Mariana A. Fernández

Synthesis and characterization of an amphiphilic cyclodextrin, a micelle with two recognition sites.

A cyclodextrin derivative (Mod-CD) was synthesized through the monoesterification of beta-cyclodextrin (beta-CD) with 3-((E)-dec-2-enyl)-dihydrofuran-2,5-dione. The compound is an interesting surfactant that can form large aggregates not only through the interaction of the hydrophobic tails as in common amphiphilic compounds but also through the inclusion of the alkenyl chain into the cavity of another Mod-CD molecule. The self-inclusion of the chain in the cavity of cyclodextrin as well as the intermolecular inclusion was demonstrated by 1H NMR measurements that were able to detect methyl groups in three different environments. Besides, in the aggregates of Mod-CD, the cavity is available to interact with external guests such as phenolphthalein, 1-amino adamantane, and Prodan. Phenolphthalein has the same binding constant with Mod-CD and beta-CD, but the equilibrium constant for the interaction with Prodan is about 2 times larger for Mod-CD than for beta-CD. The latter result is attributed to the fact that this probe interacts with the micelle in two binding sites: the cavity of the cyclodextrin and the apolar heart of the micelle as evidenced by the spectrofluorimetric behavior of Prodan in solutions containing different concentrations of Mod-CD.

Different behaviours in the solubilization of polycyclic aromatic hydrocarbons in water induced by mixed surfactant solutions

Water solubility of polycyclic aromatic hydrocarbons (PAHs), viz, naphthalene and phenanthrene, in micellar solutions at 25°C was investigated, using two series of different binary mixtures of anionic and nonionic surfactants. Tween 80 and Brij-35 were used as nonionic surfactants whereas fatty acids or amphiphilic cyclodextrins (Mod-β-CD) synthesized in our laboratory were used as anionic ones. Solubilization capacity has been quantified in terms of the molar solubilization ratio and the micelle-water partition coefficient, using UV-visible spectrophotometry. Anionic surfactants exhibited less solubilization capacity than nonionics. The mixtures between Tween 80 and Mod-β-CD did not show synergism to increase the solubilization of PAHs. On the other hand, the mixtures formed by Tween 80 and fatty acids at all mole fractions studied produced higher enhancements of the solubility of naphthalene than the individual surfactants. The critical micellar concentration of the mixtures of Tween 80/sodium laurate was determined by surface tension measurements and spectrofluorimetry using pyrene as probe. The system is characterized by a negative interaction parameter (β) indicating attractive interactions between both surfactants in the range of the compositions studied.

Inhibited Phenol Ionization in Reverse Micelles: Confinement Effect at the Nanometer Scale

We found that the absorption spectra of 2-acetylphenol (2-HAP), 4-acetylphenol (4-HAP), and p-nitrophenol (p-NPh) in water/sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane reverse micelles (RMs) at various W(0) (W(0) = [H(2)O]/[surfactant]) values studied changed with time if (-)OH ions were present in the RM water pool. There is an evolution of ionized phenol (phenolate) bands to nonionized phenol absorption bands with time and this process is faster at low W(0) values and with phenols with higher bulk water pK(a) values. That is, in bulk water and at the hydroxide anion concentration used, only phenolate species are observed, whereas in AOT RMs at this fixed hydroxide anion concentration, ionized phenols convert into nonionized phenol species over time. Furthermore, we demonstrate that, independent of the (-)OH concentration used to prepare the AOT RMs, the nonionized phenols are the more stable species in the RM media. We explain our results by considering that strong hydrogen-bonding interactions between phenols and the AOT polar head groups result in the existence of only nonionized phenols at the AOT RM interface. The situation is quite different when the phenols are dissolved in cationic benzyl-n-hexadecyldimethylammonium chloride RMs. Therein, only phenolates species are present at the (-)OH concentrations used. The results clearly demonstrate that the classical definition of pH does not apply in a confined environment, such as in the interior of RMs and challenge the general idea that pH can be determined inside RMs.

Investigation of the inclusion of the herbicide metobromuron in native cyclodextrins by powder X-ray diffraction and isothermal titration calorimetry

We report the formation of inclusion complexes between the phenylurea herbicide metobromuron [3-(p-bromophenyl)-1-methoxy-1-methylurea] and beta- and gamma-cyclodextrin in the solid state. Formation of crystalline inclusion complexes by the kneading method was confirmed by powder X-ray diffraction and further structural characterization using the principles of isostructurality followed. In addition, DeltaH degrees , DeltaS degrees , DeltaG degrees and the association constants (K) at 298K were determined for complex formation in solution using isothermal titration calorimetry. The magnitudes of K for the formation of 1:1 complexes between metobromuron and alpha-, beta- and gamma-CD were estimated as 598, 310 and 114, respectively.

