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Multicomponent Surfactant Systems: Properties, Trends and Applications

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (31 July 2022) | Viewed by 18077

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Special Issue Editor

Dr. Katarzyna Szymczyk

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Guest Editor

Department of Interfacial Phenomena, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Skłodowska University in Lublin, Maria Curie-Skłodowska Sq. 3, 20-031 Lublin, Poland
Interests: surfactants; adsorption; aggregation; contact angle; wettability; adhesion; polymer surfaces; surface and interfacial tension
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Special Issue Information

Dear Colleagues,

Surfactants constitute a unique class of chemical compounds. Due to their amphiphilic nature, surfactants exhibit specific and fascinating properties that make them fundamental substances of daily usage in every field of life from domestic to industrial, where they perform as detergents, solubilizers, and emulsifiers, as well as wetting, flotation, and foaming agents. Accordingly, the global surfactant market currently experiences a sustained growth at an annual rate of up to 3.8%. The widespread application of these compounds usually involves mixtures of two or more individual surfactants and/or their combination with other additives, e.g. co-surfactants, co-solvents, polymers. This allows us to obtain new synergistic behavior or to create new self-assembled structures at different interfaces. Surfactants are also frequently employed to enhance the solubility and/or bioavailability of otherwise insoluble compounds, such as drugs, polyphenols, or perfume raw materials by the use of micelles, liposomes, microemulsions, emulsions, etc. Taking this into account, the proposed Special Issue aims to provide a forum for the dissemination of the latest information on the properties and applications of different multicomponent systems containing surfactants.

Dr. Katarzyna Szymczyk
Guest Editor

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Keywords

surfactant
adsorption
micellization
solubilization
adhesion
wettability

Published Papers (7 papers)

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Research

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19 pages, 1605 KiB

Open AccessArticle

Mutual Influence of Some Flavonoids and Classical Nonionic Surfactants on Their Adsorption and Volumetric Properties at Different Temperatures

by Anna Taraba, Katarzyna Szymczyk, Anna Zdziennicka and Bronisław Jańczuk

Molecules 2022, 27(9), 2842; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27092842 - 29 Apr 2022

Cited by 3 | Viewed by 1368

Abstract

Due to the increasing practical use of mixtures of flavonoids with nonionic surfactants the presented studies were based on the measurements of surface tension and conductivity of aqueous solution of the quercetin (Q) and rutin (Ru) in the mixtures with Triton X-114 (TX114) and Tween 80 (T80) as well as the contact angle of model liquids on the PTFE surface covered by the quercetin and rutin layers. Based on the obtained results components and parameters of the quercetin and rutin surface tension were determined and the mutual influence of Q and Ru in the mixtures with TX114 and T80 on their adsorption and volumetric properties were considered. It was found, among others, that based on the surface tension isotherms of the aqueous solution of the single flavonoid and nonionic surfactant, the surface tension isotherms of the aqueous solution of their mixture, the composition of the mixed monolayer at the water-air interface as well as the CMC of flavonoid + nonionic surfactant mixture can be predicted. The standard Gibbs energy, enthalpy and entropy of the adsorption and aggregation of the studied mixtures were also found, showing the mechanism of the adsorption and aggregation processes of the flavonoid + nonionic surfactant mixture. Full article

(This article belongs to the Special Issue Multicomponent Surfactant Systems: Properties, Trends and Applications)

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18 pages, 4499 KiB

Open AccessArticle

Effects of Surfactant Volume Fraction on the Antioxidant Efficiency and on The Interfacial Concentrations of Octyl and Tetradecyl p-Coumarates in Corn Oil-in-Water Emulsions

by Marlene Costa, Sonia Losada-Barreiro, Fátima Paiva-Martins and Carlos Bravo-Díaz

Molecules 2021, 26(19), 6058; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26196058 - 07 Oct 2021

Cited by 2 | Viewed by 1593

Abstract

Surfactants have been used for decades in the food industry for the preparation of lipid-based emulsified food stuffs. They play two main roles in the emulsification processes: first they decrease the interfacial tension between the oil and water, facilitating droplet deformation and rupture; second, they reduce droplet coalescence by forming steric barriers. However, addition of surfactants to binary oil-water mixtures also brings up the formation of three-dimensional interfacial layers, surrounding each emulsion droplet, that significantly alter chemical reactivity. This is the case, for instance, in the inhibition reaction between antioxidants and the lipid radicals formed in the course of the spontaneous oxidation reaction of unsaturated lipids, which are commonly employed in the preparation of food-grade emulsions. The rate of the inhibition reaction depends on the effective concentrations of antioxidants, which are mostly controlled by the amount of surfactant employed in the preparation of the emulsion. In this work, we analyze the effects of the surfactant Tween 20 on the oxidative stability and on the effective concentrations of two model antioxidants derived from cinnamic acid, determining their interfacial concentrations in the intact emulsions to avoid disrupting the existing equilibria and biasing results. For this purpose, a recently developed methodology was employed, and experimental results were interpreted on the grounds of a pseudophase kinetic model. Full article

