A. Cid

Thermodynamics of sodium dodecyl sulphate-salicylic acid based micellar systems and their potential use in fruits postharvest

Micellar systems have excellent food applications due to their capability to solubilise a large range of hydrophilic and hydrophobic substances. In this work, the mixed micelle formation between the ionic surfactant sodium dodecyl sulphate (SDS) and the phenolic acid salicylic acid have been studied at several temperatures in aqueous solution. The critical micelle concentration and the micellization degree were determined by conductometric techniques and the experimental data used to calculate several useful thermodynamic parameters, like standard free energy, enthalpy and entropy of micelle formation. Salicylic acid helps the micellization of SDS, both by increasing the additive concentration at a constant temperature and by increasing temperature at a constant concentration of additive. The formation of micelles of SDS in the presence of salicylic acid was a thermodynamically spontaneous process, and is also entropically controlled. Salicylic acid plays the role of a stabilizer, and gives a pathway to control the three-dimensional water matrix structure. The driving force of the micellization process is provided by the hydrophobic interactions. The isostructural temperature was found to be 307.5 K for the mixed micellar system. This article explores the use of SDS-salicylic acid based micellar systems for their potential use in fruits postharvest.

Organic Reactivity in Aot-Stabilized Microemulsions

Microemulsions are highly versatile reaction media, which currently find many applications. In this review, we shall describe recent trends in the use of microemulsions as organic reaction media, and present models for their functioning, in particular the pseudophase model. This model allows a quantitative explanation of organic reactivity in these microheterogeneous media.

Degradation of carbofuran and carbofuran-derivatives in presence of humic substances under basic conditions

The influence of humic aggregates in water solution upon the chemical stability of carbofuran (CF) and the carbofuran-derivatives, 3-hydroxy-carbofuran (HCF) and 3-keto-carbofuran (KCF), has been investigated in basic media. An inhibition upon the basic hydrolysis of 3-hydroxy-carbofuran and 3-keto-carbofuran (≈ 1.7 and ≈ 1.5-fold, respectively) was observed and it was rationalized in terms of the micellar pseudophase model. Nevertheless, non-significant effect upon the carbofuran stability was found in the presence of humic substances. These behaviors have been compared with the corresponding ones in other synthetic colloidal aggregates.

Cyclodextrin-Surfactant Mixed Systems as Reaction Media

In recent years our reseach group has investigated the chemical behaviour of β-cyclodextrin (CD)/surfactant mixed systems and their characteristics as reaction media. The results have been interpreted in terms of a pseudophase model that takes into account the formation of both CD-surfactant and CD-substrate complexes and also, in some cases, the exchange of X- and OH- ions between the micellar and aqueous pseudophases. from the experimental results it was concluded that the presence of CD has no effect on existing micelles but raises the critical micellar concentration (cmc). on the other hand, at surfactant concentrations above the cmc, competition between the micellisation and complexation processes leads to the existence of a significant concentration of free CD in equilibrium with the micellar aggregates. The percentage of uncomplexed β-CD in equilibrium with the micellar system increases on increasing the hydrophobicity of the surfactant molecule. This behaviour was justified taking into account the existence of two simultaneous processes: complexation of surfactant monomers by CD and the process of self-assembly to form micellar aggregates. The autoaggregation of surfactant monomers is more important than the complexation process in this mixed system. Varying the hydrophobicity of the surfactant monomer enabled us to determine that the percentages of uncomplexed CD in equilibrium with the micellar system were in the range of 5-95%. When the surfactant self-assembly structure is a vesicle, the free CD in the CD/surfactant mixed system yields a percentage of 100%.

Degradation of carbofuran derivatives in restricted water environments: Basic hydrolysis in AOT-based microemulsions

