Cetylpyridinium chloride micelles as a selective fluorescence quenching solvent media for discriminating between alternant versus nonalternant polycyclic aromatic hydrocarbons

Fluorescence behavior of 41 polycyclic aromatic hydrocarbons (PAHs) dissolved in aqueous micellar cetyltrimethylammonium chloride (CTAC) solvent media and in five different cetyltrimethylammonium chloride + cetylpyridinium chloride (CPC) surfactant mixtures is reported. Experimental fluorescence measurements reveal that CPC is a selective fluorescence quenching agent for alternant PAHs. The cetylpyridinium ion effectively quenched emission intensities of the 21 alternant PAHs studied. Emission intensities of nonalternant PAHs, with a few noted exceptions, were unaffected by the presence of CPC in the mixed cationic surfactant micelles.     

Spectroscopic study on the precipitation of sodium alkyl sulfate with cetylpyridinium chloride

The precipitation of sodium alkyl sulfate with cetylpyridinium chloride was obtained under optimized conditions. The conditions for the most efficient formation of precipitates were obtained as longer alkyl chain length of alkyl sulfate (C(14)), higher pH (pH 12), 1.5 M NaCl, and equimolar ratio between anionic and cationic surfactants. The structures and physical properties of surfactant precipitates were investigated with SEM, UV-vis, and FT-IR spectroscopy and light scattering. The precipitate of sodium alkyl sulfate with cetylpyridinium chloride was studied with the pressure-area isotherm at the air/water interface. In addition, the surface morphology of the Langmuir-Blodgett film of surfactant precipitate was observed with atomic force microscopy.     

Adsorption Isotherms of Cetylpyridinium Chloride with Iron III Salts at Air/Water and Silica/Water Interfaces

The interaction of iron III salts and cetylpyridinium chloride (CPC) has been studied at the air/water and silica/water interfaces. The surface tension of cetylpyridinium chloride has been determined in aqueous solutions in the presence of iron III chloride and iron III nitrate at two constant pH values, namely, 3.5 and 1.2. It is shown that the surface tension of the cationic surfactant depends upon the ionic strength of the solution through the pH adjustment in the presence of the former salt but not in the presence of the latter. The effect of iron III nitrate on the surface tension of CPC is similar to that of potassium nitrate, indicating that the iron III various-hydrolyzed species do not interfere with the composition of the air/water interface. The competitive adsorption of iron III nitrate salt and the cationic surfactant at a silica/water interface was next investigated. The adsorption isotherms were determined at pH 3.5. It is shown that although the iron III ions, which were added to the silica dispersion in the presence of the cetylpyridinium ions, were strongly bound to the anionic surface sites, the surfactant ions are not salted out in the solution but remain in close vicinity of the silica surface. Conversely as the cationic surfactant is added first to the silica dispersion in the presence of the adsorbed iron III ions, the metal ions and the surfactant ions are both coadsorbed onto the silica surface. It is suggested that iron III hydrolyzed or free cations and the cationic surfactant molecules may not compete for the same adsorption sites onto the silica surface.     

Interaction Parameters of Anhydrous Cationic Surfactant Mixtures by Inverse Gas Chromatography

The miscibility of anhydrous cationic surfactant dodecylpyridinium chloride (DPC) and hexadecylpyridinium bromide (cetylpyridinium bromide (CPB)) mixtures has been studied by using them as stationary phases in Inverse Gas Chromatography (IGC). The temperature zone of work was determined by IGC and Differential Scanning Calorimetry (DSC) techniques. Values of the interaction parameter between the surfactants obtained at four different compositions and at four temperatures showed that the miscibility depends on the overall composition and suggested that the interactions are more favorable near the center of the composition range. Results are compared with other anhydrous cationic surfactant mixtures studied by IGC, the system didodecyldimethylammonium bromide (DDAB) and dioctadecyldimethylammonium bromide (DODAB), two twin-tailed surfactants, and are interpreted in terms of the structure of the anhydrous lamellar liquid crystals compared with that of aqueous lamellar mesophases.     

Effect of micelles on the acid hydrolysis of N-phenylbenzohydroxamic acid

The effect of cationic (cetylpyridinium bromide and cetylpyridinium chloride) anionic (sodium dodecyl sulfate and lithium dodecyl sulfate) and non-ionic (Brij-35 and Triton-X-100) micelles on the acid-catalyzed hydrolysis of N-phenylbenzohydroxamic acid in 20 vol.% dioxane medium has been investigated. The kinetic results are explained by both pseudo-phase and Piszkiewicz cooperativity models.     

