Molecular organization and dynamics of micellar phase of polyelectrolyte-surfactant complexes: ESR spin probe study

Molecular dynamics and organization of the micellar phase of complexes of linear polyelectrolytes with ionogenic and non-ionogenic surfactants was studied by the ESR spin probe method. Complexes of polyacrylic acid (PAA) and sodium polystyrenesulfonate (PSS) with alkyltrimethylammonium bromides (ATAB), as well as complexes of poly-N,N'-dimethyldiallylammonium chloride (PDACL) with sodium dodecylsulfate (SDS) were studied. The micellar phase of such complexes is highly organized molecular system, molecular ordering of which near the polymeric chain is much higher than in the 'center' of the micelle, it depends on the polymer-detergent interaction, flexibility of polymeric chain and length of carbonic part of the detergent molecule. Complexes of polymethacrylic acid (PMAA) with non-ionic detergent (dodecyl-substituted polyethyleneglycol), show that the local mobility of surfactant in such complexes is significantly lower than in 'free' micelles and depends on the number of micellar particles participating in formation of complexes.     

EPR spin probe study of polymer associative systems

Molecular dynamics of polyacrylamide gels, polymeric micelles and hydrogel of polyacrylic acid and macrodiisocyanate was investigated by the ESR spectroscopy of spin probes. The local mobility in network junction of polyacrylamide gels is found to be essentially slower than that in the micelles created by the low molecular weight detergents and does not depend on the amount and length of hydrophobic groups (C9 or C12) in the polymer chain. The immersion of 10-30 mol.% of ionic monomers into the polymer chain (sodium acrylate) influences insufficiently on the local mobility of network junctions. In aqueous solutions, polystyrene-block-poly-(N-ethyl-4-vinylpyridinium bromide) block copolymers create polymeric micelles. The local mobility in the polystyrene core of the micelles is about twice as much as that in the solid polystyrene. Partially swellable polymer network in aqueous solutions was synthesized from polyacrylic acid and macrodiisocyanate. The local mobility in hydrophobic regions of the gel is substantially lower than that in the hydrophilic regions. It was concluded that the hydrophobic and hydrophilic regions and the local dynamics of them dictate practical application of the polymer associative systems.     

Effect of pressure on the rotational mobility of spin probes in polymers

The effects of pressure on the rotational mobility of three nitroxyl radicals (spin probes) in natural rubber, polyethylene, and butadiene-nitrile rubber SRN-26 have been studied. The activation volumes, activation energies, and pre-exponential factors of spin probe rotation at constant pressure and volume have been determined. The activation volumes of probe rotation (20–70 cm³/mol) increase with increasing size of radicals and differ insignificantly from the activation volumes of the β-relaxation process. In the polar polymer SRN-26, the activation volumes of rotation of radicals are appreciably more than in the nonpolar polymers, natural rubber and polyethylene. These features are apparently due to different volumes of the kinetic chain segment controlling probe rotation. The activation volumes of radical rotation around different molecular axes differ significantly. The activation energy of probe rotation at constant volume is appreciably less than at constant pressure. It has also been shown that the energy necessary for the formation of a fluctuation hole is the main factor that determines temperature dependence of the rotational mobility of low-molecular particles in the polymer.     

Molecular mobility in micellar complexes of a nonionic surfactant and the poly(acrylic acid)-based hydrogel

The interaction between the polyelectrolyte gel of crosslinked poly(acrylic acid) (PAA) and nonionic surfactant Brij 58 based on poly(ethylene glycol) (C₁₆H₃₃(CH₂CH₂O)₂₀OH) is studied. It is established that poly(acrylic acid)-surfactant complexes are formed. Nondissociated carboxyl groups of poly(acrylic acid) and oxygen atoms of the surfactant are involved in the complexation. Surfactant micelles are a kind of bridge that connects polymer chains. The presence of the surfactant decreases the equilibrium swelling of the hydrogel. The spin probe method is employed to determine the local mobility of the hydrocarbon core of a micelle in the complex. It was shown that the local mobility is independent of the hydrogel crosslink density and is much lower in acidic than in alkaline media. In acidic media, much more surfactant molecules of micelles are involved in the complexation than in alkaline media. However, even in alkaline media, surfactant micelles cannot leave the hydrogel, while the spin probes located in micelles are at equilibrium with the spin probes present in the external aqueous medium. The prospects for applying the considered systems as carriers for controlled release drugs are discussed.     

