Sodium Decyl Sulfate Research Articles

Nonideal Mixed Micelles of Fluorinated and Hydrogenous Surfactants in Aqueous Solution. NMR and SANS Studies of Anionic and Nonionic Systems

Contrast variation SANS and (19)F chemical shifts were measured for three mixed equimolar micelle systems: sodium perfluorooctanoate (SPFO) and sodiumdecylsulfate (SDeS) in 200 mM NaCl, lithium perfluorononanate (LiPFN) and lithium dodecylsulfate (LiDS) in 200 mM LiCl, and a nonionic system C(8)F(17)C(2)H(4)(OC(2)H(4))(9) and C(12)H(25)(OC(2)H(4))(8) in water, all at 25 degrees C. The chemical shift measurements allow the calculation of the average fraction of nearest neighbors of each kind around the reporter group (the trifluoromethyl group). A preference for like neighbors were found in all systems, smallest in the SDeS/SPFO system and largest in the nonionic system, but in all cases substantially smaller than expected at critical conditions. From the SANS measurements the width of the micelle composition distribution was obtained. For the ionic systems similar values were obtained, showing a broadening compared to ideal mixtures, but not broad enough for demixing or clearly bimodal distributions. In the nonionic system the width was estimated as sigma = 0.18 and 0.22 using two different evaluation methods. These values suggest that the system is close to critical conditions. The lower value refers to a direct modeling of the system, assuming an ellipsoidal shape and a Gaussian composition distribution. The modeling showed the nonionic mixed micelles to be prolate ellipsoids with axial ratio 2.2 and an aggregation number larger than 100, whereas the two ionic systems fitted best to oblate shapes (axial ratios 0.8 and 0.65 for SDeS/SPFO and LiDS/LiPFN, respectively) and aggregation numbers of 60 for both.

Thermodynamic study of sodium decyl sulfate solutions in the region the second critical micellization concentration: 1. Volumetric and heat capacity properties

Densitometry and precision adiabatic scanning calorimetry are used to reveal a number of volumetric and heat capacity properties of sodium decyl sulfate in the region of the second critical micelle concentration. Heat capacities are established in a wide temperature range. The coefficients of thermal expansion, apparent and partial mole expandabilities, volume, heat capacities, and excess partial mole heat capacities are calculated. The analysis of variations in these thermodynamic properties occurring upon variations in concentration and temperature makes it possible to identify the structural variations in sodium decyl sulfate micelles that are relevant to the transition of micelles from globular to cylindrical forms.

Inhomogeneities in sodium decylsulfate doped 1,2-dipalmitoylphosphatidylcholine bilayer

Differential scanning calorimetry (DSC), dynamic light scattering (DLS), and turbidity measurements have been used to study the effect of sodium decylsulfate, C10OS, on 1,2-dipalmitoylphosphatidylcholine, DPPC, vesicles. DSC measurements, performed soon after addition of C10OS solutions to DPPC vesicular dispersion, at several C10OS/DPPC molar ratios, showed the contemporary presence of maxima ascribable both to transitions of an unmodified DPPC membrane and to transitions related to membrane domains in which C10OS is also present. In all the considered samples only unilamellar vesicles are present as shown by DLS measurements carried out on aqueous DPPC and C10OS–DPPC systems. Also the aging of the samples confirmed the presence of SUV in the time scale of DSC measurements. On the basis of DSC results the pseudo-phase diagram of the system was drawn. This diagram does not represent a system in equilibrium, from a thermodynamic point of view, but only kinetically probable states. In fact the prolonged aging of the solutions used both for DSC and DLS scans highlight the disappearance of the unmodified DPPC membrane and its conversion into a mixed membrane. Turbidity measurements at 25 °C, performed as a function of surfactant composition, showed that C10OS initially contributes to increase the vesicles dimensions and allowed to calculate the saturation ratio C10OS/DPPC in the membrane. In contrast, at 45 °C the presence of surfactant gives origin immediately to smaller structures in comparison to vesicles, probably gel-state micelles.

