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A novel approach to mixed micelles formation: study the interactions between bis-quaternary ammonium salts and nonionic surfactant Triton X-100

  • Patrycja Przybył

    Patrycja Przybył is a graduate of the Faculty of Chemical Technology at Poznan University of Technology. She is involved in study of extraction and newly surfactants.

         , Marta Wojcieszak

    Marta Wojcieszak is Ph.D. student in Poznan University of Technology. She is involved in study of newly designed surfactants especially which combine surface and biological activity.

     EMAIL logo     , Damian Krystian Kaczmarek

    Damian Krystian Kaczmarek is a Ph.D. in Department of Chemical Technology, Poznan University of Technology. His research interests are focused on chemistry and technology of organic compounds, and environmental technologies.

         , Damian Jankowski

    Damian Jankowski is Ph.D. student in Poznan University of Technology. He is involved in study of surfactants and surface-active ionic liquids.

         and Katarzyna Materna

    Katarzyna Materna is Professor at the Department of Chemical Technology, Poznan University of Technology. Her research interests are focused on physicochemical and functional properties of amphiphilic compounds and unconventional separation processes.

     EMAIL logo
Published/Copyright: November 28, 2023
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Tenside Surfactants Detergents
From the journal Tenside Surfactants Detergents Volume 61 Issue 1

Abstract

This article focuses on the description of novel mixed system formulations of bis-quaternary ammonium salts (bis-QASs) and the nonionic surfactant Triton X-100 (TX-100). Measurements of surface tension (γ), foam stability, contact angle (CA) and cloud point (CP) were investigated at different ratios of the given compounds. The results indicated that changes in the structure of the bis-QASs amphiphilic cation, including the length of the alkyl spacer and the presence or absence of –OH groups, affected the adsorption and micellization. Furthermore, the elongation of the alkyl spacer in the bis-QASs structure affects the increase in the CP temperature. The research carried out shows the future potential of mixed combinations (bis-QASs and TX-100) to be used in industrial applications.

Keywords: bis-quaternary ammonium salts; Triton X-100; surface activity; cloud point; foam

1 Introduction

Aqueous mixed systems are considered to be a non-destructive, environmentally friendly method for obtaining biomolecules [1], [2], [3], [4], [5], [6]. Such mixtures are composed of a nonionic surfactant (usually from the group of Triton X, Genapol and Tergitol [7], [8], [9], [10]) and a compound that indicates the properties of a co-surfactant. It is widely accepted that modifiable bis-quaternary ammonium salts (bis-QASs) can be used to assist in the formation and stabilisation of micelles or microemulsions [1], [2], [3], [4].

Bis-QASs [11], [12], [13] are an interesting group that may exhibit the same behaviour as Gemini surfactants. These compounds are known to have an amphiphilic structure consisting of two ammonium cations covalently linked by a flexible or rigid non-polar spacer. As a result, bis-QASs stand out for their ability to reduce surface tension and critical micelle concentration (CMC). Both the counterion, spacer and substituents can be varied in length and type to achieve the expected properties and applications. It should be emphasised that the biological properties, wetting and foaming abilities of these surface-active compounds are important advantages for their potential use [14, 15]. Bis-QASs are mainly used as preservatives, pharmaceuticals, disinfectants, herbicides, biocides, fungicides and as ingredients in cosmetic products [16], [17], [18]. In recent years, studies on aqueous systems containing bis-QASs have continued to investigate their aggregation and micellization behaviour [19]. It is believed that such compounds become amphiphilic by extending the aliphatic chain. The unique structure of bis-QASs affects self-aggregation, CMC, surface tension and adsorption efficiency [11, 20, 21]. Measurement of the following parameters allows us to understand the phenomena that occur in mixed systems, predict their potential application, or modify the structure of additives to obtain the expected properties [22].

