Synthesis and Physico-Chemical Properties of Sodium 3-Oxo-2-(3-(4-sulphonatophenyl)triaz-2-enyl)octadecanoate Anionic Surfactant

The novel anionic surfactant sodium 3‐oxo‐2‐(3‐(4‐sulphonatophenyl)triaz‐2‐enyl)octadecanoate (SSTO) was prepared from renewable raw materials; glycine and palmitic acid. Surface and bulk properties of SSTO were investigated by surface tension and electrical conductivity techniques at 298, 308, 318 and 328 K. Surface properties including critical micelle concentration (CMC), maximum surface excess concentration (Γ_max), minimum area per molecule (A_min), surface tension at CMC (γ_CMC), effectiveness of surface tension reduction (Π_CMC), efficiency of surface adsorption (pC₂₀), and degree of counterion dissociation (α) were determined. The thermodynamic parameters of micellization (ΔG°_mic, ΔH°_mic and ΔS°_mic) and adsorption (ΔG°_ad, ΔH°_ad and ΔS°_ad) were also investigated at 298, 308, 318 and 328 K. The effect of 3 wt% n‐propanol, n‐butanol and n‐pentanol on surface tension and conductivity at 298 K was also determined.     

The Relationship Between the Structure and Properties of Amino Acid Surfactants Based on Glycine and Serine

Two series of surfactants based on glycine and serine were synthesized with aproic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid and hexadecanoic acid. All the surfactants were characterized by MS and ¹H NMR, the structures of the synthesized surfactants are correct and the signals in MS and ¹H NMR can be explained. The reaction conditions, surface properties and foam properties were studied. For the two series of surfactants, critical micelle concentration (CMC) and γ _CMC (surface tension at CMC) decrease and surface activity is enhanced as the length of carbon chain increases. The surfactants with tetradecanoyl and hexadecanoyl groups show a good foaming property and especially, the long-chain acyl-serine performs better. These are all related to the hydromethyl group in the serine.     

Synthesis and Surface Activity of Cationic Amino Acid-Based Surfactants in Aqueous Solution

I studied the possibility of using amino acid-based surfactants as emulsifiers at the same time as preservatives. Fourteen lipopeptides were synthesized employing a solid phase peptide synthesis procedure. All compounds were designed to be positively charged from +1 to +4 and acylated with fatty acid chain—palmitic and miristic. The surface activity of the obtained lipopeptides was tested using a semi-automatic tensiometer to calculate parameters describing the behavior of lipopeptides in the air/water interface. Such parameters as CMC, surface tension at the CMC point (σ _CMC), effectiveness (π _CMC), and efficiency (pC20) were measured. Emulsifying properties of all lipopeptides were also examined. The studies reveal that the surface active properties of synthesized compounds strongly depend on the length of alkyl chains as well as on the composition of amino acid polar heads. The critical micelle concentration decreases with increasing alkyl chain length of lipopeptides with the same polar head. The effectiveness and efficiency decrease when the number of amino acids in the polar head increases. All lipopeptides established a very weak emulsification power and created unstable water/Miglyol 812 and water/paraffin oil emulsions. Results suggest that lipopeptides cannot be used as emulsifiers; nonetheless, it is possible to use them as auxiliary surfactants with disinfectant properties in combination with more potent emulsifiers.     

Effect of Amino Acids on Micellization,Surface Activity and Micellar Properties of Nonionic Surfactant Hexadecyl Alcohol Ethoxylate (25EO) in Aqueous Solutions

The effects of amino acids (dl ‐glycine, dl ‐alanine, dl ‐phenylalanine, dl ‐serine, l ‐leucine, l ‐aspartic acid, l ‐lysine) on the micellization, surface activity, viscometric and aggregation properties of hexadecyl alcohol polyethoxylate (25EO) in aqueous solution were studied. The critical micelle concentration and free energy of micellization were evaluated and discussed. The surface excess concentration, the minimum area per molecule, the surface pressure at the critical micelle concentration and the standard free energy of adsorption were obtained from surface activity studies. On the basis of the determination of the relative viscosities on concentration, the viscosity B‐coefficients of the Jones–Dole semiempirical equation were calculated for the premicellar and postmicellar regions. The method of fluorescence quenching was used for determination of the micellar aggregation number of hexadecyl alcohol polyethoxylate (25EO) in aqueous solution in the presence of amino acids. It was found that among studied amino acids serine shows behavior that is different from that of the other neutral amino acids.     

