Effect of Surfactants and Ionic Strength on Dissociation of Hydrochlorides of Phenothiazine Derivatives

Abstract

A study of the effect of the anionic surfactant dodecyl sulfate, the cationic surfactant carbethoxypentadecyl trimethyl ammonium bromide (Septonex), nonionic surfactant p-octyl phenyl polyoxyethylene (Triton X-100), and a strong electrolyte (KBr) on the dissociation of the hydrochlorides of two derivatives of phenothiazine (diethazine and fluphenazine) was made. It was found that sodium dodecyl sulfate increases the pKa value, whereas Septonex and Triton X-100 decrease this value. The presence of KBr suppresses the effect of the surfactants. A new method for the potentiometric determination of fluphenazine in an aqueous medium was proposed.     

Effect of surfactants on the determination of nitrite and nitrate in water samples

Summary The effect of four surfactants on the determination of nitrite and nitrate has been examined. The method which has been tested for nitrite is based on the formation of an azodye. The results show that cationic and non-ionic surfactants do not interfere with the determination of nitrite while anionic surfactants cause significant interferences, which could be eliminated by treating the water samples with a cationic surfactant.Two methods have been tested for the determination of nitrate in the presence of surfactants. One method is based on the nitration of salicyclic acid, while the other is based on the reduction of nitrate to nitrite. Results for the first method show that the non-ionic surfactant Triton-X causes significant interferences. Cationic and anionic surfactants do not interfere, when their concentration is relatively low. For higher concentrations an increasing interference is observed. Results for the second method show effects similar to those obtained for nitrite.

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Wirkung oberflächenaktiver Substanzen auf die Bestimmung von Nitrit und Nitrat in Wasserproben

     

Paper-substrate room-temperature phosphorescence of phenothiazine derivatives enhanced by thallium(I) nitrate and surface-active agents

The effects of anionic, non-ionic, and cationic surfactants and thallium(I) nitrate on the paper-substrate room-temperature phosphorescence (RTP) of eleven phenothiazine derivatives are described. Enhancement factors within the range 1.5–10 are observed after addition of sodium dodecylsulfate, dodecyltrimethylammonium chloride and thallium(I) nitrate. The influence of surfactant on phosphor characteristics as well as effects of moisture are discussed. Limits of detection were in the range 0.2–2 ng. Results are also reported for p-aminobenzoic acid, carbazole and o-terphenyl.     

The effect of anionic and cationic surfactants on indicators and measurement of dissociation constants with two different methods

The effects of cationic cetyltrimethylammonium bromide (CTAB), hexadecylpyridinum chloride (HDPC) and anionic sodium dodecylsulphate (SDS) surfactants on dissociation constants and transition intervals of methyl red, methyl orange and cresol red were studied spectrophotometrically. The results show that all studied indicators strongly interacted with cationic micelles (CTAB and HDPC). In the case of methyl red, relatively strong interaction with anionic surfactant (SDS) was obtained. However, no effect of SDS on dissociation constants of cresol red and methyl orange was observed. The dissociation constants of indicators were calculated with both the proposed and known chemometric (DATAN) method with a reasonable agreement on the data achieved.     

The effect of surfactants on the pH transition interval of bromothymol blue immobilized on XAD 4

Cationic, anionic and non-ionic surfactants adsorb readily from aqueous solution on to Amberlite XAD 4. The ionic surfactants cause the pH of the solution in contact with the resin to differ from that in the bulk of solution, cationic surfactants increasing the interfacial pH and anionic surfactants decreasing it. This causes a shift in the pH transition interval of a co-adsorbed pH indicator when measured with respect to the bulk solution. The quantity of ionic surfactant adsorbed tends to a constant value (presumably monolayer coverage) with increasing solution concentration, this amount being a function of the individual surfactant, whereas non-ionic surfactants readily form multilayers. Significant adsorption occurs when the surfactant possesses at least 14 carbon atoms.     

