Effect of alkyl chain length and size of the headgroups of the surfactant on solvent and rotational relaxation of Coumarin 480 in micelles and mixed micelles

The effect of alkyl chain length and size of the headgroups of the surfactant on the solvation dynamics and rotational relaxation of Coumarin 480 (C-480) has been investigated using dynamic Stokes' shift of C-480 in different types of alkyltrimethylammonium bromide micelles and mixed micelles. The rotational relaxation time increases with increase in alkyl chain length of the surfactant. The increase in the number of alkyl chains of the surfactant leads to the more close packed micelles, hence the microviscosity of the micelles increases and consequently rotational relaxation time increases. Solvation time also increases due to the increase in number of alkyl chains of the surfactant. The change in solvation and rotational relaxation time is more prominent in micelles compared to mixed micelles. The solvation and rotational relaxation time also increase with the increase in size of the headgroup of the surfactant.     

EPR spin probe and spin label studies of some low molecular and polymer micelles

The rotational mobility of spin probes of different shape and size in low molecular and polymer micelles has been studied. Several probes having nitroxide fragment localized either in the vicinity of micelle interface or in the hydrocarbon core have been used. Upon increasing the number of carbon atoms in hydrocarbon chain of detergent from 7 to 13 (sodium alkyl sulfate micelles) or from 12 to 16 (alkyltrimethylammonium bromide micelles) the rotational mobility of spin probes is decreased by the factor 1.5–2.0. The spin probe rotational mobility in polymer micelles (the complexes of alkyltrimethylammonium bromides and polymethacrylic or polyacrylic acids) is less than mobility in free micelles of the same surfactants. The study of EPR-spectra of spin labeled polymethacrylic acid (PMA) indicated that formation of water soluble complexes of polymer and alkyltrimethylammonium bromides in alkaline solutions (pH 9) does not affect the polymer segmental mobility. On the other hand, the polymer complexes formation in slightly acidic water solution (pH 6) breaks down the compact PMA conformation, thus increasing the polymer segmental mobility. Possible structures of polymer micelles are discussed.     

Photolytic and thermal properties of a new series of intramolecular bridged alkyl cobaloxime complexes

The photolytic kinetic properties of a new series of intramolecular bridged alkyl cobaloxime complexes Br(O-C(3)H(6)-(dmgH))(dmgH))Co(III)(2), [H(2)O(O-C(3)H(6)-(dmg))(dmgH(2))]Co(III)[ClO(4)(3), ]Py(O-C(3)H(6)-(dmg))(dmgH(2))[Co(III)]ClO(4)(4), [Bzm(O-C(3)H(6)-(dmg))(dmgH(2))]Co(III)[ClO(4)(5) and ]Im(O-C(3)H(6)-(dmg))(dmgH(2))[Co(III)]ClO(4)(6) and their precursor aqua-(3-bromopropyl)cobaloximes (1) were investigated by UV-Vis spectroscopy. The products of photolytic solutions were characterized by both ESI-MS and (1)H-NMR techniques. Our results revealed a carbon-center radical that is produced from Co-C bond cleavage under photolysis might be linked to the equatorial ligand and thus retained in the proximity of Co(II)-complex. The thermo-gravimetric analysis of complex 2 gives the same conclusion.     

Interaction between a partially fluorinated alkyl sulfate and gelatin in aqueous solution

The interaction of a partially fluorinated alkyl sulfate, sodium 1H,1H,2H,2H-perfluorooctyl sulfate (C6F13CH2CH2OSO3Na), with the polyampholyte gelatin has been examined in aqueous solution using surface tension and small-angle neutron scattering (SANS). The 19F chemical shift of each fluorine environment in the surfactant is unaltered by the addition of gelatin, indicating that there is no contact between the gelatin and the fluorocarbon core of the micelle. The chemical shift of the two methylene groups closest to the headgroup is altered when gelatin is present, disclosing the location of the polymer. The critical micelle concentration (cmc) of the surfactant, cmc = 17+/-1 mM, corresponds to an effective alkyl chain (CnH2n+1) length of n = 11. In the presence of gelatin, the cmc is substantially reduced as expected, cmc(1) = 4+/-1 mM, which is also consistent with an effective alkyl chain length of n = 11. In the presence of the fluorosurfactant, the monotonic decay of the SANS from the gelatin-only system is replaced by a substantial peak at an intermediate Q value mirroring the micellar interaction. At low ionic strengths, the gelatin/micelle complex can be described by an ellipsoid. At higher ionic strengths, the electrostatic interaction between the micelles is screened and the peak in the gelatin scattering disappears. The correlation length describing the network structure decreases with increasing SDS concentration as the bound micelles promote a collapse of the network.     

