Morphological Changes of Cationic Gemini Surfactants 14-s-14 (s=4,5,6) in the Presence of Additives

The effect of adding aliphatic alcohols (C₄OH, C₅OH, C₆OH) and corresponding amines (C₄NH₂, C₅NH₂, C₆NH₂) on a series of dicationic gemini surfactants with the general formula C₁₄H₂₉(CH₃)₂N⁺?C(CH₂)_s?CN⁺(CH₃)₂C₁₄H₂₉, 2Br^? (14-s-14; s=4,5,6), in the absence and presence of KNO₃, has been studied by viscosity measurements at 303.15?K. As the chain length of the additive increased, the viscosity increased with increasing additive concentration and the extent of the effect followed the sequence: C₆OH>C₅OH>C₄OH; C₆NH₂>C₅NH₂>C₄NH₂. The simultaneous presence of salt and additives showed an increase in ?? _r values due to a synergistic effect. However, for equal chain lengths in the additives, the effect was greater for the n-alcohols. The tendency for the micelles to grow from spherical to rod-like structures is mainly influenced by the spacer chain length. At 303.15?K, the micellar growth was more pronounced for the shorter spacer, i.e. s being 4, which can be interpreted in terms of the short spacer having a higher tendency for micellar growth. Contrary to the cationic geminis, no effect was observed with a conventional surfactant of equal chain length, TTAB, even in the presence of KNO₃ at the same concentration used for the geminis.     

Structural transition of bifunctional surfactants

Abstract  The effect of primary alcohols (butanol to hexanol) and n-hexylamine on the micellar properties of solutions of alkanediyl-α,ω-bis(dimethylcetylammonium bromide) (16-s-16, with s = 5, 6) in the absence and presence of KBr was investigated by viscometric studies at 30 ± 0.1°C. The viscosities were determined using an Ubbelohde viscometer. The viscosity values exhibit the order s = 5 > 6, i.e., the gemini with short spacer produces the more viscous solution with hexanol > pentanol > butanol. The high viscosities observed in these systems are interpreted in terms of a micellar sphere to rod transition that takes place over a certain range of concentration of the surfactants with added salt or organic additives or both. Micellar growth was higher in case of C₆H₁₃OH when compared to C₆H₁₃NH₂. In the presence of C₆H₁₃NH₂, the relative viscosity becomes almost constant when the concentration of the additive is increased, which has also been discussed in terms of electrostatic and hydrophobic forces operating in the solution. The positive synergistic effects of additives also confirm pronounced micellar growth. Graphical abstract        

Polyoxyethylene cholesteryl ether-based aqueous wormlike micelles

Formation of wormlike micelles (WLMs) in an aqueous mixture of polyoxyethylene cholesteryl ether (ChEO_n; where n = 20 and 30) and polyoxyethylene dodecyl ether (C₁₂EO_m; where m = 3 and 4) has been reported; rheological and small angle X-ray scattering (SAXS) measurements have been performed in the micellar solutions of ChEO_n as a function of C₁₂EO_m for the structural elucidation. When lipophilic cosurfactant, C₁₂EO_m is added to the micellar solutions of ChEO_n, it favors the sphere-to-cylinder transition due to the penetration of C₁₂EO_m in the palisade layer of ChEO_n micelle accompanying an increase in viscosity. When the concentration of C₁₂EO_m is increased, entangled network of WLMs is formed. A strong shear thinning has been observed in highly viscous samples indicating the presence of transient networks. Such samples exhibited viscoelastic behavior and could be described by the Maxwell model with a single stress relaxation mode. A maximum is observed in zero-shear viscosity-C₁₂EO_m plot. With further addition of C₁₂EO_m, viscosity declines and ultimately a phase separation occurs with the formation of turbid solution of vesicular dispersion. This decline has been interpreted in terms of micellar branching induced by an increase in endcap energy, E _c (which is compensated by the formation of branch points, having a mean curvature opposite to that of endcaps). The C₁₂EO_m induced one-dimensional micellar growth has been confirmed by SAXS.     

