Micellar Sodium Dodecyl Sulfate Research Articles

Ultrathin Micellar Foam Films of Sodium Caseinate Protein Solutions

Sodium caseinates (NaCas), derived from milk proteins called caseins, are often added to food formulations as emulsifiers, foaming agents, and ingredients for producing dairy products. In this contribution, we contrast the drainage behavior of single foam films made with micellar NaCas solutions with well-established features of stratification observed for the micellar sodium dodecyl sulfate (SDS) foam films. In reflected light microscopy, the stratified SDS foam films display regions with distinct gray colors due to differences in interference intensity from coexisting thick-thin regions. Using IDIOM (interferometry digital imaging optical microscopy) protocols we pioneered for mapping nanotopography of foam films, we showed that drainage via stratification in SDS films proceeds by the expansion of flat domains that are thinner than surrounding by a concentration-dependent step-size, and nonflat features (nanoridges and mesas) form at the moving front. Furthermore, stratifying SDS foam films show stepwise thinning, such that the step-size and terminal film thickness decrease with concentration. Here we visualize the nanotopography in protein films with high spatiotemporal resolution using IDIOM protocols to address two long-standing questions. Do protein foam films formulated with NaCas undergo drainage via stratification? Are thickness transitions and variations in protein foam films determined by intermicellar interactions and supramolecular oscillatory disjoining pressure? In contrast with foam films containing micellar SDS, we find that micellar NaCas foam films display just one step, nonflat and noncircular domains that expand without forming nanoridges and a terminal thickness that increases with NaCas concentration. We infer that the differences in adsorbing and self-assembling unimers triumph over any similarities in the structure and interactions of their micelles.

Copper Binding and Redox Activity of α-Synuclein in Membrane-Like Environment.

α-Synuclein (αSyn) constitutes the main protein component of Lewy bodies, which are the pathologic hallmark in Parkinson's disease. αSyn is unstructured in solution but the interaction of αSyn with lipid membrane modulates its conformation by inducing an α-helical structure of the N-terminal region. In addition, the interaction with metal ions can trigger αSyn conformation upon binding and/or through the metal-promoted generation of reactive oxygen species which lead to a cascade of structural alterations. For these reasons, the ternary interaction between αSyn, copper, and membranes needs to be elucidated in detail. Here, we investigated the structural properties of copper-αSyn binding through NMR, EPR, and XAS analyses, with particular emphasis on copper(I) coordination since the reduced state is particularly relevant for oxygen activation chemistry. The analysis was performed in different membrane model systems, such as micellar sodium dodecyl sulfate (SDS) and unilamellar vesicles, comparing the binding of full-length αSyn and N-terminal peptide fragments. The presence of membrane-like environments induced the formation of a copper:αSyn = 1:2 complex where Cu+ was bound to the Met1 and Met5 residues of two helical peptide chains. In this coordination, Cu+ is stabilized and is unreactive in the presence of O2 in catechol substrate oxidation.

NMR Studies on the Interaction of Anticancer Drug Doxorubicin with Membrane Mimetic SDS.

In the formulation of efficient drug delivery systems, it is essential to unravel the structural and dynamical aspects of the drug's interaction with biological membranes. This has been done for the anticancer drug-membrane system comprising doxorubicin hydrochloride (DOX), a water-soluble anticancer drug, and the micellar sodium dodecyl sulfate (SDS), the latter serving as a useful mimic for membrane proteins. Using a multimodal NMR approach involving 1H, 2H, and 13C as probe nuclei and through the determination of chemical shifts, spin-relaxation, nuclear Overhauser enhancements (NOE), and translational self-diffusion (SD), the binding characteristics of the DOX with SDS have been determined. The perturbation to 13C chemical shifts of SDS indicate the penetration of DOX into the SDS micelle, which is further revealed by 1H-1H NOESY and SD measurements. 2H spin-relaxation measurements and their analysis using a two-step model show DOX induced SDS micellar volume changes, which determine the correlation times involved in the DOX-SDS mobility.