(This article belongs to the Special Issue Multicomponent Surfactant Systems: Properties, Trends and Applications)

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16 pages, 4713 KiB

Open AccessArticle

Ethyl Lauroyl Arginate, an Inherently Multicomponent Surfactant System

by Agnieszka Czakaj, Ewelina Jarek, Marcel Krzan and Piotr Warszyński

Molecules 2021, 26(19), 5894; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26195894 - 29 Sep 2021

Cited by 10 | Viewed by 3190

Abstract

Ethyl lauroyl arginate (LAE) is an amino acid-based cationic surfactant with low toxicity and antimicrobial activity. It is widely used as a food preservative and component for food packaging. When stored, LAE decomposes by hydrolysis into surface-active components Nα-lauroyl–l-arginine (LAS) or dodecanoic (lauric) acid. There are only a limited number of reports considering the mechanism of surface activity of LAE. Thus, we analysed the surface tension isotherm of LAE with analytical standard purity in relation to LAE after prolonged storage. We used quantum mechanical density functional theory (DFT) computations to determine the preferred hydrolysis path and discuss the possibility of forming highly surface-active heterodimers, LAE-dodecanoate anion, or LAE-LAS. Applying molecular dynamics simulations, we determined the stability of those dimers linked by electrostatic interactions and hydrogen bonds. We used the adsorption model of surfactant mixtures to successfully describe the experimental surface tension isotherms. The real part surface dilational modulus determined by the oscillation drop method follows a diffusional transport mechanism. However, the nonlinear response of the surface tension could be observed for LAE concentration close to and above Critical Micelle Concentration (CMC). Nonlinearity originates from the presence of micelles and the reorganisation of the interfacial layer. Full article

(This article belongs to the Special Issue Multicomponent Surfactant Systems: Properties, Trends and Applications)

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12 pages, 3161 KiB

Open AccessArticle

Characterization of Magnesium-Polylactic Acid Films Casted on Different Substrates and Doped with Diverse Amounts of CTAB

by Margarita Hierro-Oliva, Verónica Luque-Agudo, Amparo M. Gallardo-Moreno and M. Luisa González-Martín

Molecules 2021, 26(16), 4811; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26164811 - 09 Aug 2021

Cited by 5 | Viewed by 1397

Abstract

Polylactic acid (PLA) is a good candidate for the manufacture of polymeric biodegradable biomaterials. The inclusion of metallic particles and surfactants solves its mechanical limitations and improves its wettability, respectively. In this work, cetyltrimethylammonium bromide (CTAB) and magnesium particles have been incorporated into PLA films to evaluate the changes produced in the polymeric matrix cast on glass and silicone substrates. For this purpose, the surface of the films has been characterized by means of contact angle measurements and ToF-SIMS. Depth profiles and SEM images of the cross sections of the films have also been obtained to study their morphology. The results show that the CTAB in the polymer matrix with and without magnesium improves the wettability of the films, making them more suitable for cell adhesion. The higher the hydrophilicity, the higher the surfactant concentration. The depth profiles show, for the first time, that, depending on the surfactant concentration and the presence of Mg, there is a layer-like distribution near the surface where, in addition to the CTAB + PLA mixture, a surfactant exclusion zone can be seen. This new structure could be relevant in in vitro/in vivo situations when the degradation processes remove the film components in a sequential form. Full article

(This article belongs to the Special Issue Multicomponent Surfactant Systems: Properties, Trends and Applications)

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24 pages, 3878 KiB

Open AccessArticle

Formulation of Environmentally Safe Graffiti Remover Containing Esterified Plant Oils and Sugar Surfactant

by Marcin Bartman, Sebastian Balicki and Kazimiera A. Wilk

Molecules 2021, 26(15), 4706; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26154706 - 03 Aug 2021