Synergism in cationic gemini – additive systems

A series of dicationic gemini surfactants with the general formula C₁₆H₃₃(CH₃)₂N⁺?(CH₂)_s?N⁺(CH₃)₂C₁₆H₃₃, 2Br^? (where s?=?4–6), designated as 16-s-16, were synthesised. Their interaction with organic additives: n-alcohols (C₃H₇OH, C₇H₁₅OH, C₈H₁₇OH) and the corresponding amines (C₃H₇NH₂, C₇H₁₅NH₂, C₈H₁₇NH₂) in the absence and presence of KNO₃ at 30°C was studied viscometrically to observe their effect on assembly formation and micellar transition. The simultaneous presence of KNO₃ and organics induced rich aggregates morphologies in the gemini micellar systems by giving high viscosity values. On comparing the behaviour of the gemini surfactant series for a given alkyl chain length of the organic additive, the spacer is found to markedly influence the behaviour; shorter the spacer, earlier the sphere-to-rod transition. In the case of the conventional surfactant, CTAB, the concentration of KNO₃ used with the geminis was insufficient to induce any transition.     

Growth of Gemini Surfactant Micelles Under the Influence of Additives: DLS Studies

Results are presented on the first extensive study on the influence of additives on the growth of gemini; alkanediyl α, ω - bis(dimethylcetylammonium bromide) surfactant micelles (16-s-16, with s = 5, 6); as measured by dynamic light scattering technique at 30°C. The effect of adding n-butanol, n-pentanol, n-hexanol, and n-hexylamine in the absence or presence of general ionic salt potassium bromide on 0.03 M gemini solutions were observed. The tendency for micelles to grow from spherical to rodlike structures is decisively influenced by the spacer length s. At 30°C, the micellar growth was more for s being 5, which has been interpreted in terms of short spacer having strong propensity for micellar growth. Addition of KBr plays a role in screening of the electrostatic interactions, thus promoting a change of morphology of the aggregates and giving rise to high hydrodynamic diameter (D _h ) values. The micellar growth in presence of alcohols is interpreted in terms of the formation of the gemini–alcohol mixed micelles which followed the pattern C₆OH>C₅OH>C₄OH. For equal chain length additives C₆OH and C₆NH₂, the growth was more pronounced in case of alcohol. Also, in case of C₆NH₂, the value of D _h reached to almost constancy or decreased to some extent, which is discussed in terms of its partitioning in aqueous phase. A combined presence of KBr and n-alcohols or n-hexylamine produced favorable conditions for micellar growth due to synergistic effect.     

Studies on Hydrophobic Effect and Micelle Formation of Some Surfactant-Cr(III)-Cetylamine Complexes in Non-aqueous Solvents

Surface active micelle formable surfactant-Cr(III) complexes of the type cis-α-[Cr(trien)(C₁₆H₃₃NH₂)X]²⁺ (where trien = triethylenetetramine; X = F⁻, Cl⁻, Br⁻) have been studied in n-alcohol and in formamide at different temperatures by conductance measurements. Standard Gibbs energy changes (ΔG ^o _mic), enthalpies (ΔH ^o _mic) and entropies (ΔS ^o _mic) of micelle formation have been determined by studying the variation of the Critical Micelle Concentration (CMC) with temperature. Critical micelle concentrations have also been measured as a function of percentage concentration of alcohol added. It is suggested that alcohol addition leads to an increase in formamide penetration into the micellar interface that depends on the alcohol chain length. The results are discussed in terms of an increased hydrophobic effect, dielectric constant of the medium, the chain length of the alcohols and the surfactant in the solvent mixture.     

Studies on Thermodynamics of Micellization and Solvophobic Interactions of Novel Surfactant–Cr(III) Complexes in Non-aqueous Solvents

The critical micelle concentration (CMC) of surfactant–Cr(III)–dodecylamine complexes of the type cis-α-[Cr(trien)(C₁₂H₂₅NH₂)X]²⁺ (where trien = triethylenetetramine; X = F⁻, Cl⁻, Br⁻) has been studied in n-alcohol and in formamide at different temperatures, by electrical conductivity measurements. From the CMC values as a function of temperature, various thermodynamic properties have been evaluated: standard Gibbs energy changes (Δ_mic G ⁰), standard enthalpy changes (Δ_mic H ⁰) and standard entropy changes (Δ_mic S ⁰) for micellization. Critical micelle concentrations have also been measured as a function of the percentage composition of alcohol added. The solvent composition dependences of these thermodynamic parameters were determined. It is suggested that alcohol addition leads to an increase in formamide penetration into the micellar interface that depends on the alcohol’s chain length. The results are discussed in terms of an increased hydrophobic effect, dielectric constant of the medium, the chain length of the alcohols, and the surfactant in the solvent mixture.     