Physical-Chemical Characterization of Bilayer Membranes Derived from (±) α-Tocopherol-Based Gemini Lipids and Their Interaction with Phosphatidylcholine Bilayers and Lipoplex Formation with Plasmid DNA.

Membrane formation and aggregation properties of two series of (±) α-tocopherol-based cationic gemini lipids without and with hydroxyl functionalities at the headgroup region (TnS n = 3, 4, 5, 6, 8, and 12; THnS n = 4, 5, 6, 8, and 12) with varying polymethylene spacer lengths were investigated extensively while comparing with the corresponding properties of the monomeric counterparts (TM and THM). Liposomal suspensions of each cationic lipid were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), zeta potential measurements, and small-angle X-ray diffraction studies. The length of the spacer and the presence of hydroxyl functionalities at the headgroup region strongly contribute to the aggregation behavior of these gemini lipids in water. The interaction of each tocopherol lipid with a model phospholipid, 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC)-derived vesicles, was thoroughly examined by differential scanning calorimetry (DSC) and 1,6-diphenyl-1,3,5-hexatriene (DPH)-doped fluorescence anisotropy measurements. The binding efficiency of the cationic tocopherol liposomes with plasmid DNA (pDNA) was followed by an ethidium bromide (EB) exclusion assay and zeta potential measurements, whereas negatively charged micellar sodium dodecyl sulfate (SDS)-mediated release of the pDNA from various preformed pDNA-liposomal complexes (lipoplex) was studied by an ethidium bromide (EB) reintercalation assay. The structural transformation of pDNA upon complexation with liposome was characterized using circular dichroism (CD) spectroscopic measurements. Gemini lipid-pDNA interactions depend on both the presence of hydroxyl functionalities at the headgroups and the length of the spacer chain between the headgroups. Succinctly, we performed a detailed physical-chemical characterization of the membranes formed from cationic monomeric and gemini lipids bearing tocopherol as their hydrophobic backbone and describe the role of inserting the -OH group at the headgroup of such lipids.

Surface-Induced Crystallization of Sodium Dodecyl Sulfate (SDS) Micellar Solutions in Confinement.

We investigate the role of confinement on the onset of crystallization in subcooled micellar solutions of sodium dodecyl sulfate (SDS), examining the impact of sample volume, substrate surface energy, and surface roughness. Using small angle neutron scattering (SANS) and dynamic light scattering (DLS), we measure the crystallization temperature upon cooling and the metastable zone width (MSZW) for bulk 10-30 wt% SDS solutions. We then introduce a microdroplet approach to quantify the impact of surface free energy (18-65 mN/m) and substrate roughness (Rα ≃ 0-60 μm) on the kinetics of surface-induced crystallization through measurements of induction time (ti) under isothermal conditions. While ti is found to decrease exponentially with decreasing temperature (increasing subcooling) for all tested surfaces, increasing the surface energy could cause a significant further reduction of up to ∼40 fold. For substrates with the lowest surface energy and longest ti, microscale surface roughness is found to enhance crystal nucleation, in particular for Rα ≥ 10 μm. Finally, we demonstrate that tuning the surface energy and microscopic roughness can be effective routes to promote or delay nucleation in bulk-like volumes, thus greatly impacting the stability of surfactant solutions at lower temperatures.

Micelles Embedded in Multiphasic Protein Hydrogel Enable Efficient and Air-Tolerant Triplet Fusion Upconversion with Heavy-Atom and Spin-Orbit Charge-Transfer Sensitizers.