Micellar extraction of a tin complex of phenylfluorone into a cetylpyridinium chloride-based liquid phase

Optimal conditions have been found for the modification of compact liquid phases based on a cationic surfactant, cetylpyridinium chloride, with salicylic acid. On the example of the system tin-phenylfluorone we have shown the applicability of such phases to the preconcentration of multiply charged ions readily hydrolyzed metals. The influence of concentrations on the absorbance and composition of the complex has been studied; the optimal conditions of its extraction have been found. The developed spectrophotometric procedure of tin determination with phenylfluorone using micellar-extraction preconcentration has been tested for the analysis of canned vegetables and brines.     

Detection of cationic surfactants in oral rinses and a disinfectant formulation using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Three commercial oral rinses and one commercial disinfectant formulation were analyzed for the presence of cationic surfactants using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) in the positive ion mode. The product labels on these formulations indicate the presence of cetylpyridinium chloride, tetraalkylammonium or trialkylbenzylammonium chlorides. The resulting MALDI-TOF mass spectra only showed cetylpyridinium, tetraalkylammonium, and trialkylbenzylammonium ions, apparently due to the dissociation of the salts in the ion source. We confirmed the presence of cetylpyridinium salt in the three oral formulations, whereas the disinfectant formulation consisted of a complex mixture of the salts of dioctyldimethylammonium, didecyldimethylammonium, benzylmyristyldimethylammonium, decyloctyldimethylammonium, benzyldecyldimethylammonium, and benzylcetyldimethylammonium. This work demonstrates again the potential for using meso-tetrakis(pentafluorophenyl)porphyrin as a matrix in the MALDI-TOFMS analysis of low molecular weight compounds. This study also demonstrates that the mode of ionization of quaternary ammonium compounds (cationic surfactant salts) under MALDI conditions is by dissociation, leading to the detection of only the positively charged moieties.     

Structural Changes Induced in the Surfactant System C(12)E(4)/Benzyl Alcohol/Water by the Admixture of the Cationic Surfactant Cetylpyridinium Chloride

The influence of the addition of the cationic surfactant cetylpyridinium chloride (CPyCl) on the structure of the different phases of the ternary surfactant system C(12)E(4)/benzyl alcohol/water in the dilute region has been studied by means of small angle neutron scattering (SANS) and freeze-fracture microscopy (FF-TEM). In the ternary system various different subregions of the L(alpha)-phase were identified as a function of the concentration of the cosurfactant, benzyl alcohol. Addition of small amounts of CPyCl suppresses these different L(alpha)-phases in favor of the one composed of multilamellar vesicles. Addition of somewhat larger amounts (up to 2 mol% relative to the total surfactant concentration) destabilizes the formation of bilayer structures completely and leads to the formation of micellar solutions. This demonstrates that in this surfactant system the incorporation of very small amounts of cationic surfactant has a pronounced and systematic fluence on its phase behavior and its structures. Copyright 2001 Academic Press.     

Spectrophotometric study of anionic azo-dye light yellow (X6G) interaction with surfactants and its micellar solubilization in cationic surfactant micelles

Solubilization and interaction of azo-dye light yellow (X6G) at/with cationic surfactants cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC) was investigated spectrophotometricaly. The effect of cationic micelles on solubilization of anionic azo dye in aqueous micellar solutions of cationic surfactants was studied at pH 7 and 25 degrees C. The binding of dye to micelles implied a bathochromic shift in dye absorption spectra that indicates dye-surfactant interaction. The results showed that the solubility of dye increased with increasing surfactant concentration, as a consequence of the association between the dye and the micelles. The binding constants, K(b), were obtained from experimental absorption spectra. By using pseudo-phase model, the partition coefficients between the bulk water and surfactant micelles, K(x), were calculated. Gibbs energies of binding and distribution of dye between the bulk water and surfactant micelles were estimated. The results show favorable solubilization of dye in CTAB micelles.     

Effect of the micellar surfactant nanoreactors on the reactions of 2,4-dinitrophenylhydrazine with some aldehydes

By thermogravimetry, the IR and electronic spectroscopy physicochemical characteristics of systems including aromatic aldehydes, 2,4-dinitrophenylhydrazine, and a surfactant were investigated. Selective solubilization effect of the cationic surfactant (cetylpyridinium chloride) micelles on the aci-form of hydrazone arising in the alkaline medium was found. The universal character of solubilization by the cationic surfactant micelles in the aromatic aldehyde—2,4-dinitrophenylhydrazine systems was shown by an example of the benzaldehyde derivatives with substituents of different nature. This effect leads to the increase in solubility of the reaction products and the aggregative stability of solutions.     