Synthesis and Evaluation of Surface and Biological Properties of Some Lactic Acid-Based Anionic Surfactants

In the present study, 11 lactic acid-based anionic surfactants were synthesized and evaluated for their surface and biological activities. The synthesis involved the esterification of lactic acid with a range of fatty alcohols differing in chain length as well as in branching and unsaturation. The resultant ester was sulfonated by treatment with chlorosulfonic acid followed by salt formation with aqueous NaOH solution. The surface properties of all the synthesized surfactants were determined using surface tensiometry. Synthesized surfactants showed low critical micelle concentration (CMC) values and a decreasing trend with an increase in the alkyl chain length. Alkyl branching also led to a mild change in CMC values when compared with linear counterparts having the same number of carbon atoms, though such decreases or increases were observed to be dependent on the position and number of the branching. Some of the synthesized surfactants exhibited good antimicrobial and anti-cancer activities against the tested microbial strains and cell lines.     

Synthesis,Micellization, and Surface Activity of Novel Linear-Dendritic Carboxylate Surfactants

Two generations of novel linear-dendritic carboxylate surfactants C₁₈-G₁-(COONa)₂ and C₁₈-G₂-(COONa)₄ have been synthesized by the divergent method and their structures are characterized by ¹H Nuclear Magnetic Resonance and Infrared analysis. The electrical conductivity measurement is used to measure the Krafft temperatures of C₁₈-G₁-(COONa)₂ and C₁₈-G₂-(COONa)₄, which are much smaller than those of the corresponding conventional surfactant sodium stearate. The markedly enhanced solubility of two linear-dendritic surfactants is ascribed to the high hydrophilicity of surfactant headgroups induced by the carboxylate and ester groups. The critical micelle concentration (CMC) values obtained from both the electrical conductivity and surface tension measurements indicate that the micellizations of linear-dendritic surfactants become favorable with the increase in the number of the surfactant headgroup. However, the surface activity parameters including the surface tension at the CMC, maximum surface excess, and minimum surface area reveal that C₁₈-G₁-(COONa)₂ exhibits greater efficiency in absorbing at the air/water interface compared to C₁₈-G₂-(COONa)₄, owing to their different steric repulsions of the surfactant headgroups. In addition, C₁₈-G₁-(COONa)₂ and C₁₈-G₂-(COONa)₄ have higher emulsifying ability than the conventional surfactants sodium stearate and sodium octadecyl sulfate.     

Synthesis,Characterization, Surface and Biological Activity of Diquaternary Cationic Surfactants Containing Ester Linkage

Two series of diquaternary cationic surfactants designated as E9Nm and E11Nm having two different alkyl chains in their chemical structure were synthesized. The chemical structures of these surfactants were confirmed using elemental analysis, FTIR and ¹H‐NMR spectra. The surface activities of the different surfactants were determined using surface and interfacial tension at 25 °C. The surface parameters including: critical micelle concentration, effectiveness, efficiency, maximum surface excess and minimum surface area were determined. The surface activities of the cationic surfactants were correlated with their chemical structure. The surface activities of the surfactants increased with increasing the hydrophobic chain length. The adsorption and micellization tendencies of the surfactants in solution were determined using the free energies of adsorption and micellization. The synthesized surfactants were evaluated as biocides against bacteria and fungi. Biocidal activity data showed that a gradual increase in the hydrophobic chain length of the surfactant molecules gradually increases the efficiency of these surfactants as biocides.     

Synthesis and Properties of Quaternary Ammonium Surfactants Based on Alkylamine,Propylene Oxide,and 2‐Chloroethanol

New quaternary ammonium salts are synthesized by octylamine, nonylamine, dodecylamine, and hexadecylamine reacting with propylene oxide at a mole ratio of 1:2, followed by reaction with 2‐chloroethanol. By tensiometric measurements of aqueous solutions, their surface activity has been determined. Using the results of these measurements and electroconductometric studies, important parameters such as critical micelle concentration (CMC), efficiency of surfactant adsorption, surface pressure at the CMC, changes of Gibbs free energies for micelle formation, and adsorption were estimated. By application of the Gibbs adsorption isotherm, indices such as maximum surface excess concentration and minimum surface area/molecule at the air–water interface were also calculated. Petroleum‐collecting properties of these surfactants were investigated. Among these quaternary ammonium surfactants, the surfactant based on dodecylamine, propylene oxide, and 2‐chloroethanol exhibits the highest petroleum‐collecting capacity.     

