Conventional Nonionic Surfactants Research Articles

Synthesis of environment friendly biosurfactants and characterization of interfacial properties for cosmetic and household products formulations

In this study, 2 types of zwitterionic phospholipid biosurfactants LP(A) and LP(O) were prepared using 2 different raw materials such as rapeseed oil and rapeseed acid respectively. The structure of the resulting products was elucidated by FT-IR, 1H NMR, and 13C NMR spectroscopies and the interfacial properties of LP(A) and LP(O) have been examined such as CMC, static and dynamic surface tensions, interfacial tension, wetting property, emulsion stability, and foam property. Detergency test evaluated by using a Terg-o-tometer showed moderately good detergency compared with conventional nonionic and anionic surfactants used in detergent formulations. Biodegradability, acute oral toxicity, acute dermal irritation and acute eye irritation tests revealed that LP(O) surfactant possesses excellent mildness and superior environmental compatibility, indicating the potential applicability in cosmetic and household products formulations.

Synthesis of environment friendly nonionic surfactants from sugar base and characterization of interfacial properties for detergent application

In this study, environment friendly nonionic surfactants were synthesized from sugar base and their structure was characterized by 1H-NMR, 13C-NMR and FT-IR. The newly synthesized SA08 series surfactants showed excellent interfacial properties such as low CMC, surface tension and interfacial tension, and superior foam stability. Detergency tests using three different types of artificial soils have revealed that the synthesized surfactants showed moderately good detergency presumably due to excellent interfacial properties and stereoscopic molecular structure of SA08 series surfactants. Environmental compatibility test showed that SA08-07 surfactant exhibited low toxicity compared with conventional nonionic and anionic surfactants and excellent biodegradability.

Synergistic solubilization of polycyclic aromatic hydrocarbons by mixed micelles composed of a photoresponsive surfactant and a conventional non-ionic surfactant

Abstract Surfactant-enhanced remediation is a powerful technology for soil clean-up. However, some drawbacks, such as its high cost and the secondary contamination caused by flushing agents, have hampered this technology and its commercial application has been largely limited to North American and European countries. The aim of this work is to introduce a novel reversible solubilization system composed of the photoresponsive surfactant 4-butylazobenzene-4′-(oxyethyl)trimethylammonium bromide (AZTMA) and the commercial non-ionic surfactant Tween80 for the solubilization of organic contaminants. The solubilization behavior of the AZTMA/Tween80 surfactant system toward polycyclic aromatic hydrocarbons (PAHs) has been studied. Critical micelle concentration (CMC) values indicate that the mixed system has a synergism in mixed micelle formation, and that the interaction parameter ( β ) is −2.85 when the mole ratio is 2:8. AZTMA is also predicted to be low biologic toxicity by the CMC and surface tension. The synergistic effect on molar solubilization ratio (MSR) and micelle-phase/aqueous-phase partition coefficient K mc values is related to the composition and concentration of the mixed system and follows the order pyrene > phenanthrene > acenaphthene, and these parameters are much higher than those for the single surfactants. After irradiation with UV light, more than 65% of the PAHs could be separated from the mixed micelles, and the cumulative release efficiencies of selected PAHs are consistent with the results of solubilization experiments. All of these features demonstrate that mixed AZTMA/Tween80 should be preferable to single surfactants for soil remediation, avoiding the issues associated with chemical flushing agents and decreasing remediation costs.