Adsorption of Binary Mixtures of Anionic Surfactants at Water–Air and Poly(Tetrafluoroethylene)–Water Interfaces

AbstractMeasurements of the surface tension (γLV) and the advancing contact angle (θ) on poly(tetrafluoroethylene) (PTFE) were carried out for aqueous solutions of sodium decyl sulfate (SDS) and sodium dodecyl sulfate (SDDS) and their mixtures. The results obtained indicate that the values of the surface tension and the contact angle of solutions of surfactants on PTFE surface depend on the concentration and composition of the surfactants mixture. On the curves presenting the relationship between the surface tension, contact angle and monomer mole fraction of SDDS (α) in the mixture of SDDS and SDS, there is a minimum at α equal to 0.8 which together with the negative values of the interaction parameters indicate that synergism occurs in surface tension and contact angle reduction almost in the range of concentration corresponding to the saturated monolayer of surfactants at the water–air interface. The results and calculations obtained also indicate that for single surfactants and their mixtures at a given concentration in the bulk phase, the values of surface excess concentration of the surfactants at water–air and PTFE–water interfaces are nearly the same, which suggests that the orientation of SDDS and SDS molecules at both interfaces in saturated monolayer should be vertical to the interfaces. Taking into account the values of the monomer mole fractions of the surfactants in a mixed monolayer at the water–air interface and values of the contact angle of a single surfactant on the PTFE surface, it is possible in a simple way to predict the values of the contact angle of a mixture at a given concentration and composition.

Thermodynamics of Micellization of Aqueous Solutions of Binary Mixtures of Two Anionic Surfactants

The thermodynamics of micellization of mixed anionic/anionic surfactant solutions, that is, sodium dodecyl sulfate (SDDS) and sodium decyl sulfate (SDS), have been studied by surface tension, density, and conductivity measurements. The obtained results indicate that the values of critical micelle concentration strongly depend on the composition of the mixture and that the mole fraction of surfactants in the mixed micelle calculated on the basis of Rosen and Villeneuve approaches are different from those in the bulk phase. The small negative deviation from the linear relationship between the critical micelle concentrations and composition of SDDS and SDS mixtures in the bulk phase, the values of the molecular interaction parameters, activity coefficients, and the excess Gibbs energy of mixed micelle formation calculated on the basis of Rosen and Villeneuve approaches and calculations based on the MT theory of Blankschtein proved that there is synergism in mixed micelle formation of aqueous solutions of SDDS and SDS. It was also found that the values of the standard Gibbs energy of micellization for the mixture of these two surfactants which confirm the synergetic effect can be predicted on the basis of the proposed equations which include the values of the mole fraction of surfactant in the mixed micelle and excess Gibbs energy of micellization of SDDS and SDS. Knowing the values of mole fractions of surfactants in the mixed micelle, it is also possible to calculate the volume change of surfactants after the micellization process.

Differences between Sodium Decylsulfate and Sodium Decanesulfonate when Interacting with Cationic Polyelectrolyte

Interactions between the cationic polyelectrolyte polydimethyldiallylammonium chloride (PDMDAAC) and sodium decylsulfate as well as sodium decanesulfonate were investigated by surface tension and pyrene fluorescence spectroscopy techniques. We found that although many properties of sodium decylsulfate and sodium decanesulfonate are similar, there are striking differences in their interactions with PDMDAAC. Sodium decylsulfate interacts with PDMDAAC more strongly than sodium decanesulfonate does. The experimental results in this work were explained by the data of the quantum chemical calculation.

Thermodynamic Study of Intermediate State of Papain Induced by n-Alkyl Sulfates at Two Different pH Values: A Spectroscopic Approach

The formation of the intermediate state of papain was induced by n-alkyl sulfates including sodium octyl sulfate, SOS; sodium decyl sulfate, SDeS; and sodium dodecyl sulfate, SDS at different concentrations. A systematic investigation of n-alkyl sulfates induced conformational alteration in molten globule state under an acidic condition and the native state of papain was examined by tryptophan fluorescence, 1-anilino 8-naphtalene sulfonic acid (ANS) binding and UV absorbance. The addition of n-alkyl sulfates to molten globule state at pH 2 shows a decrease in tryptophan fluorescence intensity and quenched ANS fluorescence relative to the native state that leads to enhancement in tryptophan fluorescence and an increase in ANS fluorescence as well. In the presence of n-alkyl sulfates in various conditions, two intermediate (IA and IB) with different conformations were obtained at acidic and native states, respectively. Thus, we can assume that the intermediate states in folding and unfolding pathways in various conditions have different structures. The results show that SDS is much more effective than SDeS and SOS for the formation of the intermediate states for papain in the two different pathways due to the presence of its hydrophobic tail. Therefore, hydrophobic interactions play an important role in inducing the two different intermediates along the two various thermodynamic pathways.