Self-assembly of cationic surfactants that contain thioether groups in the hydrophobic tails

Self-assembly in aqueous solutions of cationic surfactants that carry thioether groups in their hydrophobic tails has been investigated. Of particular interest was the identification of possible changes in the aggregate structure due to the presence of sulfur atoms. Solutions of four different compounds [CH(3)CH(2)S(CH(2))(10)N(CH(3))(3)(+)Br(-) (2-10), CH(3)(CH(2))(5)S(CH(2))(6)N(CH(3))(3)(+)Br(-) (6-6), CH(3)(CH(2))(7)S(CH(2))(6)N(CH(3))(3)(+)Br(-) (8-6), and CH(3)(CH(2))(7)S(CH(2))(8)N(CH(3))(3)(+)Br(-) (8-8)] were characterized by (1)H NMR, (13)C NMR, NMR diffusometry, and conductivity measurements. In addition to investigating aqueous solutions containing each of the thioethers present as the sole solute, mixtures of 2-10 or 6-6 with dodecyltrimethylammonium bromide (DTAB) were studied. The addition of a sulfide group to the hydrophobic tail causes an increase in the critical micelle concentration but has a limited effect on the aggregate structure. Micelles are formed at a well-defined concentration for all of the investigated surfactants and surfactant mixtures. However, a comparison of the behavior of concentrated solutions of 8-8 to that of solutions of hexadecyltrimethylammonium bromide (CTAB) of similar concentrations suggests that the presence of a sulfur atom decreases the tendency for micellar growth. This may be a consequence of a slightly higher preference for the micellar surface of a sulfur atom as compared to that of a methylene group in a similar position, an idea that is also supported by results for the surfactant mixtures.     

Interaction of adenosine with alkyltrimethylammonium bromides

The interaction of adenosine with alkyltrimethylammonium bromides, C_mH_2m+1N(CH₃)₃Br(m=16, 14, 12, 10, 8, and 6), has been studied by 1 H NMR spectroscopy. When surfactants exist as monomer units, the adenine ring of adenosine preferentially associates with the middle portion of the alkyl chain of the surfactants. The interaction is less specific with surfactants of shorter alkyl chains. When surfactants form micelles, no specific interaction between the adenine ring and the alkyl chain of the surfactant can be detected. A coordination of the cationic part of the surfactants with the adenine ring is suggested. The degree of association was evaluated from association constants. Similar results were obtained for purine and alkyltrimethylammonium bromide.     

Resiliently spherical micelles of alkyltrimethylammonium surfactants with multivalent, hydrolyzable counterions

A series of C(12)-C(16) alkyltrimethylammonium surfactants with hydrolyzable phosphate (PO(4)(3-), HPO(4)(2-), and H(2)PO(4)(-)), oxalate (HC(2)O(4)(-) and C(2)O(4)(2-)), and carbonate (HCO(3)(-) and CO(3)(2-)) counterions have been prepared, and their micellar solution behavior has been characterized. Critical micelle concentrations were measured using electrical conductivity and were found to depend on both the counterion and its hydrolysis state. All monovalent counterions bind less strongly to the micelle surface than does bromide or chloride, whereas multivalent species bind more strongly. Small-angle neutron scattering reveals that, unlike alkyltrimethylammonium bromides and chlorides, micelles are small and spherical in the presence of hydrolyzable counterions of all valences and remain spherical even in the presence of added electrolyte. This is consistent with the strong solvation of even strongly bound hydrolyzable counterions, which prevents the screening of repulsions between adjacent headgroups necessary for sphere-cylinder transformations. Salts of multivalent hydrolyzable counterions could thus be used to control the micelle structure in novel ways.     