Synthesis, Surface and Thermodynamic Properties of Substituted Polytriethanolamine Nonionic Surfactants

Three series of nonionic surfactants derived from polytriethanolamine containing 8, 10, and 12 units of triethanolamine were synthesized. Structural assignment of the different compounds was made on the basis of FTIR and ¹H‐NMR spectroscopic data. The surface parameters of these surfactants included critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), surfactant concentration required to reduce the surface tension of the solvent by 20 mN m^?1 (pC₂₀), maximum surface excess (Γ_max), and the interfacial area occupied by the surfactant molecules (A_min) using surface tension measurements. The micellization and adsorption free energies were calculated at 25 °C.     

Double-Tailed Single-Head Amino Acid-Based Chiral Cationic Amphiphilic Molecules: Synthesis,Characterization, and Physicochemical Properties

Two double-tailed single-head amino acid-based chiral cationic amphiphilic molecules, l -aspartic acid hydrochloride dihexylester (L-ADHE, C₆–C₆) and l -aspartic acid hydrochloride dioctylester (L-ADOE, C₈–C₈), were synthesized. ¹H NMR, ¹³C NMR, and Fourier transform infrared (FT-IR) were used to characterize the structures of the esters. Micellization, surface, and structural properties of L-ADHE and L-ADOE in aqueous solution were studied by means of a number of techniques including conductivity, pH, surface tension, density, zeta potential, and dynamic light scattering (DLS). The critical micelle concentration (CMC) of L-ADHE and L-ADOE were found to be very low compared with those of corresponding single-tailed amino acid-based amphiphilic molecules. The pK_a values of L-ADHE and L-ADOE in aqueous solutions were determined via pH measurements, and it was observed that they had acidic properties giving low pK_a values. The excellent adsorption behaviors at the air/water interface of L-ADHE and L-ADOE in aqueous medium were obtained, i.e. they efficiently lowered the surface tension of water at CMC down approximately to 24.3 and 23.4 mN m⁻¹, respectively. From the density measurements, the volume change due to the micellization process for L-ADOE was found to be quite high compared to L-ADHE, i.e. about three times more. This result and the data obtained from the DLS revealed that the increase in aggregated structures of L-ADOE may be due to vesicle formation. The dye solubilization study was performed by UV–vis absorption spectroscopy for L-ADHE. Besides, the CMC value of L-ADHE was also successfully determined without using any dye through UV–vis spectroscopy.     

Comparative Study on the Syntheses and Properties of Three N-lauroyl Aromatic Amino Acid Surfactants

Three N-lauroyl aromatic amino acid surfactants, namely, sodium N-lauroyl phenylalaninate (SLP), sodium N-lauroyl tyrosinate, and sodium N-lauroyl tryptophanate (SLTr), with aromatic group structures were synthesized via methyl ester method. Mass spectrometry, Fourier transform infrared spectroscopy, and nuclear magnetic resonance were applied for the structural representation of products. A comparative study of the three surfactants in terms of surface, foam, and emulsifying properties and decontamination performance was conducted. Results demonstrated that aromatic structure significantly influenced the properties of the three surfactants. SLTr had the best surface performance and foam property, whereas SLP had the best emulsifying property. All three surfactants exhibited strong decontamination effects on protein-soiled swatches.     

Synthesis,Characterization and Surface Activities of Cationic Polysaccharide (Aloe) Schiff Base Surfactants

Synthesis of cationic polysaccharide (Aloe) Schiff base surfactants was described and their chemical structures were confirmed by using FTIR spectroscopic, H‐NMR and UV analysis. The surface activities of these surfactants were measured, including surface tension, critical micelle concentration, effectiveness, efficiency, maximum surface excess and minimum surface area at 25 °C, interfacial tension and emulsification power at 25 °C. Adsorption and micellization free energies of these amphiphiles in their solutions showed a good tendency towards adsorption at the interfaces.     

Imidazolium‐Based Ionic Liquid as Modulator of Physicochemical Properties of Cationic,Anionic, Nonionic,and Gemini Surfactants