Electrochemically Reversible Solubilization of Polycyclic Aromatic Hydrocarbons by Mixed Micelles Composed of Redox-active Cationic Surfactant and Conventional Nonionic Surfactant

Reduplicate utilization of surfactants is a key factor for Surfactant-Enhanced Remediation (SER) technology to reduce its high operation costs. In order to achieve the reuse of surfactants, this study attempted to construct a novel reversible solubilization system for SER. Three typical polycyclic aromatic hydrocarbons (PAHs) pyrene, phenanthrene, and acenaphthene were controllably solubilized and released by the mixed micelles composed of redox-active cationic surfactant (11-Ferrocenylundecyl) trimethylammoniunm bromide (FTMA) and conventional nonionic surfactant Tween80. Solubilization of PAHs is assumed to be controlled by changing the redox states of FTMA. Cyclic voltammograms tests of FTMA showed the oxidation and reduction potential were 0.4570 and 0.4068 V, respectively, and the peak currents ratio of FTMA and FTMA+ was 1.26, verified that FTMA possesses electrochemically reversible property. In FTMA-Tween80 mixed solutions, CMC values demonstrated the nonideal interaction between the two surfactants and the interaction parameters (β) was -5.5296 when the mass ratio was FTMA:Tween80 = 2:8. Due to the synergistic solubilization effect, the apparent water solubilities of PAHs were significantly enhanced by the mixed surfactant, and they were much higher than those in single surfactant. After oxidation, more than 50% of the PAHs in mixed micelles could be released, the cumulative release efficiency of selected PAHs followed the order of pyrene > pherantherene > acenaphthene. Briefly, such results in this article provide a facile method to meliorate the SER technology.

Synthesis and Surface Activity of Nonionic Surfactants Derived from Gallic Acid

A series of nonionic surfactants were synthesized from gallic acid and polyethylene glycols with different molecular weights. Chemical structures of the surfactants were confirmed using elemental analysis, infrared and nuclear magnetic resonance (1H-NMR) spectroscopy. Surface activities of the surfactants in their solutions were determined by surface tension measurements. Increasing the polyethylene glycol chain length increased the surface activity of the surfactants in solutions. Measurements of interfacial tension between surfactants solutions and substrates with different polarity showed that the type of substrates plays functioning role on the interfacial properties. Thermodynamic properties of adsorption and micellization processes showed their tendency towards adsorption at solution interface and micellization in their solutions. Results showed reasonable surface activities compared to conventional nonionic surfactants.

Experimental and theoretical approach to mixed surfactant system of cationic gemini surfactant with nonionic surfactant in aqueous medium

The surface and mixed micellization properties of the aqueous binary mixed system of alkanediyl-α, ω-type cationic gemini surfactant, 14–4–14 and conventional nonionic surfactant, Brij-58 in an aqueous medium have been investigated over the entire mole fractions at 298.15K. The critical micelle concentration (cmc) for each mixture have been measured by tensiometric and fluorescence measurements. The solution and adsorption characteristics like composition, activity coefficients and mutual interaction parameters have been computed using different proposed theoretical models like Clint, Rosen, Rubingh, Motomura and Maeda. The strength of interaction of the surfactant is attributed to the sterical and electrical factors on mixed monolayer and micelle formation and of surfactant–surfactant interactions. The micellar aggregation number (Nagg) has also been measured using steady state fluorescence quenching method at a total concentration of ~1mM of pure components as well as their mixtures of different ratios. The micropolarity and binding constant were determined from the ratio of intensity (I1/I3) of peaks of pyrene fluorescence emission spectrum.

Study on solubilization capability of various Gemini micelles in micellar-enhanced ultrafiltration of phenol-contaminated waters

A systematic study has been conducted to have an insight into the separation efficiency of phenol with the help of Gemini surfactants and conventional nonionic surfactant in their single and mixed systems using micellar-enhanced ultrafiltration (MEUF). A flat sheet membrane with a total effective area of 0.08 m2 and a molecular weight cut-off of 10 kDa, was selected in this investigate. The effects of feed component (surfactant concentration for single surfactant system and mixed ratio for mixed surfactant system) on solubilization and filtration efficiency were researched. Some related parameters were used to estimate the performance of various surfactant systems, such as distribution coefficient (D), the phenol concentration in micellar phase (Pm), the surfactant concentration in micellar phase (Sm), the micelle loading (Lm), and the equilibrium distribution constant (K). With the increase of feed surfactant concentration or the addition of nonionic surfactant, the degree of solubilization of phenol enhances, leading to the decrease of permeate concentration and the augment of retentate concentration. Consequently, D, Pm, and Sm increases. The addition of nonionic surfactant has positive effects to recounterbalance the interior structure and improve the micellar solubilization power for phenol. Both the single and mixed C12-2-16 systems have higher D, Pm, and Sm values than these of C12-2-12, due to the longer length alkyl chain and more optimized structure. Lm and K are the significant indicators for evaluating the effectiveness of dissolving phenol. Irreversible fouling was almost eliminated with a series of cleaning solution in a short time. There results from the laboratory-scale experiments could be very useful in selection of the suitable surfactant systems for raising efficiency and could serve as valuable guide for MEUF in industrial application.