Micellization of sodium dodecyl sulfate and polyoxyethylene dodecyl ethers in solution

The effect of polyoxyethylene type nonionic surfactants (C₁₂E _n n = 3, 4, 5, 6, 7 and 8) on the aqueous solution of sodium dodecyl sulfate (SDS) in absence and presence of NaCl was examined using small-angle neutron scattering (SANS), dynamic light scattering (DLS), and viscosity measurements. Upon addition of C₁₂E _n , micellar size of SDS was found to increase significantly, and such micellar elongation was further enhanced in the presence of NaCl. Micellar growth is most significant in presence of shorter moieties of C₁₂E _n (e.g., n = 3, 4) as compared to higher ethereal oxygen content. The results of structural investigations with SANS and DLS to confirm this assumption are reported. The cloud point of C₁₂E _n has increased upon addition of SDS and decrease with NaCl, and a typical behavior is observed when both SDS and NaCl were present.     

Micelle formation of a cationic surfactant in the presence of 1,n-alkanediol and the miscibility of alcohols in micelles

Micelle formation of dodecyltrimethylammonium bromide (DTAB) was examined in the presence of α,ω-alkanediols applying conductivity measurements. Octanediol and hexanediol promoted the formation of mixed micelles of DTAB and the alcohol, but butanediol interfered with micellization. Analysis of the critical micelle concentration (cmc) based on the lattice model for mixed solution with the Bragg–Williams approximation indicated an unfavorable interaction between alcohol and water and a favorable interaction between the alcohol and surfactant, with the exception of butanediol. The exchange energy between alcohol and water was 0.5kT higher for alkanediol (C_2n(OH)₂) than for the corresponding regular alcohol (C_nOH), which is believed to have resulted from the smaller mixing entropy for the alkanediol than for the corresponding regular alcohol. It was inferred from the analysis that the cmc increase for C₄(OH)₂ was caused by favorable interaction with water but unfavorable interaction with the micellar surfactant.     

The “Borrowing Hydrogen Strategy” by Supported Ruthenium Hydroxide Catalysts: Synthetic Scope of Symmetrically and Unsymmetrically Substituted Amines

The N‐alkylation of ammonia (or its surrogates, such as urea, NH₄HCO₃, and (NH₄)₂CO₃) and amines with alcohols, including primary and secondary alcohols, was efficiently promoted under anaerobic conditions by the easily prepared and inexpensive supported ruthenium hydroxide catalyst Ru(OH)_x/TiO₂. Various types of symmetrically and unsymmetrically substituted “tertiary” amines could be synthesized by the N‐alkylation of ammonia (or its surrogates) and amines with “primary” alcohols. On the other hand, the N‐alkylation of ammonia surrogates (i.e., urea and NH₄HCO₃) with “secondary” alcohols selectively produced the corresponding symmetrically substituted “secondary” amines, even in the presence of excess amounts of alcohols, which is likely due to the steric hindrance of the secondary alcohols and/or secondary amines produced. Under aerobic conditions, nitriles could be synthesized directly from alcohols and ammonia surrogates. The observed catalysis for the present N‐alkylation reactions was intrinsically heterogeneous, and the retrieved catalyst could be reused without any significant loss of catalytic performance. The present catalytic transformation would proceed through consecutive N‐alkylation reactions, in which alcohols act as alkylating reagents. On the basis of deuterium‐labeling experiments, the formation of the ruthenium dihydride species is suggested during the N‐alkylation reactions.     

The Inhibition of the Hydrolysis of Cephanone by CTAB/n‐C5H11OH/H2O Microemulsion

Abstract

The hydrolysis of cephanone in water, cetyl trimethyl ammonium bromide (CTAB) micelle, and CTAB/n‐C₅H₁₁OH/H₂O O/W microemulsion was studied through UV‐VIS absorption spectroscopy. The mechanism of the hydrolysis and the effects of both the acidity of the media and the composition of O/W microemulsion on the hydrolysis were studied. The results show that the hydrolysis rate of cephanone increases with the acidity. Compared with water, CTAB micelle and CTAB/n‐C₅H₁₁OH/H₂O O/W microemulsion suppress this hydrolysis. The inhibition of the hydrolysis of cephanone by CTAB micelle and CTAB/n‐C₅H₁₁OH/H₂O O/W microemulsion is related to the location of cephanone in the interphases of CTAB micelles and CTAB/n‐C₅H₁₁OH/H₂O O/W microemulsion droplets.     