Aggregation Behavior of Brij-35/Perfluorononanoic Acid Mixtures

The mixed system of a nonionic hydrocarbon surfactant, polyoxyethylene (23) lauryl ether (Brij-35), and a perfluorinated surfactant, perfluorononanoic acid, was investigated by a combination of methods. The critical micelle concentrations (cmcs) have been determined over a wide range of sample compositions by fluorescence and UV-visible spectrophotometry using pyrene and N-(4-nitrophenyl) perfluorononanamide, respectively, as molecular probes. The values of the cmcs obtained were considerably different with the two techniques employed. Measurements of the (19)F nuclear magnetic resonance chemical shift of the same mixtures showed two breaks in the plots of Δδ(f) versus molar fraction of the perfluorinated surfactant. Conductivity and surface tension measurements also showed two breaks. The behavior is attributed to the formation of mixed micelles that change their composition when the fraction of the fluorinated compound increases and some segregation of the fluorinated compound takes place at a high total surfactant concentration.

Synergism in the desorption of polycyclic aromatic hydrocarbons from soil models by mixed surfactant solutions

This study investigates the effect of a mixed surfactant system on the desorption of polycyclic aromatic hydrocarbons (PAHs) from soil model systems. The interaction of a non-ionic surfactant, Tween 80, and an anionic one, sodium laurate, forming mixed micelles, produces several beneficial effects, including reduction of adsorption onto solid of the non-ionic surfactant, decrease in the precipitation of the fatty acid salt, and synergism to solubilize PAHs from solids compared with individual surfactants.

Hydrolysis of p-nitrophenyl perfluoroctanoate in mixed surfactant systems

The kinetics of the hydrolysis reaction of p-nitrophenyl perfluoroctanoate were studied in the presence of different amphiphilic systems: two hydrocarbon surfactants (sodium dodecyl sulfate, SDS, and polyoxyethylene(23)lauryl ether, Brij-35), a perfluorinated detergent (perfluorononanoic acid, PFNA) and in mixtures of SDS–PFNA and Brij-35–PFNA. The study was performed at different compositions of the mixtures (characterized by the molar fraction of PFNA, αPFNA), and for each αPFNA the concentration was varied over a wide range. The kinetic probe p-nitrophenyl perfluoroctanoate showed a very strong interaction with the surfactants. In the presence of the mixed surfactants, the behaviour of the probe changed dramatically with the composition of the mixtures, which indicates that this substrate is very sensitive to the effect of the micellar media, being a very good molecule to study these types of surfactant systems. The use of the studied ester allowed us to confirm the presence of two different aggregates in the mixture Brij-35–PFNA as was previously observed with other techniques. The presence of hydrocarbon-rich micelles at low αPFNA, as well as perfluorinated rich micelles at high αPFNA was also confirmed. The kinetic behaviour of p-nitrophenyl perfluoroctanoate in SDS–PFNA mixtures fully agreed with our previous description of the aggregates formed in this system. The presence of a practically pure PFNA micelle at high αPFNA could be also demonstrated from the kinetic results.

Cyclodextrin modified niosomes to encapsulate hydrophilic compounds

Niosomes were prepared from equimolar mixtures of two non-ionic surfactants, Span 80 and Tween 80. The capability of the vesicular systems was studied through the encapsulation of two azo dyes as molecular probes of different hydrophobicity (methyl orange (MO) and methyl yellow (MY)). To improve the efficiency of the niosomes to encapsulate the dyes, we employed an additional modification of the vesicular system, adding β-cyclodextrin (β-CD) or a modified amphiphilic β-CD (Mod-β-CD) to the niosomes. Neither the inclusion of dyes nor the incorporation of β-CD to the niosomes produces considerable modifications in size and morphology of the vesicles. However, in the presence of Mod-β-CD the niosomes became smaller, probably due to the anchoring of the cyclodextrin at the surface of vesicles through the hydrophobic chain, altering the curvature of the outer monolayer and reducing the surface charge of the interphase. The entrapment efficiency (EE) for MY was higher than that for MO in niosomes without cyclodextrin, however, the content of MO in the presence of β-CD increased considerably. Besides, the release of this dye under the same conditions was faster and reached 70% in 24 hours whereas in the absence of the macrocycle, the release was 15%, in the same time. UV-visible spectrophotometry and induced circular dichroism analysis allowed it to be established that MO is complexed with cyclodextrins inside vesicles, whereas MY interacts mainly with the niosome bilayer instead of with CD. Besides, the cavity of cyclodextrins is probably located in the interphase and preferably in the polar region of niosomes.

Kinetic Study of the Hydrolisys of Phenyl Perfluorooctanoate in Water: Deaggregation Effect of b-Cyclodextrin

The kinetics of the hydrolysis of phenyl perfluorooctanoate was studied at pH 6.00 and 9.90 in water. The substrate is aggregated under all working reaction conditions, which is indicated from the decrease in the reaction rate when the substrate concentration is raised. The addition of β-cyclodextrin produces the deaggregation of the ester catalyzing the reaction.