Determination of Critical Micelle Concentration of Anionic Surfactants by Ligand Exchange Micellar Electrokinetic Chromatography

CMC (Critical Micelle Concentration) is an important parameter of surfactant. It has been reported that it changes with ionic strength, temperature, additives, etc. Therefore, it could not be overestimated to develop the determination method of CMC of surfactants. Recently,current method using CE instrument and CE method have been reported. This paper presents an new method for determining CMC of anionic surfactants by ligand exchange micellar electrokinetic chromatography.     

Flow-injection system for determination of critical micelle concentrations of ionic and nonionic surfactants

A practical technique is presented for the rapid, accurate determination of the critical micelle concentrations (CMCs) of ionic and nonionic surfactants. The precision, speed and instrumental simplicity of a flow-injection system are combined with a gradient chamber and flow-through conductance and absorbance detection to produce a system capable of determining the CMC of surfactant solutions in less than 30 min. The exponential response gradients from the resulting system are monitored by a chart recorder and simple manual calculations yield the CMC. The validity of the technique is verified by determination of the CMC values for both ionic (cetyltrimethylammonium bromide and chloride and sodium dodecyl sulfate) and nonionic (Brij-35, Brij-56, Brij-99, Triton X-100) surfactants. The proposed technique does not require the extensive solution preparation, repetitive measurements, complex instrumentation and data manipulation typical of other methods for determining CMCs.     

Glycine-based polymeric surfactants with varied polar head group: I. synthesis, characterization, and application in micellar electrokinetic chromatography

The monomers and polymers of four anionic amide type sodium undecenoxy carbonyl glycinate (SUCG) surfactants and four anionic carbamate type sodium undecenoyl glycinate (SUG) surfactants with 1-, 2-, 3-, and 4-glycine unit as head group were synthesized and characterized. The CMC and aggregation number (A) for all eight surfactants were determined using fluorescence spectroscopy. In addition, the CMC values of these surfactants were also projected by surface tension and CE. The CMC of the monomers decreases with increases in the size of glycine head groups and correlates well when the fluorescence method was compared to CE. The A number increases and partial specific volume (V) decreases with increase in size of the head group of both monomers and polymers. However, A and V are always lower for the polymers than the corresponding monomers. The electrophoretic and chromatographic parameters of micelle polymers of SUG and SUCG were also examined. The coefficient of EOF increases with the increase in size of the head group but the electrophoretic mobility decreases which results in a decrease in the elution range. The retention data suggest that the selectivity differences among the mono-, di-, and tripeptide derivatives of poly-SUCG surfactants are relatively higher compared to the derivatives of poly-SUG series.     

Determination of the Critical Micelle Concentration of Cationic Surfactants by Capillary Electrophoresis

The determination of the critical micelle concentration (CMC) of cationic surfactants by capillary electrophoresis was demonstrated. In this study, tetradecyltrimethylammonium bromide (TTAB) and dodecyltrimethylammonium bromide (DoTAB) were selected as cationic surfactants and propazine was chosen as test solute. In the evolution of the effective electrophoretic mobility of propazine as a function of surfactant concentration, a dramatic change in slope at a particular concentration is a good indication of the CMC of this surfactant. The CMC values determined experimentally were further confirmed by a curve-fitting approach. Simulation of the electrophoretic mobility curves as a function of surfactant concentration in both micellar electrokinetic chromatography and capillary zone electrophoresis using cationic surfactants as an electrolyte modifier was performed for propazine, and the intersection of these two mobility curves allowed us to precisely predict the CMC of the surfactant. The CMC values determined for TTAB and DoTAB are 1.6 ± 0.1 and 11.0 ± 0.1 mM, respectively, in the case of an electrolytic solution consisting of 70 mM phosphate buffer at pH 6.0. Moreover, the applicability of the electroosmotic mobility as a parameter for the determination of the CMC was examined.     