Structural aspects in self-assembled systems of polyoxyethylene surfactants, as studied by the spin probe technique

Typical examples of structural characterization of self-assembled systems by the spin probes technique, selected from our representative results accumulated in the last years of systematic studies, are presented. The choice of the examples has aimed at emphasizing the potentiality of this technique in the study of self-assembled systems, in general, and of those of PEO surfactants, in particular. By using specific ESR parameters (the nitrogen hyperfine splitting (hfs), a_N, the rotational correlation time, τ_c, the order parameter, S) of a variety of properly chosen nitroxides, problems such hydration degree and profile of the PEO chains, ordering and order profile along these chains, their penetrability by the oil solvent, role of the terminal OH in the micellization, as well as differences in these quantities vs. the nature of the aggregate (micelle, reverse micelle, lamellar phase, etc.), nature of the surfactants (conventional or triblock copolymer), solubilizates (water in reverse micelles or various alcohols in micelles) and temperature have been discussed.     

Mobility of anionic spin probes in water-containing nylon 6 film

The rotational mobility of anionic spin probes in water-containing nylon 6 film was investigated by means of electron spin resonance (ESR) measurements for comparison with the results for nonionic spin probes reported previously. The extrema separation of the ESR spectra, 2Az′ increased with time owing to the evaporation of water. In the higher temperature region, 2Az′ increased steeply with time at first, and then more slowly, whereas for the nonionic spin probes, 2Az′ increased gradually and monotonically with time. This fact suggests that the anionic probe molecules are more strongly affected by water than the nonionic ones, i.e., the former probes are located in hydrophilic regions and the latter in hydrophobic regions. T_50G, which can be empirically correlated with the glass transition temperature of the polymer T_g decreased with increasing water content. The decreasing tendency for the anionic spin probes was stronger than that for the nonionic ones. This fact also indicates that the local environment around the probe molecules varies from probe to probe. The rotational correlation time τ_R decreased markedly with an increase in water content. The Arrhenius plots of τ_R showed two crossover points. The crossover points in the higher temperature region T_n decreased greatly with increasing water content. The difference in T_n between dried and water-containing films was larger than that for T_50G. The activation energy for rotation, E, also decreased with increasing water content. It is suggested that water concentrates around the anionic spin probes and makes their rotation much easier.     

Intramolecular mobility of spin labelled poly(vinylpyrrolidone) and poly(vinylcaprolactam) in solutions

The intramolecular (segmental) mobilities of poly(vinylpyrrolidone) and poly(vinylcaprolactam) in solutions have been investigated using the spin label technique. The rotational correlation times for the segments do not depend on the spin label used for their determination. The rotational correlation times and the effective segmental dimensions for poly(vinylcaprolactam) are greater than those for poly(vinylpyrrolidone), the difference being due to different dimensions of the side-groups of the macromolecules. Near the temperature of phase separation in an aqueous solution of poly(vinylcaprolactam), the hydrophobic interaction of macromolecular side-groups leads to the compression of the molecular coil. As a result, the segmental mobility diminishes, and the spatial limitations on the rotation of a spin label surrounded by bulky side-groups become more severe.     