The gibbs energy, chemical potential, and state parameters of the surface of an ionic micelle in the form of an ellipsoid of revolution

A molecular-thermodynamic model of an ionic micelle in the form of an ellipsoid of revolution was suggested. Equations for the chemical potential of an ellipsoidal micelle, the work of transfer of ions from solution volume into the micelle, and the state parameters of the surface of the micelle (fraction of free hydrophobic surface, surface tension coefficient, and surface charge density) were obtained. The Gibbs energy, chemical potential, work of transfer, and state parameters of an ellipsoidal micelle were determined as depending on the form factor of the corresponding ellipsoid. The model was verified for the example of sodium decyl sulfate micelles. The calculated parameters were close to the thermochemical data on the asymmetrization of spherical micelles in a solution of sodium decyl sulfate. The equilibrium ion-micellar solution composition was estimated.

Effects of Anionic Surfactants on the Hydride-Transfer Reaction of NADH with Methylene Blue: In Premicellar and Micellar Regions

Abstract The kinetics of the hydride-transfer reaction between methylene blue (MB) and reduced nicotinamide–adenine dinucleotide (NADH) were studied in basic buffer solutions containing anionic surfactants (sodium dodecyl sulfate (SDS), sodium decyl sulfate (SDES), and sodium tetradecyl sulfate (STS)) under oxygen-saturated conditions. Initially, the absorbance of MB at 666 nm decreased with SDES concentration, but increased gradually near and above the cmc. The observed first-order rate constant (kobsd) decreased gradually at first, more steeply with increasing SDES concentration and then reached to a small value and became constant. The changes in the absorbance of MB and the observed rate constant were explained by changes in the form of MB in the solution with increasing SDES concentration. The concentration of SDES can be divided into four regions, in connection with the changes in the absorbance and the observed rate constant. The profiles of the changes in the absorbance of MB and the apparent rate constant for SDS and STS with surfactant concentrations were very similar to those for SDES.

Monomer Concentrations in Simple Micellar Systems from NMR Relaxation Times and C‐13 Chemical Shifts

The monomer concentrations for some simple micelle forming surfactants, octylammonium bromide (OTAB), sodium decyl sulphate, SDecS, and dodecyltrimethylammonium bromide (DTAB) were determined from the NMR‐paramagnetic relaxation enhancement experiment (the NMR‐PRE) on the H‐1 spin lattice relaxation times for the surfactant protons as a function of the surfactant concentration above and below the critical micelle concentration (cmc region). The NMR relaxation times, determined from the inversion recovery method, decrease steadily as the concentration of the surfactant is increased above the cmc value. A second, simple method is proposed whereby the p‐value of the surfactant in the micelle is determined from the two‐site model via extrapolation of the observed relaxation rate data to high concentrations. The p‐values and the calculated monomer concentrations are compared to each other and to those obtained using the mass‐action and phase separation models. In most cases, the monomer concentrations appear to remain constant at concentrations up to 2–3 times the cmc value, and then begin to decrease thereafter. These results are compared to the trends in monomer concentrations obtained from other NMR experiments in other surfactant systems.

Wetting Behavior of Aqueous Solutions of Binary Surfactant Mixtures to Poly(tetrafluoroethylene)

Measurements of the surface tension (γ LV) and advancing contact angle () on poly(tetrafluoroethylene) (PTFE) were carried out for aqueous solutions of cetyltrimethylammonium bromide (CTAB), cetylpyridynium bromide (CPyB), sodium decylsulfate (SDS), sodium dodecylsulfate (SDDS), p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethylene glycol)s, Triton X-100 (TX100) and Triton X-165 (TX165) and their mixtures. The results obtained indicate that the values of the surface tension and wettability of PTFE depend on the concentration and composition of the surfactants mixture. In contrast to Zisman finding, there was no linear dependence between cos and the surface tension of aqueous solutions of surfactants and their mixtures for all studied systems, but a linear dependence existed between the adhesional tension and solution surface tension for PTFE in the whole concentration range, the slope of which was –1, indicating that the surface excess concentration of surfactant at the PTFE–solution interface was the same as that at the solution–air interface for a given bulk concentration. It was also found that the work of adhesion of aqueous solutions of surfactants and their mixtures to PTFE surface did not depend on the type of surfactant, its concentration and composition of the mixture. This means that for the studied systems the interaction across PTFE–solution interface was constant, and it was largely of Lifshitz–van der Waals type. On the basis of the surface tension of PTFE and the Young equation and thermodynamic analysis of the work of adhesion of aqueous solutions of surfactants to the polymer surface it was found that in the case of PTFE the changes of the contact angle as a function of the total mixture concentration in the bulk phase resulted only from changes of the polar component of the solution surface tension.