Immobilization and recovery of au nanoparticles from anion exchange resin: resin-bound nanoparticle matrix as a catalyst for the reduction of 4-nitrophenol

The immobilization of gold nanoparticles in anion exchange resin and their quantitative retrieval by means of a cationic surfactant, cetylpyridinium chloride, is studied. The resin-bound gold nanoparticles (R-Au) have been used successfully as a solid-phase catalyst for the reduction of 4-nitrophenol by sodium borohydride. At the end of the reaction, the solid matrix remains activated and separated from the product. The recycling of catalyst particles after the quantitative reduction of 4-nitrophenol and the recovery of gold nanoparticles with unaffected particle morphology from the resin-bound gold nanoparticle entity have been reported.     

Resonance Rayleigh scattering for the determination of cationic surfactants with Eosin Y

Resonance Rayleigh scattering (RRS) of cationic surfactants–Eosin Y systems and their analytical application have been studied. In aqueous solution at pH 2～3, Eosin Y reacts with a monomer of cationic surfactants (CS), such as Zephiramine (Zeph), tetradecylpyridinium bromide (TPB), cetylpyridinium bromide (CPB), cetylpyridinium chloride (CPC) and cetyltrimethylammonium bromide (CTMAB), to form an ion associate and a new RRS spectrum appears. The spectral characteristics of the five ion associates are similar and their maximum scattering wavelengths (λ_max) are all at 313 nm. The intensity of RRS at λ_max of the ion associate is directly proportional to the concentration of CS in the range of 0～3.0 μg/25 mL. The technique has high sensitivity for the determination of CS; their detection limit is between 5.57 ng/mL and 7.60 ng/mL depending on the CS. In this case, most metal and non-metal ions, NH₄ ⁺ and some anionic surfactants do not interfere, so that the method has a good selectivity. It can be applied to the determination of trace amounts of cationic surfactants in water samples.     

Cetylpyridinium Chloride as a Regulator in Paper Separation of 2,4‐Dichlorophenol and 2,4,6‐Trichlorophenol in Water

2,4‐Dichlorophenol (2,4‐DCP) and 2,4,6‐trichlorophenol (2,4,6‐TCP) by the use of cetylpyridinium chloride (CPCl) as a regulator was studied for their separation by the paper capillary permeation adsorption (PCPA) separation technique. The effect of pH, the type of PCPA treatment, the concentration of cetylpyridinium chloride, and various inorganic salts on the separatability has been investigated. A nearly 100% separatability was obtained at pH values 5–11 and 5–11, respectively, for 2,4‐dichlorophenol and 2,4,6‐trichlorophenol when cetylpyridinium chloride was present. It was confirmed that 2,4‐dichlorophenol and 2,4,6‐trichlorophenol are separated by adsorption on the fiber surface as ion pairs at the pH. Addition of inorganic salts decreases the separatability.     

Application of sequential injection analysis to the determination of cationic surfactants based on the sensitized molybdenum-bromopyrogallol red reaction.

The aim of this work was to develop a simple, automatic system for the evaluation of cationic surfactants by combining sequential injection analysis and the sensitized effect of cationic surfactants on the reaction between metal ions and chelating dyes. This reaction is based on the increase in absorbance of the complex formed among molybdenum, bromopyrogallol red and increasing concentrations of cationic surfactants. Under optimum conditions, two calibration plots were obtained for a concentration range between 2.50 x 10(-7) mol dm(-3) (detection limit) and 5.00 x 10(-4) mol dm(-3) of cetylpyridinium chloride, used as standard. Solubilization of water insoluble complexes formed for concentrations of cationic surfactants greater than 1.00 x 10(-4) mol dm(-3) were successfully achieved with Triton X-405. RSD values lower than 5.0% were obtained in all cases. The quality of the results obtained for 18 water samples were evaluated by comparison with conventional methods, with no statistically significant differences for a 95% confidence level.     

Study of interaction in the system copper(II)-3-(2-hydroxy-3-sulfo-5-nitrophenylazo)pentadion-2,4-cationic surface-active substances

Interaction in the system of 3-(2-hydroxy-3-sulfo-5-nitrophenylazo)pentadion-2,4 (H₂L) and cationic surface-active substances (CSASs: cetylpyridinium chloride (CPCl), cetylpyridinium bromide (CPBr), and cetyltrimethylammonium bromide (CTABr)) is studied in the presence and absence of copper(II). It is found that, as the stability of associates increases (H₂L-CPCl > H₂L-CPBr > H₂L-CTABr), the detection limit of copper(II) in the reaction of complexation with H₂L-CSAS decreases and the stability constants of their complexes grow in the order Cu(HL)₂-CPCl > Cu(HL)₂-CPBr > Cu(HL)₂-CTABr. The effect of foreign ions and masking substances on the complexation is studied. A procedure for the photometric determination of copper(II) in igneous rock is developed.     