Cited by 8 | Viewed by 2921

Abstract

The removal of graffiti or over-painting requires special attention in order to not induce the surface destruction but to also address all of the important eco-compatibility concerns. Because of the necessity to avoid the use of volatile and toxic petroleum-based solvents that are common in cleaning formulations, much attention has recently been paid to the design of a variety of sustainable formulations that are based on biodegradable raw materials. In the present contribution we propose a new approach to graffiti cleaning formulations that are composed of newly synthesized green solvents such as esterified plant oils, i.e., rapeseed oil (RO), sunflower oil (SO), or used cooking oil (UCO), ethyl lactate (EL), and alkylpolyglucosides (APGs) as surfactants. Oil PEG-8 ester solvents were synthesized through the direct esterification/transesterification of these oils using monobutyltin(IV) tris(2-ethylhexanoate) and titanium(IV) butoxide catalysts under mild process conditions. The most efficient formulations, determined by optimization through the response surface methodology (RSM) was more effective in comparison to the reference solvents such as the so-called Nitro solvent (denoting a mixture of toluene and acetone) and petroleum ether. Additionally, the optimal product was found to be effective in removing graffiti from glass, metal, or sandstone surfaces under open-field conditions in the city of Wrocław. The performed studies could be an invaluable tool for developing future green formulations for graffiti removal. Full article

(This article belongs to the Special Issue Multicomponent Surfactant Systems: Properties, Trends and Applications)

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21 pages, 6006 KiB

Open AccessArticle

Adsorption Properties of Hydrocarbon and Fluorocarbon Surfactants Ternary Mixture at the Water-Air Interface

by Bronisław Jańczuk, Katarzyna Szymczyk and Anna Zdziennicka

Molecules 2021, 26(14), 4313; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26144313 - 16 Jul 2021

Cited by 6 | Viewed by 1785

Abstract

Measurements were made of the surface tension of the aqueous solutions of p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethylene glycols) having 10 oxyethylene groups in the molecule (Triton X-100, TX100) and cetyltrimethylammonium bromide (CTAB) with Zonyl FSN-100 (FC6EO14, FC1) as well as with Zonyl FSO-100 (FC5EO10, FC2) ternary mixtures. The obtained results were compared to those provided by the Fainerman and Miller equation and to the values of the solution surface tension calculated, based on the contribution of a particular surfactant in the mixture to the reduction of water surface tension. The changes of the aqueous solution ternary surfactants mixture surface tension at the constant concentration of TX100 and CTAB mixture at which the water surface tension was reduced to 60 and 50 mN/m as a function of fluorocarbon surfactant concentration, were considered with regard to the composition of the mixed monolayer at the water-air interface. Next, this composition was applied for the calculation of the concentration of the particular surfactants in the monolayer using the Frumkin equation. On the other hand, the Gibbs surface excess concentration was determined only for the fluorocarbon surfactants. The tendency of the particular surfactants to adsorb at the water-air interface was discussed, based on the Gibbs standard free energy of adsorption which was determined using different methods. This energy was also deduced, based on the surfactant tail surface tension and tail-water interface tension. Full article

(This article belongs to the Special Issue Multicomponent Surfactant Systems: Properties, Trends and Applications)

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Review

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22 pages, 4081 KiB

Open AccessReview

A Surfactant Concentration Model for the Systematic Determination of the Critical Micellar Concentration and the Transition Width

by Wajih Al-Soufi and Mercedes Novo

Molecules 2021, 26(17), 5339; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26175339 - 02 Sep 2021

Cited by 14 | Viewed by 4696

Abstract

The critical micellar concentration (cmc) is a fundamental property of surfactant solutions. Many proposed methods for the definition and determination of the cmc from property-concentration plots yield values, which depend on the studied property, on the specific technique used for its analysis and in many cases on the subjective choice of the chosen type of plot and concentration interval. In this focus review, we revise the application of a surfactant concentration model we proposed earlier that defines the cmc directly based on the surfactant concentration. Known equations for the concentration-dependence of different surfactant properties can then be combined with this concentration model and fitted to experimental data. This modular concept makes it possible to determine the cmc and the transition width in a systematic and unambiguous way. We revise its use in the literature in different contexts: the determination of the cmc of surfactants and their mixtures from different properties (electrical conductivity, NMR chemical shift, self-diffusion, surface tension, UV-Vis absorption, fluorescence intensity and fluorescence correlation). We also revise the dependence of the width of the transition region on composition, detailed studies of the properties of fluorescent probes and the aggregation of non-surfactant systems, namely amyloid peptides. Full article

(This article belongs to the Special Issue Multicomponent Surfactant Systems: Properties, Trends and Applications)

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