Photophysics of a Cationic Biological Photosensitizer in Anionic Micellar Environments: Combined Effect of Polarity and Rigidity

A steady-state and time-resolved photophysical study of a cationic phenazinium dye, phenosafranin (PSF), has been investigated in well-characterized biomimetic micellar nanocavities formed by anionic surfactants of varying chain lengths, namely, sodium decyl sulfate (S(10)S), sodium dodecyl sulfate (S(12)S), and sodium tetradecyl sulfate (S(14)S). In all these micellar environments, the charge transfer fluorescence of PSF shows a large hypsochromic shift along with an enhancement in the fluorescence quantum yield as compared to that in aqueous medium. A reduction in the nonradiative deactivation rate within the hydrophobic interior of micelles led to an increase in the fluorescence yield and lifetime. The present work shows the degree of accessibility of the fluorophore toward the ionic quencher in the presence of surfactants of different surfactant chain lengths. The fluorometric and fluorescence quenching studies suggest that the fluorophore resides at the micelle-water interfacial region. The enhancements in the fluorescence anisotropy and rotational relaxation time of the probe in all the micellar environments from the pure aqueous solution suggest that the fluorophore binds in motionally restricted regions introduced by the micelles. Polarity and viscosity of the microenvironments around the probe in the micellar systems have been determined. The work has paid proper attention to the hydrophobic effect of the surfactant chain length on photophysical observations.

A study of the structure of mixed micellar solutions based on heptaethylene glycol monotetradecyl ether and sodium (lithium) dodecyl sulfate by the small-angle neutron scattering method

The micellization in mixed aqueous systems based on a new nonionic surfactant, namely, heptaethylene glycol monotetradecyl ether (C14E7), and an anionic surfactant, namely, sodium dodecyl sulfate, sodium decyl sulfate, or lithium dodecyl sulfate, is studied by small-angle neutron scattering. Preliminary results of the investigation into the behavior of C14E7 aqueous solutions (at two concentrations, 0.17 and 0.50%) upon addition of small amounts of three different classical anionic surfactants are reported.

Extraction preconcentration with anionic surfactants in acidic solutions

Extraction preconcentration with anionic surfactants in acidic solutions on the basis of the cloud point was studied. Advantages and disadvantages of this method were considered. Conditions of the phase separation of some anionic surfactants (sodium decyl sulfate, sodium dodecyl sulfate, sodium dodecyl sulfonate, and sodium dodecylbenzene sulfonate) in acidic solutions were studied. With the example of pyrene and its derivatives, it was demonstrated that these surfactants can be used for extraction preconcentration. Analytical characteristics of the determination of pyrene and its derivatives in model aqueous solutions by the fluorimetric method in combination with extraction preconcentration with sodium dodecyl sulfate were obtained

Surfactant Chain-Length-Dependent Modulation of the Prototropic Transformation of a Biological Photosensitizer: Norharmane in Anionic Micelles

A photophysical study of norharmane (NHM), an efficient cancer cell photosensitizer, has been undertaken in well-characterized biomimetic micellar nanocavities formed by anionic surfactants of varying chain length, namely, sodium decyl sulfate (S10S), sodium dodecyl sulfate (S12S), and sodium tetradecyl sulfate (S14S), using steady-state and time-resolved fluorescence spectroscopy. The effect of the hydrophobic chain length on the structural dynamism of the fluorophore has been reported. Experimental results demonstrate that the equilibrium of this dynamism is sensitive to the environment. Variation in the surfactant chain length plays an important role in promoting a specific prototropic form of the probe molecule. A striking feature of the present study is that an increase in the surfactant chain length (hydrophobicity) favors the cationic species of NHM. This has been rationalized on the basis of changes in the local pH and the aggregation number of the micelles. A fluorescence quenching study of the micelle-bound probe using ionic quencher Cu2+ corroborates this.

Self-Aggregation of Ionic C10 Surfactants Having Different Headgroups with Special Reference to the Behavior of Decyltrimethylammonium Bromide in Different Salt Environments: A Calorimetric Study with Energetic Analysis

Self-aggregation of C10 ionic surfactants with different head groups, viz., decylpyridinium chloride, sodium decylsulfate, decylammonium bromide, decyldimethylammonium bromide, and decyltrimethylammonium bromide, was studied in the aqueous medium by microcalorimetric and conductometric methods. The effects of temperature and different salts (NaF, NaCl, NaBr, NaI, Na2SO4, Na2S2O7, Na-benzoate, and Na-salicylate) were also studied on decyltrimethylammonium bromide representatives. The cmc, counterion binding, and energetics of micellization were evaluated and discussed. The energetic parameters, enthalpy, entropy, and specific heat of micellization obtained from direct calorimetry and the indirect van't Hoff method were compared and discussed.