Combination of micellar and chemical catalysis as a means of enhancing the sensitivity of catalytic kinetic determinations

The combined effects of micellar and chemical catalysis were studied to improve the features of catalytic kinetic determinations. The bromate oxidative coupling reaction of p-phenetidine with catechol, catalysed by vanadium(V), was studied in the presence and absence of micelles of cetylpyridinium chloride (CPC). This cationic surfactant increased the reaction rate, which in turn resulted in an increase in the sensitivity by an order of magnitude in the kinetic determination of vanadium(V). A detailed study of the kinetics of both reactions is reported. The mechanism by which CPC and vanadium(V) exert their action was elucidated and the role of micellar media in catalytic kinetic methods is discussed.     

Micellar extraction preconcentration of barium with phases of nonionic surfactants at the cloud point

The micellar extraction of barium with phases of nonionic surfactant Triton X-100 was studied in the presence of aliphatic monocarboxylic acids, crown ethers, and Carboxyarsenazo and its mixtures with cetylpyridinium chloride and octylamine. It was shown that the complete extraction of barium into the micellar phase was attained using Carboxyarsenazo and cationic surfactants in the presence of octylamine through the formation of a ternary hydrophobic complex. The conditions for the determination of the atomic absorption of barium in water with preconcentration into the nonionic surfactant phase at the cloud point temperature were developed.     

Amperometric method for determining the degree of complexation of polyelectrolytes with cationic surfactants

The complexation of sodium polystyrene sulfonate with monovalent cationic surfactants at a microsized liquid/liquid interface has been studied using electrochemistry. The method is based on measurement of surfactant ion transfer across the interface between two immiscible electrolyte solutions (ITIES). The complexation of various cationic surfactants (alkylpyridinium- and trimethylammonium-) with oligosized polystyrene sulfonate was measured. Binding isotherms were used to determine the degree of binding as a function of the surfactant chain length and type of head group. It was found that the hydrophobicity of the surfactant was the predominant factor. The effect of the polyelectrolyte chain length on the binding mechanism was studied using cetylpyridinium chloride as a complexing agent. It was found that binding affinity, as well as cooperativity of the binding process, decreases with decreasing polyelectrolyte chain length. Thermodynamics of surfactant binding was measured using titration microcalorimetry. The thermodynamic data obtained show that the enthalpy of surfactant binding is not dependent on polymer chain length, but an increase in chain length makes the binding process entropically more favorable.     

Studies of mixed micelle formation between cationic gemini and cationic conventional surfactants

Mixed micellization of dimeric cationic surfactants tetramethylene-1,4-bis(hexadecyldimethylammonium bromide)(16-4-16), hexamethylene-1,6-bis(hexadecyldimethylammonium bromide) (16-6-16) with monomeric cationic surfactants hexadecyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB), cetylpyridinium chloride (CPC), and tetradecyltrimethylammonium bromide (TTAB) have been studied by conductivity and steady-state fluorescence quenching techniques. The behavior of mixed systems, their compositions, and activities of the components have been analyzed in the light of Rubingh's regular solution theory. The results indicate synergism in the binary mixtures. Ideal and experimental critical micelle concentrations (i.e., cmc(*) and cmc) show nonideality, which is confirmed by beta values and activity coefficients. The micelle aggregation numbers (N(agg)), evaluated using steady-state fluorescence quenching at a total concentration of 2 mM for CTAB/16-4-16 or 16-6-16 and 5 mM for TTAB/16-4-16 or 16-6-16 systems, indicate that the contribution of conventional surfactants was always more than that of the geminis. The micropolarity, dielectric constant and binding constants (K(sv)) of mixed systems have also been evaluated from the ratios of respective peak intensities (I(1)/I(3) or I(0)/I(1)).     

Effect of cationic micelles on the formation of the complex oxalate-Alizarin Red S-Zr(IV) Application to the sensitive fluorescence determination of oxalate ion

The effect of several surfactants on the formation of the fluorescent ternary complex oxalate-Alizarin Red S-zirconium(IV) has been studied. In weakly acidic medium and in the presence of cationic surfactants, such as cetylpyridinium chloride, total complex formation is achieved, whereas in aqueous medium or in the presence of non-cationic micelles no significant changes are obtained in comparison with the formation of the non-fluorescent binary complex Alizarin Red S-zirconium(IV). The fluorescence characteristics of this system allowed the establishment of a simple and very sensitive method for the spectrofluorimetric determination of oxalate. The ternary complex formed exhibits its highest fluorescence signal at 605 nm with excitation at 490 nm. In these conditions, the method presents a IUPAC detection limit of 4.4 ng ml(-1). The procedure has been satisfactorily applied to a biological fluid and a vegetal tissue.