A review on experimental studies of surfactant adsorption at the hydrophilic solid-water interface

The progresses of understanding of the surfactant adsorption at the hydrophilic solid-liquid interface from extensive experimental studies are reviewed here. In this respect the kinetic and equilibrium studies involves anionic, cationic, non-ionic and mixed surfactants at the solid surface from the solution. Kinetics and equilibrium adsorption of surfactants at the solid-liquid interface depend on the nature of surfactants and the nature of the solid surface. Studies have been reported on adsorption kinetics at the solid-liquid interface primarily on the adsorption of non-ionic surfactant on silica and limited studies on cationic surfactant on silica and anionic surfactant on cotton and cellulose. The typical isotherm of surfactants in general, can be subdivided into four regions. Four-regime isotherm was mainly observed for adsorption of ionic surfactant on oppositely charged solid surface and adsorption of non-ionic surfactant on silica surface. Region IV of the adsorption isotherm is commonly a plateau region above the CMC, it may also show a maximum above the CMC. Isotherms of four different regions are discussed in detail. Influences of different parameters such as molecular structure, temperature, salt concentration that are very important in surfactant adsorption are reviewed here. Atomic force microscopy study of different surfactants show the self-assembly and mechanism of adsorption at the solid-liquid interface. Adsorption behaviour and mechanism of different mixed surfactant systems such as anionic-cationic, anionic-non-ionic and cationic-non-ionic are reviewed. Mixture of surface-active materials can show synergistic interactions, which can be manifested as enhanced surface activity, spreading, foaming, detergency and many other phenomena.     

Role of surfactants in clouding phenomenon of imipramine hydrochloride

The clouding behavior of tricyclic antidepressant drug imipramine hydrochloride (IMP) in aqueous solution has been studied in presence of surfactants. A pH increase in the presence as well as in the absence of surfactants decreased the CP. Drug molecules become neutral at high pH and therefore head–head repulsion decreases which lead to CP decrease. Addition of non-ionic and cationic surfactants increased the CP whereas anionic surfactants showed a peaked profile. Effect of CTAB/TX-100 at different fixed drug concentrations showed that at all surfactant concentrations the CP value was higher for higher drug concentrations. However, variation of pH produced opposite effect: CP at all CTAB/TX-100 concentrations decreased with increasing pH. All results are interpreted in terms of increase in hydrophobicity or hydrophilicity of micelles on addition of surfactants.     

Micelle-sequestered dissociation of cationic DNA-intercalated drugs: unexpected surfactant-induced rate enhancement

Detergent sequestration using micelles as a hydrophobic sink for dissociated drug molecules is an established technique for determination of dissociation rates. The anionic surfactant molecules are generally assumed not to interact with the anionic DNA and thereby not to affect the rate of dissociation. By contrast, we here demonstrate that the surfactant molecules sodium dodecyl sulfate (SDS), sodium decyl sulfate, and sodium octyl sulfate all induce substantial rate enhancements of the dissociation of intercalators from DNA. Four different cationic DNA intercalators are studied with respect to surfactant-induced dissociation. Except for the smallest intercalator, ethidium, the dissociation rate constants increase monotonically with surfactant concentration both below cmc and (more strongly) above cmc, much more than expected from electrostatic effects of increased counterion concentration. The rate enhancement, most pronounced for the bulky, multicationic, hydrophobic DNA ligands in this study, indicates a reduction of the activation energy for the ligand to pass out from a deeply penetrating intercalation site of DNA. The discovery that surfactants enhance the rate of dissociation of cationic DNA-intercalators implies that rate constants previously determined by micelle-sequestered dissociation may have been overestimated. As an alternative, more reliable method, we suggest instead the addition of excess of dummy DNA as an absorbent for dissociated ligand.     

Rheological properties of the aqueous solution for fluorocarbon‐containing hydrophobically modified sodium polyacrylic acid with various surfactants

The interaction of fluorocarbon‐ containing hydrophobically modified sodium polyacrylic acid (FMPAANa) (0.5 wt%) with various surfactants (anionic, nonionic and cationic) has been investigated by rheological measurements. Different rheological behaviors are displayed for ionic surfactants and nonionic surfactants. Fluorinated surfactants have stronger affinity with polyelectrolyte hydrophobes comparing with hydrogenated surfactants. The hydrophobic association of FMPAANa with a cationic surfactant (CTAB) and a fluorinated nonionic surfactant (FC171) is much stronger than with a nonionic surfactant (NP7. 5) and an anionic surfactant (FC143). Further investigation of the effects of temperature on solution properties shows that the dissociation energy E_m is correlated to the strength of the aggregated junctions.     