Rapid determination of surfactant critical micelle concentrations using pressure-driven flow with capillary electrophoresis instrumentation

This work demonstrates a novel, convenient utilization of capillary electrophoresis (CE) instrumentation for the determination of critical micelle concentrations (CMCs). Solution viscosity differences across a range of surfactant concentrations were monitored by hydrodynamically forcing an analyte towards the detector. Upon reaching the surfactant's CMC value, migration times were observed to change drastically. CMC values for four commonly employed anionic surfactants were determined—sodium dodecyl sulfate: 8.1 mM; sodium caprylate: 300 mM; sodium decanoate: 86 mM; sodium laurate: 30 mM; and found to be in excellent agreement with values previously reported in the literature. The technique was then applied to the less well-characterized nonionic surfactants poly(oxyethylene) 8 myristyl ether (CMC ∼ 9 M), poly(oxyethylene) 8 decyl ether (CMC ∼ 0.95 mM) and poly(oxyethylene) 4 lauryl ether.     

Flow-injection chemiluminescence method for determination of critical micelle concentration of surfactants

In this study, chemiluminescence (CL) behaviour of Luminol-H₂O₂ in the presence of the different concentrations of four surfactants, cetyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB), sodium dodecyl sulphate (SDS) and polyoxyethylene dodecyl ether (Brij-35), was investigated. A novel method for the direct determination of critical micelle concentration (CMC) of the surfactants using flow-injection CL is described. Under the optimum conditions, the luminescence intensity of the Luminol-H₂O₂ system increased gradually with increasing concentration of the surfactants before the CMC, but rapidly reached to the emission maximum at the CMC, followed by a decrease after the CMC. The concentrations of the surfactants corresponding to the luminescence maximum are in agreement with the literature CMC values. The main factors affecting the determination of CMC are discussed. The mechanistic studies show that the luminescence peaks observed in the experiment were mainly because of the protective effect of the micelle against the transition of the excited species and the retarding effect of the micelle structures on the CL reaction rate.     

Polymeric sulfated surfactants with varied hydrocarbon tail: I. Synthesis, characterization, and application in micellar electrokinetic chromatography

The influence of surfactant hydrocarbon tail on the solute/pseudostationary phase interactions was examined. Four anionic sulfated surfactants with 8-, 9-, 10-, and 11-carbon chains having a polymerizable double bond at the end of the hydrocarbon chain were synthesized and characterized before and after polymerization. The critical micelle concentration (CMC), polarity, and aggregation number of the four sodium alkenyl sulfate (SAIS) surfactants were determined using fluorescence spectroscopy. The partial specific volume of the polymeric SAIS (poly-SAIS) surfactants was estimated by density measurements and capillary electrophoresis (CE) was employed for determination of methylene selectivity as well as for elution window. The CMC of the monomers of SAIS surfactants decrease with increase in chain length and correlated well when fluorescence method was compared to CE. The physicochemical properties (partial specific volume, methylene selectivity, electrophoretic mobility, and elution window) increased with an increase in chain length. However, no direct relationship was found between the aggregation number and the length of hydrophobic tail of poly-SAIS surfactants. These polymeric surfactants were then used as pseudostationary phases in micellar electrokinetic chromatography (MEKC) to study the retention behavior and selectivity factor of 36 benzene derivatives with different chemical characteristics. Although variation in chain length of the polymeric surfactants significantly affects the retention of nonhydrogen bonding (NHB) benzene derivatives, these effects were less pronounced for hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD) benzene derivatives. Therefore, hydrophobicity of poly-SAIS surfactants was found to be a major driving force for retention of NHB derivatives. However, for several benzene derivatives (NHB, HBA, and HBD) significantly higher selectivity factor was observed with longest chain polymeric surfactant (e.g., poly(sodium 10-undecenyl sulfate), poly-SUS) compared to shorter chain polymeric surfactant (e.g., poly(sodium 7-octenyl sulfate), poly-SOcS). In addition, the effect of the surfactant hydrophobic chain was also found to have some impact on migration order of NHB, HBA, and HBD benzene derivatives.     