Molecular structure and dynamics of poly(methacrylic acid) and poly(acrylic acid) complexes with dodecyl-substituted poly(ethylene glycol)

The molecular dynamics and the structure of molecular complexes formed by micelles of dodecyl-substituted poly(ethylene glycol) with poly(methacrylic acid) and poly(acrylic acid) in aqueous solutions were studied by viscosimetry, pH measurement, and electron spin resonance spin-probe techniques. At low surfactant concentrations, the conformation of the complex is a compact globule. The local mobility of surfactant molecules in such a complex is much slower than that in the free micelle. At high surfactant concentration, the nonionic micelles and polyacids form hydrophilic associates. The associates have the conformation of extended coils. In an associate, a major part of the micellar poly(ethylene glycol) groups is free. The local mobility of the micellar phase depends on the number of micelles involved in an associate. The mobility of surfactant molecules is slower in the complexes of poly(methacrylic acid) than in the complexes of poly(acrylic acid).     

Macroscopic, mesostructured cationic surfactant/neutral polymer films: structure and cross-linking

Mesostructured films of alkyltrimethylammonium bromides or cetylpyridinium bromide and polyethylenimines that spontaneously self-assemble at the air/water interface have been examined using a range of surface sensitive techniques. These films are unusual in that they can be micrometers thick and are relatively robust. Here we show that the films can be cross-linked and thus removed from the liquid surface where they form, as solid, mesostructured polymer-surfactant membranes. Cross-linking causes little change in the structure of the films but freezes in the metastable mesostructures, enhancing the potential of these films for future applications. Cross-linked films, dried after removal from the solution surface, retain the ordered nanoscale structure within the film. We also report grazing incidence X-ray diffraction (GID), which shows that most films display scattering consistent with 2D-hexagonal phase crystallites of rodlike surfactant micelles encased in polymer. Polymer branching makes little difference to the film structures; however, polymer molecular weight has a significant effect. Films with lower polymer MW are generally thinner and more ordered, while higher polymer MW films were thicker and less ordered. Increased pH causes formation of thicker films and improves the ordering in low MW films, while high MW films lose order. To rationalize these results, we propose a model for the film formation process that relates the kinetic and thermodynamic limits of phase separation and mesophase ordering to the structures observed.     

Mobility of spin probes having a primary,secondary, tertiary,or quaternary amino group in drawn and undrawn nylon 6 film

The mobility of spin probes having a secondary, tertiary, or quaternary amino group in dried nylon films was investigated by means of electron spin resonance (ESR) measurements and compared with the behavior of previously investigated spin probes having a primary amino group, a carboxylate group, or a sulfate group. The spin probes having a primary or secondary amino group showed effects of drawing on the mobility, while the other probe molecules did not. This result could be interpreted by considering the interactions between the spin probes and the nylon chains. In the undrawn nylon film, the mobilities of the nonionic spin probes were almost the same, and smaller than those of the charged spin probes, suggesting that the location in the nylon film is different for the uncharged and charged spin probes. These results are discussed in detail using separation of extrema of the ESR spectra, rotational correlation times, and anisotropy parameters.     

Local mobility of micelles of new cationic surfactants and their interactions with hydrophobically modified polyacrylamides

The local dynamics and organization of micelles of new long-chain cationic surfactants with saturated hydrocarbon fragments (from C₁₆ to C₂₂) are investigated via the EPR spin-probe technique. The local mobility of spin probes in the hydrocarbon core of a micelle changes insignificantly, while the order parameter noticeably increases with lengthening of the hydrocarbon fragment of the surfactant molecule. The specific features of the interaction of the surfactants with network junctions of the gels formed by two types of hydrophobically modified polyacrylamides??either containing charged groups (sodium acrylate) in the backbone or lacking these groups??are studied. In both cases, the local mobility of network junctions of the gel increases after the introduction of the surfactant (C₁₈). Moreover, for surfactant with a long alkyl group (C₂), the microscopic viscosity of the gel based on the uncharged polymer decreases, although the local mobility of the network junctions increases. Possible causes of the observed specific features are discussed.     