The applications of triplet-triplet annihilation-based photon upconversion (TTA-UC) in solar devices have been limited by the challenges in designing a TTA-UC system that is efficient under aerobic conditions. Efficient TTA-UC under aerobic conditions is typically accomplished by using soft matter or solid-state media, which succeed at protecting the triplet excited states of upconverters (sensitizer and annihilator) from quenching by molecular oxygen but fail at preserving their mobility, thus limiting the TTA-UC efficiency (ΦUC). We showcase a protein/lipid hydrogel that succeeded in doing both of the above due to its unique multiphasic design, with a high ΦUC of 19.0 ± 0.7% using a palladium octaethylporphyrin sensitizer. This hydrogel was made via an industrially compatible method using low-cost and eco-friendly materials: bovine serum albumin (BSA), sodium dodecyl sulfate (SDS), and water. A dense BSA network provided oxygen protection while the encapsulation of upconverters within a micellar SDS environment preserved upconverter mobility, ensuring near-unity triplet energy transfer efficiency. In addition to heavy atom-containing sensitizers, several completely organic, spin-orbit charge-transfer intersystem crossing (SOCT-ISC) Bodipy-based sensitizers were also studied; one of which achieved a ΦUC of 3.5 ± 0.2%, the only reported SOCT-ISC-sensitized ΦUC in soft matter to date. These high efficiencies showed that our multiphasic design was an excellent platform for air-tolerant TTA-UC and that it can be easily adapted to a variety of upconverters.

Anion binding to surfactant aggregates: AuCl4− in cationic, anionic and zwitterionic micelles

Quenching of the fluorescence of pyrene by AuCl4− ion was investigated in aqueous micellar solutions of hexadecyltrimethylammonium chloride (CTAC) and 3-(N,N-dimethylmyristylammonio)propanesulfonate (SB3–14) in the presence of 0.010 mol L−1 HCl. Because AuCl4− is excluded from anionic sodium dodecyl sulfate (SDS) micelles due to electrostatic repulsion effects, no quenching of pyrene fluorescence by AuCl4− was observed in micellar SDS. Absorption spectral shifts show that AuCl4− binds strongly to both CTAC and SB3–14 micelles and time-resolved fluorescence results indicate that the quenching of the fluorescence of micelle-solubilized pyrene by AuCl4− is dynamic in nature. Fits of the pyrene fluorescence decays with the Tachiya model for micelle quenching in the limit of slow exchange of quenchers between the aqueous phase and micelles provided estimates of the micelle aggregation numbers that are slightly smaller than those determined with other quenchers, and intramicellar quenching rates 3–4 times higher than those observed with known collisional quenchers. The strong interaction of AuCl4− with SB3–14 and CTAC led to the stabilization of gold nanoparticles, highlighting the use of zwitterionic surfactants for the synthesis of stable and biocompatible gold nanoparticles.

Hybrid micro-emulsion of aniline in sodium dodecyl sulfate micellar solution and sulfonic acids: morphology, electrical, thermal and kinetic studies

Hybrid micro-emulsion of aniline in sodium dodecyl sulfate micellar solution and sulfonic acids: morphology, electrical, thermal and kinetic studies

Conformational Characterization of Native and L17A/F19A-Substituted Dutch-Type β-Amyloid Peptides.

Some mutations which occur in the α/β-discordant region (resides 15 to 23) of β-amyloid peptide (Aβ) lead to familial Alzheimer’s disease (FAD). In vitro studies have shown that these genetic mutations could accelerate Aβ aggregation. We recently showed that mutations in this region could alter the structural propensity, resulting in a different aggregative propensity of Aβ. Whether these genetic mutations display similar effects remains largely unknown. Here, we characterized the structural propensity and aggregation kinetics of Dutch-type Aβ40 (Aβ40(E22Q)) and its L17A/F19A-substituted mutant (Aβ40(L17A/F19A/E22Q)) using circular dichroism spectroscopy, nuclear magnetic spectroscopy, and thioflavin T fluorescence assay. In comparison with wild-type Aβ40, we found that Dutch-type mutation, unlike Artic-type mutation (E22G), does not reduce the α-helical propensity of the α/β-discordant region in sodium dodecyl sulfate micellar solution. Moreover, we found that Aβ40(L17A/F19A/E22Q) displays a higher α-helical propensity of the α/β-discordant region and a slower aggregation rate than Aβ40(E22Q), suggesting that the inhibition of aggregation might be via increasing the α-helical propensity of the α/β-discordant region, similar to that observed in wild-type and Artic-type Aβ40. Taken together, Dutch-type and Artic-type mutations adopt different mechanisms to promote Aβ aggregation, however, the L17A/F19A mutation could increase the α-helical propensities of both Dutch-type and Artic-type Aβ40 and inhibit their aggregation.