Effect of surfactants on the polymerization of acrylamide in aqueous solutions

The polymerization of acrylamide in aqueous surfactant solutions, initiated by potassium persulfate, has been investigated, dilatometry being used to follow the conversion. It has been shown that below the critical micellar concentration (CMC), cationic, anionic and non-ionic surfactants have no effect, while above the CMC only cationic soaps have an effect, lowering both the rate of polymerization and the molecular weight of the resultant polymer.     

Spectrophotometric study of interaction and solubilization of procaine hydrochloride in micellar systems

The interaction of Procaine hydrochloride (PC) with cationic, anionic and non-ionic surfactants; cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and triton X-100, were investigated. The effect of ionic and non-ionic micelles on solubilization of Procaine in aqueous micellar solution of SDS, CTAB and triton X-100 were studied at pH 6.8 and 29°C using absorption spectrophotometry. By using pseudo-phase model, the partition coefficient between the bulk water and micelles, K_x, was calculated. The results showed that the micelles of CTAB enhanced the solubility of Procaine higher than SDS micelles (K_x = 96 and 166 for SDS and CTAB micelles, respectively) but triton X-100 did not enhanced the solubility of drug because of weak interaction with Procaine. From the resulting binding constant for Procaine-ionic surfactants interactions (K_b = 175 and 128 for SDS and CTAB surfactants, respectively), it was concluded that both electrostatic and hydrophobic interactions affect the interaction of surfactants with cationic procaine. Electrostatic interactions have a great role in the binding and consequently distribution of Procaine in micelle/water phases. These interactions for anionic surfactant (SDS) are higher than for cationic surfactant (CTAB). Gibbs free energy of binding and distribution of procaine between the bulk water and studied surfactant micelles were calculated.      

Enhanced skin permeation of cationic drug ketotifen through excised guinea pig dorsal skin by surfactants with different electric charges

Using excised guinea pig dorsal skin, we examined the effects of three surfactants, anionic sodium dodecylsulfate (SDS), cationic n-dodecyltrimethylammonium bromide and non-ionic n-dodecyl-beta-D-maltoside, all of which commonly have an n-dodecyl group, on in vitro skin permeation of the cationic drug ketotifen. All these three surfactants increased the skin permeation of ketotifen. Among the surfactants tested, anionic SDS had the largest enhancement effects, and significantly increased the permeation at concentrations over 1 mM. The enhancement effect of the same anionic surfactant on the permeation of anionic salicylate was smaller and similar to that of cationic n-dodecyltrimethylammonium. The enhancement effects of SDS on ketotifen permeation were more marked than those of the cationic surfactant but differed from previous findings of their effects on other drugs permeation. Analysis of the retention of ketotifen in the skin suggested that SDS-induced increase in the transfer of hydrophilic ketotifen to the skin is the main reason for the marked increase in skin permeation.     

Characterization of nano-cerias synthesized in microemulsions by N2 sorptiometry and electron microscopy

A surfactant-stabilized microemulsion method was used to prepare nano-sized particles (<10 nm) of cubic-CeO2 exposing surfaces of not only highest specific areas (142-201 m(2)/g) ever reported for polycrystalline ceria, but also high thermal stability at 800 degrees C. Three different surfactants, a non-ionic, an anionic and a cationic, were used to form the microemulsions. Then, N2 sorptiometry and pore volume distribution calculations, were used to reveal microporous and mesoporous structures of these cerias as a function of surfactant type. Transmission electron microscopy was used to visualize consequent particle behaviors. Suggestions have been made as to the textural attributes of the high surface area and thermal stability. Accordingly, cationic surfactants, in the presence or absence of added non-ionic surfactant, are seen to assist in producing cerias of promising surface textural properties for the chemical makeup of combustion catalysts.     

Determination of poly(oxyethylene) non-ionic surfactants by two-phase titration

The solvent extraction of non-ionic surfactants with sodium hydroxide and tetraphenylborate has been studied, and a method developed for the determination of non-ionic surfactants by two-phase titration. A hydrophobic indicator system was used. The method is valid only when the concentration of anionic surfactant in the sample solution is lower than 1 x 10(-4)M.     