Investigation on Gas Storage in Methane Hydrate

The effect of additives (anionic surfactant sodium dodecyl sulfate (SDS), nonionic surfactantalkyl polysaccharide glycoside (APG), and liquid hydrocarbon cyclopentane (CP)) on hydrate inductiontime and formation rate, and storage capacity was studied in this work. Micelle surfactant solutions werefound to reduce hydrate induction time, increase methane hydrate formation rate and improve methanestorage capacity in hydrates. In the presence of surfactant, hydrate could form quickly in a quiescentsystem and the energy costs of hydrate formation were reduced. The critical micelle concentrations of SDS and APG water solutions were found to be 300x 10-6 and 500x 10-6 for methane hydrate formation systemrespectively. The effect of anionic surfactant (SDS) on methane storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduced hydrate induction time and improved hydrateformation rate, but could not improve methane storage in hydrates.     

Micellar catalysis of Diels-Alder reactions: substrate positioning in the micelle

We have studied the kinetics of the Diels-Alder reactions of cyclopentadiene, sorbyl alcohol, and sorbyltrimethylammonium bromide with a series of N-substituted maleimides in micellar media. Micellar rate constants have been determined and were found to be 20-40 times lower than the respective aqueous rate constants. Nevertheless, it was found that upon addition of sodium dodecyl sulfate the observed rate constants could be enhanced up to a factor of about 4.5. The low micellar rate constants can be attributed to the relatively apolar (water-poor) region of the micelle, in which the reactions take place. NMR experiments indicate that the reactants usually reside near the alpha- or beta-CH2 groups of the surfactant molecules in the micelle. Comparison of the micellar rate constants with rate constants in water/1-propanol mixtures suggests a concentration of water of 10-15 M in the micellar region where the diene and dienophile react.     

When do water-insoluble polyion-surfactant ion complex salts "redissolve" by added excess surfactant?

The redissolution of water-insoluble polyion-surfactant ion complexes by added excess of surfactant has systematically been investigated in experimental and theoretical phase equilibrium studies. A number of stoichiometric polyion-surfactant ion "complex salts" were synthesized and they consisted of akyltrimethylammonium surfactant ions of two different alkyl chain lengths (C(12)TA(+) and C(16)TA(+)) combined with homopolyions of polyacrylate of two different lengths (PA(-)(25) and PA(-)(6000)) or copolyions of acrylate and the slightly hydrophobic nonionic comonomers N-isopropylacrylamide (PA(-)-co-NIPAM) or N,N-dimethylacrylamide (PA(-)-co-DAM). The complex salts were mixed with water and excess alkyltrimethylammonium surfactant with either bromide or acetate counterions (C(n)TABr or C(n)TAAc). Factors promoting efficient redissolution were (i) very short polyions, (ii) a large fraction of NIPAM or DAM comonomers, and (iii) acetate, rather than bromide, as the surfactant counterion. Added C(12)TAAc gave an efficient redissolution of C(12)TAPA(25) but virtually no redissolution of C(12)TAPA(6000). A very efficient redissolution by added C(12)TAAc was obtained for PA(-)-co-NIPAM with 82 mol % of NIPAM. The C(12)TAPA-co-NIPAM/C(12)TAAc/H(2)O ternary phase diagram closely resembled the corresponding diagram for the much-studied pair cationic hydroxyethyl cellulose-(sodium) dodecyl sulfate. The simple Flory-Huggins theory adopted for polyelectrolyte systems successfully reproduced the main features of the experimental phase diagrams for the homopolyion systems, including the effect of the surfactant counterion. The efficient redissolution found for certain copolyion systems was explained by the formation of soluble polyion-surfactant ion complexes carrying an excess of surfactant ions through an additional hydrophobic attraction.     