Matrix Polymerization of Trimethylmetacryloyloxyethylethylammonium Methyl Sulfate in Sodium Dodecyl Sulfate Micellar Solutions

Matrix Polymerization of Trimethylmetacryloyloxyethylethylammonium Methyl Sulfate in Sodium Dodecyl Sulfate Micellar Solutions

Theory of surfactant diffusion in micellar systems with variable aggregation numbers

The theory of diffusion of both nonionic and ionic surfactants in micellar systems is extended to the case with variable aggregation numbers. General relationships for the mobility and diffusion coefficient of surfactants are derived, and their dependence on the aggregation number variability is analyzed. Theoretical reasoning is supplemented by numerical calculations on the example of the sodium dodecyl sulfate micellar solution. It is shown that the effect of the aggregation number variability can be significant even for spherical micelles when investigating the surfactant diffusion in the vicinity of the critical micelle concentration.

Impact of Micellar Surfactant on Supersaturation and Insight into Solubilization Mechanisms in Supersaturated Solutions of Atazanavir.

The goals of this study were to determine: 1) the impact of surfactants on the "amorphous solubility"; 2) the thermodynamic supersaturation in the presence of surfactant micelles; 3) the mechanism of solute solubilization by surfactant micelles in supersaturated solutions. The crystalline and amorphous solubility of atazanavir was determined in the presence of varying concentrations of micellar sodium dodecyl sulfate (SDS). Flux measurements, using a side-by-side diffusion cell, were employed to determine the free and micellar-bound drug concentrations. The solubilization mechanism as a function of atazanavir concentration was probed using fluorescence spectroscopy. Pulsed gradient spin-echo proton nuclear magnetic resonance (PGSE-NMR) spectroscopy was used to determine the change in micelle size with a change in drug concentration. Changes in the micelle/water partition coefficient, K m/w , as a function of atazanavir concentration led to erroneous estimates of the supersaturation when using concentration ratios. In contrast, determining the free drug concentration using flux measurements enabled improved determination of the thermodynamic supersaturation in the presence of micelles. Fluorescence spectroscopic studies suggested that K m/w changed based on the location of atazanavir solubilization which in turn changed with concentration. Thus, at a concentration equivalent to the crystalline solubility, atazanavir is solubilized by adsorption at the micelle corona, whereas in highly supersaturated solutions it is also solubilized in the micellar core. This difference in solubilization mechanism can lead to a breakdown in the prediction of amorphous solubility in the presence of SDS as well as challenges with determining supersaturation. PGSE-NMR suggested that the size of the SDS micelle is not impacted at the crystalline solubility of the drug but increases when the drug concentration reaches the amorphous solubility, in agreement with the proposed changes in solubilization mechanism. Micellar solubilization of atazanavir is complex, with the solubilization mechanism changing with differences in the degree of (super)saturation. This can result in erroneous predictions of the amorphous solubility and thermodynamic supersaturation in the presence of solubilizing additives. This in turn hinders understanding of the driving force for phase transformations and membrane transport, which is essential to better understand supersaturating dosage forms.

Small-angle X-ray scattering in sodium dodecyl sulfate solutions and micelle clustering

The small-angle X-ray scattering (SAXS) in micellar sodium dodecyl sulfate solutions has been studied in the range of overall concentrations c from 8 mM (CMC1) to 300 mM and the absolute values of scattering vector q from 0.07 to 3.0 nm–1. The total intensity of isotropic scattering has been revealed to increase with solution concentration. At c > 27 mM, the SAXS spectra have been found to exhibit an interference peak, which testifies a correlation in the arrangement of micelles in the bulk solution. This peak corresponds to the magnitude of q close to 1.55 nm–1. Using the position of this maximum, average distance r 0 between the centers of micelles has been determined, which is equal to 4.1 nm and remains almost unchanged upon an increase in the overall concentration of sodium dodecyl sulfate. The observed regularities have been explained in terms of the DLVO theory taking into account the electrostatic and molecular intermicellar interaction.