The aggregation morphology of 2 cationic surfactants (cetyldimethylethanolammonium bromide and cetyldiethylethanolammonium bromide), an anionic surfactant (sodium dodecylbenzenesulfonate), a nonionic surfactant (Triton X‐100), and 2 gemini surfactants (16‐4‐16,2Br^?[butanediyi‐1,4‐bis(dimethyldohexylammonium bromide)] and 16‐6‐16,2Br^?[hexanediyi‐1,6‐bis(dimethyldohexylammonium bromide)]) in the presence of the ionic liquid (IL) 1‐ethyl‐3‐methylimidazoliumbromide [Emim][Br] is studied using various techniques such as surface tension, conductivity, and UV–visible and fluorescence spectroscopy. Increasing the concentration of [Emim][Br] results in a decrease in the critical micelle concentration (CMC) value of the surfactants. Various interfacial properties, namely the surface excess concentration (Г_max), minimum area per molecule at the air–water interface (A_min)_, and surface pressure at the CMC (π_cmc), as well as the thermodynamic parameters such as free energy of the given air/water interface (), Gibbs free energy of micelle formation (), Gibbs free energy of micellization per alkyl tail (), Gibbs energy of transfer (), and standard free energy of adsorption () were also investigated. The aggregation number (N_agg) was determined by the fluorescence method. It was observed that N_agg decreased with increasing weight‐percent of the IL.     

Synthesis and Properties of Novel Surface Active Monomers Based on Derivatives of 4‐Hydroxybutyric Acid and 6‐Hydroxyhexanoic Acid

Novel surface active maleate and methacrylate monomers based on derivatives of ω‐hydroxy carboxylic acids have been synthesized. The monomers are comprised of hydrophobic alkyl chains and hydrophilic poly(ethylene glycol), quaternary ammonium, sulfonate and carboxylic fragments. Synthesized monomers sufficiently reduce surface tension at the aqueous solution‐air interface. The copolymerization of synthesized monomers with 5‐tert‐butylperoxy‐5‐methyl‐2‐hexene‐3‐yne monomer and N‐vinylpyrrolidone in solvent and emulsion copolymerization of synthesized peroxide containing surface active monomer with styrene have been carried out. The synthesized surface active monomers have been shown to be suitable emulsifiers for obtaining polystyrene colloid dispersions. It has been ascertained that the surface active copolymers obtained can form stable interpolyelectrolyte complexes with oppositely charged polymers.     

Synthesis of Cleavable Aryl Sulfonate Anionic Surfactants and a Study of their Surface Activity

A series of cleavable aryl sulfonate anionic surfactants were synthesized from cyanuric chloride, aliphatic amine and H-acid mono sodium salt. Their structures were identified by ¹H NMR, Infrared Spectrum (IR) and Elementary Analysis (EA). Their critical micelle concentrations (CMC) in aqueous solutions at 25 °C were determined by a steady-state fluorescence probe method and a surface-tension method. With the increasing length of the carbon chain, the value of their CMCs and surface tensions under CMC (γ _CMC) initially decreased and then reached a minimum (respectively 2.63 × 10⁻⁵ mol L⁻¹ and 28.29 mN m⁻¹) when the carbon number was 10. The CMC and γ _CMC then increased when the carbon number was increased to 12. The results showed that, compared with sodium dodecyl benzene sulfonate (SDBS), such kinds of surfactants have much lower surface adsorption amounts and greater molecular areas on the aqueous surface.

Surface Parameters and Biological Activity of <Emphasis Type="Italic">N</Emphasis>-(3-(Dimethyl Benzyl Ammonio) Propyl) Alkanamide Chloride Cationic Surfactants

Three cationic surfactants containing amide groups were prepared by quaternization of dimethylaminopropylamine with benzyl chloride. FTIR and ¹H-NMR spectroscopy were used to confirm the chemical structure of the prepared cationic surfactants. The surface parameters were estimated using surface tension measurements at three different temperatures. The prepared cationic surfactant showed a lower CMC than conventional cationic surfactants. Thermodynamic parameters of adsorption and micellization depend mainly of alkyl chain length and temperature. The adsorption process is more favorable than micellization. The biological activity of the three surfactants was estimated using inhibition zone showing that amidoamine cationic surfactants have good activity and the surfactants C12Bn is the most effective one.     

Synthesis and Surface Activities of Novel Succinic Acid Double-Tailed Sulfonate Fluorinated Surfactants

In this study, four environmentally friendly succinic acid double-tailed sulfonate fluorinated surfactants were synthesized from maleic anhydride, fluoroalkyl alcohols, namely 1-(1H,1H,7H-Dodecafluoroheptyloxy) ethanol, 1-(1H,1H,5H -octafluoropentyloxy) ethanol, 1-(1H,1H,3H-tetrafluoropropoxy) ethanol, and 1-(1H,1H -trifluoroethyoxy) ethanol, and sodium hydrogensulfite. The surfactant structure was characterized by FT-IR, ¹H NMR, and ¹⁹F NMR . Thermogravimetric results showed that the fluorinated surfactants were stable up to relatively high temperature. The Krafft points of the four novel succinic acid double-tailed sulfonate fluorinated surfactants were all below 0 °C. The lowest CMC value for the synthesized four double-tailed fluorine surfactants is about 0.076 mmol L^?1, far less than that of ammonium perfluorooctanoate (PFOA), demonstrating that double-tailed surfactants have higher surface activity than surfactants with one fluoroalkyl chain. The replacement of alkyl groups with oxyethylene groups enhances the hydrophilicity of the obtained fluorinated surfactants. Based on these findings, the synthesized surfactants may be environmentally friendly alternatives to PFOA and exhibit promising potential in industry applications.     

