Modification of reversed-phase separations of small molecules using non-ionic surfactants and mixed ionic-non-ionic surfactants

The effects of non-ionic surfactants, Tween 20 and Tween 60, on reversed-phase separations of small molecules have been examined. Tween compounds were found to partition irreversibly into the ODS material used, markedly decreasing capacity factors for the compounds tested. Compounds which could hydrogen bond were less affected. Ion pairing using either anionic or cationic surfactants was possible in the presence of the non-ionic surfactants. While reversed-phase effects predominate under these conditions, secondary effects on retention order were observed and attributed to hydrogen bonding. Primary amines were retained longer than the corresponding secondary amine while catechols were retained longer than the corresponding methoxyphenols.     

Studies on the electrocapillary curves of anionic surfactants in presence of non-ionic surfactants

Polyoxyethylated non-ionic surfactants such as Tween 20, Tween 40, Nonidet P40 and Nonex 501 have been supposed to be associated with cationic characteristics. Studies on the effect of these surfactants on the electrocapillary curves of the anionic surfactants Aerosol IB, Manaxol OT and sodium lauryl sulphate (SLS), show that the electrocapillary maxima shift towards positive potentials. The order of adsorption of the anionic surfactants is SLS > Manaxol OT > Aerosol IB while the shift in maxima is in the order Aerosol IB ~ Manaxol OT > SLS which confirms association of cationic characteristics with the micelles of these non-ionic surfactants. The magnitude of the shift in electrocapillary maxima is Nonex 501 > Nonidet P40 > Tween 20 > Tween 40 which may be the order of magnitude of the positive charge carried by these non-ionic surfactants.     

Adsorption of surfactants on low-charged layer silicates Part II: Adsorption of non-ionic surfactants

Nonionic surfactants were adsorbed on low-charged layer silicates in the interlayers. After drying, the surfactants were arranged in densely packed double layers. However, in suspension considerably higher basal spacings are measured by x-ray diffraction which indicate that large quantities of non-ionic surfactants are adsorbed. With the aid of calorimetry, enthalpies of displacement were recorded which suggest strong interactions of the non-ionic surfactants with smectites. In analogy to tests on hydrophilic SiO₂, the adsorption of smectites is found to depend on the degree of ethoxylation of the non-ionic surfactant. The adsorption declines with increasing EO content.List of symbols n ^s adsorbed amount of surfactants (mmol/g) - n _max ^s maximal adsorbed amount of surfactants - d _L basal spacing (nm) - d _L interlayer separation because of adsorption - V _M molar volume of surfactant - V _max ^s volume of adsorbed surfactants (cm³/g) - V _int volume between the silicate layers (interlayer volume) (cm³/g) - H enthalpy of displacement (J/g) - h _max max. molar enthalpy of displacement (kJ/mol) Part I: Prog. Colloid Polymer Sci. 84, 206This paper is part of W. Röhl's doctorial dissertation at the Heinrich-Heine University, Düsseldorf     

Cobalt-catalyzed synthesis of α-arylpropionic and diarylacetic acids

The cobalt-catalyzed carbonylation of ArCH(R)X (R = CH₃, C₆H₅; X = Cl, Br) in alcoholic solvents under atmospheric pressure of CO is reported. Selective, high yield syntheses of the corresponding acids ArCH(R)COOH can be achieved within a very narrow range of experimental conditions by controlling kinetically the reversible interconversion of intermediate aryl and alkylcobalt complexes. The important roles of the base and of the alcoholic medium are briefly discussed.     

Extractive spectrophotometric determination of non-ionic surfactants in water

The solvent extraction of non-ionic surfactants with potassium chloride and tetrabromophenolphthalein ethyl ester potassium salt has been studied, and a method developed for determining trace amounts of non-ionic surfactants in water spectrophotometrically. Various non-ionic surfactants of general type RO(CH(2)CH(2)O)(n)H (where R is an alkyl or alkylphenyl group and n is the number-average degree of polymerization) are extracted quantitatively into o-dichlorobenzene from the water sample, and reacted in the organic phase with tetrabromophenolphthalein ethyl ester potassium salt to give a coloured product, the absorbance of which is measured at 620 nm.     