As mentioned above, nonionic surfactants are the key component of mixed systems. TX-100 (2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, [19, 20, 23, 24]) has been used in cosmetic and cleaning products. It is also useful as a biopharmaceutical stabilizer in the solubilization of non-polar drug formulations. It has been proven that the solubility of nonionic aqueous solutions decreases with the increasing temperature. This dependence results in the formation of a two-phase micellar system, which is valuable for the separation of biological compounds, while limiting the use of organic solvents currently used for this process. Furthermore, this nonionic surfactant reveals its clouding behaviour when its aqueous solution reaches a cloud point (CP). This occurrence is possible due to the dehydration of the polyoxyethylene part of TX-100 at this temperature [25], [26], [27].

A good approach is to use mixed systems to prevent unwanted destabilization or decomposition of solutions. Unfortunately, despite scientists’ attempts to understand the phenomena occurring in mixed systems, there is still a relatively poor understanding of their effects. We aim to fill this gap, as knowledge of the surfactant properties of the mixed surfactant systems is of great interest to colloid and interface science. Moreover, it will not only assist in the evaluation and analysis of the role, but also emphasize the importance of the benefits that mixed systems could bring to the future applications.

The aim of the present work is to experimentally determine the surface activity in mixed systems containing TX-100 and bis-QASs. To the best of our knowledge, the study of the interaction between bis-QASs with alkane-1,ω-bis(decyldimethylammonium), alkane-1,ω-bis((2-hydroxyethyl)dimethylammonium) or alkane-1,ω-bis(di(2-hydroxyethyl)methylammonium) cations dibromide anions and TX-100 have not been reported yet. Furthermore, we would like to create mixed micelles to invent novel and highly promising systems with technical and application target, as a future goal, where the studied bis-QASs can behave as co-surfactants for micellar use.

2 Experimental

2.1 Materials

Decyldimethylamine (90 %), 2-dimethylaminoethanol (99.5 %), 2,2′-methyliminodiethanol (96 %), 1,8-dibromooctane (98 %), 1,10-dibromodecane (97 %), 1,12-dibromododecane (98 %), acetonitrile (99 %), acetone (99 %), ethyl acetate (99 %), were purchased from Sigma-Aldrich and used without further purification. Water was deionized using the HLP Smart 1000 demineralizer (Hydrolab). The nonionic surfactant, Triton X-100, was purchased from Sigma-Aldrich, (purity grade > 99 %), and used as received.

2.2 Methods

2.2.1 Preparation of bis-ammonium quaternary salts

The preparation and characterization of bis-ammonium quaternary salts with alkane-1,ω-bis(decyldimethylammonium), alkane-1,ω-bis((2-hydroxyethyl)dimethylammonium) or alkane-1,ω-bis(di(2-hydroxyethyl)methylammonium) cations and dibromide anions were carried out according to the methodology described in the literature [27, 28]. 1,8-Dibromooctane, 1,10-dibromodecane or 1,12-dibromododecane (0.01 mol) and decyldimethylamine, 2-dimethylaminoethanol or 2,2′-methyliminodiethanol (0.02 mol) were added to the reactor and dissolved in 30 cm3 of acetonitrile. The reactions were conducted at 60 °C for 24 h. Subsequently, the solvents were evaporated, and the product of the reaction was dissolved in ethyl acetate or acetone. After adding the solvent, bis-ammonium dibromides precipitated as white solids and were isolated by filtration. The products were dried under a reduced pressure at 70 °C for 24 h.

2.3 Characterization of bis-ammonium quaternary salts

Infrared (IR) spectra were collected on the Nexus Nicolet 5700 Fourier Transform Infrared Spectrophotometer (FTIR, Thermo Electron Scientific Instruments Corporation, Madison, WI, USA) equipped with an attenuated total reflection (ATR) accessory, with a diamond crystal (T = 25 °C, range 4000–500 cm−1, resolution 4 cm−1 at 64 scans).

Spectroscopic data of the synthesized bis-QASs:

  • 1a, IR [cm−1] = 571, 722, 902, 922, 1470, 2851, 2919.

  • 2a, IR [cm−1] = 572, 722, 892, 922, 1471, 2848, 2920.

  • 3a, IR [cm−1] = 422, 528, 725, 893, 1471, 2848, 2921.