EPR spin labelling studies of molecular dynamics in elastomer-silica composites

Novel methods of nitroxyl spin labelling suitable for molecular dynamics studies within the interface regions of SBR elastomer/silica composites have been developed and used together with the nitroxyl spin probe technique. Fast and slow motional components have been identified within the interface regions and the corresponding rotational diffusion tensors have been measured as a function of the temperature and the SiO₂ concentration. The fast rotational frequency is found to be orders of magnitude slower than that measured in the absence of SiO₂. This difference is suggested to arise from a closer packing of the macromolecules near the silica surface caused by the van der Waals bonding interactions. Increase of the SiO₂ concentration results in a decrease of the molecular mobility. This effect has been imputed to the overlapping of the bonding interaction regions. Spin probe measurements in the SBR-SiO₂ matrices using TEMPO, strongly suggest that the hindrance to chain segmental motion induced by the SiO₂-SBR interactions propagates beyond the interface regions thus involving the bulk polymer matrix. It is suggested that the information on the segmental chain dynamics obtained through the spin labelling and spin probe measurements can be developed as a method for investigating the polymer/filler interactions within the reinforcing mechanism by the filler.     

NEW PROBES FOR SURFACTANT SOLUTIONS: PHOSPHORESCENT LABELLED DETERGENTS

Abstract— A series of alkyltrimethylammonium bromides containing terminal phosphorescent chromo-phores have been prepared and characterized. 10-(4-bromo, l-naphthoyl)decyltrimethylammonium bromide(BND–10) has a critical micelle concentration (CMC) of 14 mM and a micellar mean aggregation number ( ) of 105. Analogous detergents,BND–11, -8, and -5 have also been prepared; in each case, the naphthoyl group is located at the terminal carbon of an alkyl chain of the indicated length. The normal behavior of increasing and decreasing CMC with increasing aliphatic chain length is observed. When compared with unsubstituted alkyltrimethylammonium bromides, the 4-bromo, 1-naphthoyl chromo-phore is roughly equivalent to 6 methylenes with respect to hydrophobic contribution. A broad phosphorescence maximizing at about 590 nm is readily detected upon photoexcitation of the BND molecules in various solvents. The weak fluorescence of the probes is consistent with efficient intersystem crossing of the BND molecules. BND–10 has a phosphorescence yield of 0.023 and a lifetime of 1 ms in water at 25₀C. The probes are useful for the study of micelle-detergent exchange dynamics.     

Molecular Dynamics and Organization of Micellar Complexes of Poly(acrylic acid) with Poly(ethylene glycol)-Based Surfactants

The structure and molecular dynamics of complexes of poly(acrylic acid) with dodecyl-substituted poly(ethylene glycol)s in aqueous solutions are studied by viscometry and spin probe ESR spectroscopy. It is shown that, at low surfactant concentrations, the complexes have a compact globular conformation. The local mobility of the surfactant molecules in the complexes under consideration is much lower than their mobility in free micelles. As a result of increasing surfactant concentration in solution, the hydrophilic associates of the surfactant micelles with the polyacid having an unfolded coil conformation are formed. In an associate, a significant fraction of poly(ethylene glycol) fragments incorporated into micelles is in the free state, i.e., these fragments are not bound with a polymer chain. The local mobility of the surfactant molecules in the associate is considerably higher than in the complex with a compact conformation, and this mobility grows with the increasing number of micelles involved in the associate.     

Peptide‐poly(tert‐butyl methacrylate) conjugate into composite micelles in organic solvents versus peptide‐poly(methacrylic acid) conjugate into spherical and worm‐like micelles in water: Synthesis and self‐assembly