Photoreactivity of the nonsteroidal anti-inflammatory 2-arylpropionic acids with photosensitizing side effects.

The photoreactivity of the nonsteroidal anti-inflammatory 2-arylpropionic acids benoxaprofen, carprofen, naproxen, ketoprofen, tiaprofenic acid, and suprofen is reviewed with special emphasis on fundamental photophysical and photochemical properties. The absorption and emission properties of the excited states of these drugs as well as their main photodegradation routes are summarized. The photochemical mechanisms are discussed on the basis of product studies and detection of short-lived intermediates by means of laser flash photolysis. After dealing with the unimolecular processes, attention is focused on the photosensitized reactions of key biomolecules, such as lipids, proteins or nucleic acids. Finally, a short section on the photobiological effects on simple biological models is also included. Although some earlier citations are included, the literature coverage is in general limited to the last decade.     

Study on dynamics characteristics of wet air oxidation of non-ionic surfactants

Wet air oxidation is an effective method to deal with highly concentrated nondegradable emulsification wastewater which contains non-ionic surfactants. This article illustrates our investigation on dynamic characteristics of wet air oxidation of typical non-ionic surfactants like polyether, phenol ether and widely used alcohol ether. The experimental results indicated that the oxidation rate of polyether, phenol ether and alcohol ether obviously ascended as the temperature rose. A good oxidation effect was available at 240℃. The TOC removal rate could reach 88.0%, 94% and 91.5%, after 125 min reaction. Alcohol ether was prone to an easier oxidation compared with polyether and phenol ether when the temperature was 220℃ or below. The oxidation rate of alcohol ether was higher than that of polyether at 160℃, while the oxidation rate of polyether was higher than that of phenol ether between 180℃ and 220℃. During the later period of the reaction at 240℃, the rate of phenol ether was higher than that of alcohol ether, which was still higher than that of polyether. Partitioned first order kinetics model analy-sis showed that the apparent activation energy of alcohol ether was lower than that of both polyether and phenol ether in the leading stage and lagging stage, and it was easy to acquire a higher oxidation rate for alcohol ether at low temperature. Three parameter general dynamics model analyses showed that the reason why the oxidation rate of polyether was lower than that of alcohol ether was that the oxidation of polyether was more apt to be converted to intermediate production than that of alcohol ether, whereas between 200℃ and 220℃, the direct oxidation rate of polyether and the oxidation rate of intermediate product were obviously lower than that of alcohol ether. The apparent activation energy of direct and indirect oxidation of polyether was 43.37 and 60.45 kJ?mol?1, respectively, while the corre-sponding apparent activation energy of alcohol was 38.74 and 58.09 kJ·mol?1, respectively.     

A radiometric method for the determination of non-ionic surfactants

A radiometric method for the determination of non-ionic surfactants of ethylene oxide type has been elaborated. The principle of the method is the formation of an associate¹³³Ba-non-ionic surfactant — dicarbolide and its extraction into a mixture nitrobenzene-chloroform /41/. The extracted activity of¹³³Ba is proportional to the non-ionic surfactant concentration in the sample. The factors influencing the determination of non-ionic surfactants in the real waste solution after washing have been studied. The possibility of the determination of non-ionic surfactants by the calibration graph method and by the method of standard addition was verified.     