Electrical percolation in micellar sodium dodecyl sulfate solutions. a phenomenological consideration

Effects of electrical percolation accompanying variations in overall surfactant concentration с have been studied by the example of micellar sodium dodecyl sulfate solutions. It has been found that, in the studied concentration range of 0.001–1.2 M, dependences of electrical conductivity K on c may exhibit at least three break points, with the dK/dc derivatives changing in the vicinities of these points. At two of these points, which are reliably identified and correspond to critical micelle concentrations (CMC1 and CMC2), they decrease. At the third concentration, lying between CMC1 and CMC2, the dK/dc derivative increases. A substantiated assumption has been put forward that this break point, at which the dK/dc derivative increases, results from the clustering of micelles and the appearance of channels with a higher specific conductivity, which is provided by the contribution from the electrical conductivity of the diffuse and dense parts of micelle electrical double layers, upon the formation of clusters. The ionic surfactant concentration that corresponds to the break point at which the dK/dc value increases has been denoted as the critical percolation concentration.

Isothermal Crystallization Kinetics of Sodium Dodecyl Sulfate–Water Micellar Solutions

The crystallization mechanisms and kinetics of micellar sodium dodecyl sulfate (SDS) solutions in water, under isothermal conditions, were investigated experimentally by a combination of reflection optical microscopy (OM), differential scanning calorimetry (DSC), and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The rates of nucleation and growth were estimated from OM and DSC across temperatures ranging from 20 to −6 °C for 20% SDS-H2O, as well as for 10 and 30% SDS-H2O at representative temperatures of 6, 2, and −2 °C. A decrease in temperature increased both nucleation and growth rates, and the combined effect of the two processes on the morphology was quantified via both OM and ATR-FTIR. Needles, corresponding to the hemihydrate polymorph, become the dominant crystal form at ≤ −2 °C, while platelets, the monohydrate, predominate at higher temperatures. Above 8 °C, crystallization was only observed if seeded from crystals generated at lower temperatures. Our results pr...

Studies on the anticancer drug mitoxantrone–DNA–sodium dodecyl sulfate system

The interaction of anticancer drug mitoxantrone with sodium dodecyl sulfate (SDS) in the presence of two fixed DNA concentrations (1.75×10−5M, when electrostatic binding of positively charged mitoxantrone at negatively charged DNA prevails and 1.50×10−4M, when mitoxantrone molecules intercalate between DNA base pairs) was investigated by UV–Visible absorption spectroscopy.For both DNA concentrations, the spectral results indicate two processes: process I in premicellar SDS concentration assigned to electrostatic interaction between positively charged mitoxantrone and negatively charged SDS monomers, and process II in micellar SDS concentration when the surfactant micelles are formed and mitoxantrone is encapsulated in micelles as monomer. Absorption and circular dichroism spectroscopy, and thermal denaturation studies evidenced the exclusion of intercalated mitoxantrone from DNA and further their encapsulation in SDS micelles.The values of the total binding free energies show that the interaction of (mitoxantrone–DNA)complex with SDS is favored in the presence of low DNA concentration (−15.96kcal/mol), when drug molecules are electrostatically bound to DNA, than in the presence of high DNA concentration (−10.62kcal/mol) when drug molecules are intercalated between base pairs of DNA. This difference in the total binding free energies can be attributed to the cost of the deintercalation process of mitoxantrone from DNA.

A nano self-assembled artificial peroxidase: spectroscopic and electrochemical investigations

A nano-micelle with highly efficient peroxide activity was constructed by self-assembly of sodium dodecyl sulfate micellar, histidine and hematin in 50 mM phosphate buffer at 25 °C. UV–Vis spectrometry methods were utilized for characterization of the nanostructured material or artificial peroxidase (AP). The Michaelis–Menten (K m) and catalytic rate (k cat) constants of the AP were obtained to be 5.5 μM and 0.06 s−1, respectively, in 50 mM phosphate buffer solution at pH 8.0. The catalytic efficiency of AP was evaluated to be 0.011 μM−1 s−1. The AP was also immobilized on a functional multi-wall carbon nanotubes-gold nanoparticles (AuNPs) nano-complex modified glassy carbon electrode (GCE). The transmission electron microscopy method was utilized for the characterization of the nano-materials. The electron-transfer rate constant (k s) and the apparent Michaelis–Menten constant K m app of the AP modified GCE were evaluated to be 1.36 s−1 and 0.19 μM, respectively. For a biosensor without a redox protein, the properties of the AP modified GCE were significant and will further benefit from additional studies and improvement.