Synthesis and Surface Properties of SiO<sub>2</sub> Modified Fluorosilicone Acrylic Copolymer Hybrids

SiO2 modified fluorosilicone acrylic copolymer hybrids were synthesized via seeding emulsion polymerization in the presence of conventional nonionic and anionic surfactants, in which methyl methacrylate (MMA) and butyl acrylate (BA) were used as main monomers, small amount of methacrylic acid (MAA) and 2-hydroxyethyl methacrylate (HEMA) were used as functional monomers to confer adhesion, hardness and strength upon the latex film, while trifluoroethyl methacrylate (TFMA) and vinyl triethoxy silane (VTES) were used as fluorine- and silicon- containing monomers respectively. Meanwhile, tetraethoxysilane (TEOS) used as the precursor to prepare in-situ SiO2 nanoparticles, was added during the polymerization process, which resulted in SiO2 enhanced fluorosilicone acrylic copolymer latexes. SiO2 nanoparticles were produced in-situ during the polymerization. The nanocomposite latex film revealed better thermal resistance and wear resistance properties as compared with the counterpart free of SiO2 nanoparticles prepared under similar polymerization conditions.

Mixed Micellization Behavior of Gemini (Cationic Ester-Bonded) Surfactants with Conventional (Cationic, Anionic and Nonionic) Surfactants in Aqueous Medium

Abstract Two cationic ester-bonded cleavable gemini surfactants of different hydrophobic chain length ethane-1,2-diyl bis(N,N-dimethyl-N-alkylammoniumacetoxy)dichloride, C n H2n+1(CH3)2N+(CH2COOCH2)2N+(CH3)2C n H2n+1. 2Cl- (n-E2-n, n=12, 16), having ester linkage in the spacer, were synthesized adopting the reported procedure. Physicochemical properties of the single and binary gemini-conventional mixed micelles of different mole fractions were studied by conductivity measurements at 30 ºC. The conventional surfactants used were: DTAC (dodecyltrimethylammonium chloride), CTAC (hexadecyltrimethylammonium chloride), CPC (cetylpyridinium chloride), SDS (sodium dodecyl sulfate), SDBS (sodium dodecylbenzene sulfonate), TX-100 (t-octylphenoxypolyethoxyethanol) and Brij 58 (polyoxyethylene (20) cetyl ether). Whereas the critical micelle concentration (cmc) values for the dicationic geminis (12-E2-12 and 16-E2-16) were found to be very low as compared to the respective monomeric surfactant with the same number of carbon atoms in the hydrophobic chain per hydrophilic head group, those for all the binary systems were found to be less than the ideal cmc values studied at different mole fractions of the geminis. This synergistic interaction between the surfactants has been analyzed in the light of various theoretical models such as Clint, Rubingh, Motomura and Maeda.