Counterion binding on mixed anionic/cationic micelles

Measurements of counterion binding in mixtures of surfactant aqueous solutions have been performed to study the structure of the anionic/cationic mixed micelle/solution interface. The mixtures studied were SDS/DDAC and STS/TDPC. The binding of chloride and sodium ions to mixed anionic/cationic micelles was measured using ion-specific electrodes. Counterion binding was found to be strongly dependent on the molar ratio of surfactants present. The mixed micelle/solution interface includes the headgroups of both surfactants and counterions of surfactant in excess. The addition of oppositely charged surfactant caused an increasing dissociation of counterions.     

Fluorescence drainage profiles of thin liquid films

Fluorescence drainage-profiles of thin liquid films formed from Rhodamine solutions containing anionic, cationic and non-ionic surfactants have been investigated. It is found that the influence of system variables such as electrolyte concentration, dye concentration, film environment and solution viscosity can be evaluated by means of the profiles. The addition of sodium chloride leads to the expansion (non-ionic surfactant), or contraction (anionic surfactant) of the profiles. In the case of the cationic surfactant, it reduces the number of fringes in the profiles. The height of selected fringes changes linearly with dye concentration, and no fringes are observed when the films are submerged in non-polar solvents. The influence of solution viscosity on film thickness and drainage rate is demonstrated by the number and frequency of fringes in the profile. The formation of first and second "black films" from solutions containing varying concentrations of sodium chloride can be shown.     

阴阳离子表面活性剂体系超低油水界面张力的应用

通过阴阳离子表面活性剂复配,在实际油水体系中获得了超低界面张力.通过在阴离子表面活性剂分子结构中加入乙氧基(EO)链段,以及采用阴阳离子加非离子型表面活性剂的三组分策略,有效解决了混合表面活性剂在水溶液中溶解度问题.进而研究了阳离子表面活性剂结构、非离子表面活性剂结构、三者组分配比、表面活性剂总浓度等因素对油水界面张力的影响,从而在胜利油田多个实际油水体系中获得了较大比例范围和较低浓度区域的油水超低界面张力,部分体系甚至达到了10-4 mN·m-1.由于阴阳离子表面活性剂间强烈的静电吸引作用,相关体系具有很好的抗吸附能力.经过石英砂48 h吸附后,体系仍然具有很好的超低界面张力.     

酞菁化合物光敏化氧化-还原反应的研究——Ⅲ.在胶束体系中光敏化还原甲基紫精的研究

本文报道我们合成的几种锌酞菁衍生物在胶束体系中,在电子给体EDTA的存在下,光敏化还原甲基紫精(MV²⁺)的研究.结果表明,锌酞菁及其衍生物在阳离子表面活性剂的胶束体系中,其敏化效果比在中性或阴离子表面活性剂的胶束体系中更为有效.结构不同的锌酞菁衍生物的敏化效果亦有显著的差异,其中锌酞菁磺酰丁胺敏化效果最好,锌酞菁羧酸次之.用它们作敏化剂时,MV²⁺形成的量子产率一般高达0.4—0.7,比没有取代基的锌酞菁的敏化效果高.     

AGGREGATION CHARACTERISTICS OF LASER DYE RHODAMINE 6G IN AQUEOUS SURFACTANT SOLUTIONS

Abstract— –The role of surfactants as deaggregating agents for the laser dyes is investigated by spectrophotometry using Rhodamine 6G as a representative. A method to estimate the fraction of dye present as monomer, dimer and as a monomer-surfactant (monomer or micelle) complex is described. It is shown that among the surfactants, cetyl trimethyl ammonium bromide, Triton X-100, sodium lauryl sulfate (SLS) and potassium oleate, the anionic ones are the most effective in suppressing the aggregation of Rhodamine 6G. While the non-ionic surfactant is found to be effective only above its critical micellar concentration, the cationic surfactant has no effect on aggregation. The optimum concentration of SLS needed for suppression of dye-dimers is estimated.     

Disassembly of conjugated polyelectrolyte aggregates and their application for colorimetric detection of surfactants in water

A colorimetric strategy based on conjugated polyelectrolyte aggregates has been applied to determine and distinguish anionic, cationic and non-ionic surfactants.