  • 1b, IR [cm−1] = 567, 726, 886, 917, 970, 1010, 1040, 1085, 1364,1420, 1480, 2858, 2922, 3274.

  • 2b, IR [cm−1] = 597, 743, 868, 909, 974, 1024, 1055, 1091, 1122,1424, 1478, 2848, 2907, 3302.

  • 3b, IR [cm−1] = 631, 841, 888, 927, 949, 970, 1008, 1096, 1347, 1459, 1495, 2856, 2918, 3216.

  • 1c, IR [cm−1] = 599, 748, 816, 863, 903, 927, 968, 988, 1049, 1105, 1482, 2961, 3275.

  • 2c, IR [cm−1] = 565, 740, 822, 858, 905, 953, 1073, 1094, 1166, 1456, 2856, 2907, 3302.

  • 3c, IR [cm−1] = 617, 719, 798, 860, 892, 917, 1050, 1085, 1162, 1482, 2849, 2919, 3293.

2.4 Surface activity studies

The surface tension (γ) and contact angle (CA) measurements were performed using the DSA100 Drop Shape Analyzer (Krüss GmbH, Hamburg, Germany), at 25 °C. The Fisherbrand FBH604 thermostatic bath allowed to maintain certain conditions with an accuracy of ± 0.1 °C.

The drop shape method was used to obtain surface tension measurements by creating an axisymmetric drop at the tip of the syringe needle. The image was processed and digitised based on the analysis of the drop profile using the Laplace equation. Based on the results obtained from the surface tension measurement method described above, the standard Gibbs free energy of adsorption (ΔG0ads) and the adsorption efficiency (pC20) were calculated using the following equations, which were used in our previous works [29, 30].

Adsorption efficiency (pC20)

(1) pC 20 = − log C 20

where:

  • C20 – compound concentration in the bulk phase required to reduce the surface tension of water by 20 mN m−1.

Standard Gibbs free energy of adsorption (ΔG0ads), which characterizes the interactions between the bulk phase and the surface phase:

(2) ∆ G ads 0 = − R T ln A sz

where:

  • R – gas constant,

  • T – absolute temperature,

  • Asz – Szyszkowski equation constant.

In the present considerations, the basis for determining the contact angle was the image of the drop placed on the tested hydrophobic paraffin surface. Measurements were made to an accuracy of ± 0.1°. After determining the actual shape of the deposited drop and the contact line, the contour was fitted to the mathematical model used to calculate the contact angle (CA) value. The Young-Laplace equation was used as the most accurate method of calculating the values. This resulted in the determination of the contact angle as the slope of the contour line at the three-phase contact point (solid/liquid/air).

2.5 Cloud point (CP) determination

The behaviour of two-phase aqueous systems, containing bis-QASs in the presence of the nonionic surfactant TX-100 at the different ratios, was determined by the cloud point method. To determine the CP temperature at which a homogeneous mixture becomes cloudy, the prepared mixtures at CMC were heated above their CP until they became cloudy, then slowly cooled and mixed vigorously until a clear liquid was obtained. The CP temperature was measured three times for all aqueous systems with an accuracy of ±0.1 °C [27, 31].

2.6 Foamability

The foam height and stability experiment was carried out in a 10 ml graduated glass cylinder using 6 cm3 of the solution. 2 cm3 of the mentioned mixture was carefully transferred into the cylinder to avoid foaming. The remainder of the intended test solution was placed in the syringe and dispensed from a height of 5 cm. The height of the foam formed in the cylinder was measured after 30 s and 5 min. The measurements were repeated three times. The experiment described above was based on the standard and literature data [32]. The foamability of the investigated systems was determined by the foam stability index (FSI). The FSI values were obtained from Equation (3):

(3) FSI = ( h 2 h 1 ) * 100 %

where:

  • h1 – height of foam after 30 s,

  • h2 – height of foam after 5 min.