Characterization of the aggregates of N-alkyl-N-methylpyrrolidinium bromide surfactants in aqueous solution

We have characterized a new class of surfactant molecules using fluorescence spectroscopic and light-scattering techniques. Our results suggest that this homologous series of N-alkyl-N-methlypyrrolidinium bromide (CnMPB) surfactants with n = 10, 12, 14, 16, and 18 represents a bridge between the well-characterized alkyltrimethylammonium bromide (CnTAB) and dialkyldimethylammonium bromide (di-CnDAB) surfactant series. For the smaller members of the CnMPB series with n = 10, 12, and 14, our results are consistent with the formation of spherical micelles as the surfactant concentration is increased. With increasing alkyl chain length, we observe that the critical micelle concentration decreases and the aggregation number increases, typical of single-tail surfactants. For C16MPB, the formation of micelles at dilute concentrations (0.10 mM) is likely, followed by the coexistence of micelles and small unilamellar vesicles at higher concentrations up to 0.82 mM where only vesicles are present. For C18MPB, our data are consistent with the formation of vesicles only. We demonstrate in this study that the combination of spectroscopic and light-scattering methods is a powerful approach to reveal aspects of aggregate structure and morphology in aqueous CnMPB surfactant systems. In particular, the sensitivity of the fluorescence probe prodan to the polarity of its microenvironment enables the rich complexity of surfactant aggregates exhibited by this series of amphiphilic molecules to be detected.     

Aggregation properties of supralong-chain surfactants with double or triple quaternary ammonium head groups

Double or triple quaternary ammonium head groups were designed to improve the solubility of supralong alkyl chain surfactants. In the surfactant head group, quaternary ammonium groups are connected by an ethylene spacer. Micellar shapes of divalent surfactants [C(n)H(2n)(+1)N(+)(CH(3))(2)-(CH(2))(2)-N(+)(CH(3))(3) 2Br(-): C(n)-2Am (n=18, 20, and 22)] and trivalent surfactants [C(n)H(2n)(+1)N(+)(CH(3))(2)-(CH(2))(2)-N(+)(CH(3))(2)-(CH(2))(2)-N(+)(CH(3))(3) 3Br(-): C(n)-3Am (n=18, 20, and 22)] were studied in aqueous solutions by means of dynamic light scattering (DLS) and transmission electron microscopy (TEM). Changes in the surfactant concentration have a small influence on the apparent hydrodynamic radii (r(h)) of the molecular aggregates in both surfactant series. Average values of r(h) of aggregates are 60-90 nm for C(n)-2Am (n=18, 20, and 22) and 2-40 nm for C(n)-3Am (n=18, 20, and 22). TEM micrographs showed that aggregates of C(n)-2Am (n=18, 20, and 22) typically formed rod-like micelles. In contrast, trivalent surfactants of C(n)-3Am (n=18, 20, and 22) formed spherical (C(18)-3Am) or ellipsoidal micelles (C(20)-3Am and C(22)-3Am). Moreover, the degree of micellar counterion binding for these surfactants was determined by using a bromide ion-selective electrode, which indicated relatively high values (0.8-0.9) for C(n)-2Am (n=18, 20, and 22) and more common values (0.5-0.8) for C(n)-3Am (n=18, 20, and 22). The size of the aggregates is closely related to the degree of counterion binding.     

Solubilization properties of aqueous solutions of alkyltrimethylammonium halides toward a water-insoluble dye

The solubility of a water-insoluble dye, Sudan Red B, in aqueous sodium halide solutions of tetradecyl-, cetyl-, and stearyltrimethylammonium halides has been measured at different surfactant and salt concentrations, and the dependence of solubilization properties on alkyl chain length has been discussed with reference to the micelle size and shape. At low ionic strengths where only spherical micelles exist, the solubilization power of micellar surfactant slightly increases with increasing the ionic strength, but it sharply increases at high ionic strengths above the threshold value of sphere-rod transition. However, the solubilization power becomes independent of the ionic strength, if their rodlike micelles are sufficiently long. The solubilization capacity increases linearly with increasing the molecular weight, almost independent of counterion species, but the rod-like micelle has a higher solubilization capacity than the spherical micelle. The solubilization capacity is larger for a surfactant with longer alkyl chain, indicating that the dye is solubilized more readily in a larger hydrophobic core. The solubilized dye is situated in a rodlike micelle of alkyltrimethylammonium halides, on average, 4.5–7.5 nm apart from each other.     