Mixed Micellization Behavior of Gemini (Cationic Ester-Bonded) Surfactants with Conventional (Cationic, Anionic and Nonionic) Surfactants in Aqueous Medium

Mixed Micellization Behavior of Gemini (Cationic Ester-Bonded) Surfactants with Conventional (Cationic, Anionic and Nonionic) Surfactants in Aqueous Medium

A multi-headed surfactant as an efficient tool in solubilization of dimyristoylphosphatidycholine (DMPC) vesicles

In this study, the solubilization of DMPC (dimyristoylphosphatidycholine) vesicles by a novel multi-headed surfactant, C18N3, is reported. The headgroup of the surfactant contains two types of amine groups, which are protonated at different pH values. The protonation of the headgroup has significant effect on the solubilization process. The penetration of the surfactant into a DMPC monolayer was measured at different initial surface pressures and at different pH values. A linear relationship was found between the initial surfactant pressure (π) and the increase of the surfactant pressure (Δπ). Furthermore, turbidity titration shows that at low pH, the phase behavior with increasing surfactant concentration in the DMPC solution is similar to conventional ionic surfactants. This can be explained by the three-stage model. TEM images at different C18N3 concentrations confirmed the process of solubilization of DMPC vesicles, and small aggregates were observed at 1mmol/L C18N3. However, at higher pH, where the headgroup is deprotonated, the surfactant was not able to solubilize the DMPC vesicles. TEM images shows a coexistence of vesicles and a lamellar phase. The surfactant/lipid ratio of the multi-headed surfactant at pH 4 and 7 was compared to conventional nonionic surfactants with the same cross-sectional area of the headgroup, and a much lower ratio was observed for the new surfactant.

Enhanced aqueous solubility of naphthalene and pyrene by binary and ternary Gemini cationic and conventional nonionic surfactants

A systematic study has been carried out to get insight into the micellar behavior of Gemini cationic and conventional nonionic in their single as well as equimolar bi and ternary mixed state using the technique of tensiometry. The models proposed by Clint, Rubingh and Motomura et al. have been employed to interpret the formation of mixed micelles and find out synergism. The obtained experimental CMCs are lower than the ideal CMCs, indicating negative deviation from ideal behavior for all multi-component mixed micelles formation. The solubilization capacities of selected equimolar bi and ternary surfactant systems towards polycyclic aromatic hydrocarbons (PAHs), naphthalene and pyrene, have been evaluated from measurements of the molar solubilization ratio (MSR), the micelle–water partition coefficient (Km), the deviation ratio (R) and the free energy of solubilization (ΔGs0) of PAHs. The results show that the solubility of naphthalene and pyrene over that in water in case of Gemini cationic surfactant is dramatically enhanced by adding equimolar nonionic surfactant in both bi and ternary mixed surfactant systems. The studied equimolar ternary surfactant system shows higher solubilizing efficiency than Gemini cationic binary system but lower than their cationic–nonionic counterpart. In addition, the solubilizing power of multi-component mixed surfactants towards naphthalene and pyrene increases with increasing logKow of PAHs. Certainly, the solubilization abilities of the selected surfactants not only depend on their structure and mixing effect but also associate with solubilizing microenvironment and chemical nature of organic solutes.

Study on Aggregation Behaviour of Mixture of Alkylbenzene Sulfonate Gemini Surfactant Ib and Nonionic Surfactant Triton X-100

The interaction between the anionic Gemini surfactant Ib and the conventional nonionic surfactant Triton X-100 was investigated. The critical micelle concentrations (cmc) of different mixtures were measured by surface tension measurement at 298 K. The results showed that the cmc of different mixtures at any mole ratio was lower than that of either pure Ib or Triton X-100, indicating synergetic behavior. And the interaction parameter ß values for the mixed micelles were negative, showing attractive interaction between these surfactant molecules. Besides, the micelle aggregation number (N) was measured using a steady state fluorescence quenching method. The N values of the mixed surfactant system were larger than that of pure Ib but lower than pure Triton X-100 at any ratio.