3 Results and discussion

3.1 Synthesis

The methodology previously described in the literature was used to obtain the bis-QASs used in this study [28, 33]. The homologous series of bis-ammonium dibromides were synthesized by the reaction of decyldimethylamine, 2-dimethylaminoethanol or 2,2′-methyliminodiethanol with the corresponding dibromoalkane at 60 °C in acetonitrile. Bis-QASs 1-3a, 1-3b and 1-3c shown in Figure 1, were obtained with yields above 90 % and remained as white solids at room temperature. Moreover, the solubility of the synthesized bis-QASs in water was analyzed, which was important for further studies. The water solubility of all prepared bis-QASs was dependent on the structure of both the substitution and the alkyl spacer. Nevertheless, the poor solubility of some bis-QASs was still sufficient to prepare aqueous solutions for surface activity studies.

Figure 1: The structures of bis-ammonium cations.
Figure 1:

The structures of bis-ammonium cations.

3.2 Surface activity studies

In order to discuss the surface activity of the compounds, specific parameters were determined, the values of which are summarized in Table 1. However, the basis of the experiments carried out was the micellization phenomenon and the values of surface tension, γ, as a function of compound concentrations, which were used to describe the adsorption behaviour of aqueous solution of bis-QASs, TX-100 and mixed systems at the air / compound interface. As a result, surface tension isotherms were determined for the studied solutions and are shown in the Supplementary Materials (Figure A.1., A.2., and A.3.). The critical micelle concentration (CMC), surface tension at CMC (γCMC), the standard Gibbs free energy of adsorption (ΔG0ads) and adsorption efficiency (pC20) can be assessed by surface tension measurements. The contact angle (CA) was determined as described in Section 2.4.

Table 1:

Summary of surface properties of studied bis-QASs in aqueous solutions and mixed aqueous systems bis-QASs + Triton X-100, at 25 °C.

Aqueous solution
Bis-QASs
Abbreviation CMC (mmol L−1) γCMC (mN m−1) pC20 ΔG0ads (kJ mol−1) CA (°)
1a 2.46 37.7 3.15 −20.14 61.5
2a 2.28 37.4 3.20 −22.93 86.3
3a 1.90 37.3 3.52 −25.28 89.4
1b 248.34 41.0 1.02 −6.82 62.6
2b 214.91 37.5 1.18 −9.55 86.8
3b 162.61 38.3 1.30 −13.82 89.5
1c 150.03 39.2 1.26 −9.34 58.2
2c 137.98 31.4 1.95 −14.52 68.4
3c 110.93 36.6 1.61 −12.32 79.6
Triton X-100
TX-100 0.26

0.24–0.27 [32, 34], [35], [36]		 31.5

29.8 [23]		 4.69

4.73 [37]		 −33.12

(−46.0) – (−46.2) [38]		 52.7

55.0 [23]
Bis-QASs:Triton X-100 9:1 (M ratio)
1a 1.09 37.1 3.75 −26.16 59.7
2a 1.18 38.2 3.87 −28.94 63.0
3a 0.81 36.5 4.73 −38.16 68.8
1b 2.86 31.8 3.70 −26.66 52.5
2b 2.44 31.5 3.64 −25.49 53.2
3b 1.96 31.1 3.62 −24.18 59.8
1c 3.19 31.7 3.69 −26.93 53.9
2c 3.02 31.3 3.61 −30.54 57.5
3c 2.54 31.3 3.65 −25.69 68.3
Bis-QASs:Triton X-100 1:9 (M ratio)
1a 0.39 31.6 4.73 −33.50 52.5
2a 0.36 31.1 4.58 −30.71 54.6
3a 0.32 32.9 4.57 −31.70 56.0
1b 0.39 31.5 4.66 −32.55 48.7
2b 0.36 32.7 4.61 −31.62 51.0
3b 0.34 31.5 4.49 −30.10 51.8
1c 0.32 32.4 4.54 −30.80 56.6
2c 0.35 32.0 4.52 −32.14 52.6
3c 0.41 31.0 4.45 −31.42 54.7