Electroosmotic flow reversal for the determination of inorganic anions by capillary electrophoresis with methanol-water buffers

Manipulation of the electroosmotic flow (EOF) is essential for achieving optimized separations of small anions by capillary electrophoresis (CE). In this work, efficient suppression or reversal of EOF is achieved upon addition of small amounts of the cationic surfactants, cetyltrimethylammonium bromide (CTAB) or didodecyldimethylammonium bromide (DDAB) to the electrophoretic buffer. Highly stable and reversed EOF are achieved using the surfactants in the presence of up to 50% MeOH. In aqueous and low methanol containing solutions (up to 30%, v/v) surface aggregation of the surfactants at the capillary wall occurs at a concentration below the critical micelle concentration (CMC). The impact of MeOH on reversed EOF is predominantly a function of the diminished zeta potential of the silica, and to a lesser extent on the CMC in the bulk solution of the surfactant. Fast baseline separation and selectivity changes for small inorganic anions are observed when mixed aqueous-organic buffers are employed. Changes in EOF, micellar properties of the surfactant and selectivity for inorganic anions upon addition of various percent of methanol are also discussed.     

Determination of critical micelle concentrations of ionic and nonionic surfactants based on relative viscosity measurements by capillary electrophoresis

The critical micelle concentration (CMC) can be obtained by measuring the distinct physical properties of surfactant molecules in the monomeric and micellar states. In this study, two linear increments of relative viscosity with distinct slopes were obtained when increasing surfactant concentrations from dilute solution to above the CMC, which was then determined by the intersection of the two linear extrapolations. Using a capillary electrophoresis (CE) instrument and Poiseuille’s law, the viscosities of surfactants at a series of concentrations covering the monomeric and micellar regions could be obtained by measuring the hydrodynamic flow rates of the corresponding surfactant solutions. We applied this method to determine the CMC values of various types of surfactants including anionic, cationic, zwitterionic, and nonionic surfactants. The resulting CMC values were all in good agreement with those reported in literature. Using this method, the multiple-stage micellization process of a short-chain surfactant was revealed. We have also demonstrated that the CE-based viscometer was applicable to the study of CMC variation caused by organic or electrolyte additives.     

CE frontal analysis employing contactless conductivity detection for determination of CMCs of non-UV absorbing charged surfactants

Micellar systems composed of surfactants are used extensively in academia and industry for many different applications. In this work a highly versatile CE method for determination of CMCs of charged surfactants has been developed. In the case of positively charged surfactants a coating procedure of the fused-silica capillary was used, whereas negatively charged surfactants were analyzed using uncoated capillaries. The CE method is based on frontal analysis (FA) employing use of contactless conductivity and UV detection. The main advantages of the method are that it can be used for non-UV absorbing surfactants without introducing marker compounds which previously has been found to affect CMCs, requires very limited sample volume and is easily implemented and automated using standard CE equipment. The fact that counterions and different aggregated states are separated allows a detailed characterization of the micelle systems using the developed method. In the case of UV absorbing surfactants similar results were obtained employing contactless conductivity and UV detection. Finally, CMCs obtained using conductometry gave similar results as compared to the developed CE-FA procedure.     

Investigation Static/Dynamic Surface and Interfacial Tension of Some Synthesized Polymeric Surfactants to Enhance the Egyptian Jet Fuel A1 Atomization

In the present work some exthoxylated polyalkylphenol surfactants have different alkyl chains (nonyl and dodecyl) were synthesized. The static surface tension for these surfactants in water and jet fuel A1 was measured and the critical micelle concentration (CMC) for each surfactant was determined. The data show the general trend of decreasing the CMC against the molecular weight of the synthesized polymeric surfactants. The HLB of these surfactants was also calculated. The dynamic surface tension for the synthesized surfactants was measured at CMC. The dynamic interfacial tension for these surfactants with jet fuel A1 at CMC was also measured using the spinning drop technique. The results showed that the effect of the synthesized surfactants on deceasing the time of droplet maturation was significant remarked. The decrease of this time leads to enhance of jet fuel atomization.     

Determination of critical micelle concentration by hyper-rayleigh scattering

The critical micelle concentration (CMC) of several surfactants that contain an NLO chromophore, either at the hydrocarbon tail, or at the hydrophilic headgroup, or even as a counterion, was determined by hyper-Rayleigh scattering (HRS). In all cases, the HRS signal exhibited a similar variation with surfactant concentration, wherein the CMC is inferred from a rather unprecedented drop in the signal intensity. This drop is attributed to the formation of small pre-micellar aggregates, whose concentrations become negligible above CMC. In addition, a probe molecule, which upon protonation yielded a species with significantly enhanced HRS intensity, was developed and its utility for the determination of the CMC of simple fatty acids was demonstrated.     