Interaction between cationic and conventional nonionic surfactants in the mixed micelle and monolayer formed in aqueous medium

Mixed micellization and surface properties of cationic and nonionic surfactants dimethyl decyl-, tetradecyl- and hexadecyl phosphineoxide mixtures are studied using conductivity and surface tension measurements. The models of Rubingh, Rosen, and Clint, are used to obtain the interaction parameter, minimum area per molecule, mixed micelle composition, free energies of mixing and activity coefficients. The micellar mole fractions were always higher than ideal values indicating high contributions of cationics in mixed micelles. Activity coefficients were less than unity indicating synergism in micelles. The negative free energies of mixing showed the stability of the surfactants in the mixed micelles.

Cyclic voltammetry and viscosity measurements of aggregated assemblies of anionic surfactants with nonionic surfactants and triblock copolymers

Cyclic voltammetry (CV) and viscosity measurements have been employed to study the aggregation behavior of mixed micellar systems of anionic surfactant (dioctyl sulfosuccinate sodium salt, AOT) with conventional nonionic surfactants such as Brij 35/TritonX-100/Tween 20/Tween 80/Myrj 45 and two triblock copolymers (L64 and F68). Critical micelle concentration (cmc) values have been determined for various micellar systems from CV measurements using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as an electroactive probe at 25 °C. Diffusion coefficient (D) has been evaluated from Randles–Sevcik equation which showed an overall decrease for most of the binary systems. The negative values of interaction parameters (β) obtained from regular solution theory suggest the synergistic behavior in all the binary systems except AOT + Tween 80 mixtures. The mixed systems of AOT with triblock copolymers showed stronger synergistic interactions than that of mixed systems of AOT with nonionic surfactants. A comparative evaluation of mixed systems of anionic surfactants AOT and sodium dodecyl sulfate with Myrj 45 and AOT + L64 and F68 has been made on the basis of different micellar parameters and structural properties of surfactants. Viscosity measurements also show similar type of interactions in the mixed micelles.

Systems based on nonionic amphiphilic compounds: aggregation and catalytic properties

The micellization properties, solubilization capability, and catalytic effect of conventional nonionic surfactants and amphiphilic compounds of oligomeric (Tyloxapol) and polymeric (Synperonic F-68, Pluronic F-127) structure were compared. The systems studied demonstrate a marked catalytic effect toward basic hydrolysis of p-nitrophenyl laurate, which exceeds the effect of aqueous alkali solutions by two orders of magnitude. Correlations between the solubilization capacity of aggregates and their catalytic effect were observed. The maximum efficiency was found for the Tyloxapol solution. The synergetic enhancement of the catalytic effect was observed for the mixed Tyloxapol-cetyltrimethylammonium bromide systems in the presence of small amounts of cationic surfactant

Solution behavior of mixed systems based on novel amphiphilic cyclophanes and Triton X100: Aggregation, cloud point phenomenon and cloud point extraction of lanthanide ions

Aggregation and cloud point (CP) behavior, as well as CP extraction of lanthanide ions have been studied for novel non-ionic cyclophanic surfactants with the varied length of polyoxyethylene and hydrophobic moieties (CnEm) based on calix[4]arene platform in their mixtures with Triton X100 (TX100). The dynamic light scattering data reveal the contribution of the large size lamellar or stack like mixed aggregates in CnEm–TX100 solutions. Aggregation and CP behavior of TX100–CnEm mixed solutions are quite different from those of conventional non-ionic surfactants. The effect of the hydrophobic substituents and polyoxyethylene chains length of CnEm on the CP extraction of La(III), Gd(III) and Lu(III) in the mixed TX100–CnEm micellar solutions is discussed in the correlation with their aggregation and cloud point behavior. The obtained data elucidate the cyclophanic structure of CnEm as the key reason of the formation of large lamellar-like aggregates with TX100, exhibiting the unusual CP behavior and CPE efficiency.