Oxidation of aliphatic alcohols with the lead tetraacetate—metal halide system under mechanical activation

The mechanochemical oxidation ofn-pentanol,n-hexanol, andn-octanol with the Pb(OAc)₄-MHal system (M=Li, K; Hal=Cl, Br) in the absence of a solvent affords esters. and secondary alcohols with the composition C₈H₁₇OH and C₉H₁₉OH give ketones. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1870–1873, November, 2000.     

An ab initio molecular orbital study of the deprotonation of amines

The geometries of the amines NH₂X and amido anions NHX^?, where X = H, CH₃, NH₂, OH, F, C₂H, CHO, and CN have been optimized using ab initio molecular orbital calculations with a 4-31G basis set. The profiles to rotation about the N? X bonds in CH₃NH^?, NH₂NH^?, and HONH^? are very similar to those for the isoprotic and isoelectronic neutral compounds CH₃OH, NH₂OH, and HOOH. The amines with unsaturated bonds adjacent to the nitrogen atoms undergo considerable skeletal rearrangement on deprotonation such that most of the negative charge of the anion is on the substituent. The computed order of acidity for the amines NH₂X is X = CN > HCO > F ≈ C₂H > OH > NH₂ > CH₃ > H and for the reaction NHX^? + H⁺ → NH₂X the computed energies vary over the range 373–438 kcal/mol.     

Thermodynamic and Dynamic Properties of Micellar Aggregates of Nonionic Surfactants with Short Hydrophobic Tails

The densities and viscosities of binary aqueous mixtures of poly(ethylenoxide)hexanols [C₆H₁₃(OCH₂CH₂)_mOH, C₆E_m] (m= 3, 4, and 5) have been studied in the micellar composition range. For the same surfactants the self-diffusion coefficients in mixtures with heavy water have been determined by the spin-echo pulsed field gradient method. The volumetric data are interpreted by means of the phase separation model, and values of the CMC, volume change, and standard free energy change of micellization are obtained. From the viscosity data the hydration numbers of the surfactant hydrophilic head in the micellar state are computed; they are in agreement with those obtained from HDO self-diffusion data. The surfactant self-diffusion data are used to calculate the apparent micelle radius and the aggregation number. The micellization parameters obtained for the different surfactants are compared and discussed.     

Interactions between anionic mixed micelles and α-cyclodextrin and their inclusion complexes: conductivity, NMR and fluorescence study

Mixed micelle formation of anionic surfactants sodium dodecyl sulfate (SDS) and sodium lauroyl sarcosine (SLAS) have been studied in water and in 5, 10, and 15 mM concentrations of α-cyclodextrin (α-CD) over mole fraction range of α _SDS from 0 to 1. From the conductivity curves, the critical micellar concentration (CMC) for the pure and binary mixtures were evaluated. The degree of counterion association (χ) or counterion dissociation (δ), the equivalent ionic conductivities of the monomeric species (Λ _m), the associated species (Λ _assc), and the micelle (Λ _mic) were evaluated from the slope of the conductivity vs concentration plots. The CMC values have been used to calculate the thermodynamic parameters such as the standard free energy of micelle formation and a transfer of standard free energy of micelle from the aqueous medium to additive medium computed. The apparent CMC of the surfactants varies linearly with α-CD concentrations. From the dependence of CMC of the surfactants on α-CD concentration, we are able to determine the association constant (K) of surfactant-α-CD inclusion complexes assuming 1:1 stoichiometry. Mixed micelle behaves ideally in the pure water as well as at the different concentrations of α-CD, which was evaluated by using the Clint equation, the regular solution approximation, and Motomura’s formulation. Self-diffusion coefficients of the micelle increased upon the induction of SDS into the micelle. 2D-rotating frame Overhauser effect spectroscopy spectra of SDS and SLAS were recorded in the presence of α-CD to investigate the interaction between H-atoms of the alkyl chain of the surfactants and H-atoms of the hydrophobic cavity of α-CD indicating multiple complexation. The fluorescence anisotropy of rhodamine B has been measured to observe the structural behavior of mixed micelle.     

