Partition and water/oil adsorption of some surfactants

Adsorption isotherms have been determined at the water/oil interface for five biphasic systems involving surfactants (non-ionic and ionic) present in both phases at partition equilibrium. The systems studied were polyoxyethylene(23)lauryl ether (Brij35) in water/hexane and four ionic surfactants, hexadecyltrimethylammonium bromide (CTAB), and a series of three tetraalkylammonium dodecylsulfate (TEADS, TPADS, and TBADS) in water/CH 2Cl 2. Interfacial tension measurements performed at the water/air and water/oil interfaces provided all the necessary information for the determination of the adsorption parameters by taking partition into account. These measurements also allowed the comparison of the adsorption properties at both interfaces which showed an increase of the adsorption equilibrium constant and a decrease of the maximum surface concentration at the water/oil interface compared to water/air. The values of the critical aggregation concentration showed, in all cases, that only the surfactant dissolved in the aqueous phase contribute to the decrease of the water/oil interfacial tension. In the case of the four ionic surfactants, the critical aggregation concentration obtained in biphasic conditions were lowered because of the formation of mixed surfactant-CH 2Cl 2 aggregates.     

Facilitated transport from ternary cation mixtures through water—chloroform—water membrane systems containing macrocyclic ligands

Cation fluxes were determined for various three-component, equimolar mixtures of alkali metal, alkaline earth, and Pb²⁺ cations in a H₂O---CHCl₃---H₂O liquid membrane system incorporating macrocyclic polyethers as carriers. Carrier ligands studied were 18-crown-6, dicyclohexano-18-crown-6, 1,10-diaza-18-crown-6, 21-crown-7, dibenzo-24-crown-8, and cryptand [2.2.2]. Correlations were found between transport and relative cation:polyether cavity radii, the type of substituents present on the polyether ring, and the type and number of donor atoms present. All the ligands studied transported Pb²⁺ at higher rates than the other Mⁿ⁺ in the mixtures. Transport behavior in these multi-cation systems can be predicted from Mⁿ⁺—polyether complex stability constant data in most cases.     

Separation of rhenium by extraction with crown ethers and flow-injection extraction—spectrophotometric determination with Brilliant Green

The extraction behavior of perrhenate with crown ethers was studied and methods for the separation and determination of rhenium were developed. The distribution ratio of perrhenate with dicyclohexano-18-crown-6 (DC18C6) increases with increases in the dielectric constant of organic solvents and in the potassium ion concentration of aqueous solution. The molar ratios of crown ether to KReO₄ in the extracted species are probably 1:1 for DC18C6, dibenzo-18-crown-6 and 18-crown-6 and 2:1 for benzo-15-crown-5 and 15-crown-5. Microgram amounts of rhenium were satisfactorily separated from large amounts of molbdenum(VI) by extraction with DC18C6 in 1,2-dichloroethane from 2 M potassium hydroxide solution containing tartrate and by back-extraction with sodium phosphate buffer solution after the addition of a twofold volume of hexane to the organic phase. Rhenium was determined by the flow-injection extraction-photometric method with Brilliant Green. Rhenium was satisfactory determined in molybdenite and other ore samples.     

Studies on the Complexation of Transition Metal Ions with Macrocyclic Compounds in Mixed Solvents by Competitive Potentiometry and Polarography

Complexation of Cu(II), Zn(II), Ni(II), Co(II), Pb(II), Cd(II), Cr(III) and Fe(III) ions with 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, dibenzo-24-crown-8, 5,6,14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadeca-5,14-diene, 1,4,10-trioxa-7,13-diazacyclopentadecane and cyclam has been investigated in 75% (v/v) DMF+water using the silver(I) ion as an auxiliary cation at 0.05?M ionic strength adjusted with tetrabutylammonium perchlorate (TBAP) by competitive potentiometry. Stability constant values obtained for the metal ion–aza macrocyclic complexes are higher than those for the oxa crowns. Shifts in the peak potential and reduction in the peak current in the differential pulse polarography (DPP) method were also used to determine the stability constants of some of the metal ions with aza and tosylated-aza macrocycles using TBAP as supporting electrolyte in 75% (v/v) DMF+water and 90% (v/v) DMSO+water media. Stability constant values determined both by shifts in the potential and by reduction in the peak current were found to be in good agreement with each other.     

