbons by green diester-linked cationic gemini surfactants and their binary solutions
J. Mol. Struct.
Solubilization of polycyclic aromatic hydrocarbons by gemini-conventional mixed surfactant systems
J. Mol. Liq.
Efficiency of single and mixed gemini/conventional micelles on solubilization of phenanthrene
Chem. Eng. J.
Different behaviors in the solubilization of polycyclic aromatic hydrocarbons in water induced by mixed surfactant solutions
Chemosphere
Pyrene absorption can be a convenient method for probing critical micellar concentration (cmc) and indexing micellar polarity
J. Colloid Interface Sci.
Hydrolysis of phenyl trifluoroacetate in mixed surfactant systems
J. Phys. Org. Chem
Cited by (14)
Amphiphilic N-oxyethylimidazolium calixarenes: Synthesis, micellar solubilization and molecular recognition of Adenine-containing nucleotides
2022, Colloids and Surfaces A: Physicochemical and Engineering AspectsCitation Excerpt :Calixarenes with their unique three-dimensional structure and easy functionalization of their upper and lower rims have become important molecular platform in molecular recognition, sensing and self-assembly, catalysis, nanotechnology, drug delivery etc. [15–17]. The presence of the molecular cavity as well as the possibility to arm with several functional polar groups The main motivation for investigation of amphiphiles is to impart biocompatibility, increase solubilization properties to the systems based on them, therefore design of novel types of amphiphilic compounds are of importance [18,19]. The amphiphiles bearing imidazolium head groups demonstrate capability to fabricate complexes with various protein macromolecules, drugs and nucleic acids.
Micelle‐to‐vesicle transition of lipoamino Gemini surfactant induced by metallic salts and its effects on antibacterial activity
2022, Journal of Molecular LiquidsCitation Excerpt :An extra experiment using CuCl2 was performed to assess the counterion effect on complex formation, but addition of chloride salt did not result in significant changes and the same greenish solution was obtained. SDDC forms core–shell type triaxial ellipsoidal micelles in aqueous solution as was determined by small-angle X-ray scattering measurements (SAXS) and previously described [32]. SDDC micelles were not observed by TEM, but SDDC in presence of the metallic salt forms vesicles that can be clearly observed by TEM, even without the addition of TEM staining agents.
Effect of surfactant on quality and performance attributes of topical semisolids
2021, International Journal of PharmaceuticsBinary mixture of short and long chain glycolipids and its enhanced surface activity
2020, Colloids and Surfaces A: Physicochemical and Engineering AspectsIonic hydrogen-bonding interaction controlled electrophilicity and nucleophilicity: Mechanistic insights into the synergistic catalytic effect of lipase and natural deep eutectic solvents in amidation reaction
2020, Journal of CatalysisCitation Excerpt :Recently, lipoamino acids (LAA), also known as N-acyl amino acids, which are entirely consist of natural materials, fatty acid and amino acids, have emerged as a promising new generation of efficient, green and safety surfactants in healthy-related areas [27,28], and their production was commonly considered as a classical amidation reaction. As a new generation of LAA, Gemini lipoamino acids (GLAA) are a compound family, which were consist of two fatty acids or two amino acids, with extremely high surface activity [29], Generally, the critical micelle concentration (CMC) of GLAA is several orders of magnitude lower than traditional single chain lipoamino acids (SLAA) [27,30–32], Recently, Xiao and co-workers synthesized a serious of novel L-lysine based GLAA and suggested they exhibited a very high antibacterial activity in broad spectrum of Gram-positive and Gram negative bacteria [33]. Despite all the above attractions, up to date, GLAA can only be laboriously synthesized by complex and multi-step organic synthesis, which bring out large amounts of by-products and environmental problems [34].
Preparation and dissolution characteristic evaluation of carvedilol-Kollicoat IR solid dispersions with HPMC and MC as combined carriers
2020, Powder TechnologyCitation Excerpt :On the outside of the micelle is a hydrophilic group, and on the inside is a hydrophobic group. Due to the hydrophobicity of CAR SD, they will be encapsulated into the micelle, thus increasing the solubility of CAR SD in the solution [25]. CAR SDs were formulated with Kollicoat IR, Kollicoat IR/HPMC, and Kollicoat IR/MC carriers using the solvent evaporation method.