The effect of sodium bis(2-ethylhexyl)sulfosuccinate/isooctane/water microemulsions on the stability of 2,2-dimethyl-2,3-dihydro-1-benzofuran-7-yl methylcarbamate (carbofuran, CF), 3-hydroxy-2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate (3-hydroxycarbofuran, HCF) and 3-keto-2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate (3-ketocarbofuran, KCF) in basic media has been studied. The presence of these microheterogeneous media implies a large basic hydrolysis of CF and HCF on increasing surfactant concentration and, also, on increasing water content in the microemulsion. The hydrolysis rate constants are approximately 2- and 10-fold higher than those in pure water for HCF and CF, respectively. In contrast, a steep descent in the rate of decomposition for KCF was observed. These behaviours can be ascribed to the presence of CF derivatives both in the hydrophilic phase and in the lipophilic phase, while the hydroxyl ions are only restricted to the water pool of the microemulsion (hydrophilic phase). The kinetic rate constants for the basic hydrolysis in AOT-based microemulsions have been obtained on the basis of a pseudophase model. Taking into account that an important part of soils are colloids, the possibility of the presence of restricted water environments implies that soil composition and its structure will play an important role in the stability of these carbamates. In fact, we observed that the presence of these restricted aqueous media in the environment, in particular in watersheds and in wastewaters, could reduce significantly the half-life of these pesticides (33% and 91% for HCF and CF, respectively).

Combined determination and confirmation of ethylenethiourea and propylenethiourea residues in fruits at low levels of detection.

In this work, a new method for the determination of ethylenethiourea (ETU) and propylenethiourea (PTU) in fruits and vegetables is presented. Different extraction and purification techniques, including matrix solid phase dispersion (MSPD) and solid-liquid extraction (SLE), followed by a clean-up step by solid phase extraction (SPE), were compared. The determination of ETU and PTU was performed by high performance liquid chromatography with diode array detection (HPLC/DAD) or by gas chromatography with mass spectrometry detection (GC/MS). The effect of several parameters on the extraction, separation and detection was studied. The proposed method based on solid-liquid extraction with acetonitrile, clean-up with Envicarb II/PSA cartridges and subsequent analysis by HPLC/DAD was characterised and applied to the analysis of fruits and vegetables from different countries. Analytes recoveries were between 71% and 94% with relative standard deviations (RSDs) ranging from 8% to 9.5%. Quantification limits obtained for ETU and PTU with the HPLC/DAD method were 7 and 16 μg kg⁻¹ in strawberries (fresh weight), respectively. For apples, they were 11 and 25 μg kg⁻¹, respectively.

Artificial Intelligence for Electrical Percolation of AOT-based Microemulsions Prediction

Abstract Different Artificial Neural Network architectures have been assayed to predict percolation temperature of AOT/i-C8/H2O microemulsions. A Perceptron Multilayer Artificial Neural Network with five entrance variables (W value of the microemulsions, additive concentration, molecular weight of the additive, atomic radii and ionic radii of the salt components) was used. Best ANN architecture was formed by five input neurons, two middle layers (with eleven and seven neurons respectively) and one output neuron. Root Mean Square Errors (RMSEs) are 0.18°C (R = 0.9994) for the training set and 0.64°C (R = 0.9789) for the prediction set.

Influence Prediction of Small Organic Molecules (Ureas and Thioureas) Upon Electrical Percolation of AOT-Based Microemulsions Using Artificial Neural Networks

Abstract In order to predict percolation temperature of AOT-Based microemulsions (AOT/iC8/H2O w/o microemulsions) in the presence of small organic molecules (ureas and thioureas), different Artificial Neural Network architectures (ANN) have been carried out using a Perceptron Multilayer Artificial Neural Network with three entrance variables (W = value of the microemulsion, additive concentration, logP value). Best ANN architecture consists in three input neurons, one middle layer (with two neurons) and one output neuron. Correlation values were R = 0.9251 for the training set and R = 0.9719 for the prediction set.

Stability study of Iprodione in alkaline media in the presence of humic acids

The influence of humic aggregates in water solution upon the chemical stability of Iprodione has been investigated under basic conditions. Taking into account that an important part of soils are colloids, the possibility of its presence implies that soil composition and its structure will play an important role in the stability of this pesticide. A kinetic model was applied to this system and the kinetic coefficients were obtained. An inhibition upon the alkaline hydrolysis of Iprodione (2-fold) was observed and it was rationalized in terms of the micellar pseudophase model. These results have been compared with the corresponding ones in the same natural colloidal aggregates in the presence of other pesticides.

Alkaline fading of triarylmethyl carbocations in self-assembly microheterogeneous media

This review reports on the alkaline fading of crystal violet and other related carbocations in the presence of different microheterogeneous media (micelles, microemulsions and vesicles).