A stereoselective reduction of dibenzo-18-crown-6 ether to dicyclohexyl-18-crown-6 ether

Dibenzo-18-crown-6 ether is reduced to dicyclohexano-18-crown-6 ether under very mild conditions (room temperature and atmospheric hydrogen pressure) in the presence of rhodium salt and phase-transfer reagents. Control over the stereoselectivity of the reduction can be achieved through the proper choice of the phase-transfer agent. Moreover, at higher pressure, the stereoselectivity can be increased up to a 95/5 ratio of the syn/anti isomers of the dicyclohexano-18-crown-6 ether.     

Convective instability in a liquid-liquid system due to complexation with a crown ether

Periodic convective instability has been observed in a biphasic system during the complexation reaction of alkali picrate and dicyclohexano-18-crown-6 which undergoes mass transfer from the hexane phase into the aqueous phase. The convection was visualized by means of precipitated crystals that are formed in both phases by the complexation reaction. The fluid motion was observed with an optical microscope and further analyzed with the particle image velocimetry (PIV) technique. The partition at the extraction of cesium into the organic phase was followed by means of the radioactive isotope (137)Cs. The type of the hydrodynamic instability is governed by the alkali metal expressed via its stability constants for the complex formed. More stable complexes trigger a higher precipitation, thereby favoring a Raleigh-Taylor instability. Complexes with a lower stability constant induce Marangoni cells which show a pulsating character in a cubic container. Depending on the confinement of the experiment cell the fluid motion can also follow a back-and-forth movement. Possible mechanisms for the occurring oscillations are discussed.     

Study of gas-phase molecular recognition using Fourier transform ion cyclotron resonance mass spectrometry (FTICR/MS)

The application of Fourier transform ion cyclotron resonance (FTICR) mass spectrometry to the quantitative study of molecular recognition in the gas phase is reviewed. Because most quantitative measurements are dependent on accurate determination of the pressure of a neutral reagent, methods for accurate pressure measurement in FTICR, including gauge calibration using a reaction with known rate constants (the traditional method), exothermic proton transfer rate measurement (often the best method when accurate neutral pressures in the trapping cell are desired), and linewidth measurement (a little-used, but generally applicable method) are discussed. The use of rate constant measurements in molecular recognition is illustrated with examples employing natural abundance isotopic labeling to study self-exchange and 2 : 1 ligand:metal complex formation kinetics in crown ether-alkali cation systems. Self-exchange rates do not correlate with alkali cation/crown cavity size relationships, whereas 2 : 1 complex formation kinetics correlate strongly with size relationships. The use of exchange equilibrium constant measurements to characterize molecular recognition is illustrated by alkali cation exchanges between 18-crown-6 and the isomers of dicyclohexano-18-crown-6. These experiments show that the alkyl-substituted ligand binds alkali cations better than unsubstituted 18-crown-6 in the gas phase, in accordance with expectations based on the higher polarizability of the alkyl-substituted ligand. Further, the metal binding thermochemistry differs for the two dicyclohexano-18-crown-6 isomers, with the bowl-shaped cis-syn-cis isomer binding all the alkali cations more strongly than the cis-anti-cis isomer. The measurement of entropies and enthalpies associated with one of the most subtle forms of molecular recognition, enantiomeric discrimination, is illustrated by studies of the discrimination between enantiomers of chiral amines by dimethyldiketopyridino-18-crown-6. This chiral ligand binds chiral primary ammonium cations that have the opposite absolute configuration at their stereocenter more strongly than the enantiomer with the same absolute configuration. Gas-phase studies show that this enantiomeric discrimination is enthalpic in origin, likely related to more favorable pi-pi stacking for the preferred enantiomer. Entropy disfavors binding of the preferred enantiomer.     

Preparation and decomposition of potassium alkalide-lipophilic crown ether complexes in tetrahydrofuran

Cyclohexano-15-crown-5, cyclohexano-18-crown-6, dicyclohexano-15-crown-5, and dicyclohexano-18-crown-6, but not dicylohexano-16-crown-5, in THF dissolve potassium metal to form dark blue potassium alkalide solutions at ambient temperature. On standing, the potassium alkalide complexes decompose and the solutions turn colorless at differing rates. Identification of the products provides insight into the decomposition mechanism.     

Determination of Phenol and Guaiacol in Aqueous Solutions Using Extraction-Chromatographic Preconcentration

Compositions of stationary phases based on tributyl phosphate and dicyclohexano-18-crown-6 were optimized for the efficient extraction of phenol and guaiacol from aqueous solutions. Procedures were developed for the total and selective determination of these compounds in aqueous solutions, in particular, at trace level.     