Peptide–polymer conjugates are versatile class of biomaterials composed of a peptide block covalently linked with a synthetic polymer block. This report demonstrates the synthesis of peptide‐poly(tert‐butyl methacrylate) (Peptide‐P^tBMA) conjugates of varying molecular weights via a “grafting from” atom transfer radical polymerization (ATRP) technique using as‐synthesized peptide‐based initiator in toluene. Peptide‐P^tBMA conjugate is soluble in many organic solvents and undergoes self‐assembly into micro/nanospheres in DMF/THF as observed from both FESEM and DLS results. The conjugate micro/nanospheres are nothing but the composite micelles formed by the secondary aggregation of primary micelles generated initially in these organic solvents. The hydrolysis of tert‐butyl groups of Peptide‐P^tBMA conjugate leads to the formation of peptide‐poly(methacrylic acid) (Peptide‐PMA) conjugate. The circular dichroism (CD) analysis exhibits the presence of β‐sheet conformation of peptide moiety in synthesized conjugates. The formed Peptide‐PMA conjugate is soluble in water and owing to its amphiphilic character, the conjugate molecules self‐assemble into spherical micelles as well as worm‐like micelles upon increasing the concentration of conjugate in water. However, the sodium salt of Peptide‐PMA conjugates (Peptide‐PMAS) self‐assembles into only spherical swollen micelles in water at higher (pH ～10). The critical aggregation concentrations (CACs) of both Peptide‐PMA and Peptide‐PMAS micelles are measured by fluorescence spectroscopy. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3019–3031     

Electrical conductivity study on micelle formation of long-chain imidazolium ionic liquids in aqueous solution

Electrical conductivity was measured for aqueous solutions of long-chain imidazolium ionic liquids (IL), 1-alkyl-3-methylimidazolium bromides with C(12)-C(16) alkyl chains. The break points appeared in specific conductivity (kappa) vs concentration (c) plot indicates that the molecular aggregates, i.e., micelles, are formed in aqueous solutions of these IL species. The critical micelle concentration (cmc) determined from the kappa vs c plot is somewhat lower than those for typical cationic surfactants, alkyltrimethylammonium bromides with the same hydrocarbon chain length. The electrical conductivity data were analyzed according to the mixed electrolyte model of micellar solution, and the aggregation number, n, and the degree of counter ion binding, beta, were estimated. The n values of the present ILs are somewhat smaller than those reported for alkyltrimethylammonium bromides, which may be attributed to bulkiness of the cationic head group of the IL species. The thermodynamic parameters for micelle formation of the present ILs were estimated using the values of cmc and beta as a function of temperature. The contribution of entropy term to the micelle formation is superior to that of enthalpy term below about 30 degrees C, and it becomes opposite at higher temperature. This coincides with the picture drawn for the micelle formation of conventional ionic surfactants.     

Temperature dependence of ESR spectra of nitroxide spin probe in glassy polymers

Temperature dependencies of ESR spectra of nitroxide spin probes in glassy polymers near and below glass transition temperature were examined in detail. Three temperature ranges, each characterized by specific changes in spectral shape, were defined. (i) In the low temperature range, ESR spectra of nitroxide radical in glassy polymer matrix weakly depend on temperature and remain qualitatively the same. (ii) In the intermediate temperature range, significant changes in the shape of spectra are observed. (iii) A new phenomenon was revealed near and below glass transition temperature: narrowing of linewidths occurs while the ratio of amplitudes of different components varies insignificantly. Analysis of molecular rotational mobility was carried out by means of commonly used empirical approaches. It was shown that widely used formulas and empirical approaches are not applicable for characterization of molecular mobility in glassy polymers. Mechanisms of rotational molecular movements in glassy polymers are discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 563–575, 2009     

Local mobility and structure of cationic amphiphilic diblock copolymer micelles in aqueous solutions

The local mobility and organization of micelles formed by the cationic diblock copolymer PS-poly(N-ethyl-4-vinylpyridinium bromide) in dilute aqueous solutions is studied by spin-probe ESR spectroscopy. Micelles composed of a hydrophobic PS core and a lyophilizing polyelectrolyte corona are prepared by two methods: dialysis from a nonselective solvent and direct dispersion of the diblock copolymer in water under long-term heating. Velocity-sedimentation studies and static and dynamic light-scattering measurements show that the micelles obtained by dialysis have smaller mean hydrodynamic sizes and weight-average molecular masses and are less polydisperse than micelles prepared by direct dispersion. The ESR spectra of spin probes localized in micelles of both types are found to be identical. This finding suggests that their local structure is independent of the dispersion procedure and molecular-mass characteristics. Probes are localized in the outer layer of the PS core near the core/shell boundary, and their local mobility is a factor of ∼2 higher than the local mobility of probes in the phase of the solid PS. It is inferred that the structure of the outer layer of the PS core in micelles is looser than the structure of PS in the solid phase. The localization sites of spin probes are partially penetrated by water.     