青霉素G钾盐对SDS水溶液物理化学性质的影响及其在SDS/n-C5H11OH/H2O体系中的释放

The effects of penicillin potassium salt （PenK） on the solubility, Krafft temperature TK, critical micelle concentration CMC of SDS micelle and the phase behavior of SDS/n-C5H11OH/H2O system were studied. The partial phase diagrams of SDS/PenK/H2O system at different temperatures were determined. The release amounts of PenK in SDS/n-C5H11OH/H2O system and the distribution coefficient of PenK between micelle and water were measured by UV-Vis spectroscopy. The results show that in the presence of PenK, the CMC of SDS was decreased while the TK of SDS was increased and the solubility of SDS in both water and SDS/n-C5H11OH/H2O oil in water （O/W） microemulsion was decreased, but increased in water in oil （W/O） microemulsion. SDS micelles and SDS/n- C5H11OH/H20 O/W microemulsion could accelerate the release rate of PenK. The addition of SDS and water could both increase the release rate of PenK, whereas the presence of n-C5H11OH reduced the release rate of PenK. The above results were related to the electrostatic repulsion between PenK and SDS.     

Hydrolysis of Cephanone in SDS／n－C5H11OH／H2O System

The hydrolysis of cephanone in SDS micelle and SDS/n-C5H11-OH/H2O O/W microemulsion was studied through Uv-vis ab-sorption spectroscopy. The change of pH value in the hydrolysis of cephanone was determined. The result shows that pH value decreases in the process of the hydrolysis, and that the SDS ml-celle and SDS/n-C5H11OH/H2O O/W microemulsion accelerate the hydrolysis of cephanone compared with water.     

The effect of electrolyte on the micellar properties of an anionic-nonionic detergent in aqueous solution

Summary The effect of sodium chloride on the micellar properties of an anionic-nonionic detergent C₁₆H₃₃(OCH₂·CH₂)₇OSO₃Na has been investigated and the results have been compared with previous measurements on the nonionic analogue C₁₆H₃₃(OCH₂·CH₂)₇OH. Light scattering and viscosity measurements showed that, over the electrolyte concentration range studied (0–1.0M NaCl), the micelles were very much smaller (m.m.w.=74,800 in 0.1M NaCl) than those of the nonionie analogue and exhibited no similar variation of size, shape or hydration with temperature, indicating that addition of electrolyte caused insufficient shielding of the micellar charge to induce nonionic behaviour. Viscosity results suggested a reduction in the micellar hydration with increase in electrolyte concentration to a limiting value of 0.28 g H₂O/g of detergent for salt concentrations greater than 0.01M. A possible explanation of this effect is proposed. The effect of electrolyte on the c.m.c. was determined from surface tension measurements and was described by the equation, log c.m.c.=−6.4−0.54 log (c.m.c.+salt conc.) Comparison with data reported for sodium hexadecylpolyoxyethylene sulphates with shorter ethylene oxide chain lengths indicated a decrease in the c.m.c. in salt-free systems with increase in the chain length, the data obeying the equation, log c.m.c.=−3.5−0.20n wheren is the number of ethylene oxide groups in the chain.     

High-molecular-weight poly(p-phenyleneterephthalamide) by CaCl2 promoted direct polycondensation with thionyl chloride in N-methylpyrrolidone

The direct polycondensation of terephthalic acid and p-phenylenediamine hydrochloride (PPD.2HCl) with thionyl chloride was found to be significantly promoted in N-methylpyrrolidone (NMP) by dissolved CaCl₂ and tertiary amines. The inherent viscosity of the polymer obtained varied with the amount of CaCl₂ and tertiary amines added. The reaction, when effectively promoted by CaCl₂, proceeded homogeneously in the early state of polycondensation, and then resulted in a highly swollen gel. CaCl₂ had to be present in the PPD.2HCl/tertiary amines/NMP solution as well as in the TPA/SOCl₂/NMP mixture for the polycondensation to proceed to high molecular weight. Complexes of CaCl₂, PPD.2HCl, and tertiary amines in NMP similar to the well known complex, CaCl₂ · nNH₃ (n = 2, 4, 8) was proposed to facilitate the polycondensation.     

Pentacoordinated Carboxylate π‐Allyl Nickel Complexes as Key Intermediates for the Ni‐Catalyzed Direct Amination of Allylic Alcohols

Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5‐cyclooctadiene)₂] and 1,1′‐bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu₄NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu₄NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η³‐allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.