Scanning electrochemical microscopy (SECM) studies of oxygen transfer across phospholipid monolayers under surface pressure control: comparison of monolayers at air/water and oil/water interfaces

Scanning electrochemical microscopy has been used in combination with a specially designed Langmuir trough to compare the kinetics of oxygen transfer across an L-alpha-phosphatidylethanolamine, distearoyl monolayer spread at three different interfaces: air/water, air/water in contact with an oil lens, and oil/water. The monolayer is shown to reduce the kinetics of interfacial transport, and rate constants for the transport of oxygen across each interface, at different surface pressures, have been evaluated. The results obtained for each interface are compared, and the implications for studies of passive diffusion across cell membranes are discussed.     

Further study of extraction equilibrium of uranium(VI) with dicyclohexano-18-crown-6 and its application to separating uranium and thorium

In our publication (1), the extraction of uranium with dicyclohexano-18-crown-6 (mixed isomers) has been described. The extraction equilibrium of uranium(VI) from aqueous hydrochloric acid solution with dicyclohexano-18-crown-6 isomer A (Ia) and isomer B (Ib) in 1,2-dichloroethane is presented in this paper. The extracted species are found to be 1:2 (metal/crown) for Ia and 2:3 for Ib from slope analysis and direct determination of extracted complexes. The extraction equilibrium constants (Kex) have been determined at 25°C, and equal 29.5 for the former and 0.208 for the latter. It is concluded that Ia has stronger coordinate ability for uranium than Ib. The different orientation of the lone pairs of the oxygen atoms in both isomers will be taken into account for interpreting above results. The extraction of uranium(VI) with dicyclohexano-18-crown-6 (mixed isomers) or Ia from aqueous hydrochloric acid solution is effective and selective. In 0.1M crown ether-1,2-dichloroethane-6N HCl system, the separation factor U(VI)/Th(IV) exceeds 1000. The result can be taken in separating uranium and thorium.     

2,4-dithiouracil: the reproducible H-bonded structural motifs in the complexes with 18-membered crown ethers

2,4-dithiouracil (DTU) forms in the crystals the H-bonded monohydrates of a 1:1:1 ratio with 18-crown-6 (18C6) 1, cis,syn,cis-isomer of dicyclohexano-18-crown-6 (DCH6A) 2, and benzo-18-crown-6 (B18C6) 3, while the anhydrous adduct with cis,anti,cis-isomer of dicyclohexano-18-crown-6 (DCH6B) 4 is of a 2:1 ratio. In 1-3 the components reproducibly alternate in the chains, while in 4 the chains are built of the alternative centrosymmetric dimers of 2,4-dithiouracil and the molecules of the cis,anti,cis-isomer of dicyclohexano-18-crown-6.     

Crown ether complexes of potassium and thallium(I) 2- and 4-nitrophenoxides

18-Crown-6 and dicyclohexano-18-crown-6 complexes of potassium 2- and 4-nitrophenoxide, and 18-crown-6 complexes of thallium(I) 2- and 4-nitrophenoxide have been synthesized. Solvent effects on the visible spectra of the nitrophenoxide anions are independent of the nature of the cation and the nature of the complexing agent. The 18-crown-6 complex of thallium(I) 2-nitrophenoxide is a 1:2 complex. All the other complexes are 1:1. X-ray crystallographic examination of the potassium dicyclohexano-18-crown-6 complexes showed the potassium ion is octacoordinated in the 2-nitrophenoxide and heptacoordinated in the 4-nitrophenoxide.     

Chemical Mechanism of the Solid-Phase Extraction of Metal Complexes: Barium Complexes with Crown Ethers

The adsorption of barium complexes of dibenzo-18-crown-6 (DB18C6) and dicyclohexano-18-crown-6 (DCH18C6) ethers on alkylated silica gel in the presence of sodium dodecylsulfonate was studied. The adsorbent capacity for the barium complex of DCH18C6 was higher than that for the complex of DB18C6 by a factor of about 4. Depending on the proton-acceptor ability of the adsorbate, the surface layer of alkyl radicals and residual silanol groups behaves as a solid surface or a liquid phase. In the latter case, a supramolecular cavity complementary to the adsorbate is formed in the surface phase. Thus, alkylated silica gel undergoes self-organization with regard to the properties of the adsorbate. This hypothesis explains the unusual adsorption of barium complexes.     