Complexing Properties of Acid Alizarin Violet with Copper, Cobalt and Nickel in Micellar Media Containing SDS, CTAB and TX-100

The interaction of the dye acid alizarin violet (AVN) with three transition metals was followed spectrophotometrically in water and in micellar solutions of the cationic cetyltrimethylammonium bromide (CTAB), the anionic sodium dode- cyl sulfate (SDS) and the nonionic triton X-100 (TX-100). The stoichiometric ratios for the complexes of AVN with each metal ion were determined by the mole ratio and the continuous variation methods. In water, the metal to dye ratios in the complexes were 1:2, 1:3 and 1:1 for Cu2+, Co2+ and Ni2+, respectively. For Ni2+ the ratio changed to 1:3 in micellar CTAB. All other ratios were unchanged in the three micellar solutions. The formation constant (βn) of the complex in water was 1.00 × 1010 for Cu2+, 4.66 × 1014 for Co2+ and 9.03 × 104 for Ni2+. βn decreased in micellar TX-100: for Cu2+ to 6.88 × 108, for Co2+ to 1.56 × 1014 and for Ni2+ to 8.65 × 104. By contrast, micellar CTAB increased βn for Cu2+ and Ni2+. For Cu2+, the increase was to 5.19 × 1010, but for Ni2+ a large jump was observed, to 1.16 × 1015. For Co2+, βn dropped to 2.16 × 1014 in CTAB. Micellar SDS decreased βn for Cu2+ and Co2+ complexes to 5.38 × 109 and 1.76 × 1014, respectively, but increased that of the Ni2+ complex to 4.40 × 105. These observations were explained in terms of structural properties.

Conformational Behavior and Aggregation of Ataxin-3 in SDS

Spinocerebellar ataxia type 3 (SCA3) is one of nine polyglutamine (polyQ) diseases all characterized by the presence of intraneuronal inclusions that contain aggregated protein. Aggregation of ataxin-3, the causative protein of SCA3, has been well characterized in vitro, with both pathogenic and non-pathogenic length ataxin-3 undergoing fibrillogenesis. However, only ataxin-3 containing an expanded polyQ tract leads to SCA3. Therefore other cellular factors, not present in previous in vitro studies, may modulate aggregation during disease. The interactions between fibrillar species and cell membranes have been characterized in a number of amyloid diseases, including Huntington’s Disease, and these interactions affect aggregation and toxicity. We have characterized the effects of the membrane mimetic sodium dodecyl sulfate (SDS) on ataxin-3 structure and aggregation, to show that both micellar and non-micellar SDS have differing effects on the two stages of ataxin-3 aggregation. We also demonstrate that fibrillar ataxin-3 binds phospholipids, in particular phosphorylated phosphotidylinositols. These results highlight the effect of intracellular factors on the ataxin-3 misfolding landscape and their implications in SCA3 and polyQ diseases in general are discussed.

Sodium dodecyl sulfate in water: greener approach for the synthesis of quinoxaline derivatives

A mild and efficient synthetic method has been developed for the preparation of biologically important quinoxalines in excellent yield from relatively safe precursor α-bromoketones and 1,2-diamines using catalytic amount of micellar sodium dodecyl sulfate in water at ambient temperature. The method is also found effective for the introduction of quinoxaline moiety into the ring A of pentacyclic triterpenoid, friedelin. Ambient reaction conditions, renewable catalytic condition, inherently safer chemistry, excellent product yields, and water as a reaction medium display both economic and environmental advantages.