According to the results obtained, the surface tension of pure aqueous solutions (γCMC) decreased from 72.8 mN m−1 (value of pure water) to a minimum of 31.4 mN m−1 to 41.0 mN m−1 for the investigated bis-QASs and 31.5 mN m−1 for TX-100, at which a plateau occurred. The γCMC values for mixed system solutions ranged from 31.1 mN m−1 to 38.2 mN m−1 for the mixture bis-QASs:TX-100 at a M ratio of 9:1 and from 31.0 mN m−1 to 32.9 mN m−1 for bis-QASs:TX-100 at a M ratio of 1:9. The above-mentioned values obtained for mixed systems are considered to be the consequence of two factors. The first one concerns the interference of supramolecular structure of bis-QASs by TX-100 molecules due to the strong interactions with the quaternary ammonium salt phase. The second factor could be related to the ratio between bis-QASs and nonionic surfactant [19, 23, 24, 39, 40]. The example of the surface tension profile of bis-QAS 1a, TX-100 and their mixed systems in aqueous solutions is shown in Figure 2, while in Figure A.1., A.2. and A.3 (Supplematray Material) the plots of γ as a function of the concentration C (log C) of the pure solutions of the compounds or mixtures are presented.

Figure 2: Surface tension of bis-QAS 1a, TX-100 and mixed systems in the aqueous solutions at 25 °C.
Figure 2:

Surface tension of bis-QAS 1a, TX-100 and mixed systems in the aqueous solutions at 25 °C.

The CMC values obtained for the bis-QASs (1a, 1b, and 1c) in aqueous solutions were found in the range of 1.90 mmol L−1 to 248.34 mmol L−1 and the highest value was observed for 1b. For all the compounds mentioned above, the CMC value increased with the length of the spacer chain. Thus, a lower surface activity was observed for bis-QASs with two –C2H4OH groups compared to the structures with four similar substituents. This could be related to the number of hydrogen bonds between water and the amphiphilic moieties of these compounds [41]. The effect of bis-QASs on TX-100 is strongly dependent on their tendency to interact in the solvent. This means that quaternary ammonium salts, due to their hydrophobicity, interact strongly with nonionic surfactant, which affects the morphology of the mixed micelles. In this context, studies of CMC values have been justified [42]. Following this idea, the analysed bis-QASs can diffuse into TX-100 micelles to form mixed micelles, which was observed at lower CMC values for solutions containing nonionic surfactant [42], [43], [44]. Furthermore, a slight increase in the concentration of TX-100 in the solution clearly reflected the increased ability to form micelles. The lowest CMC value was observed for 3a and 1c corresponding to 0.32 mN m−1, for mixed systems containing bis-QASs:TX-100 at a M ratio of 1:9. Thus, at this ratio, the mixed composite films show a similar surface activity at the interface to the micelles of the TX-100 solution. It was reported that the CMC values of the groups (a, b, and c) analyzed were shifted to a lower concentration with increasing spacer length. As a result, the elongation of the alkyl spacer of the bis-QASs affects the increase of the interactions between their particles and TX-100. This hydrophobically driven CMC phenomenon involving surface-active compounds has been well discussed in the literature [19, 45, 46].

The determination of the surface activity is possible by using different parameters, in particular the adsorption efficiency (pC20). Analyzing the high values obtained for the pC20 parameter, it can be concluded that bis-QASs adsorb more efficiently at the interface and consequently reduce the surface tension by 20 mN m−1 more effectively. Moreover, all compounds (a, b, and c) in mixed systems of bis-QASs:TX-100 at 1:9 M ratio and for 3a in bis-QAS:Triton X-100 at 9:1 M ratio resulted in pC20 values greater than 4.0, confirming the highest surface activity of the aqueous systems analyzed.

The negative values of ΔG0ads for all systems studied (a, b, and c) indicate that the process proceeds spontaneously, regardless of the presence of a nonionic surfactant in the aqueous solution.