The partition of ethoxylated non-ionic surfactants between two non-miscible phases

The partition of a polydispersed ethoxylated non-ionic surfactant in equilibrated oil–water systems has been studied at 25 °C. The model surfactant used was a commercial sample of nonylphenol ethoxylated with 10 moles of ethylene oxide (NPEO₁₀). The partition isotherms over the range of surfactant concentration including the critical micelle concentration (CMC) were made with n-hexane, i-octane and n-decane as oil phases. Each partition isotherm exhibits a change of slope that matched the CMC value of surfactant determined by surface tension measurements on aqueous solutions. During the partition of NPEO₁₀ in the oil–water systems, the oligomer distribution in the oil and water phases changed because of fractionation. Below CMC, the mean ethoxylation degree in the oil phase was smaller, whereas in water it was higher than the mean initial value of the surfactant. Moreover, the mean ethoxylation degree in both oil and water phase was practically independent of surfactant concentration. Above CMC, the mean distribution of ethoxymers decreased in both phases. This was ascribed to the competition between micelles from water and the oil phase for the more hydrophobic species of the surfactant. The mean distribution of ethoxymers in the aqueous phase asymptoted to a value that was the mean of the surfactant itself, whereas it steeply decreased in the organic phase.     

Combination of cyclodextrins and polymeric surfactants for chiral separations

A cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) method was applied to the enantioseparation of three binaphthyl derivatives using neutral CDs (i.e., beta- and gamma-CD) in combination with various chiral amino acid-based polymeric surfactants (PSs). Both the D- and L-configurations of poly(sodium N-undecanoyl alaninate), poly(sodium N-undecanoyl leucinate), and poly(sodium N-undecanoyl valinate) (poly(L-SUV)) were synthesized. The retention behavior of the three binaphthyl derivatives under optimum electrophoretic conditions using a single chiral additive (PS or CD) is discussed. In addition, the effect of CD cavity size and stereochemical configuration of polymeric surfactants on selectivity (alpha) and resolution (Rs) was investigated. The enantioseparation of (+/-)1,1'-binaphthyl-2,2'-diamine gave a reversal of enantiomeric order when using beta-CD in combination with any of the three D-configuration PS. However, better enantioseparation is obtained when using the corresponding L-configuration PS with beta-CD. A reversal of migration order (RMO) for the enantiomers of (+/-)1,1'-bi-2-naphthol was observed upon the addition of 10 mM gamma-CD to poly(L-SUV). However, no RMO of (+/-)1,1'-bi-2-naphthol was seen when either beta-CD or gamma-CD was combined with D-PS. The enantiomers of (+/-)1,1'-binaphthyl-2,2'-diyl hydrogen phosphate showed little enantioselective behavior toward the PS alone. However, combined D- or L-PS and beta-CD or gamma-CD systems gave increased Rs and alpha values. The chiral recognition of binaphthyl derivatives observed resulting from the various combinations of two chiral selectors is discussed.     

HPLC determination of non-ionic surfactants used in tertiary oil recovery

Summary Having developed a chromatographic technique with a diol bonded phase for the study of the distribution versus ethylene oxide number (E.O.) for various non-ionic polyoxyethylated surfactants used in enhanced oil recovery (KL 6, ; KM 11, and KM 20, ) we report here the titration of one of these surfactants (KL 6) in the presence of an ionic surfactant (S 385, sulfonated petroleum fraction) and other non-ionic surfactants (KM 11 and/or KM 20) which are the conditions found in enhanced oil recovery. This work has been carried out in brine and in n-decane, as a model for the petroleum phase. Obviously in the case of aqueous phases it was necessary to carry out a thorough dehydration before the chromatographic analyses. We have shown that it is possible, under these conditions, to determine the KL 6 surfactant in the concentration range 500 to 6000 ppm with a precision of 70 ppm without experiencing interference from KM 11 or KM 20 non-ionic surfactants or S 385 ionic surfactant. Furthermore, from some of the samples studied which were in contact with the rock shale, we showed that strong adsorption of the KL 6 occurs. Chromatographic analyses show that this surfactant is only desorbed from the rock shale when employing a non-ionic surfactant such as KM 25 which is much more polar than the KL 6.     