System peaks in micellar electrophoresis: I. Utilization of system peaks for determination of critical micelle concentration

A new way to determine the critical micelle concentration (CMC) based on the mobilities of system peaks is presented. A general approach for the CMC determination is based on the change of the slope or on finding the inflection point in the plot of a physical property of solution as a function of surfactant concentration. The determination of CMC by system peaks in CE utilizes a "jump" instead of a continuous change in the measured quantity. This phenomenon was predicted by the program PeakMaster, which was modified for simulation of micellar systems. The simulation of the steep change in mobilities of the anionic system peaks showing the CMC value was verified experimentally in a set of measurements, where the concentration of the surfactant was varied while the ionic strength was kept constant. The experimental work fully proved our model. A comparative electric current measurement was carried out. The proposed method seems to offer easier CMC determination as compared to the standard methods.     

Water-Based Oil Spill Dispersants Based on Rosin Formaldehyde Resins

Water-soluble surfactants based on rosin acids were synthesized from condensed rosin acid-formaldehyde. This was completed by esterification of series of rosin acid formaldehyde resins with poly(ethylene glycol) having different molecular weights to produce series of rosin esters. The structure of the produced resins was determined by infrared and ¹HNMR analysis. The molecular weight of the produced surfactants was determined by gel permeation chromatography (GPC) technique. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The surface tension, critical micelle concentration (CMC), and surface activities were determined at different temperatures. Surface parameters such as surface excess concentration (Γmax), the area per molecule at interface (A_min), and the effectiveness of surface tension reduction (πCMC) were determined from the adsorption isotherms of the prepared surfactants. Some thermodynamic data for the adsorption process were calculated and are discussed. The dispersion efficiency of the prepared surfactants as petroleum oil spill dispersants was determined and correlated with the surface activity, concentrations of the prepared surfactants and type of petroleum crude oil.     

Comprehensive study on critical micellar concentrations of SDS in acetonitrile–water solvents

The CMC is one of the fundamental characteristics of surfactants and its determination is crucial for detail understanding of micelles formation. In this study the CMC of SDS in presence of ACN was determined by two independent experimental techniques, capillary electrophoresis and fluorescence correlation spectroscopy (FCS). Yet, studies of SDS micellization in solutions containing ACN as organic modifier are sparse and inconsistent in literature. The measurements were performed for various ACN contents in the range of 0–50% v/v. At ACN contents of up to 10% v/v the CMC is lower when compared to the aqueous solution, while increasing ACN content causes a significant increase of the CMC. Formation of micelles was observed up to ACN concentrations of 35% v/v, which is in contrast to most of the reports in literature. Based on the results of the FCS experiments, we were able to confirm that presence of ACN causes a gradual increase of the size of the micelles with increasing concentration of SDS. Simultaneously, we proved that the classical conductivity approach for the determination of the CMC does not yield reliable results in the presence of higher content of an organic modifier such as ACN.     

Capillary electrophoresis-based methods for the determination of lipids--a review

Capillary electrophoresis (CE) is a high-resolution technique for the separation of complex biological and chemical mixtures. CE continues to emerge as a powerful tool in the determination of lipids. Here we review the analytical potential of CE for the determination of a wide range of lipids. The different classes of lipids are introduced, and the different modes of CE and optimization methods for the separation of lipids are described. The advantages and disadvantages of the different modes of CE compared to traditional methods like gas chromatography (GC) and liquid chromatography (LC) in the determination of lipids are discussed. Finally, the potential of CE in the determination of lipids in the future is illustrated.     