The contact angle measurements can be crucial in determining the correct use of surfactants in industrial applications. However, the wettability of compounds can be tuned by using a suitable additive depending on the desired application. According to the observations of the results obtained (see Table 1), the best wettability was marked by the solution containing bis-QASs with eight carbon atoms in the spacer. The exception was 2c in 1:9 M ratio of bis-QAS: TX-100, for which the lowest contact angle value was recorded. Moreover, it is clearly evident that the CA values of the studied solutions were below 90°, which corresponds to good surface wettability in the literature [24, 47], [48], [49].

It is well known that changes in the physicochemical properties of dilute aqueous micellar solutions upon addition of bis-QASs can potentially extend and improve the overall performance of aqueous surfactant solutions. In this case, focusing on the correlation of surfactant parameters is one way to gain relevant knowledge of mixed systems. The correlation of CA and CMC values for bis-QASs:TX-100 (M ratio of 9:1) is shown in Figure 3.

Figure 3: Exemplary comparison of CMC and CA values of bis-QASs: TX-100 (9:1 M ratio).
Figure 3:

Exemplary comparison of CMC and CA values of bis-QASs: TX-100 (9:1 M ratio).

In general, the results (see Figure 3) show a strong micellization effect accompanied by a lower wettability. The exceptions were 2a (9:1 M ratio of bis-QAS:TX-100) and 2c (1:9 M ratio of bis-QAS:TX-100). The above statement does not alter the fact that the mixed systems exhibit good wettability, making them satisfactory replacements for commercial systems in various industrial applications.

The ability to foam in solution generally depends on the adsorption of surface-active monomers at the gas-liquid interface and their micellar stability in the bulk [23, 50]. However, foamability is not only a property of surfactants but is also useful in describing surfactant compounds, of which bis-QASs are representatives. The foamability of the systems analysed can be described by the foam stability index, the values of which are shown in Figure 4.

Figure 4: Foam stability index for studied systems.
Figure 4:

Foam stability index for studied systems.

From Figure 4 and Table A.1. it can be concluded that the above solutions have a negative effect on the formation of stable foam. On the other hand, interesting reports were presented in the publication by Kumar et al. [50], where researchers compared the foamability and foam stability of single chain cationic surfactants with their Gemini analogues. Their research showed that these properties were significantly influenced by the length of the hydrocarbon chain. They also demonstrated the double-chain surfactants are better foam stabilisers than conventional single-chain surfactants. Their research indicated differences between the compounds N,N′-didodecyl-N,N,N′,N′-tetramethyl-N,N′-ethanediyl-diammonium dibromide, N,N′-dihexadecyl-N,N,N′,N′-tetramethyl-N,N′-ethanediyl-diammonium dibromide and N-dodecyl-N′-hexadecyl-N,N,N′,N′-tetramethyl-N,N′-ethanediyl-diammonium dibromide. The first one was found to have the highest foam height of the Gemini compounds considered. This was due to its low hydrophobicity and high solubility, as evidenced by rapid surface tension equilibration. On the other hand, the second compound was unable to produce foam due to increased hydrophobicity, which was confirmed by increased diffusion at the air-water interface, resulting in lower interfacial film strength and lower foaming ability [51]. In our research we found the opposite trend, an increase in foaming properties with the length of the alkyl substituents. The influence of a single chain surfactant on a mixed system was also observed. A higher proportion of TX-100 reduces the foaming properties, whereas in the case of the 9:1 M ratio it can be assumed that TX-100 at the appropriate concentration supports foam formation. In this case, this is probably explained by a better surface activity of the mixed molecules for adsorption at the air-water interface, resulting in the formation of a stable foam [23, 51].

3.3 Cloud point determination

As mentioned in the literature [27], different cation polarities, length of alkyl spacer, and type of substituent molecule linked with a quaternary nitrogen atom can differently affect the CP. The performed measurements determining the CP of pure TX-100 and bis-QASs mixtures in various concentrations were shown in Figure 5a and b and Table A.2.

Figure 5: Cloud point values of different solutions: a) Bis-QASs:TX-100 in 9:1 M ratio; b) Bis-QASs:TX-100 in 1:9 M ratio; red line refers to the pure solution of TX-100.
Figure 5:

Cloud point values of different solutions: a) Bis-QASs:TX-100 in 9:1 M ratio; b) Bis-QASs:TX-100 in 1:9 M ratio; red line refers to the pure solution of TX-100.