Dynamic nuclear polarization enhanced nuclear magnetic resonance and electron spin resonance studies of hydration and local water dynamics in micelle and vesicle assemblies

We present a unique analysis tool for the selective detection of local water inside soft molecular assemblies (hydrophobic cores, vesicular bilayers, and micellar structures) suspended in bulk water. Through the use of dynamic nuclear polarization (DNP), the (1)H NMR signal of water is amplified, as it interacts with stable radicals that possess approximately 658 times higher spin polarization. We utilized stable nitroxide radicals covalently attached along the hydrophobic tail of stearic acid molecules that incorporate themselves into surfactant-based micelle or vesicle structures. Here, we present a study of local water content and fluid viscosity inside oleate micelles and vesicles and Triton X-100 micelles to serve as model systems for soft molecular assemblies. This approach is unique because the amplification of the NMR signal is performed in bulk solution and under ambient conditions with site-specific spin labels that only detect the water that is directly interacting with the localized spin labels. Continuous wave (cw) electron spin resonance (ESR) analysis provides rotational dynamics of the spin-labeled molecular chain segments and local polarity parameters that can be related to hydration properties, whereas we show that DNP-enhanced (1)H NMR analysis of fluid samples directly provides translational water dynamics and permeability of the local environment probed by the spin label. Our technique therefore has the potential to become a powerful analysis tool, complementary to cw ESR, to study hydration characteristics of surfactant assemblies, lipid bilayers, or protein aggregates, where water dynamics is a key parameter of their structure and function. In this study, we find that there is significant penetration of water inside the oleate micelles with a higher average local water viscosity ( approximately 1.8 cP) than in bulk water, and Triton X-100 micelles and oleate vesicle bilayers mostly exclude water while allowing for considerable surfactant chain motion and measurable water permeation through the soft structure.     

Removal of solvent-based ink from printed surface of HDPE bottles by alkyltrimethylammonium bromides: effects of surfactant concentration and alkyl chain length

Three alkyltrimethylammonium bromides (i.e., dodecyl-, tetradecyl-, and hexadecyltrimethylammonium bromide or DTAB, TTAB, and CTAB, respectively) were used to remove a blue solvent-based ink from a printed surface of high-density polyethylene bottles. Either an increase in the alkyl chain length or the surfactant concentration was found to increase the deinking efficiency. Complete deinking was achieved at concentrations about 3, 8, and 24 times of the critical micelle concentration (CMC) of CTAB, TTAB, and DTAB, respectively. For CTAB, ink removal started at a concentration close to or less than its CMC and increased appreciably at concentrations greater than its CMC, while for TTAB and DTAB, significant deinking was only achieved at concentrations much greater than their CMCs. Corresponding to the deinking efficiency of CTAB in the CMC region, the zeta potential of ink particles was found to increase with increasing alkyl chain length and concentration of the surfactants, which later leveled off at some higher concentrations. Wettability of the surfactants on an ink surface increased with increasing alkyl chain length and concentration of the surfactants. Lastly, solubilization of ink binder in the surfactant micelles was found to increase with increasing alkyl chain length and surfactant concentration. We conclude that adsorption of surfactant on the ink pigment is crucial to deinking due to modification of wettability, zeta potential, pigment/water interfacial tension, and dispersion stability. Solubilization of binder (epoxy) into micelles is necessary for good deinking because the dissolution of the binder is required before the pigment particles can be released from the polymer surface.