Determination of the aggregation threshold of non-UV-absorbing, neutral or charged surfactants by frontal- and vacancy-frontal analysis continuous capillary electrophoresis

Supplementing our recent work on UV-absorbing anionic surfactants, new protocols based on frontal analysis continuous capillary electrophoresis (FACCE) were developed for the investigation of the aggregation threshold of non-UV absorbing anionic, cationic and neutral surfactants, and exemplified with sodium dodecyl sulfate (SDS), tetradecyltrimethylammonium bromide (TTABr) and Brij 35. Contrary to UV-absorbing surfactants, the critical micelle concentration (CMC) determination of non-UV absorbing surfactants requires the use of a marker providing adequate detection capabilities. UV-absorbing markers were selected, according to the charge of the studied surfactant (neutral for SDS and TTABr, anionic for Brij 35). In all cases, the free marker concentration was quantified as a function of the total surfactant concentration. In addition, a modified implementation of FACCE, that we called vacancy FACCE (VFACCE), was employed for the case of the neutral surfactant. VFACCE entails first filling the capillary with the system components to be studied in the background electrolyte, next continuously introducing the plain BGE electrokinetically. The salient theoretical features of FACCE and VFACCE were compared. These new protocols were successfully applied to yield reliable CMC values within short operational time and with low sample consumption.     

Determination of critical micelle concentration with the rotating sample system

A novel experimental approach using the rotating sample system (RSS) is proposed here for the determination of the critical micelle concentration (CMC) of surfactants. The RSS has been conceived in our laboratory as a convection platform for physicochemical studies and analyses in microliter-sized sample drops. The scheme allows for vigorous rotation of the drop despite its small size through efficient air-liquid mechanical coupling. Thus, changes in surface properties of aqueous samples result in corresponding modulation of the hydrodynamic performance of the RSS, which can be utilized to investigate interfacial phenomena. In this work, we demonstrate that the RSS can be used to study the effects of surfactants on the surface and in the bulk of very small samples with hydrodynamic electrochemistry. Potassium ferrocyanide is employed here with cyclic voltammetry to probe the air-water interface of solutions containing Triton X-100. The CMC of this surfactant determined using this approach is 140 ppm, which agrees well with reported values obtained with conventional methods in much larger samples. The results also demonstrate that besides the CMC, variations in bulk rheological properties can also be investigated in very small specimens using the RSS with a simple method.     

Aggregation-induced emission of tetraphenylethene derivative as a fluorescence method for probing the assembling/disassembling of amphiphilic molecules

The aggregation-induced emission (AIE) of a 1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE) was explored as a novel fluorescence method for probing the assembling/disassembling of amphiphilic molecules. The fluorescence intensity was able to monitor the formation of micelles and determine the critical micelle concentration (CMC) of surfactants. The temperature-dependent micellization of the pharmaceutically important PEO-PPO-PEO copolymer, Pluronic F127, was further studied by using the TPE fluorescence spectrum intensity. Our results showed good agreement with those reported in the literature by using other methods. The special advantage of the AIE probe method was further explored to determine the assembling/disassembling process of the colored amphiphilic molecule, 1-[4-(3-phenylazophenoxy)butyl]triethylamine bromide (AzoC4), whose CMC value has not previously been described. Since the TPE fluorescence signal mainly comes from the aqueous phase, not from the inside of hydrophobic core, it provides a possible platform to study the CMC of those colored surfactants. Based on the novel fluorescence properties of TPE in the aggregated and dispersed states, one can conclude that the TPE method is a promising method for the determination of the CMC and critical micellization temperature (CMT), particularly having a special advantage to determine the assembling/disassembling process of colored amphiphilic molecules.     

Trace analysis of surfactants using chromatographic and electrophoretic techniques

Because of the widespread use, increased application of new formulations and immense impact on organisms and ecology surfactants are still in the focus of analytical chemistry. The development of methods with higher selectivity and lower detection limits is important to meet the requirements of greater responsibility for health of people and environment. Efficient separation methods, like HPLC, GC and CE, in combination with sensitive detection, like MS, are to be preferred over collective techniques which can suffer from interfering components. A review on trace analysis of ionic and neutral surfactants including sample preparation steps is presented, considering especially those methods which provide information about homologous and isomeric distribution of surfactant mixtures. Examples for the determination of linear alkylbenzene sulfonates in river water by HPLC and CE are discussed to show the capability of these methods for environmental analyses. As future trends increased applications of LC/MS (very high sensitivity) and also of CE (robustness and possibility for rapid method development) can be predicted.