Based on the values presented in Figure 5 and Table A.2, it was observed that the temperature at the CP varies with the spacer chain length of bis-QASs. Therefore, for each group, there is an increase in the CP temperature with the elongation of the aliphatic hydrophobic spacer in bis-QASs. Moreover, in the case of 1b and 1c (in the molar ratio of 9:1, bis-QASs:TX-100), the values of CP were similar to those of pure TX-100 and increased to about 68 °C corresponding to compounds 3b and 3c. On the other hand, for all mixed systems in the M ratio of 1:9 of bis-QASs and TX-100, the same tendency as mentioned above was observed, but the CP values differed slightly from the literature value of the pure solution of TX-100 [27, 52, 53]. From these observations it can be concluded that the aliphatic spacer of bis-QASs has an affinity for the hydrophobic part of TX-100. Therefore, the polar cation interacts with the hydrophilic part of the non-ionic surfactant. In addition, the structure of the bis- QASs as a co-surfactant affects the CP. In the case of 1-3a in both ratios, no result was obtained. It is predicted that such a phenomenon is influenced by the absence of –OH groups, which determined the CP effect noticeable for 1-3b and 1-3c compounds. In conclusion, the study of CP temperatures at different ratios will be crucial for a possible industrial application, as it is known that this allows a more efficient extraction of biomolecules at lower temperatures, reducing the risk of protein denaturation [54].

4 Conclusions

This work was devoted to the synthesis and characterization of pure solutions and mixed systems containing bis-quaternary ammonium salts and nonionic surfactant. Overall, the analyses carried out focused on two aspects of the research. The first was to determine the effect of cation structure on surface activity, understood by linker elongation and the presence of different functional groups. It was shown that as the distance between two amphiphilic centres increases, the possibility of treating the compound as two separate individuals with surface activity increases. It was also shown that the introduction of additional long alkyl chains (as in alkane-1,ω-bis(decyldimethylammonium) dibromides) resulted in lower CMC values and higher adsorption efficiencies (pC20) than compounds with alkane-1,ω-bis-((2-hydroxyethyl)dimethylammonium) or alkane-1,ω-bis-(di(2-hydroxyethyl)methylammonium) cations. The second aspect focused on the composition of the solutions analysed. Mixed formulations (bis-QAS and TX-100) had a better ability to aggregate in water than pure amphiphilic compounds. Compared to pure aqueous solutions, mixed systems seem to have a higher propensity for wettability, foamability, ability to effectively lower surface tension and more spontaneous adsorption. We strongly believe that our results will encourage further extensive research to use bis-quaternary ammonium salts and nonionic surfactants as mixed systems to invent promising mixed formulations. In addition, these unique combinations described may pave the way for the development of bis-QASs with surface activity and may be a favourable replacement for conventional surfactants in some applications.

Corresponding authors: Marta Wojcieszak and Katarzyna Materna, Department of Chemical Technology, Poznan University of Technology, ul. Berdychowo 4, Poznan 60-965, Poland, E-mail: (M. Wojcieszak), (K. Materna)

Parts of this work have been presented at the European Detergents Conference (EDC) 2023 in Berlin.

About the authors

Patrycja Przybył

Patrycja Przybył is a graduate of the Faculty of Chemical Technology at Poznan University of Technology. She is involved in study of extraction and newly surfactants.

Marta Wojcieszak

Marta Wojcieszak is Ph.D. student in Poznan University of Technology. She is involved in study of newly designed surfactants especially which combine surface and biological activity.

Damian Krystian Kaczmarek

Damian Krystian Kaczmarek is a Ph.D. in Department of Chemical Technology, Poznan University of Technology. His research interests are focused on chemistry and technology of organic compounds, and environmental technologies.

Damian Jankowski

Damian Jankowski is Ph.D. student in Poznan University of Technology. He is involved in study of surfactants and surface-active ionic liquids.