Amino Acid-Functionalized Calix[4]Resorcinarene Solubilization by Mono- and Dicationic Surfactants

Poorly water-soluble calix[4]resorcinarenes modified with amino acid (Ala, Val) at the upper rim formed a water-soluble mixed system with micelles of monocationic surfactants cetyltrimethylammonium bromide, cetyldimethyl(2-hydroxyethyl)ammonium bromide, and dicationic (gemini) surfactants, alkanediyl-α,ω-bis(dimethyltetradecylammonium bromides (14-s-14, where s = 2, 4, or 6). UV–Vis and DLS methods demonstrated that the micellar systems of surfactant/functionalized calix[4]resorcinarene underwent structural changes within a relatively narrow concentration range followed by changes in solubilization capacity and polydispersity. Gemini surfactants and monocationic/gemini mixed surfactant systems were provided selectivity in their interaction with calix[4]resorcinarene depending on the bulkiness of the substituent at the upper rim of calix[4]resorcinarene, gemini surfactant spacer length, and mixed micelles. These systems represent a direction to create biocompatible water-soluble functionalized calix[4]resorcinarene composition and may open perspectives in designing organized systems with controllable properties.     

一种不对称阴离子Gemini表面活性剂的合成及表面活性研究

以α-溴代十四酸乙酯和4-癸基苯酚为原料,经Williamson醚化、磺化及皂化反应制备了一种不对称阴离子Gemini表面活性剂α-(4-癸基-2-磺基)-苯氧基十四酸钠,简写为C12CO2Na-p-C10SO3Na,考察了醚化反应条件,并用FTIR和1HNMR表征了中间体及目标产物结构。结果表明,醚化反应的最佳条件为:以N,N-二甲基甲酰胺(DMF)和甲苯作溶剂,无水K2CO3作缚酸剂,物料比n(α-溴代十四酸乙酯)∶n(4-癸基苯酚)=1.05∶1,回流反应3 h,醚化产物收率为77.2%(以4-癸基苯酚计)。采用吊片法测定了目标产物的表面活性,其表面张力最低可降至26 mN/m左右,临界胶束浓度(CMC)为3.28×10-6mol/L,比相应常规单链表面活性剂十四烷酸钠和间癸基苯磺酸钠的CMC低3个数量级,体现出Gemini表面活性剂优异的表面活性。     

Synthesis and Surface Properties of Anionic Gemini Surfactants having N-acylamide and Carboxylate Groups

A straightforward synthetic strategy to an anionic gemini surfactant having both N-acylamide and carboxylate groups in a molecule has been demonstrated. The surface properties of the anionic gemini surfactant, such as CMC (critical micelle concentration), C₂₀ (the concentration required to reduce the surface tension of the solvent by 20 mN/m), γ _CMC (the surface tension at the CMC), ∏ _CMC (the surface pressure at the CMC), Γ _max (the maximum surface excess concentration at the air/aqueous solution interface), A _min (the minimum area per surfactant molecule at the air/water interface), and the CMC/C₂₀ ratio (a measure of the tendency to form micelles relative to adsorbtion at the air/water interface), have been studied. The influence of the different concentrations of NaCl on the surface properties of the gemini surfactant has been discussed. The results have shown that the CMC values decreased with an increase in the concentration of NaCl indicating that the Na⁺ preferentially adsorbs onto the surface of the charged aggregate and facilitates the aggregate growth by suppressing the main impediment of electrostatic repulsion among head groups. Additionally, the values of Γ _max are always higher in salt solutions as compared to those in pure water due to their salting out effect. The larger pC₂₀ value indicates that the surfactant adsorbs more efficiently at the air/water interface and reduces surface tension more efficiently. In addition, the geminis in water show little or no break in their specific conductance versus surfactant molar concentration plots. This is attributable to protonation of the carboxylate group and strong Na⁺ release during micellization.