Adsorptive removal of non-ionic surfactants from water using granite sand

The adsorption of Triton X-100 in aqueous solution on the granite sand has been investigated to evaluate its ability as an adsorbent. Various parameters such as agitation time, adsorbent dose, adsorbent size, initial concentration of adsorbate, pH, temperature, and effect of interference ions were studied on the laboratory scale to establish optimum conditions for the removal of TX-100 from the effluents of different industries. Isotherm data were analyzed for possible agreement with the Langmuir and Frendlich adsorption isotherm equations. The first order rate equation by Lagergren was tested on the kinetic data. The rate of adsorption was conformed a pseudo first order kinetics with good correlation coefficient. The value of activation energy of sorption (E_a) was obtained as 44.6 kJ mol^?1. Results showed that granite sand exhibit reasonably good surfactant removals for nonionic types. The possible role of the adsorbent in a chromatographic column was also worked out.     

Determination of non-ionic and anionic surfactants in environmental water matrices

Solid-phase extraction (SPE) combined with liquid chromatography electrospray mass spectrometry (LC-(ESI)MS) was used to determine 16 non-ionic and anionic surfactants in different environmental water samples at ng L⁻¹ levels. The proposed method is sensitive and simple and has good linear range and detection limits (less than 50 ng L⁻¹) for most compound classes.The effect of ion suppression was studied in aqueous matrices from several treatment plants—including urban and industrial wastewater treatment plants (WWTPs), drinking-water treatment plants (DWTPs) and seawater desalination plants (SWDPs)—and it was considered when quantifying our samples. In addition, conventional treatments and tertiary treatments that use advanced membrane technologies, such as ultrafiltration (UF) and reverse osmosis (RO) were evaluated in order to determine their efficiency in eliminating these compounds.The concentrations of non-ionic surfactants in the raw waters studied ranged from 0.2 to 100 μg L⁻¹. In effluents, the concentrations ranged from 0.1 to 5 μg L⁻¹, which reflects consistent elimination. Anionic surfactants were present in all waters studied at higher levels. Levels up to 3900 μg L⁻¹ of linear alkylbenzene sulfonates (LASs) and 32,000 μg L⁻¹ of alkyl ethoxysulfates (AESs) were detected in urban WWTP influents, while levels up to 25 μg L⁻¹ of LASs and 114 μg L⁻¹ of AESs were found in drinking-water and desalination treatment plants.The results indicate that conventional processes alone are not sufficient to completely remove the studied surfactants from waste streams. Tertiary treatments that use advanced membrane technologies such as UF and RO can further reduce the amount of target compounds in the effluent water.     

Mixed micellization and surface properties of non-ionic/cationic surfactants

We investigate the surface properties of aqueous binary mixtures of our cationic surfactant O-dodecyl-N,N′-diisopropylisourea hydrochloride (ISO-DIC C₁₂) with commercially available nonionic surfactant polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether (TritonX-100) at different temperatures (288 to 303?K). The micellization behavior of the binary systems is studied by determining the surface tension and other important physicochemical parameters, such as the critical micelle concentration (CMC), surface tension at the CMC(γ_cmc), Krafft Temperature (T_K), maximum excess concentration (Γ_max), minimum surface area per molecule (A_min), surface pressure at the CMC (П_cmc), and the adsorption efficiency (pC20) at the air/water interface. The study has additionally covered the calculation of thermodynamic parameters of micellization, including the standard Gibbs free energy, the standard enthalpy, the standard entropy, the free energy, and the Gibbs free energy of adsorption at air/water interface. The CMC values of the binary systems determined by experimental data are used to evaluate the micellar composition in the mixed micelle, the interaction parameter β and the activity coefficients f₁(ISO-DIC C₁₂) and f₂ (polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether) using the theoretical treatment proposed by Clint and Rubingh. Our results reveal that the proposed binary systems possess enhanced surface activity compared to those of the individual surfactants.