Synergistic extraction of americium(III) with 2-thenoyltrifluoroacetone and crown ethers

Extracton, of Am³⁺ in benzene with 2-thenoyltrifluoroacetone (HTTA) and crown ethers (CEs) such as 15-crown-5, 18-crown-6, dicyclohexano-18-crown-6, dibenzo-18-crown-6, dicyclohexano-24-crown-8, and dibenzo-24-crown-8 was investigated. Synergistic effect by CE was observed regardless of the kind of CE examined. The extracted species was found to be Am(TTA)₃(CE), and adduct formation constants between Am(TTA)₃ and CE in the organic phase were determined. The sequence of constant could not be explained only by basicity of CE and the steric effect of CE should be taken into account to elucidate the adduct complex formation.     

Ion-pair extraction of tetravalent plutonium from hydrochloric acid medium using crown ethers

Ion-pair extraction behaviour of plutonium (IV) from varying concentrations of HCl solution was studied employing crown ethers (benzo-l5-crown-5 (B15C5), 18-crown-6, (18C6), dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6, (DC18C6), dibenzo-24-crown-8 (DB24C8) and dicyclohexano-24-crown-8 (DCH24C8)) in nitrobenzene as the extractant. Ammonium metavanidate was used as the holding oxidant in the aqueous phase and the conditions necessary for the quantitative extraction of the tetravalent ion were found. The co-extraction of species of the type [HL⁺].[HPu(Cl) ₆ ^– ] and [HL⁺]2·[Pu(Cl) ₆ ^2– ] as ion-pairs (where L represents the crown ether) is suggested.     

Spectrophotometric Study of the Complexation of Some Lanthanide (III) Ions with a Series of 18-Crowns-6 in DMSO Solution Using Murexide as a Metallochromic Indicator

The complexation of La(III), Ce(III), Pr(III) and Er(III) with 18-crown-6(18C6), dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DCY18C6) anddibenzopyridino-18-crown-6 (DBPY18C6) has been studied in dimethylsulfoxide(DMSO) by means of a competitive spectrophotometric method using murexide asa metal ion indicator. The formation constants of the 1 : 1 complexeswere found tovary in the order La(III) > Ce(III) > Pr(III) > Er(III). It was foundthat the structure influences the formation and stability of the resultingcomplexes. The effects ofvarious parameters on complexation are discussed. The order of the stabilityconstants of each lanthanide ion with these macrocycles are18C6 > DC18C6 > DB18C6 > DBPY18C6.     

Synthesis and structures of molecular complexes of the cis-anti-cis diastereomer of dicyclohexano-18-crown-6 with o-nitroanilines

In the reaction of the cis-syn-cis and cis-anti-cis diastereomers of dicyclohexano-18-crown-6 with 2-nitro and 2,4-dinitroaniline crystalline complexes with a 1:2 stoichiometric composition were obtained only when the cis-anti-cis diastereomer was used. The three-dimensional structure of the complex of the cis-anti-cis diastereomer of dicyclohexano-18-crown-6 with 2,4-dinitroaniline was determined by an x-ray diffraction study. The complexing of o-nitroanilines with the cis-anti-cis diastereomer is explained by the topological conformity of the interacting compounds. The isolation of the individual cis diastereomers from the mixture of them formed as a result of the catalytic hydrogenation of dibenzo-18-crown-6 was accomplished by means of the selective formation of the crystalline complex of the cis-anti-cis diastereomer with 2-nitroaniline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1190–1195, September, 1988.     

Dynamics of mixed protein–surfactant layers adsorbed at the water/air and water/oil interface

Drop and bubble shape tensiometry experiments are performed at the water/air and water/hexane interfaces in order to get more information about the differences in the adsorption layer structure of mixed protein/surfactant systems. For mixtures of β-lactoglobulin and sodium dodecyl sulphate the adsorption at the water/air interface is essentially a competitive process between protein/surfactant complexes and free surfactant molecules, while the water/oil interface is essentially covered by the complexes.     

Interfacial rheology of natural silk fibroin at air/water and oil/water interfaces

The interfacial viscoelastic behavior of natural silk fibroin at both the air/water and oil/water interfaces is reported. This natural multiblock copolymer is found to be strongly amphiphilic and forms stable films at these interfaces. The result is an interfacial layer that is rheologically complex with strong surface elastic moduli that are only slightly frequency-dependent. The kinetics of surface viscoelastic evolution are reported as functions of time for various concentrations of the spread films. Films deposited by Langmuir-Blodgett deposition were studied by scanning electron microscopy (SEM) to reveal a fibrous structure at the interface. The production of stable O/W emulsions by silk fibroin further confirms the generation of the elastic films at the oil/water interfaces.