Research on the vesicle-micelle transition by 1H NMR relaxation measurement

We have investigated how the dynamics of surfactant molecules changes with the vesicle-micelle transition by (1)H NMR relaxation studies on the sodium decyl sulfate (SDeS)-decyltrimethylammonium bromide (DeTAB)-deuterium oxide system. The study has been planned with reference to the phase diagram of the SDeS-DeTAB-water system deduced from thermodynamic analysis of the surface tension data. The spin-lattice relaxation time (T(1)) and the spin-spin relaxation time (T(2)) are measured at 90 and 400 MHz at various total molalities, m, and compositions, X(2), of the surfactants. The data were analyzed according to the "two-step" model developed by Wennerstr?m et al. and molecular dynamics of the surfactant is discussed from the viewpoint of correlation time tau(f) associated with the local fast motion of the surfactant molecule, correlation time tau(s) associated with the slow overall motions of the aggregate and surfactant molecules within it, and local order parameter S. We find tau(s) of vesicles is an order of magnitude larger than that of micelles signifying that the tumbling of vesicle particles and surfactant diffusion over the vesicle are much slower than those for micelle. Tau(f) and S for vesicles are also larger than those for micelles. Molecular environments of the surfactant are also discussed from the dependence of the chemical shifts on m at constant X(2) or from that on X(2) at constant m. When the chemical shifts in vesicle and micelle are compared at constant m, the chemical shifts in vesicle are displaced to a lower magnetic field than those in micelle, which implies that the surfactant molecules are arranged more closely to each other in the vesicle than in the micelle.     

Solution properties of mixed surfactant systems (IV)

Electric properties of mixed anionic-nonionic surfactant systems in aqueous solutions above the CMC have been studied in terms of pNa values, electrical conductivities, and dielectric constants; these systems are sodium 3, 6, 9-trioxaicosanoate (ECL) — alkyl polyoxyethylene ethers (C_mPOE; m=12, 14, 16, and 18). The degree of ionic dissociation of mixed micelle increases with increasing the number of carbon atoms of the alkyl group in the nonionic surfactant. The electrical conductivity increases with increasing the alkyl chain length in the nonionic surfactant, in spite of the increase of the activation energy for conduction. The size of mixed micelles also increases with increasing alkyl chain length. This may be attributed to the fact that the mixed micelle is formed more easily by a nonionic surfactant including long alkyl chains than for one having shorter alkyl chains.     

Fading phenomena of azo oil dye in anionic-nonionic surfactant solutions II. Effects of alkyl and/or oxyethylene groups in nonionic surfactant on the fading rate

The effects of alkyl and/or oxyethylene groups in a nonionic surfactant on the fading phenomena of 4-phenylazo-1-naphthol (4-OH), which occur in aqueous solutions of anionic-nonionic surfactant systems, are described; these systems are sodium dodecyl sulfate (SDS) — alkyl poly(oxyethylene) ethers (C_mPOE_n, m=12,14,16, and 18 at n=20; n=10, 20, 30, and 40 at m=16). The fading phenomenon is observed when 4-OH is added to the anionic-nonionic mixed surfactant solutions at a molar ratio of 11. A singlet oxygen, which is caused by the hydrophilic-hydrophilic interaction between two surfactants, is thought to attack the tautomer of 4-OH. The fading rate of 4-OH accelerates with increasing alkyl chain length or with decreasing oxyethylene chain length in the nonionic surfactant molecule. The effect on the fading behavior of 4-OH would be larger for a system which can easily form a mixed micelle than for a system in which two kinds of micelles coexist.     