Katarzyna Materna

Katarzyna Materna is Professor at the Department of Chemical Technology, Poznan University of Technology. Her research interests are focused on physicochemical and functional properties of amphiphilic compounds and unconventional separation processes.

  1. Research ethics: Not applicable.

  2. Author contributions: Patrycja Przybył: Validation, methodology, investigation, data curation, writing- original draft, writing- review and editing; Marta Wojcieszak: Conceptualization, methodology, writing- original Draft, investigation, writing- review and editing, validation, data curation, supervision; Damian Krystian Kaczmarek: Methodology, investigation, data curation, writing- original draft; Damian Jankowski: Methodology, investigation, data curation, writing- original draft; Katarzyna Materna: Supervision, resources, project administration, funding acquisition.

  3. Competing interests: The authors state no conflict of interest.

  4. Research funding: This work was funded by the Ministry of Education and Science in Poland (0912/SBAD/2308).

  5. Data availability: Not applicable.

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Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/tsd-2023-2548).

Received: 2023-07-20
Accepted: 2023-09-29
Published Online: 2023-11-28
Published in Print: 2024-01-29

© 2023 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Bis-Quaternary Ammonium Salts
  3. A novel approach to mixed micelles formation: study the interactions between bis-quaternary ammonium salts and nonionic surfactant Triton X-100
  4. Applications
  5. Brevity is the soul of wit – how time, temperature and detergent choice impact the cleaning performance in domestic dishwashers
  6. The preparation of a novel modified chitosan: application to the removal of lead and cephalexin
  7. Removal of acid dye from wastewater by cloud point extraction and regeneration of surfactant by pH regulation
  8. Effect of glauconite and SLS surfactant on phosphate and calcite rheology
  9. Physical Chemistry
  10. Iterative evaluation of micellar and thermodynamic properties of 12-2-12 in 1 % BSA aqueous solution in the presence of organic solvents and temperature
  11. Novel Surfactants
  12. Corrosion inhibition of pure iron by Eurohypnum leptothallum extract in 0.5 mol L−1 H2SO4: an experimental and GC-MS based study
  13. Study on rheology of a novel UV-light sensitive trimeric anionic–cationic surfactant/trans-o-methoxycinnamic acid micellar system
  14. Biosurfactants
  15. An overview on trehalolipids: a promising eco-friendly bio-surfactant
  16. A mini review on synthetic and biosurfactants: origin and structure, physicochemical properties, applications, cost of production, toxicity, biodegradability and environmental effects
https://doi.org/10.1515/tsd-2023-2548
Keywords for this article
bis-quaternary ammonium salts; Triton X-100; surface activity; cloud point; foam

Articles in the same Issue

  1. Frontmatter
  2. Bis-Quaternary Ammonium Salts
  3. A novel approach to mixed micelles formation: study the interactions between bis-quaternary ammonium salts and nonionic surfactant Triton X-100
  4. Applications
  5. Brevity is the soul of wit – how time, temperature and detergent choice impact the cleaning performance in domestic dishwashers
  6. The preparation of a novel modified chitosan: application to the removal of lead and cephalexin
  7. Removal of acid dye from wastewater by cloud point extraction and regeneration of surfactant by pH regulation
  8. Effect of glauconite and SLS surfactant on phosphate and calcite rheology
  9. Physical Chemistry
  10. Iterative evaluation of micellar and thermodynamic properties of 12-2-12 in 1 % BSA aqueous solution in the presence of organic solvents and temperature
  11. Novel Surfactants
  12. Corrosion inhibition of pure iron by Eurohypnum leptothallum extract in 0.5 mol L−1 H2SO4: an experimental and GC-MS based study
  13. Study on rheology of a novel UV-light sensitive trimeric anionic–cationic surfactant/trans-o-methoxycinnamic acid micellar system
  14. Biosurfactants
  15. An overview on trehalolipids: a promising eco-friendly bio-surfactant
  16. A mini review on synthetic and biosurfactants: origin and structure, physicochemical properties, applications, cost of production, toxicity, biodegradability and environmental effects
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