Synthesis, Antimicrobial Activity and Micellization of Gemini Anionic Surfactants in a Pure State as Well as Mixed With a Conventional Nonionic Surfactant

AbstractNew gemini anionic surfactants were prepared from sodium salts of monoalkyl sulfosuccinate esters of ethylene glycol having variably long tails (C12, C16, C18) and dichloroethane. The chemical structures of the prepared surfactants were confirmed using different spectroscopic techniques. The surfaces tension values of the synthesized surfactants were measured at 25 °C individually or mixing at different molar fractions with ethoxylated alkylphenol. In all cases, mixed micellar aggregates were formed and critical micellar concentrations of binary mixtures containing different mole fractions of the surfactants were measured. The micellization processes of the individual and mixed surfactants were investigated. The effect of different alkyl chains of gemini anionic surfactants on properties of binary systems and molar ratio in the mixed aggregates were deduced. The critical micelle concentration of mixed surfactants shifted to lower values compared to those of the single surfactants. Effectiveness values increased with decreases in the mole fraction of gemini anionic surfactants. The negative values of interaction parameter (β) increased with increases in the chain length of anionic surfactants. The activity coefficient (f1, f2) and total minimum surface area of mixed solution were calculated. Also, the gemini anionic surfactants prepared have moderate antimicrobial activity towards bacteria and not active towards fungi.

Mixed Micellization of Alkylbenzene Sulfonate Gemini Surfactant Ia and Nonionic Surfactant Triton X-100 in Aqueous Solution

AbstractThe interaction between the alkylbenzene sulfonate Gemini surfactant Ia and the conventional nonionic surfactant Triton X-100 was investigated. The critical micelle concentrations of different mixtures were measured by surface tension measurement in aqueous solution at 298 K. The results suggested that the critical micelle concentration of different mixtures at any mole ratio was lower than that of either pure Ia or Triton X-100 surfactant, indicating synergetic behavior. And the interaction parameter (ßvalues) for the mixed micelles were negative, showing attractive interaction between these surfactant molecules. Furthermore, the micelle aggregation number (N) was measured using a steady state fluorescence quenching method. TheNvalues of the mixed surfactant system were larger than that of pure Ia but lower than pure Triton X-100 at all mole ratios. And the micropolarity of micelles becomes small gradually with the increase of the mole ratio of the Gemini surfactant Ia.

Spreading of Aqueous Solutions of Trisiloxanes and Conventional Surfactants over PTFE AF Coated Silicone Wafers

Kinetics of spreading of aqueous trisiloxane surfactant T(n) (with n = 4, 6, and 8 ethoxy groups) solutions and conventional aqueous surfactant solutions (Tween 20, C12E4, SDS) over silicon wafers coated with PTFE AF is experimentally investigated. It has been found that trisiloxane solutions spread on highly hydrophobic PTFE AF coated silicone wafers; however, they do not show superspreading behavior on these highly hydrophobic substrates. Solutions of conventional nonionic surfactants investigated show kinetics of spreading similar to trisiloxanes. Three regimes of spreading have been identified (i) complete non-wetting during the spreading process at low concentrations, (ii) a transition from initial nonwetting to partial wetting at the end of the spreading process at intermediate concentrations, and (iii) partial wetting both at the beginning and the end of the spreading process at higher concentrations. Transition from the first regime (i) to the second regime (ii) takes place at the critical aggregation concentration (CAC) or critical micelle concentration (CMC), transition from regime (ii) to regime (iii) happens at the critical wetting concentration (CWC). In the case of regime (i) the spreading of nonionic surfactants solutions investigated on PTFE AF coated silicone wafers is slow and follows a theoretically predicted law (Starov; et al. J. Colloid Interface Sci. 2000, 227 (1), 185). In the case of regimes (ii) and (iii), the spreading of the nonionic surfactant solutions investigated proceeds in two stages: the fast short first stage, which is followed by a much slower second stage. It is shown that the slow stage develops according to a previously described theoretical model. According to this theory the surfactant molecules adsorb in front of the moving three-phase contact line (autophilic phenomenon), which results in a partial hydrophilisation of an initially hydrophobic substrate and a spreading as a consequence. We assume that the first stage of the spreading is related to the disintegration of surfactant aggregates in the vicinity of the moving three-phase contact line.