Mesoscopic and Microscopic Investigation on Poly(vinyl alcohol) Hydrogels in the Presence of Sodium Decylsulfate

The structure of poly(vinyl alcohol) (PVA) hydrogels formed as a result of freeze/thaw treatments of aqueous solutions of the polymer (11 wt % PVA) in the freshly prepared state is analyzed through the combined use of small (SANS) and ultrasmall (USANS) angle neutron scattering techniques. The structure of these hydrogels may be described in terms of polymer rich regions, with dimensions of the order of 1-2 microm, dispersed in a water rich phase, forming two bicontinuous phases. The PVA chains in the polymer rich phase form a network where the cross-linking points are mainly crystalline aggregates of PVA having average dimensions of approximately 45 A. The structural organization of freeze/thaw PVA hydrogel membranes does not change either after rehydration of dried gels or in the presence of a tensile force. Finally, addition of surfactant micelles inside the gel provides a formulation with both hydrophobic and hydrophilic regions, which demonstrates the potential of the system for drug delivery. Both SANS and EPR measurements show that sodium decylsulfate (C10OS) micelles do not significantly interact with the PVA gel. Variation of the gel structure by the number of freeze/thaw cycles should modulate the rate of release of an active constituent, for example, in a dermal patch.

The effects of alkyl sulfates on the analysis of phenolic compounds by microchip capillary electrophoresis with pulsed amperometric detection

The effects of different surfactants (sodium 2-ethylhexyl sulfate, sodium decyl sulfate, sodium dodecyl sulfate and sodium tetradecyl sulfate) on the analysis of phenolic compounds by microchip-CE with pulsed amperometric detection were investigated. Using sodium decyl sulfate as a model surfactant, the effects of concentration and pH were examined. Under the optimized conditions, the analysis of six phenolic compounds was performed and compared with control runs performed without surfactant. When these surfactants were present in the run buffer, decreases in the migration time and increases in the run-to-run reproducibility were observed. Systematic improvements in the electrochemical response for the phenolic compounds were also obtained. According to the results presented, surfactants enhance the analyte-electrode interaction and facilitate the electron transfer process. These results should allow a more rational selection of the surfactants based on their electrophoretic and electrochemical effects.

Electrochemical Behavior of Catecholamines and Related Compounds at In Situ Surfactant Modified Carbon Paste Electrodes

AbstractThe voltammetric characteristics of catecholamines: epinephrine (E) and norepinephrine (NE) and related compounds: isoproterenol, metanephrine, L‐dopa, methyldopa, vanillylmandelic acid (VMA), and homovanillic acid (HVA) at unmodified and in situ surfactant‐ modified carbon paste electrodes were comparatively evaluated. For the basic and amphoteric compounds the modification of the electrode surface with submicellar concentrations of anionic surfactants (sodium dodecylsulfate, sodium decylsulfate or sodium dodecylsulfonate) produce an important current enhancement in its oxidation and reduction peak current together with the improvement in the reversibility of the processes. These effects were explained in basis on electrostatic and hydrophobic interactions. On the other hand, the oxidation of acidic metabolites, HVA and VMA, was studied at electrodes modified in situ with cationic surfactants. Under certain conditions the surfactant could stabilise some of the electrochemical reaction intermediates, thus explaining the different voltammetric behaviour of HVA and VMA.

Physico-chemical and structural properties of hydrogels formed by chitosan, in the presence and absence of poly(vinylpyrrolidone) and sodium decylsulfate

The structure of chemically-crosslinked chitosan and chitosan-poly(vinylpyrrolidone) (PVP) hydrogels is investigated by means of the combined use of small-angle neutron scattering (SANS), electron paramagnetic resonance spectroscopy (EPR), intradiffusion, and swelling degree measurements. These hydrogels may be described in terms of an inhomogeneous structure composed by polymer-rich and polymer-poor regions. The polymer-rich regions, whose correlation distance zeta is ranged between approximately 600 and approximately 850 A, are, in turn, characterized by the presence of a network formed by the chemical crosslinks, with a mean correlation distance xi approximately 90 A. The structures of chitosan and chitosan-PVP hydrogels have also been analyzed in the presence of sodium decylsulfate micelles that could provide a multidomain system useful, in principle, for drug delivery applications. Both SANS and EPR measurements show that sodium decylsulfate micelles do not significantly interact with both the gels. Finally, intradiffusion and swelling degree measurements show an improved hydrophilicity of chitosan-PVP gels, even further magnified by the presence of C10OS surfactant.