Formation and coexistence of the micelles and vesicles in mixed solution of cationic and anionic surfactant

In the aqueous mixtures of sodium alkylcarboxylate and alkyltrimethylammonium bromide, large unilamelar vesicles can be formed spontaneously or by sonication as the total carbon number in the HC chains is 19 (or larger). Vesicle formation can be influenced by changes of pH, molar ratio of the two surfactant components, and the polar head group of cationic surfactant. Micelles may coexist with the vesicles in these mixed systems. The larger hydrodynamic radius (200 nm) and aggregation number (800) illustrate that the shape of the micelle in 1:1 C₉H₁₉COONa–C₁₀H₂₁N(CH₃)₃Br is rod-like. In some mixed systems, the micelles can be transformed into stable vesicles by sonication — a phenomenon revealed for the first time. The surface-chemical properties of these catanionic surfactant solutions and the stabilities of vesicle have been studied systematically.     

Atomistic structure of a micelle in solution determined by wide Q-range neutron diffraction

The accepted picture of the structure of a micelle in solution arises from the idea that the surfactant molecules self-assemble into a spherical aggregate, driven by the conflicting affinity of their head and tail groups with the solvent. It is also assumed that the micelle's size and shape can be explained by simple arguments involving volumetric packing parameters and electrostatic interactions. By using wide Q-range neutron diffraction measurements of H/D isotopically substituted solutions of decyltrimethylammonimum bromide (C(10)TAB) surfactants, we are able to determine the complete, atomistic structure of a micelle and its surroundings in solution. The properties of the micelle we extract are in agreement with previous experimental studies. We find that ~45 surfactant molecules aggregate to form a spherical micelle with a radius of gyration of 14.2 ? and that the larger micelles are more ellipsoidal. The surfactant tail groups are hidden away from the solvent to form a central dry hydrophobic core. This is surrounded by a disordered corona containing the surfactant headgroups, counterions, water, and some alkyl groups from the hydrophobic tails. We find a Stern layer of 0.7 bromide counterion per surfactant molecule, in which the bromide counterions maintain their hydration shells. The atomistic resolution of this technique provides us with unprecedented detail of the physicochemical properties of the micelle in its solvent.     

Dynamics of solvent and rotational relaxation of Coumarin 153 in a room temperature ionic liquid, 1-butyl-3-methylimidazolium octyl sulfate, forming micellar structure

The solvent and rotational relaxation of Coumarin 153 (C-153) was investigated by picosecond time-resolved fluorescence spectroscopy in a room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium octyl sulfate ([C4mim][C8SO4]). This is a typical RTIL, which form micellar structure above certain concentration of the RTIL (0.031 M). Dynamic light scattering (DLS) measurements show that the average hydrodynamic diameter ( Dh) of a [C4mim][C8SO4]-water micelle is 2.8 (+/-0.2) nm. Both the solvent and rotational relaxation of C-153 are retarded in this micelle compared to the solvation time of a similar type of dye in neat water. However, the solvent relaxation in this ionic liquid surfactant is different from that of a conventional ionic surfactant. The slow component of the solvation dynamics in C8H17SO4Na or TX-100 micelle is on the nanoseconds time scale, whereas in [C4mim][C8SO4] micelle the same component is on the subnanoseconds time scale. The different molecular motions with different time scale is the main reason behind this difference in the solvation time in micelles composed of RTIL with other conventional micelles.     

The Spectral Displacement Technique for Determining the Binding Constants of β-Cyclodextrin – Alkyltrimethylammonium Inclusion Complexes

A survey of the literature reveals that the spectroscopic displacement method, in which phenolphthalein is used as a competitive chromophore to determine binding constants of β-cyclodextrin with surfactants was successful in the case of homologous hydrocarbon and fluorocarbon anionic surfactants. We show here that this method can be applied also for homologous alkyltrimethylammonium bromides (with alkyl varying from octyl- to hexadecyl) under the condition that the concentration of the cationic surfactant is distinctly lower than the value of itscritical micelle concentration.